NC200 Carbon Group Research Program Team work ; Norli, Imran, Ali

Outline Carbon Work Flow Results Future Program

Carbon Work Program Phase IVPhase II Phase I Phase III

Phase I : Development Commercial Activated Carbon (AC) as catalysts support via Chemical treatment. AC commercial SOFG hydrophobic pH~ 10 contains inorganic element (Na,K,Al,Zn, P, N, Fe, Ca) – ash 24% surface area 1124m 2 /g AC as support less hydrophobic (acid base titration) SOFG, more acidic pH ~3 ash content 2.3% (TGA) surface area 1237m 2 /g Washing –5M HNO 3 at RT for 24hrs. V ratio V/V 1AC:4mlH + Drying – 200 o C 2hrs Grind and sieve - <50  m Objectives : To studies the effect of acid treatment on the properties of activated carbon.

Phase II : Synthesis of CNF on AC supported Ni Catalysts Objectives : to have a controlled growth of filamentous nanocarbon on carbon support, with the growth concentration is either inside the macroporosity of the AC support and/or on the external surface Nanocarbon Growth (Thermal-CVD) Characterization Calcination: 250 o C, 1hr [5%O 2 in N 2 ] Reduction : 300 o C, 1hr [5%H 2 in N 2 ] Growth : varied o C/H2 2hrs [30ml C2H4] Calcination: 250 o C, 1hr [5%O 2 in N 2 ] Reduction : 300 o C, 1hr [5%H 2 in N 2 ] Growth : varied o C/H2 2hrs [30ml C2H4] Compositional analysis (XRD) Morphology/Structure analysis (SEM, HRTEM, TEM) Texture/Surface Area analysis (BET) Thermal Gravimetric Analysis(TG) TPRO Compositional analysis (XRD) Morphology/Structure analysis (SEM, HRTEM, TEM) Texture/Surface Area analysis (BET) Thermal Gravimetric Analysis(TG) TPRO CNT/CNF Impregnation Substrate (AC) Substrate (AC) incipient wetness wet impregnation incipient wetness wet impregnation

Phase II : Synthesis of CNF on AC supported Ni Catalysts ParameterObjectiveFindings 1. Impregnation type Incipient wetness Wet impregnation - to get optimum method for highly dispersed active sites Significant increment in CNF dispersion on AC, and uniform morphology. 2. Increased [ H 2 ]50, 100, 200, 300 -to get optimum parameter 200 ml/min is the best 3. Varied temperature of growth 550, 600, 700 O C, 850oC550 o C with heat treatment gives uniform and small diameter with high yield of CNF 850 o C, MWCNT 4. Varied the Ni wt% loading 0.5, 1, 21wt%Ni give the best diameter distribution and high yield 5. Varied the support type activated carbon, Char, Graphite to study effect of supportManage to grow CNF on AC, Char and graphite 6. Varied amount of sample loading 1.5, 5, 10Scale up optimizationUnder similar condition, increasing the the loading result in lower yield (5gram heat-treatment optimum growth)

Phase II : Synthesis of CNF on AC supported Ni Catalysts ParameterObjectiveFindings 1. Impregnation type Incipient wetness Wet impregnation - to get optimum method for highly dispersed active sites Significant increment in CNF dispersion on AC, and uniform morphology. 2. Increased [ H 2 ]50, 100, 200, 300 -to get optimum parameter 200 ml/min is the best 3. Varied temperature of growth 550, 600, 700 O C, 850oC550 o C with heat treatment gives uniform and small diameter with high yield of CNF 850 o C, MWCNT 4. Varied the Ni wt% loading 0.5, 1, 21wt%Ni give the best diameter distribution and high yield 5. Varied the support type activated carbon, Char, Graphite to study effect of supportManage to grow CNF on AC, Char and graphite 6. Varied amount of sample loading 1.5, 5, 10Scale up optimizationUnder similar condition, increasing the the loading result in lower yield (5gram heat-treatment optimum growth) Incipient wetnessWet impregnation

Phase II : Synthesis of CNF on AC supported Ni Catalysts ParameterObjectiveFindings 1. Impregnation type Incipient wetness Wet impregnation - to get optimum method for highly dispersed active sites Significant increment in CNF dispersion on AC, and uniform morphology. 2. Increased [ H 2 ]50, 100, 200, 300 -to get optimum parameter 200 ml/min is the best 3. Varied temperature of growth 550, 600, 700 O C, 850oC550 o C with heat treatment gives uniform and small diameter with high yield of CNF 850 o C, MWCNT 4. Varied the Ni wt% loading 0.5, 1, 21wt%Ni give the best diameter distribution and high yield 5. Varied the support type activated carbon, Char, Graphite to study effect of supportManage to grow CNF on AC, Char and graphite 6. Varied amount of sample loading 1.5, 5, 10Scale up optimizationUnder similar condition, increasing the the loading result in lower yield (5gram heat-treatment optimum growth) Range (nm) %(nm) DiameterH 2 flow ml/min

