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Summary of NC200 work
Imran & NorliUpdated: 2/8/2007
Objectives
To get high dispersion of nanocarbon on AC.
To get homogeneous nanocarbon.
Experimental Route Diagram
Washing(removes impurities;
eg: Al, Si, Fe, K)
Washing(removes impurities;
eg: Al, Si, Fe, K)
Catalyst Development
Catalyst Development
Nanocarbon Growth
(Thermal-CVD)
Nanocarbon Growth
(Thermal-CVD)
CharacterizationCharacterization• Monometallic (Iron)
• Bimetallic
• Monometallic (Iron)
• Bimetallic
• Compositional analysis (EDX,XRF)
• Morphology/Structure analysis (SEM, HRTEM)
• Texture/Surface Area analysis (BET)
• Mechanical & Electrical Properties Analysis
• Compositional analysis (EDX,XRF)
• Morphology/Structure analysis (SEM, HRTEM)
• Texture/Surface Area analysis (BET)
• Mechanical & Electrical Properties Analysis
• Carbon source (C2H4)
• Carrier gas (H2, N2)
• Carbon source (C2H4)
• Carrier gas (H2, N2)
Substrate (AC)
Substrate (AC)
ImpregnationImpregnation
CNT/FCNT/F
CNT/F Applicatio
n
CNT/F Applicatio
n
• treat with 5M HNO3, T=30oC, 24 hr
• wash with deionized water, dried T=200oC, 2 hr
• treat with 5M HNO3, T=30oC, 24 hr
• wash with deionized water, dried T=200oC, 2 hr
• Cat. + acetic acid/ ethanol
• under ultrasonic, 30 min, 25oC (water bath)
• aging 45hr/12hr, RT, Drynoza
• Cat. + acetic acid/ ethanol
• under ultrasonic, 30 min, 25oC (water bath)
• aging 45hr/12hr, RT, Drynoza
• Acid Base Titration• Iodine Number• Butane Activity
• Acid Base Titration• Iodine Number• Butane Activity
Working Summary
Drying method: Previous: Oven Current: Drynoza
UTP Temperature Programme: Previous: Calcination: 250oC, 5% O2 in
N2, 1hr, Reduction: 300oC, 5% H2 in N2, 1hr, Growth: 700oC, 30mL C2H4, 200mL H2, 2 hrs
Current: Calcination: 250oC, 5% O2 in N2, 1hr, Reduction: 500oC/700oC, 5% H2 in N2, 1hr, Growth: 700oC, 30mL C2H4, 200mL H2, 2 hrs
Parameters
SampleImpregnati
onDrying Calcination Reduction Growth
Weight of product
NC2FA1
Iron(II)Acetate 1wt%, Acetic Acid
Pure concentratio
n
60oC, Oven, 12hr
250oC, 5% O2 in N2, 1hr
300oC, 5% H2 in N2, 1hr
700oC, 30mL C2H4, 200mL H2, 2
hrs
3.85g
3.93g
3.68g
3.20g
NC2FA2
Iron(II)Acetate 1wt%, Acetic Acid
1M
60oC, Oven, 15hr
NC2FA360oC,
Furnace, 48hr 700oC, 5%
H2 in N2, 1hr
NC2FA4RT, Drynoza, 45hr
Iron (II) Acetate
SampleImpregnati
onDrying Calcination Reduction Growth
Weight of product
E087Iron (II) Nitrate 1 wt%, Ethanol
RT, Drynoza, 12hr
250oC, 5% O2 in N2, 1hr
500oC, 5% H2 in N2, 1hr 700oC,
30mL C2H4, 200mL H2, 2 hrs
2.16g
E090Iron (II) Nitrate 1 wt%, Ethanol
RT, Drynoza, 12hr
700oC, 5% H2 in N2, 1hr 1.20g
Iron (II) Nitrate
Temperature Programme (New)
Temperature Programme for CNF/CNT Growth using UTP
30 30
700700
200
250
0
100
200
300
400
500
600
700
0 100 200 300 400 500 600
Time (min)
Tem
p (
oC
)
Calcination Reduction Growth Cooling
30 min
44 min
60 min
10 min60 min
100 min
60 min 120 min
134 min
SEM images for CNT/AC
NC2FA1(B4)
SEM images for CNT/AC
NC2FA1(Growth)
CNT diameter: 6-11nm.Some CNT growth from the pore.Dispersion was not very good.High concentration of solution.
