Optimization of bi-metallic (Fe–Co) catalyst on kaolin support for carbon nanofiber growth in a CVD reactor

  • K. Y. MudiEmail author
  • A. S. Abdulkareem
  • O. S. Azeez
  • A. S. Kovo
  • J. O. Tijani
  • E. J. Eterigho
Original Article


This study focused on the development of Fe–Co/kaolin catalyst by a wet impregnation method. Response surface methodology was used to study the influence of operating variables such as drying temperature, drying time, mass of support and stirring speed on the yield of the catalyst. The catalyst composite at best synthesis conditions was then calcined in an oven at varied temperature and time using 22 factorial design of experiment. The catalyst with optimum surface area was then utilized to grow carbon nanofiber (CNF) in a chemical vapour deposition (CVD) reactor. Both the catalyst and CNF were characterized using high-resolution scanning electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy. On the influence of operating variables on the yield of catalyst, the results showed that an optimum yield of 96.51% catalyst was obtained at the following operating conditions: drying time (10 h), drying temperature (110 °C), stirring speed (100 rpm) and mass of support (9 g). Statistical analysis revealed the existence of significant interactive effects of the variables on the yield of the catalyst. The HRSEM/XRD/BET/TGA analysis revealed that the particles are well dispersed on the support, with high surface area (376.5 m2/g) and thermally stable (330.88 °C). The influence of operating parameters on the yield of CNF was also investigated and the results revealed an optimum yield of 348% CNF at the following operating conditions: reaction temperature (600 °C), reaction time (40 min), argon flow rate (1416 mL/min) and acetylene/hydrogen flow rate (1416 mL/min). It was found from statistical analysis that the reaction temperature and acetylene/hydrogen flow rates exerted significant effect on the CNF yield than the other factors. The contour and surface plots bi-factor interaction indicated functional relationship between the response and the experimental factors. The characterization results showed that the synthesized CNF is thermally stable, twisted and highly crystalline and contain surface functional groups. It can be inferred from the results of various analyses that the developed catalyst is suitable for CNF growth in a CVD reactor.


Bi-metallic catalyst Carbon nanofiber Optimization Characterization Chemical vapour deposition 



This is to acknowledge and appreciate the support received from the Tertiary Education Trust Fund (TETFUND) of Nigeria under Grant number TETFUND/FUTMINNA/2017/09. The authors also thank The Centre for Genetic Engineering and Biotechnology (CGEB) FUTMinna who offered us direct access to their facilities. We are also grateful to the following people that helped analyze the samples: Dr. Remy Bucher, (iThemba Labs), Cape Town, South Africa for XRD; Dr. Franscious Cummings, Electron Microscope Unit (EMU), Physics Department, University of Western Cape (UWC), South Africa for HRTEM; Adrian Joseph, Physics department, UWC, South Africa for HRSEM and Prof. W. D. Roos, Physics Department, University of the Free State, South Africa for XPS.