Phase II : Synthesis of CNF on AC supported Ni Catalysts ParameterObjectiveFindings 1. Impregnation type Incipient wetness Wet impregnation - to get optimum method for highly dispersed active sites Significant increment in CNF dispersion on AC, and uniform morphology. 2. Increased [ H 2 ]50, 100, 200, 300 -to get optimum parameter 200 ml/min is the best 3. Varied temperature of growth 550, 600, 700 O C, 850oC550 o C with heat treatment gives uniform and small diameter with high yield of CNF 850 o C, MWCNT 4. Varied the Ni wt% loading 0.5, 1, 21wt%Ni give the best diameter distribution and high yield 5. Varied the support type activated carbon, Char, Graphite to study effect of supportManage to grow CNF on AC, Char and graphite 6. Varied amount of sample loading 1.5, 5, 10Scale up optimizationUnder similar condition, increasing the the loading result in lower yield (5gram heat-treatment optimum growth)

Phase II : Synthesis of CNF on AC supported Ni Catalysts ParameterObjectiveFindings 1. Impregnation type Incipient wetness Wet impregnation - to get optimum method for highly dispersed active sites Significant increment in CNF dispersion on AC, and uniform morphology. 2. Increased [ H 2 ]50, 100, 200, 300 -to get optimum parameter 200 ml/min is the best 3. Varied temperature of growth 550, 600, 700 O C, 850oC550 o C with heat treatment gives uniform and small diameter with high yield of CNF 850 o C, MWCNT 4. Varied the Ni wt% loading 0.5, 1, 21wt%Ni give the best diameter distribution and high yield 5. Varied the support type activated carbon, Char, Graphite to study effect of supportManage to grow CNF on AC, Char and graphite 6. Varied amount of sample loading 1.5, 5, 10Scale up optimizationUnder similar condition, increasing the the loading result in lower yield (5gram heat-treatment optimum growth)

Phase II : Synthesis of CNF on AC supported Ni Catalysts ParameterObjectiveFindings 1. Impregnation type Incipient wetness Wet impregnation - to get optimum method for highly dispersed active sites Significant increment in CNF dispersion on AC, and uniform morphology. 2. Increased [ H 2 ]50, 100, 200, 300 -to get optimum parameter 200 ml/min is the best 3. Varied temperature of growth 550, 600, 700 O C, 850oC550 o C with heat treatment gives uniform and small diameter with high yield of CNF 850 o C, MWCNT 4. Varied the Ni wt% loading 0.5, 1, 21wt%Ni give the best diameter distribution and high yield 5. Varied the support type activated carbon, Char, Graphite to study effect of supportManage to grow CNF on AC, Char and graphite 6. Varied amount of sample loading 1.5, 5, 10Scale up optimizationUnder similar condition, increasing the the loading result in lower yield (5gram heat-treatment optimum growth) Graphite Char NC AC NC200 Range (nm)amount%Diameter (nm) SA after growth m2/gSupport AC CharGraphite

Phase II : Synthesis of CNF on AC supported Ni Catalysts ParameterObjectiveFindings 1. Impregnation type Incipient wetness Wet impregnation - to get optimum method for highly dispersed active sites Significant increment in CNF dispersion on AC, and uniform morphology. 2. Increased [ H 2 ]50, 100, 200, 300 -to get optimum parameter 200 ml/min is the best 3. Varied temperature of growth 550, 600, 700 O C, 850oC550 o C with heat treatment gives uniform and small diameter with high yield of CNF 850 o C, MWCNT 4. Varied the Ni wt% loading 0.5, 1, 21wt%Ni give the best diameter distribution and high yield 5. Varied the support type activated carbon, Char, Graphite to study effect of supportManage to grow CNF on AC, Char and graphite 6. Varied amount of sample loading 1.5, 5, 10Scale up optimizationUnder similar condition, increasing the the loading result in lower yield (5gram heat-treatment optimum growth)

