Engineering Accessible Adsorption Sites in Metal Organic Frameworks for CO2 Capture
Saki T. Golafale, Kennedi Trice, Taylor Sledge
Dr. Conrad W. Ingram (PI), Dr. Tandabany C. Dinadayalane (Co-PI)Department of Chemistry, Clark Atlanta University, Atlanta, GA
30314
DOE contract No.: DE-FE00229522017 Crosscutting Research & Rare Earth Elements Portfolios
Review March 20-23, 2017 Pittsburgh, PA
1
• Background• Research goal and objectives • Progress
• Diaza-crown ether MOFs
• Ultra large pore stilbene based MOFs
• Stilbene and pyrazine based MOFs
• CO2 adsorption studies• Summary• Acknowledgement
2
Post-combustion Capture: capturing carbon dioxide from flue gas after fossil fuel combustion
~14% CO2 captured from flue gas
Current techniques pursued • adsorption on a solid
• hybrid processes, such as adsorption/membrane systems
• absorption into a liquid
Flue gas contains about 15% of CO2, 75% of N2, 5% of H2O, 3% of O2,
3
Drawback large amounts of heat are needed to release absorbed CO2
amine is corrosive and unstable, and the liquid is hard to handle.
4
state of the art technology
Required characteristics for solid adsorbents
• High storage capacity,
• Excellent selectivity over other gases,
• Chemically stable under flue gas of power plants,•• Easy to regenerate with minimal energy input, and•• Easily synthesized with low capital cost
5
• Activated carbon
• Zeolites and other inorganic porous materials
• Metal-organic frameworks
Unique properties of MOFs• Highly crystalline nature• Permanent porosity• Uniformed pore-size and large surface area (> 5,000 m2/g)• Tunable chemistry
6
Metal ion + Organic linker MOF material
HO
OHHO
O O
O
Ditopic linker tritopic linker polytopic linker
Examples of Metal salts
Mg(NO3)2 . 6H2O
Zn(NO3)2 . 6H2O
ZrCl4
Metal salts
Examples of organic linkers
7
GoalTo develop metal organic framework (MOFs) materials with improved sites accessibility, thus enhance their CO2 adsorption and selectivity properties
Objectives• To synthesize MOFs with metal ions adsorption sites in more accessible
locations
• To synthesize MOFs with nitrogen containing-ligand/linker as a possible improved alternative to amine-functionalized
• To understand the nature of the adsorption sites and mechanism(s) by computational studies relevant to the adsorption of CO2 within our metal organic frameworks
8
3D interpenetrated Cobalt MOF
+ Co2+
9
Synthesis of nitrogen diaza-crown containing MOFs with metal in center for CO2 adsorption
Ongoing work
3D MOFs using diaza crown ether ligand and with metal within center of crown ether but the structure is nonporous
10
Summary of diaza-crown ether MOFs
O
OHO
OH
HO O
OHO
NH2
H2N
HO O
OHO
NO2
O2N
N
N
OH
O
HO
O
Stilbene linkers Pyrazine linkers
• Rigid or flexible MOFs• Non-interpenetration in MOFs
11
MOFs from stilbene and pyrazine linkers
O
OHO
OH
Mathis II, Stephan R., Saki T. Golafale, John Bacsa, Alexander Steiner, Conrad W. Ingram, F. Patrick Doty, Elizabeth Auden, and Khalid Hattar. Dalton Transactions 46, no. 2 (2017): 491-500.