Compliance with ethical standards

Conflict of interest

The authors reported no potential conflict of interest relevant to this study


  1. 1.
    Krijn P, De J, John W (2000) Carbon nanofibers: catalytic synthesis and applications. Catal Reform Sci Eng J 42:4Google Scholar
  2. 2.
    Feng L, Xie N, Zhong J (2014) Carbon nanofibers and their composites: a review of synthesizing, properties and applications. Mater J. Google Scholar
  3. 3.
    Eun-Sil P, Jong-Won K, Chang-Seop L (2014) Synthesis and characterization of carbon nanofibers on Co and Cu catalysts by chemical vapor deposition. Bull Korean Chem Soc 35:6. Google Scholar
  4. 4.
    Navaporn K, Surawut C, Takashi S (2016) Control of physical properties of carbon nanofibers obtained from coaxial electrospinning of PMMA and PAN with adjustable inner/outer nozzle ends. Nanoscale Res Lett 11:186. CrossRefGoogle Scholar
  5. 5.
    Yehya MA, Abdullah A, Ahmad TJ, Ma’anFahmi RA (2016) Synthesis and characterization of carbon nanofibers grown on powdered activated carbon. J Nanotechnol. Google Scholar
  6. 6.
    Al-Saleh MH, Sundararaj UA (2009) Review of vapor grown carbon nanofiber/polymer conductive composites. Carbon J. Google Scholar
  7. 7.
    Tawfik AS (2015) Carbon-based nanomaterials for desulfurization: classification, preparation, and evaluation. Adv Chem Mater Eng Book Ser (ACME). Google Scholar
  8. 8.
    Teo KBK, Singh C, Chhowalla M, Milne WI (2003) Catalytic synthesis of carbon nanotubes and nanofibers. In: Nalwa HS (ed) Encyclopedia of nanoscience and nanotechnology. American Scientific Publishers, Stevenson Ranch, pp 665–686Google Scholar
  9. 9.
    Couteau E, Hernadi K, Seo JW, Thien-Nga L, Miko C, Gaal R, Forro L (2003) CVD synthesis of high-purity multiwalled carbon nanotubes using CaCO3 catalyst support for large-scale production. Chem Phys Lett 378:9CrossRefGoogle Scholar
  10. 10.
    Kazunori K, Kozo S (2005) Modeling CVD synthesis of carbon nanotubes: nanoparticle formation from ferrocene. Carbon J 43:252–257Google Scholar
  11. 11.
    Ding Q, Xueyin S, Xiujuan Y, Xiaosi Q, Chak-Tong A, Wei Z, Youwei D (2013) Large-scale and controllable synthesis of metal-free nitrogen-doped carbon nanofibers and nanocoils over water-soluble Na2CO3. Nanoscale Res Lett 8:545CrossRefGoogle Scholar
  12. 12.
    Afolabi AS (2009) Development of platinum electro catalytic electrodes for proton exchange membrane fuel cell. Ph.D. thesis, University of the Witwatersrand, Johannesburg, South AfricaGoogle Scholar
  13. 13.
    László G, Goran B, Erno K (2010) Bimetallic cobalt based catalysts catalysis. Rev Sci Eng 52:133–203CrossRefGoogle Scholar
  14. 14.
    Manafi SA, Badiee SH (2007) Production of carbon nanofibers using a CVD method with lithium fluoride as a supported cobalt catalyst. Res Lett Mater Sci. Google Scholar
  15. 15.
    Lim S, Shimizu A, Yoon S-H, Korai Y, Mochida I (2004) High yield preparation of tubular carbon nanofibers over supported Co–Mo catalysts. Carbon 42(7):1279–1283. CrossRefGoogle Scholar
  16. 16.
    van der Lee MK, van Dillen AJ, Geus JW et al (2006) Catalytic growth of macroscopic carbon nanofiber bodies with high bulk density and high mechanical strength. Carbon J 44:629–637CrossRefGoogle Scholar
  17. 17.
    Eunyi J, Heai-Ku P, Jong-Ha C et al (2015) Synthesis and characterization of carbon nanofibers grown on Ni and Mo catalysts by chemical vapor deposition. Bull Korean Chem Soc 36:1452–1459CrossRefGoogle Scholar
  18. 18.
    Aliyu A (2016) Synthesis and characterization of carbon nanotubes via novel support in catalytic chemical vapour deposition method. M.Eng. thesis, Federal University of Technology, Minna, NigeriaGoogle Scholar
  19. 19.
    Mamun AA, Ahmed YM, Muyibi SA, Al-Khatib MFR, Jameel AT, AlSaadi MA (2016) Synthesis of carbon nanofibers on impregnated powdered activated carbon as cheap substrate. Arab J Chem. Google Scholar
  20. 20.
    Prasantha RM, Larisa IN, Albert GN, Andrzej C, Markus V, Karin H, Jari EM, Maarit JK, Vesa P, Tatiana SK, Oleg VT, Esko IK (2009) Synthesis of carbon nanotubes and nanofibers on silica and cement matrix materials. J Nanomater. Google Scholar
  21. 21.
