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

1. NC200Carbon Group Research ProgramTeam work ;Norli, Imran, Ali

2. Outline • Carbon Work Flow • Results • Future Program

3. Carbon Work Program Phase I Phase IV Phase II Phase III

4. Phase I : Development Commercial Activated Carbon (AC) as catalysts support via Chemical treatment. Objectives : To studies the effect of acid treatment on the properties of activated carbon. AC commercial AC as support • SOFG • hydrophobic • pH~ 10 • contains inorganic element (Na,K,Al,Zn, P, N, Fe, Ca) – ash 24% • surface area 1124m2/g • less hydrophobic (acid base titration) • SOFG, more acidic • pH ~3 • ash content 2.3% (TGA) • surface area 1237m2/g Washing –5M HNO3 at RT for 24hrs. V ratio V/V 1AC:4mlH+ Drying – 200oC 2hrs Grind and sieve - <50 m

5. 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 CNT/CNF Substrate (AC) Nanocarbon Growth (Thermal-CVD) Impregnation • incipient wetness • wet impregnation • Calcination: 250oC, 1hr • [5%O2 in N2] • Reduction : 300oC, 1hr • [5%H2 in N2] • Growth : varied oC/H2 2hrs [30ml C2H4] Characterization • Compositional analysis (XRD) • Morphology/Structure analysis (SEM, HRTEM, TEM) • Texture/Surface Area analysis (BET) • Thermal Gravimetric Analysis(TG) • TPRO

6. Phase II : Synthesis of CNF on AC supported Ni Catalysts

7. Phase II : Synthesis of CNF on AC supported Ni Catalysts Incipient wetness Wet impregnation

8. Phase II : Synthesis of CNF on AC supported Ni Catalysts H2 flow ml/min Diameter (nm) % Range (nm) 50 10.5 34 6 100 10.5 22 5 200 10.5 50 4 300 19 10 15

9. Phase II : Synthesis of CNF on AC supported Ni Catalysts

10. Phase II : Synthesis of CNF on AC supported Ni Catalysts

11. Phase II : Synthesis of CNF on AC supported Ni Catalysts Support SA after growth m2/g Diameter (nm) amount% Range (nm) AC NC200 1389 6.5 32 6.5 Char NC100 857.2 7.5 45 5.5 Graphite 199.5 11.5 11 25 Char Graphite AC

12. Phase II : Synthesis of CNF on AC supported Ni Catalysts

13. Phase III : Synthesis of CNF on AC supported Fe Catalysts Objectives : to get high density and homogeneous of filamentous growth on AC Substrate (AC) Washing CNT/CNF • 1,3,5wt% • Fe nitrate / acetate in ethanol • 1ml Fe sol : 9ml solvent • Sonification • (25-32oC, 30 min) • Drying (drynoza/convectional oven Nanocarbon Growth (Thermal-CVD) Impregnation • Calcination: 250oC, 1hr • [5%O2 in N2] • Reduction : 500oC/700oC, 1hr • [5%H2 in N2] • Growth :700oC, 2hrs • [30ml C2H4/200ml H2] Characterization • Compositional analysis (XRD) • Morphology/Structure analysis (SEM, HRTEM) • Texture/Surface Area analysis (BET) • Thermal Gravimetric Analysis(TG) • TPRO

14. Phase III : Synthesis of CNF on AC supported Fe Catalysts

15. Phase III : Synthesis of CNF on AC supported Fe Catalysts Fe-nitrate Fe-acetate

16. Phase III : Synthesis of CNF on AC supported Fe Catalysts

17. Phase III : Synthesis of CNF on AC supported Fe Catalysts

18. 5 3 Fe loading (wt%) 1 H2 concentration (ml/min) 5 10 20

19. Phase III : Synthesis of CNF on AC supported Fe Catalysts

20. Phase IV : Synthesis of CNF on AC supported Fe Catalysts (Next Program) • Metal: Fe • wt% : 1, 3, 5 • excess impreg: • 1: 9ml • 1: 3ml • 250oC, 1hrs • 350oC, 3hrs • 400oC, 3hrs • Temp,ToC • 500oC, 1hr • 600oC, 1hr • 700oC, 1hr • Faster drying Heat Treatment • 700oC, 1hrs • 5%H2 • Pore digging by catalytic process • [H2] 1wt% Fe/AC • 5% • 10% • 20% CNF/CNT growth Cat. Preparation Synthesis Calcination Reduction UTP Tube • Bulb tube Growth • 700oC, 2 hrs • 30ml C2H4 • 200ml H2 • Time • 60, 90, 120 mins

21. Phase IV : Application CNT Applications Adsorbent Catalysts Nanofluid ODH NH3 Splitting

22. CNT/AC for ODH catalyst • Catalyst amount: 3 g • Inert amount: 100 g • EB flow: 3.3 ml(liquid)/h • O2 flow: 12.5 ml/min • N2 flow: 1.31 l/min • Reaction Tª: 375 ºC Experimental perform by Carbon group, FHI, Berlin. CNT before reaction • CNT/AC shows • - poor mechanical and chemical stability CNT after reaction

23. CNT/clay for ODH catalyst CNT before reaction CNT after reaction • 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)

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

25. Problem? AC as support

26. Catalytic Gasification…. Fe/AC 5%H2 Fe Ion current A Activated carbon Graphene layer encapsulation • 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 Feo • the presence of Feo to gasify carbon to CH4 Fe

27. Characterizations CNT Characterization SEM TPDRO BET I2 Value Acid Base Titration TEM TGA FTIR XRD

28. 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. Schlögldraft 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 ACA. Rinaldi, N. Abdullah, A. Muataz , S. B Abd. Hamid, D.S. Su, R. SchlöglPoster 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. SchloeglSICC 5, 16-19 Dec 2007, Singapore • The influence of different carbon supports on Ni-catalyzed CNF synthesis: a preliminary study. Ali Rinaldia,b,*, Jean-Philippe Tessonnierb, Norly Abdullaha , Dang Sheng Sub, Robert Schlöglb, Sharifah Bee Abd Hamida14th ICC, Seoul, Korea, 2008

29. THANK YOU

30. Future Workplan

31. 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 …