Try to use 1M acetic acid solution
SEM images for CNT/AC
NC2FA2(B4) with 1M acetic acid solution
SEM images for CNT/AC
NC2FA2(Growth)
No/less CNT growth (most probably because of the drying factor/solution concentration.
Try to use different drying method
SEM images for CNT/AC
NC2FA4(B4) DRYNOZA+new temp. programme
SEM images for CNT/AC
NC2FA4(Growth)
CNT diameter: 5-12 nmDrynoza+new temp. programmeDispersion still not very good.
Check the catalyst dispersion after reduction process (in progress)
SEM images for CNT/AC
E084 (500oC)
• Less growth, most probably Fe is not fully reduce
• not cover all AC substrate
• diameter 8nm – 15nm
SEM images for CNT/AC
E090 (700oC)stick
SEM images for CNT/AC
E090 (700oC)loos
e
BET
Sample
Pore Volume(mesopore)
Surface Area
(m2/g)
Pore volume(cc/g)
Average pore
width (nm)
Total PoreVolume
(cc/g)
Growth
Before
AGBefor
eAG
Before
AGBefor
eAG
Before
AG
NC2FA1
0.0501
0.0635
1205 10190.517
30.444
53.489
3.798
0.5674
0.5080
NC2FA2
0.0345
0.0522
1074962.
70.457
30.416
63.328
3.695
0.4918
0.4688
BET data for NC2FA3 & NC2FA4 still in progress.
BET Isoterm & DFT
0,0 0,2 0,4 0,6 0,8 1,0100
150
200
250
300
350
400
Vol
ume (c
c/g)
Relative Pressure (P/P0)
NC2FA1 NC2FA1(AG) NC2FA2 NC2FA2(AG)
0 10 20 30 40 50 60
0,00
0,02
0,04
0,06
0,08
0,10
Pore
Vol
ume (c
c/A/g
)
Pore Width (A)
NC2FA1 NC2FA1 (AG) NC2FA2 NC2FA2 (AG)
Isoterm DFT
All samples show isoterm type I (micropore) and hysteresis H3 (inuniform slit type). DFT proved that this sample are micropore which diameter between 3-20 A.
Iron (II) Acetate
Thermal AnalysisThermal Analysis condition = air, 32oC – 900oC, rate 5oC/min
• less 200oC loss of water molecules, moisture and nitrate
• 500oC – 750oC – removal of SOFG
• 350oC – 600oC – reduction of Fe nitrate. The width and density of the endothermic peak refers to the contact between the metal and carbon surface in other words it shows the characteristic of metal dispersion of the iron / nickel on AC. (prove from TG of sample Ni/AC 1wt%/2wt%)
• some literature mention, the 4th peak in TGA refers to the second activation of the Fe after being covered by coke and/or the Fe is in a different position in AC matrix, AC raw dont have this peak maybe probably because they present in a different state (Fe silicates etc).
0 100 200 300 400 500 600 700 800 900 1000
0
20
40
60
80
100
we
igh
t lo
ss (
%)
Temperature (ToC)
AC raw-wash impreg. CNF-loose CNF-stick
0 100 200 300 400 500 600 700 800 900 1000
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0.0
A009 impreg CNF-loose CNF-stick
TG
ATemperature (ToC)
Iron (II) Nitrate
Thermal Analysis
Thermal Analysis condition = air, 32oC – 900oC, rate 5oC/min
0 100 200 300 400 500 600 700 800 900-2.0
-1.8
-1.6
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
AC raw Fresh Catalyst 500oC reduce 700oC reduce
surface oxygen functional group (SOFG) removal
TG
A
Temperature (oC)
* App. Catal A. 192 (2000) 29-42
Species released Temp. oC (based on TPD exp ref *)
CO2 (carboxylic) 237
CO2 (lactone) 667
CO (Phenol) 632
CO (carbonyl) 807
CO + CO2 (anhydride) 547
CO (ether) 700
CO (quinone) 807
Iron (II) Nitrate
FTIR – Surface Oxygen functional group
4000 3800 3600 3400 3200 3000 2800 26000.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
29
19
29
53
28
84
34
41
Ab
sorb
an
ce
wavenumber [cm-1]
Fresh catalyst 500oC reduce 700oC reduce - stick 700oC reduce - loose
2500 2000 1500 1000 500
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
76
8
10
99
13
85
Ab
sorb
an
ce
wavenumber [cm-1]
fresh catalyst 500oC reduce 700oC reduce -stick 700oC reduce- loose
17
36
Absorption band [cm-1]
assignment
3417 O-H stretching vibrations, existence of surface hydroxylic groups and chemisorb water, asymmetric of
this band indicates strong hydrogen bonds2916, 2850 Aliphatic species, -CH3 –CH2-
1731 Aromatic rings and double bond vibrations
1579 Conjugated system such as ketone, keto-ester, ketol-enol structures
1385 NOx species from HNO3
1102 Symmetrical stretching vibration of ether ; epi-oxide and phenolic structure in different environmental.* Carbon 36 (1998)
1821-1831
Iron (II) Nitrate
XRD Diffractogram
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 900
50
100
150
200
gra
phite
(00
2)
gra
ph
ite (
002)
700oC reduce, growth 700oC
500oC reduce, growth 700oC
Fe3
C (
121
)
inte
nsi
ty
2-Theta
XRD diffractogram of samples was indexed to Fe3C and graphite.