    Ali S, Muthana M, Ahmad D (2015) Synthesis of carbon nanofibers from decomposition of liquid organic waste from chemical and petrochemical industries. Int Conf Technol Mater Renew Energy Environ Sustain 74:4–14Google Scholar
  22. 22.
    Sang-Suk K, Ki-Won K, Hyo-Jun A, Kwon-Koo C (2008) Characterization of graphitic nanofibers synthesized by the CVD method using nickel–copper as a catalyst. J Alloys Compd 449:274–278CrossRefGoogle Scholar
  23. 23.
    Qian D, Xueyin S, Xiujuan Y, Xiaosi Q, Chak-Tong A, Wei Z, Youwei D (2013) Large-scale and controllable synthesis of metal-free nitrogen-doped carbon nanofibers and nanocoils over water-soluble Na2CO3. Nanoscale Res Lett 8:545CrossRefGoogle Scholar
  24. 24.
    Junfeng G, Ian AK, Charanjeet S, Vladimir BG, Brian FGJ, Milo SP, Syali L, Alan HW (2005) Production of carbon nanofibers in high yields using a sodium chloride support. J Phys Chem B. Google Scholar
  25. 25.
    Benjamín VS, Nicolás DS, Nicola N, Mario CA, José M, Bastidas R, Roumen Z, Margarita S (2017) Synthesis of carbon nanofibers with maghemite via a modified sol–gel technique. J Nanomater. Google Scholar
  26. 26.
    Roman MK, Yuri IB, Alexander MV, Ilya VM, Aleksey AV (2018) Synthesis of carbon nanofibers by catalytic CVD of chlorobenzene over bulk nickel alloy. Russ Fed Appl Surf Sci. Google Scholar
  27. 27.
    Jian-Ying M, Hwang DW, Narasimhulu KV, Lin P-I, Yit-Tsong C, Sheng-Hsien L, Lian-Pin H (2004) Synthesis and properties of carbon nanospheres grown by CVD using kaolin supported transition metal catalysts. Carbon J 42:813CrossRefGoogle Scholar
  28. 28.
    Zong-Xiang X, Jing-Dong L, Roy VAL, Yan O, Dai-Wei L (2005) Catalytic synthesis of carbon nanotubes and carbon spheres using kaolin supported catalyst. Mater Sci Eng J B 123:102–106CrossRefGoogle Scholar
  29. 29.
    Aliyu A, Kovo AS, Abdulkareem AS et al (2017) Synthesize multi-walled carbon nanotubes via catalytic chemical vapour deposition method on Fe–Ni bimetallic catalyst supported on kaolin. Carbon Lett. Google Scholar
  30. 30.
    Abdulkareem AS, Suleiman B, Abdulazeez AT et al (2016) Factorial design of optimization of monometallic cobalt catalyst on calcium carbonates support for carbon nanotube synthesis. In: Proceedings of the World congress on engineering and computer science, San Francisco, USAGoogle Scholar
  31. 31.
    Hu M, Peiling D, Zhang Y, Gao J, Ren X (2016) Effect of reaction temperature on carbon yield and morphology of CNTs on copper loaded nickel nanoparticles. J Nanomater 2016:1–5Google Scholar
  32. 32.
    Mhlanga SD, Mondal KC, Carter R et al (2009) The effect of synthesis parameters on the catalytic synthesis of multiwalled carbon nanotubes using Fe–Co/CaCO3 catalysts. S Afr J Chem 62:67–76Google Scholar
  33. 33.
    Surowiec Z, Wiertel M, Budzyński M, Gac W (2013) Synthesis and characterization of iron-cobalt nanoparticles embedded in mesoporous silica MCM-41. Nukleonika 58:87–92Google Scholar
  34. 34.
    Francisca UN (2014) Application of zeolite 4a—metakaolin matrix for the removal of some heavy metals from crude oil tank farm wastewater. Ph.D. thesis, Ahmadu Bello University, ZariaGoogle Scholar
  35. 35.
    Bawa SG, Ahmed AS, Okonkwo PC (2016) The study of thermal effect on the surface properties of gamma-alumina synthesized from Kankara Kaolin. Niger J Technol 35:1Google Scholar
  36. 36.
    Kumar S, Panda AK, Singh RK (2013) Preparation and characterization of acids and alkali treated kaolin clay. Bull Chem React Eng Catal 8:1CrossRefGoogle Scholar
  37. 37.
    Diko ML, Ekosse GE (2013) Characterisation of two kaolin facies from Ediki, Southwest Cameroon. Acad J 8:18. (ISSN 1992-2248) Google Scholar
  38. 38.
    Kovo AS (2011) Development of zeolites and zeolite membranes from Ahoko Nigerian Kaolin. Ph.D. thesis, The University of Manchester, Manchester, UKGoogle Scholar
  39. 39.
    Shani S, Paolo R, Nigel M, Kate W (2011) Dehydroxylation of kaolinite to metakaolin—a molecular dynamics study. J Mater Chem. Google Scholar
  40. 40.
    Lenka V, Eva P, Silvie V, Ivan K (2011) Characterization and differentiation of kaolinites from selected Czech deposits using infrared spectroscopy and differential thermal analysis. Acta Geodyn 8:59–67Google Scholar