Phase III : Synthesis of CNF on AC supported Fe Catalysts Objectives : to get high density and homogeneous of filamentous growth on AC Washing Nanocarbon Growth (Thermal-CVD) Characterization Calcination: 250 o C, 1hr [5%O 2 in N 2 ] Reduction : 500 o C/700 o C, 1hr [5%H 2 in N 2 ] Growth :700 o C, 2hrs [30ml C2H4/200ml H2] Calcination: 250 o C, 1hr [5%O 2 in N 2 ] Reduction : 500 o C/700 o C, 1hr [5%H 2 in N 2 ] Growth :700 o C, 2hrs [30ml C2H4/200ml H2] Compositional analysis (XRD) Morphology/Structure analysis (SEM, HRTEM) Texture/Surface Area analysis (BET) Thermal Gravimetric Analysis(TG) TPRO Compositional analysis (XRD) Morphology/Structure analysis (SEM, HRTEM) Texture/Surface Area analysis (BET) Thermal Gravimetric Analysis(TG) TPRO Substrate (AC) Substrate (AC) Impregnation CNT/CNF 1,3,5wt% Fe nitrate / acetate in ethanol 1ml Fe sol : 9ml solvent Sonification (25-32 o C, 30 min) Drying (drynoza/convectional oven 1,3,5wt% Fe nitrate / acetate in ethanol 1ml Fe sol : 9ml solvent Sonification (25-32 o C, 30 min) Drying (drynoza/convectional oven

Phase III : Synthesis of CNF on AC supported Fe Catalysts ParameterObjectiveFindings 1. Varied precursor Nitrate, Acetate - to studies the influence of different precursors Manage to grow CNF from both precursor 2. Varied the Fe wt% loading 1, 3, 5- to get high yields5wt% higher yields but bigger CNF diameter. 3. Varied H 2 concentration 5, 10, 20,100- to improve the reduction of metal – better yield of CNF Increase 5 to 10 % - Yield of CNF improved. For 5 wt % Fe, 10% H 2 – Mixture of CNF+ CNT formed 4. Varied temperature reduction 500, 600, 700 o C - to get optimum parameter thickness of the CNT decrease to the lower diameter size 5. Reduction Time60, 90, 120- to improve the reduction of metal – better yield of CNF In progress

Phase III : Synthesis of CNF on AC supported Fe Catalysts ParameterObjectiveFindings 1. Varied precursor Nitrate, Acetate - to studies the influence of different precursors Manage to grow CNF from both precursor Fe-nitrateFe-acetate

Phase III : Synthesis of CNF on AC supported Fe Catalysts ParameterObjectiveFindings 1. Varied precursor Nitrate, Acetate - to studies the influence of different precursors Manage to grow CNF from both precursor 2. Varied the Fe wt% loading 1, 3, 5- to get high yields5wt% higher yields but bigger CNF diameter. 3. Varied H 2 concentration 5, 10, 20,100- to improve the reduction of metal – better yield of CNF Increase 5 to 10 % - Yield of CNF improved. For 5 wt % Fe, 10% H 2 – Mixture of CNF+ CNT formed 4. Varied temperature reduction 500, 600, 700 o C - to get optimum parameter thickness of the CNT decrease to the lower diameter size 5. Reduction Time60, 90, 120- to improve the reduction of metal – better yield of CNF In progress

Phase III : Synthesis of CNF on AC supported Fe Catalysts ParameterObjectiveFindings 1. Varied precursor Nitrate, Acetate - to studies the influence of different precursors Manage to grow CNF from both precursor 2. Varied the Fe wt% loading 1, 3, 5- to get high yields5wt% higher yields but bigger CNF diameter. 3. Varied H 2 concentration 5, 10, 20,100- to improve the reduction of metal – better yield of CNF Increase 5 to 10 % - Yield of CNF improved. For 5 wt % Fe, 10% H 2 – Mixture of CNF+ CNT formed 4. Varied temperature reduction 500, 600, 700 o C - to get optimum parameter thickness of the CNT decrease to the lower diameter size 5. Reduction Time60, 90, 120- to improve the reduction of metal – better yield of CNF In progress

H 2 concentration (ml/min) Fe loading (wt%)

Phase III : Synthesis of CNF on AC supported Fe Catalysts ParameterObjectiveFindings 1. Varied precursor Nitrate, Acetate - to studies the influence of different precursors Manage to grow CNF from both precursor 2. Varied the Fe wt% loading 1, 3, 5- to get high yields5wt% higher yields but bigger CNF diameter. 3. Varied H 2 concentration 5, 10, 20,100- to improve the reduction of metal – better yield of CNF Increase 5 to 10 % - Yield of CNF improved. For 5 wt % Fe, 10% H 2 – Mixture of CNF+ CNT formed 4. Varied temperature reduction 500, 600, 700 o C - to get optimum parameter in progress 5. Reduction Time60, 90, 120- to improve the reduction of metal – better yield of CNF In progress

