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Metal-Organic Frameworks의
합성 및 응용
Metal-Organic Frameworks의
합성 및 응용
2010 825
2010 제올라이트학교KAIST 응용 공학동
그린화학연구단 바이오리파이너연구센터
황영규
Introduction
Synthesis of MOFs
Applications
목 차목 차
Characteristics of MOFs
Introduction
Page sect 4
What is Metal-organic framework (MOF)
Metal-Organic Frameworks arecrystalline compounds consisting ofmetal ions or clusters coordinatedto often rigid organic molecules toform one- two- or three-dimensional structures that can beporous (Wikipediaorg)
Coordination polymers(CP)Metal-organic frameworks(MOF)Porous coordination network(PCN)Porous coordination polymer(PCP)MIL (Material from Institute Lavoisier)POST-1HKUST-1UMCM-1
Crystal Growth amp Design 9 2969-2970 (2009)
Page sect 5
Evolution of Coordination Polymers (or MOFs)
Hoskins and Robson J Am
Chem Soc 112 1546 (1990)
Yaghi et al J Am Chem Soc 117 10401 (1995)
Yaghi et al Nature 378 703 (1995)
Tomic et al J Appl Polym Sci 9 3745 (1965)
Addressed as MOFs coordination polymers
or supramolecularstructures
15-Dihydroxynaphthalene-26-dicarboxylic acid formed
coordination polymers with Zn Ni Al and Fe+3
1960s Early 1990s Middle 1990s
Bailar et al Prep Inorg React 1 1 (1964)
Copper 44prime-bipyridyl complex that exhibited extended metal-organic interactions
Page sect 6
A Various Organic Linkers
Page sect 7
A Various Organic Linkers
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Introduction
Synthesis of MOFs
Applications
목 차목 차
Characteristics of MOFs
Introduction
Page sect 4
What is Metal-organic framework (MOF)
Metal-Organic Frameworks arecrystalline compounds consisting ofmetal ions or clusters coordinatedto often rigid organic molecules toform one- two- or three-dimensional structures that can beporous (Wikipediaorg)
Coordination polymers(CP)Metal-organic frameworks(MOF)Porous coordination network(PCN)Porous coordination polymer(PCP)MIL (Material from Institute Lavoisier)POST-1HKUST-1UMCM-1
Crystal Growth amp Design 9 2969-2970 (2009)
Page sect 5
Evolution of Coordination Polymers (or MOFs)
Hoskins and Robson J Am
Chem Soc 112 1546 (1990)
Yaghi et al J Am Chem Soc 117 10401 (1995)
Yaghi et al Nature 378 703 (1995)
Tomic et al J Appl Polym Sci 9 3745 (1965)
Addressed as MOFs coordination polymers
or supramolecularstructures
15-Dihydroxynaphthalene-26-dicarboxylic acid formed
coordination polymers with Zn Ni Al and Fe+3
1960s Early 1990s Middle 1990s
Bailar et al Prep Inorg React 1 1 (1964)
Copper 44prime-bipyridyl complex that exhibited extended metal-organic interactions
Page sect 6
A Various Organic Linkers
Page sect 7
A Various Organic Linkers
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Introduction
Page sect 4
What is Metal-organic framework (MOF)
Metal-Organic Frameworks arecrystalline compounds consisting ofmetal ions or clusters coordinatedto often rigid organic molecules toform one- two- or three-dimensional structures that can beporous (Wikipediaorg)
Coordination polymers(CP)Metal-organic frameworks(MOF)Porous coordination network(PCN)Porous coordination polymer(PCP)MIL (Material from Institute Lavoisier)POST-1HKUST-1UMCM-1
Crystal Growth amp Design 9 2969-2970 (2009)
Page sect 5
Evolution of Coordination Polymers (or MOFs)
Hoskins and Robson J Am
Chem Soc 112 1546 (1990)
Yaghi et al J Am Chem Soc 117 10401 (1995)
Yaghi et al Nature 378 703 (1995)
Tomic et al J Appl Polym Sci 9 3745 (1965)
Addressed as MOFs coordination polymers
or supramolecularstructures
15-Dihydroxynaphthalene-26-dicarboxylic acid formed
coordination polymers with Zn Ni Al and Fe+3
1960s Early 1990s Middle 1990s
Bailar et al Prep Inorg React 1 1 (1964)
Copper 44prime-bipyridyl complex that exhibited extended metal-organic interactions
Page sect 6
A Various Organic Linkers
Page sect 7
A Various Organic Linkers
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 4
What is Metal-organic framework (MOF)
Metal-Organic Frameworks arecrystalline compounds consisting ofmetal ions or clusters coordinatedto often rigid organic molecules toform one- two- or three-dimensional structures that can beporous (Wikipediaorg)