  41. 41.
    Aroke UO, El-Nafaty UA, Osha OA (2013) Properties and characterization of kaolin clay from Alkaleri, North-Eastern Nigeria. Int J Emerg Technol Adv Eng 3:11.…/281378945
  42. 42.
    Alhassan MI (2016) Formulation of bimetallic (Fe–Co) catalyst on CaCO3 support for carbon nanotube synthesis. M.Eng. thesis, Federal University of Technology, Minna, NigeriaGoogle Scholar
  43. 43.
    Mahmoud GN, Elias BS, Hossein AA, Abdul HS, Mansor H (2010) Simple synthesis and characterization of cobalt ferrite nanoparticles by a thermal treatment method. J Nanomater. Google Scholar
  44. 44.
    Lilia A, Najeh ML, Bessaïs V, Madigou S, Villain S, Leroux C (2014) Magnetic, electric and thermal properties of cobalt ferrite nanoparticles. Mater Res Bull. Google Scholar
  45. 45.
    Honarbakhsh S, Farahmandjou M, Behroozinia S (2016) synthesis and characterization of iron cobalt (FeCo) nanorods prepared by simple co-precipitation method. J Fundam Appl Sci 8:892–900CrossRefGoogle Scholar
  46. 46.
    Amogh NK, Virginia AD, Bruce JT (2012) Carbon nanofiber synthesis within 3-dimensional sintered nickel microfibrous matrices: optimization of synthesis conditions. J Nanotechnol. Google Scholar
  47. 47.
    Antonio L, Agustı G, Paula S, Amaya R, Jose LV (2005) Growth of carbon nanofibers from Ni/Y zeolite based catalysts: effects of Ni introduction method, reaction temperature, and reaction gas composition. Ind Eng Chem Res. Google Scholar
  48. 48.
    Rinaldia A, Abdullaha N, Ali M et al (2009) Controlling the yield and structure of CNF grown on a nickel/activated carbon catalyst. Carbon 47:3023–3033CrossRefGoogle Scholar
  49. 49.
    Mustafa M, Mohammed AA, Rasel D et al (2018) Optimization of the synthesis of superhydrophobic carbon nanomaterials by chemical vapor deposition. Sci Rep. Google Scholar
  50. 50.
    Idowu AO (2016) Development of a suitable bimetallic (Fe–Co) catalyst on kaolin support for carbon nanotube synthesis. M.Eng. thesis, Federal University of Technology, Minna, NigeriaGoogle Scholar
  51. 51.
    Chang-Seop L, Yura H (2016) Preparation and characterization of CNF and its composites by chemical vapor deposition. Open Book Publication, CambridgeGoogle Scholar
  52. 52.
    Zhanbing H, Jean-Luc M, Aurélien G, Chang SL, Didier P, Costel SC (2011) Iron catalysts for the growth of carbon nanofibers: Fe, Fe3C or both? Chem Mater 23:5379–5387. 10.1021/cm202315j|Google Scholar
  53. 53.
    Wei X (2006) Synthesis, characterization and catalytic application of carbon- and silica-based nanocomposites. Ph.D. dissertation, Ruhr-University Bochum, Hebei, ChinaGoogle Scholar
  54. 54.
    Kim YI, Soundararajan D, Park CW et al (2009) Electrocatalytic properties of carbon nanofiber web-supported nanocrystalline Pt catalyst as applied to direct methanol fuel cell. Int J Electrochem Sci 4:1548–1559Google Scholar
  55. 55.
    Jing-Hong Z, Zhi-Jun S, Jun Z, Ping L, De C, Ying-Chun D, Wei-Kang Y (2007) Characterization of surface oxygen complexes on carbon nanofibers by TPD, XPS and FT-IR. Carbon J. Google Scholar
  56. 56.
    Yaru N (2012) Surface silanization of CNF and nanotubes for altering the properties of epoxy composites. PhD Thesis, Ilmenau University of Technology, Thuringia, pp 32–33Google Scholar
  57. 57.
    Tijmen GR, Adrianus JD, John WG, Diederik CK (2002) Surface oxidation of carbon nanofibres. Chem Eur J 8:5.;2-%23 CrossRefGoogle Scholar

Copyright information

© Korean Carbon Society 2019

Authors and Affiliations

  • K. Y. Mudi
    • 3
    • 4
    Email author
  • A. S. Abdulkareem
    • 1
    • 4
  • O. S. Azeez
    • 1
  • A. S. Kovo
    • 1
    • 4
  • J. O. Tijani
    • 2
    • 4
  • E. J. Eterigho
    • 1
  1. 1.Department of Chemical EngineeringFederal University of TechnologyMinnaNigeria
  2. 2.Department of ChemistryFederal University of TechnologyMinnaNigeria
  3. 3.Department of Chemical EngineeringKaduna PolytechnicKadunaNigeria
  4. 4.Nanotechnology Research Group, Centre for Genetic Engineering and BiotechnologyFederal University of TechnologyMinnaNigeria

Personalised recommendations