XRD diffraction patterns recorded after the reactions shows that the pattern of Fe oxide is no longer present after CVD and the phases present were graphite and Fe carbide.
Some literature says that Fe oxide precursor was converted to Fe3C either during or after the CVD process. Fe3C also expected to form at the reaction conditionsa.
Active phase could be iron carbide or some form of iron carbon solid solutiona.* Carbon 44(2006) 2273-2280
Iron (II) Nitrate
XRD
061127X2_NC2FA2_AG
01-1267 (D) - Iron - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86070 - b 2.86070 - c 2.86070 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.4108 - 50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - Operations: Smooth 0.150 | Import061127X2_NC2FA2_AG - File: 061127X2_NC2FA2_AG.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 6 s - 2-Theta:
Lin
(C
ount
s)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
2-Theta - Scale
2 10 20 30 40 50 60 70 80 90
(1,1
,0)
(0,0
,2)
(1,2
,0)
(1,0
,3)
(1,1
,3)
(1,2
,3)
(1,1
,0)
(2,0
,0)
(2,1
,1)
061124X3_NC2FA2
06-0696 (*) - Iron, syn - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86640 - b 2.86640 - c 2.86640 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.5511 -50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - Operations: Smooth 0.150 | Import061124X3_NC2FA2 - File: 061124X3_NC2FA2.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 8 s - 2-Theta: 2.000 ° -
Lin
(C
ount
s)
0
100
200
300
400
500
600
700
800
900
2-Theta - Scale
2 10 20 30 40 50 60 70 80 90
(1,1
,0)
(0,0
,2)
(1,2
,0)
(1,0
,3)
(1,1
,3)
(1,2
,3)
(1,1
,0)
(2,0
,0)
(2,1
,1)
061124X2_NC2FA1_AG
06-0696 (*) - Iron, syn - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86640 - b 2.86640 - c 2.86640 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.5511 -50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - Operations: Smooth 0.150 | Import061124X2_NC2FA1_AG - File: 061124X2_NC2FA1_AG.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 9 s - 2-Theta:
Lin
(C
ount
s)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2-Theta - Scale
2 10 20 30 40 50 60 70 80 90
(1,1
,0)
(0,0
,2)
(1,2
,0)
(1,0
,3)
(1,1
,3)
(1,2
,3)
(1,1
,0)
(2,0
,0) (2,1
,1)
061123X2_NC2FA1
50-0926 (I) - Carbon - C - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Hexagonal - a 11.92800 - b 11.92800 - c 10.62000 - alpha 90.000 - beta 90.000 - gamma 120.000 - 1308.55 - 06-0696 (*) - Iron, syn - Fe - Y: 50.00 % - d x by: 1. - WL: 1.5406 - Cubic - a 2.86640 - b 2.86640 - c 2.86640 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centred - Im-3m (229) - 2 - 23.5511 -Operations: Smooth 0.150 | Import061123X2_NC2FA1 - File: 061123X2_NC2FA1.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 90.000 ° - Step: 0.010 ° - Step time: 2. s - Temp.: 25 °C (Room) - Time Started: 8 s - 2-Theta: 2.000 ° -
Lin
(C
ount
s)
0
100
200
300
400
500
600
700
800
900
1000
1100
2-Theta - Scale
2 10 20 30 40 50 60 70 80 90
(1,1
,0)
(2,0
,0)
(2,1
,1)(1,1
,0)
(0,0
,2) (1
,2,0
)
(1,0
,3)
(1,1
,3)
(1,2
,3)
Iron (II) Acetate
Current & Future Planning
Produce large amount of Fe/AC for iodine number and acid base titration (each experiment require 10gram of sample)
To set-up apparatus to perform n-butane activity.
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