Coordination polymers(CP)Metal-organic frameworks(MOF)Porous coordination network(PCN)Porous coordination polymer(PCP)MIL (Material from Institute Lavoisier)POST-1HKUST-1UMCM-1
Crystal Growth amp Design 9 2969-2970 (2009)
Page sect 5
Evolution of Coordination Polymers (or MOFs)
Hoskins and Robson J Am
Chem Soc 112 1546 (1990)
Yaghi et al J Am Chem Soc 117 10401 (1995)
Yaghi et al Nature 378 703 (1995)
Tomic et al J Appl Polym Sci 9 3745 (1965)
Addressed as MOFs coordination polymers
or supramolecularstructures
15-Dihydroxynaphthalene-26-dicarboxylic acid formed
coordination polymers with Zn Ni Al and Fe+3
1960s Early 1990s Middle 1990s
Bailar et al Prep Inorg React 1 1 (1964)
Copper 44prime-bipyridyl complex that exhibited extended metal-organic interactions
Page sect 6
A Various Organic Linkers
Page sect 7
A Various Organic Linkers
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 5
Evolution of Coordination Polymers (or MOFs)
Hoskins and Robson J Am
Chem Soc 112 1546 (1990)
Yaghi et al J Am Chem Soc 117 10401 (1995)
Yaghi et al Nature 378 703 (1995)
Tomic et al J Appl Polym Sci 9 3745 (1965)
Addressed as MOFs coordination polymers
or supramolecularstructures
15-Dihydroxynaphthalene-26-dicarboxylic acid formed
coordination polymers with Zn Ni Al and Fe+3
1960s Early 1990s Middle 1990s
Bailar et al Prep Inorg React 1 1 (1964)
Copper 44prime-bipyridyl complex that exhibited extended metal-organic interactions
Page sect 6
A Various Organic Linkers
Page sect 7
A Various Organic Linkers
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 6
A Various Organic Linkers
Page sect 7
A Various Organic Linkers
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 7
A Various Organic Linkers
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 8
Isoreticular IRMOFs and Unique Properties
Applications- Gas storagesepartion- CatalystsAdsorbents- Drug delivery- Sensor- Templates
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 9
Metal-organic framework MOF-5(IRMOF-1)
HO O
OHO
H2BDC =
Benzene dicarboxylic acidYaghi et al Nature 402 276-279 (1999)
14-BDC + Zn2+ agrave [Zn4O(RCO2)6] agrave MOF-5
SBULinker
LinkerFlexibility
VoidCavity
+
Highly Stable and Porous MOF
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 10
Pore volumeVP = 104 cm3g
= 060 cm3cm3
Surface areaSL = 2900 m2g
Sorption Isotherms
Faujasite
VP = 048 cm3g
SL = 500 m2g
amou
nt s
orbe
d (m
gg)
PP0
Sorption Properties of MOF-5
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 11
MOF-177 [Zn4(O)(BTB)215DEF3H2O]
H3BTB + Zn(NO3)2 bull 6 (H2O)
Zn4(O)(BTB)2bull 15DEF bull 3H2OMOF-177
Chae H K Kim J Go Y Eddaoudi M A J Matzger Yaghi O M Nature 2004 427 523
BTB 135-benzenetribenzoate
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 12
0
300
600
900
1200
1500
0 02 04 06 08 1
Am
ount
sor
bed
(mg
g)
PP0
N2 sorptionN2 desorption
Surface area = 4500 m2gPore volume = 159 cm3g
(069 cm3cm3)
N2 sorption isotherm for Zn4O(BTB)2 (MOF-177)
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 13
Yaghi
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 14
Ultrahigh Porosity in Metal-Organic Frameworks
Kim et al Science 329 424 (2010)
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 15
A Chromium Terephthalate MIL-101
Giant cell volume~702000Aring
Langmuir surface area~5900 m2g
Large pore size30-34Aring
Ferey et al Science 309 2040 (2005)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 16
Porous Coordination Polymers
A rigid metalndashorganic coordination framework
[Co2(44-bipy)3(NO3)4]4H2O]n
Angew Chem Int Ed 36 1725 (1997)
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 17
A Chemically Functionalizable MOF Cu3(BTC)2(H2O)3]n
HKUST-1SBET = 1390 m2g
SY Chui et al Science 283 1148 (1999)
17
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 18
Zeolite Imidazolate Frameworks
ZIF-20 Hayashi et al Nat Mat 2007
Metal-Organic Polyhedra(MOP)
Eddaoudi et al JACS 2001
New Types of Crystalline Porous Hybrids
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 19
On The Road German adventurer Zietlowposes in Egypt in November 2006 during his 28000-mile driving expedition in a natural-gas-fueled vehicle The vehicle was equipped with fuel tanks that were modified with MOF compounds to increase their storage capacity