Phase IV : Synthesis of CNF on AC supported Fe Catalysts (Next Program) CNF/CNT growth Cat. PreparationSynthesis CalcinationReduction Growth 700 o C, 2 hrs 30ml C 2 H 4 200ml H 2 Temp,T o C 500 o C, 1hr 600 o C, 1hr 700 o C, 1hr [H 2 ] 1wt% Fe/AC 5% 10% 20% Heat Treatment 700oC, 1hrs 5%H 2 Metal: Fe wt% : 1, 3, 5 excess impreg: 1: 9ml 1: 3ml Faster drying 250 o C, 1hrs 350 o C, 3hrs 400 o C, 3hrs Pore digging by catalytic process UTP Tube Bulb tube Time 60, 90, 120 mins

CNT Applications AdsorbentCatalystsNanofluid ODHNH 3 Splitting Phase IV : Application

CNT/AC for ODH catalyst  Catalyst amount: 3 g  Inert amount: 100 g  EB flow: 3.3 ml(liquid)/h  O 2 flow: 12.5 ml/min  N 2 flow: 1.31 l/min  Reaction Tª: 375 ºC Experimental perform by Carbon group, FHI, Berlin. CNT before reaction CNT after reaction CNT/AC shows - poor mechanical and chemical stability

CNT/clay for ODH catalyst CNT/clay shows superior activity in comparison to the commercial CNTs possibly due to : -open structure of the bentonite support materials and -the amount of defects present in the CNTs on clay (defects=active sites) CNT before reaction CNT after reaction

Mechanical stability test for CNT/Clay CNTs are still attached to the clay support!! Mechanically stable. After After 2 hours ultrasonification

Problem? AC as support

Catalytic Gasification…. Fe/AC 5%H 2 Early introduction of carbon into the surface and/or bulk of catalyst” during catalytic gasification Evolution of CH4 taken as a sign for presence of Fe o the presence of Fe o to gasify carbon to CH 4 Ion current A Fe Activated carbon Graphene layer encapsulation

Characterizations CNT Characterization SEMTPDROBETI 2 Value Acid Base Titration TEM TGAFTIRXRD

Publications Paper –Synthesis of CNF on Supported Ni Catalysts and the Effect of Pretreatment on the Growth Improvement at Low Temperature, A. Rinaldi, N. Abdullah, A. Muataz, S. B Abd. Hamid D.S. Su, R. Schlögl draft submitted to Prof Schlögl in Progress –The influence of carbon support on the structure and the productivity of carbon nanofibers, Ali Rinaldi, Jean-Philippe Tessonnier, Norly Abdullah, Dang Sheng Su, Robert Schlögl, Sharifah Bee Abd Hamid in progress Poster –Improving the Quality and quantity of CNT growth on AC A. Rinaldi, N. Abdullah, A. Muataz, S. B Abd. Hamid, D.S. Su, R. Schlögl Poster for Kracow, Institute of Catalysis Proceeding –The Synthesis of Carbon Nanotube on Activated Carbon S.B Abd Hamid, N. Abdullah, I.S Mohamad, A. Rinaldi, R. Schloegl Nanotech Malaysia 2007, 29-1 Dec 2007, PWTC –Synthesis of Carbon – Based Supporting Material followed by Carbon Nanostructures Growth for Catalysis S.B Abd Hamid, N. Abdullah, I.S Mohamad, A. Rinaldi, S. Zakaria, R. Schloegl SICC 5, Dec 2007, Singapore –The influence of different carbon supports on Ni-catalyzed CNF synthesis: a preliminary study. Ali Rinaldi a,b,*, Jean-Philippe Tessonnier b, Norly Abdullah a, Dang Sheng Su b, Robert Schlögl b, Sharifah Bee Abd Hamid a 14th ICC, Seoul, Korea, 2008

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Future Workplan

Characterizations What can we get: ➲ Fast detection whether the experiments produce significant filaments ➲ By transmission mode; to detect CNF or tubular filaments ➲ To detect big metal particles (BSE mode) ➲ To semi-quantify small metal particles by EDAX ➲ Nitrate decompositions: ● Influenced by initial SOFG on AC, atmosphere, temperature and rate of temperature. ● CO2 evolutions ➲ H2O from metal oxide reduction ● Water evolution profile can show certain level of reduction kinetics which are influenced by; particle size, metal-support interaction. ➲ CH4 from catalytic gasifications ● metal-CH4-CO dynamics ● Level of carbon contamination on metal catalyst Isoterm Type of pore Pore changes DFT Surface Area Pore Volume Pore Diameter …