Non-interpenetrating structure
Ultra-large pores (dimensions of 23 Å x 12 Å)
Accessible channels
Diamond-shaped open framework
+ Ln3+
12
Stilbene lanthanide MOFs
0 5 10 15 20 25 30 35 40 45 50 550
160003200048000
06100
1220018300
05700
1140017100
0170034005100
Cou
nts
2 Theta
TmSDC
TmSDCH2O
TmSDCMeOH
TmSDCCH3Cl3
X-ray diffraction patterns of solvent exchanged stilbene lanthanide MOFs
Framework could adjust depending on solvent used
13
CO2 adsorption analysis
Micromeritics ASAP 2020
Samples are degassedat temperatures depending on thermal stability
Degassed samples are then analyzed atat 273K and 298K using CO2 as adsorbate gas
Analysis of CO2 capture shows amount adsorbed as a function of pressure (0 to 1 bar)
CO2 adsorption isotherms of stilbenelanthanide MOF
0.18
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
Amou
nt A
dsor
bed
(mm
ol/g
)
Ln-SDC-AS-273 K Ln-SDC-AS-298 K
0.0 0.2 0.4 0.6 0.8 1.0Relative Pressure (P/Po)28
0.04
0.02
0.06
0.14
0.12
0.10
0.08
Amou
ntAd
sorb
ed(m
mol
/g)
Ln-SDC-H2O-273 KLn-SDC-H2O-298 K
0.000.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/Po)
29
CO2 adsorption isotherms of s t i lbene lanthanide stilbene MOF soaked in H2O
HO O
OHO
NH2
H2N
Contains amine functional groups Open and accessible frameworkCO2 adsorption studies ongoing
+ Ln3+
Amino-stilbene Lanthanide MOFs
17
HO O
OHO
NH2
H2N
+ Cd2+
18
Amino-stilbene based transition metal MOFs
Layered structure bridged via H-bonding and metal-O/N coordinationExploring different synthesis conditions
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Mixed Ligand Hafnium MOFHO O
OHO
NO2
O2N
O
OHO
OHVery low density MOF ~0.73 g/cm3
Average Hf-O bond length is 2.1 A
Hf(IV)+ +
20
Inner core Hf6-cluster with strong Hf-O bond key to
stability
Hf-coordinated carboxylates
Mixed Ligand Hafnium MOF
21
Very low density MOF ~0.73 g/cm3
Average Hf-O bond length is 2.1 A
Thermally and structural stable when soaked in acetone for 12 h
Mixed Ligand Hafnium MOF
Space filling model
22
Powder x-ray diffraction and TGA of fresh and solvent exchanged Hafnium MOF
Thermograms of fresh and solvent exchanged HfMOFSolvent exchange show more thermally stable material
Powder X-ray diffraction patterns show no change in structure!
0 200 400 600 800 1000
40
60
80
100
Wei
ght %
Temperature (C)
HfMOF HfMOFacetone
0 5 10 15 20 25 30 35 40 45 50 550
210
420
630
8400
300
600
900
Cou
nts
2 Theta
HfMOF
HfMOFacetone
23
CO2 adsorption isotherm of HfMOF
24
HfMOF
CO2 adsorption isotherm at 25 degrees C showing increasing CO2 adsorption as a function of pressure
CO2 adsorption up to 0.7 mmol/g
N
N
OH
O
OH
O
Pyrazine based MOFs
Metals usedGd3+, Eu2+, Mn2+, Zn2+ Ca2+
Metals usedZr(IV) and Hf(IV)
25
+Gd/or Tb
Open framework Large channels ~ 12Å
Kinetic diameter CO2 3.3Å
Channels contain non-coordinating water
{[Gd4(C8N2O8)3(H2O)11]10H20}n
26Ingram et al. Crystengcommun 2015
0.18
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00Amou
nt A
dsor
bed
(mm
ol/g
)
Ln-SDC-AS-273 K Ln-SDC-AS-298 K
0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/Po)28
Gd-PZTC as synthesized
0.0 0.2 1.0
0.2
0.4
0.6
0.8
1.0Am
ount
adso
rbed
(mm
ol/g
)
0.4 0.6 0.8
Relative pressure (P/Po)
Ln-PZTCA273 K LnPTCA298 K
Gd-PZTC after solvent exchange with chloroform
+Zn2+
29Golafale, Ingram et al. submitted 2017
Calcium pyrazine MOF
+ Ca2+
Golafale, Ingram et al. submitted 2017
+Mn2+
Golafale, Ingram et al. submitted 2017
Zirconium Pyrazine MOF
0 10 20 30 40 50
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
Inte
nsity
(cts
)
2 Theta
Zrpzdc-S4 Zrpzdc-S3 Zrpzdc-S2 Zrpzdc-S1 Zrpzdc-S0
S0 to S4 represent increasing volume of acetic acid added
S0 = no acetic acid added
N
N
OH
O
OH
O
+ Zn(IV)Powder X-ray diffraction
Microcrystalline powder
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Acetic acid has been used as additive to enhance crystallinity of Zirconium MOF
CO2 adsorption isotherms of Zrpzdc
CO2 Adsorption isotherm at 0 degrees C
0.0 0.2 0.4 0.6 0.8 1.00.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Qua
ntity
Ads
orbe
d (m
mol
/g)
P/Po
Zrpzdc273K
0.0 0.2 0.4 0.6 0.8 1.0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40 Zrpzdc298K
Qua
ntity
Ads
orbe
d (m
mol
/g)
P/Po
33
CO2 Adsorption isotherm at 25 degrees C
Langmuir Transform model
60 80 100 120 140 160 180 200 220
300
350
400
450
500
550
P/Q
(mm
Hg.