Now In Stores A worker packages MOF materials produced in kilogram batches at BASFs pilot plant in Ludwigshafen Germany
Heading To Market With MOFs
Methane Hoarder This framework compound dubbed PCN-14 is composed of dicopper paddlewheel units and linkers based on an anthracene derivative Among porous materials PCN-14 holds the record for methane storage Cu is turquoise C is gray and O is red
Room To SpareChromium trimers (left center) and the carboxylate linkers trimesate (left top) and terephthalate(left bottom) combine to form supertetrahedra from which the framework compounds MIL-100 and MIL-101 are constructed Each compound contains smaller and larger nanometer-sized cages accessible via interconnecting windows The MIL-100 small cage is 25 Aring in diameter MIL-100 large cage 29 Aring MIL-101 small cage 29 Aring MIL-101 large cage 34 Aring Cr is yellow C is white O is red and H2O is green
CampEN Cover 200805
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 20
The pervasive chemistry of metal-organic frameworks
Chem Soc Chem 38 1213 (2009)
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Synthesis
sect SolvothermalHydrothermal synthesissect Microwave or Sonochemical synthesissect Electrochemical synthesissect Ionothermal synthesis
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 22
Molecular Building Blocks (or Secondary Building Blocks) Self-Assembly Crystalline Solids
How to design or synthesize
If appropriate SBUs andligands chose desired MOFcan be formed depending on reaction condition
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 23
Yaghi et al Nature 402 276-279 (1999)
Solvothermal Syntheses of MOFs
SynthesisSolvothermal bomb placed in autoclaveat 10~100bar and 100oC for 1-4daysScale 30 ~500mgReaction control ManualMonitoring None
Small scale slow reaction
Mueller et al J Mater Chem16 626 (2006)
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 24
In Situ Diffraction Study of solvothermal Crystallization
Millange et al Angew Chem Int Ed 48 1 (2009)
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 25
Microwave (or sonochemical) Syntheses of MOFs
Jhung et al Adv Mater 19 121 (2007)
Ahn et al Chem Commun 6336 (2008)
MOF-5
HKUST-1
Hwang et al Micropor Mesopor Mater 119 331 (2009)
Rapid synthesis of MOFs through microwave-irradiation- Homogeneous and selective heating- fast nucleation and crystallization
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 26
Microwave Synthesis of MIL-101(Cr)
Jhung et al Adv Mater 19 121 (2007)
(c)
(a)
(d)
(b)
200nm
500nm500nm
1 min
10 min
20 min
40 min
200nm
TEM
Nanoparticles
Microwave synthesisMicrowave synthesis at 483 K for 1 ndash 40 min10 Cr(NO3)3middot9H2O 10 BDC 10 HF 280 H2O (BDC = terephthalic acid)
MIL-101 Cr3F(H2O)2O[C6H4(CO2)2]3nH2O n~25
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 27
Ionothermal syntheses of MOFs
Russell E Morris Chem Commun 2990 (2009)
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 28
High-throughput Syntheses of Cobalt Succinates
Forster et al Angew Chem Int Ed 44 7608 (2005)
pH Temperature Concentration and Time
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 29
Electrochemical Synthesis of HKUST-1
Mueller et al J Mater Chem16 626 (2006)
150 min at a 12-19V 13ASBET 1820 m2g
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 30
Large Scale Syntheses of MOFs
Muller et al Chem Soc Rev 38 1284 (2009)
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 31
Nanoscale Syntheses of MOFs
Lin et al Angew Chem Int Ed 47 129 (2008)Lin et al Eur J Inorg Chem 3725 (2010)
Surfactant-assisted synthesis of nanoscaleGadolinium MOFsCTAB1-hexanoln-heptanewater Microemulsions
Ga2(bhc)H2O)6
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 32 Mellot-Draznieks et al Z Anorg Allg Chem 630 2599 (2004)
Computational Design of MILs
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 33
Crystal growth of HKUST-1 by AFM
Whittingham et al Crytstal Growth Design 6 2419 (2006)
How Molecules turn into MOFs
