Summary of NC200 work Imran & Norli Updated: 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 Nanocarbon Growth (Thermal-CVD) Characterization 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 (C 2 H 4 ) Carrier gas (H 2, N 2 ) Carbon source (C 2 H 4 ) Carrier gas (H 2, N 2 ) Substrate (AC) Substrate (AC) Impregnation CNT/F CNT/F Application treat with 5M HNO 3, T=30 o C, 24 hr wash with deionized water, dried T=200 o C, 2 hr treat with 5M HNO 3, T=30 o C, 24 hr wash with deionized water, dried T=200 o C, 2 hr Cat. + acetic acid/ ethanol under ultrasonic, 30 min, 25 o C (water bath) aging 45hr/12hr, RT, Drynoza Cat. + acetic acid/ ethanol under ultrasonic, 30 min, 25 o C (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: 250 o C, 5% O 2 in N 2, 1hr, Reduction: 300 o C, 5% H 2 in N 2, 1hr, Growth: 700 o C, 30mL C 2 H 4, 200mL H 2, 2 hrs  Current: Calcination: 250 o C, 5% O 2 in N 2, 1hr, Reduction: 500 o C/700 o C, 5% H 2 in N 2, 1hr, Growth: 700 o C, 30mL C 2 H 4, 200mL H 2, 2 hrs

Parameters SampleImpregnationDryingCalcinationReductionGrowth Weight of product NC2FA1 Iron(II)Acetate 1wt%, Acetic Acid Pure concentration 60 o C, Oven, 12hr 250 o C, 5% O 2 in N 2, 1hr 300 o C, 5% H 2 in N 2, 1hr 700 o C, 30mL C 2 H 4, 200mL H 2, 2 hrs 3.85g 3.93g 3.68g 3.20g NC2FA2 Iron(II)Acetate 1wt%, Acetic Acid 1M 60 o C, Oven, 15hr NC2FA3 60 o C, Furnace, 48hr 700 o C, 5% H 2 in N 2, 1hr NC2FA4 RT, Drynoza, 45hr Iron (II) Acetate SampleImpregnationDryingCalcinationReductionGrowth Weight of product E087 Iron (II) Nitrate 1 wt%, Ethanol RT, Drynoza, 12hr 250 o C, 5% O 2 in N 2, 1hr 500 o C, 5% H 2 in N 2, 1hr 700 o C, 30mL C 2 H 4, 200mL H 2, 2 hrs 2.16g E090 Iron (II) Nitrate 1 wt%, Ethanol RT, Drynoza, 12hr 700 o C, 5% H 2 in N 2, 1hr 1.20g Iron (II) Nitrate

Temperature Programme (New) CalcinationReductionGrowthCooling 30 min 44 min 60 min 10 min 60 min 100 min 60 min120 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 nm Drynoza+new temp. programme Dispersion still not very good. Check the catalyst dispersion after reduction process (in progress)

SEM images for CNT/AC E084 (500 o C) Less growth, most probably Fe is not fully reduce not cover all AC substrate diameter 8nm – 15nm

SEM images for CNT/AC E090 (700 o C) stick

SEM images for CNT/AC E090 (700 o C) loose

BET Sample Pore Volume (mesopore) Surface Area (m 2 /g) Pore volume (cc/g) Average pore width (nm) Total Pore Volume (cc/g) GrowthBeforeAGBeforeAGBeforeAGBeforeAGBeforeAG NC2FA NC2FA BET data for NC2FA3 & NC2FA4 still in progress.

BET Isoterm & DFT IsotermDFT 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 Analysis Thermal Analysis condition = air, 32 o C – 900 o C, 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 4 th 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). Iron (II) Nitrate

Thermal Analysis Thermal Analysis condition = air, 32 o C – 900 o C, rate 5oC/min * App. Catal A. 192 (2000) Species releasedTemp. o C (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 Absorption band [cm-1]assignment 3417O-H stretching vibrations, existence of surface hydroxylic groups and chemisorb water, asymmetric of this band indicates strong hydrogen bonds 2916, 2850Aliphatic species, -CH 3 –CH Aromatic rings and double bond vibrations 1579Conjugated system such as ketone, keto-ester, ketol-enol structures 1385NOx species from HNO Symmetrical stretching vibration of ether ; epi-oxide and phenolic structure in different environmental. * Carbon 36 (1998) Iron (II) Nitrate

XRD Diffractogram 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 conditions a. Active phase could be iron carbide or some form of iron carbon solid solution a. * Carbon 44(2006) Iron (II) Nitrate

XRD 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.