g/m
mol
)
Pressure (mmHg)
Raw data Zrpzdc273K Linear fit
Langmuir Equation P/Q=1/qm*b+P/qPlot P/Q v PIntercept 183.03975 ± 7.3Slope 1.8457 ± 0.0515R-Square 0.99611
60 80 100 120 140 160 180 200 220
700
750
800
850
900
950
1000
Raw data Zrpzdc298K Linear fit
P/Q
(mm
Hg·
g/m
mol
)Pressure (mmHg)
Langmuir Equation P/Q=1/qm*b+P/qmPlot P/Q v PIntercept 584.8749 ± 13.026Slope 1.99026 ± 0.0939R-Square 0.98679
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𝑷𝑷𝑸𝑸
= ⁄𝟏𝟏 𝒒𝒒𝒎𝒎 ∗ 𝒃𝒃 + ⁄𝑷𝑷 𝒒𝒒𝒎𝒎 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 =𝟏𝟏𝒒𝒒𝒎𝒎 𝑰𝑰𝑰𝑰𝑰𝑰𝑺𝑺𝑰𝑰𝑰𝑰𝑺𝑺𝑺𝑺𝑰𝑰 =
𝟏𝟏𝒒𝒒𝒎𝒎 ∗ 𝒃𝒃
@ 𝟐𝟐𝟐𝟐 𝒅𝒅𝑺𝑺𝒅𝒅𝑰𝑰𝑺𝑺𝑺𝑺𝒅𝒅 𝑪𝑪,𝒒𝒒𝒎𝒎 = 𝟎𝟎.𝟐𝟐𝟎𝟎𝟐𝟐𝒎𝒎𝒎𝒎𝑺𝑺𝑺𝑺𝒅𝒅
; @ 𝟎𝟎 𝒅𝒅𝑺𝑺𝒅𝒅𝑰𝑰𝑺𝑺𝑺𝑺 𝑪𝑪 𝒒𝒒𝒎𝒎 = 𝟎𝟎.𝟐𝟐𝟓𝟓𝟐𝟐𝒎𝒎𝒎𝒎𝑺𝑺𝑺𝑺𝒅𝒅
Adsorption models to be used
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@ 𝟐𝟐𝟐𝟐 𝒅𝒅𝑺𝑺𝒅𝒅𝑰𝑰𝑺𝑺𝑺𝑺𝒅𝒅 𝑪𝑪,𝒒𝒒𝒎𝒎 = 𝟎𝟎.𝟐𝟐𝟎𝟎𝟐𝟐𝒎𝒎𝒎𝒎𝑺𝑺𝑺𝑺𝒅𝒅
; @ 𝟎𝟎 𝒅𝒅𝑺𝑺𝒅𝒅𝑰𝑰𝑺𝑺𝑺𝑺 𝑪𝑪 𝒒𝒒𝒎𝒎 = 𝟎𝟎.𝟐𝟐𝟓𝟓𝟐𝟐𝒎𝒎𝒎𝒎𝑺𝑺𝑺𝑺𝒅𝒅
@ 𝟎𝟎 𝒅𝒅𝑺𝑺𝒅𝒅𝑰𝑰𝑺𝑺𝑺𝑺 𝑪𝑪,𝒃𝒃 = 𝟎𝟎.𝟎𝟎𝟏𝟏𝟎𝟎𝟏𝟏@ 𝟐𝟐𝟐𝟐 𝒅𝒅𝑺𝑺𝒅𝒅𝑰𝑰𝑺𝑺𝑺𝑺𝒅𝒅 𝑪𝑪,𝒃𝒃 = 𝟎𝟎.𝟎𝟎𝟎𝟎𝟎𝟎𝟓𝟓
Langmuir constant
Finally, we can use the Langmuir constants and the temperatures at 0 and 25 degrees to determine the
thermodynamics of adsorption
Gibbs free energy (G), enthalpy (H), and entropy (S)
Quantity adsorbed
Summary
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• Synthesized MOFs with metals in accessible sites for CO2adsorption but no CO2 capacity
• Synthesized nitrogen functionalized non-interpenetrating MOFs structure showing promising CO2 capacity
US Department of Energy, National EnergyTechnology Laboratory
DOE Contract FE0022952
Chemistry Department, Clark Atlanta University
Dr. Conrad W. Ingram (PI)
Dr. Tandabany C. Dinadayalane (Co-PI)
Taylor Sledge (Undergraduate)
Kennedi Trice (Undergraduate)