R Morris ChemPhysChem 10 327 (2009)Attfield et al Angew Chem Int Ed 47 8525 (2008)
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 34
Characteristics of MOFs
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 35
Functions of MOFs (Nanospace laboratory)
Kitagawa et al Angew Chem Int Ed 43 2334 (2004)
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 36
Guest-induced transformation of MOFs
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 37 Gerard Ferey Chem Soc Rev 37 191 (2008)
Dynamic frameworks and Breathing of MOFs
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 38
Zeolite A Imidazolate Frameworks (ZIF)
Breakthrough curves
CO2
CH4
Sorption Isothems at 298 K
CO2
CH4
LTA Topology
Yaghi and co-workers Nature Mater 6 501 (2007)
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Applications
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 40 40
Hydrogen storage capacities of MOFs
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 41
Hydrogen storage of HKUST-1
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 42
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 43
Carbon Dioxide Capture of MOFs
0 10 20 30 40 500
200
400
600
800
Pressure (bar)Am
ount
ads
orbe
d (c
m3 g
)
0
10
20
30
40
Amount adsorbed (m
molg)
COCO22 SpongeSponge
MOF-177 Adsorption isotherms of MIL-101at 303 K
Chang et al Langmuir 24 7245 (2008)
176 wt176 wt at 303 K and 50 bars
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 44
Sulfur Sorption of HKUST-1
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 45
Summary of catalytic reaction employing MOFs
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 46
Catalytic Oxidation of Sulfides with H2O2 over MIL-101
aThe reaction time was 12 h bH2O2benzyl phenyl sulfide = 2 cH2O2 efficiency () = 100 x (mole of oxygenated products)(total mole of H2O2 converted)
nCUS = ca 1 mmolg
FOH
H2O H2OCUS
FOH
at 150oC
CUS- 2H2O
m3-O bridged Cr(III) trimer
CrCrCr
CrCrCr
Sulfoxidation
Formation of CUS
Appl Cata A Gen 2009
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 47
CdCl2 + L [Cd3Cl6L3](1)
Ti(OiPr)4
W Lin J Am Chem Soc 127 8940(2005)
Chiral Catalysis in MOF
Kim et al 404 982 (2000)
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 48
Water Resistance of HKUST-1
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 49
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 50
Water Resistance of MOFs
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 51
a
b c
d
e
Surface Functionalization of Cr-MIL-101
Chang et al Angew Chem Int Ed 47 4144-4148 2008 (Cover Figure)
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 52
Ph H
ONC CO2Et H2O
H
Ph CN
CO2Et
+ +
Knoevenagel Condensation over Amine-grafted MIL-101
Reaction conditions 1 mmol of benzaldehyde 1 mmol of ethylcyano-acetate and 20 mg of catalyst20 mg of catalyst in 25 ml of cyclohexane at 80oC
0 5 10 15 200
20
40
60
80
100
Conv
ersi
on o
f CEA
()
Reaction time (h)
APS-MIL-101 DETA-MIL-101 ED-MIL-101 APS-SBA-15
APS-SBA-15(reference)
353 K
cf ED ethylene diamine DETA diethylene triamine APS 3-aminopropyl- triethoxysilane
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 53
Post-functionalization of MOFs
Cohen Chem Soc Rev 38 1315 (2009)
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 54
Depostion of MOFs on Surfaces
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 55
Thin Films of HKUST-1 on Functionalized Surfaces
XRD Patterns of HKUST-1
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 56
Layer-by-Layer growth of Interpenetrated MOFs
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 57
Sensor Device of HKUST-1
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 58
Molecular Sieve Membrane of ZIF-7
Microwave-assisted secondary growth of ZIF-7
ZIF-7 membrane showed a high H2 selectivity for targeting H2CO2 separation
Soladite topology ZIF-7(Zni(bim)2) Hydrophobic thermally stable
small pore(03nm)
Bim benzimidazolate
CO2 033nmH2 029nm
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 59
Drug Delivery of MILs
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
Page sect 60 Chemistry amp Industry 2008
Future of MOFs
경청해 주셔서 감사합니다
경청해 주셔서 감사합니다
