Abstract
The incorporation of 1 mass % of group VI metals (chromium, molybdenum, and tungsten) into 4 mass % of Ni/MgO catalysts was evaluated for the synthesis of carbon nanotubes (CNTs) by the catalytic chemical vapour deposition of ethylene. All materials were characterised by XRD, surface area, TEM, SEM, Raman spectroscopy, and TGA-DTA. The resulting data demonstrated that the addition of group VI metals improved the surface area and metal dispersion, thereby achieving a remarkable enhancement in catalytic growth activity. Among the metals of group VI, Mo was found to be the most effective promoter for catalysing the CNTs’ growth. From TEM observation, long CNTs with a higher degree of graphitization were obtained on the Ni-Mo/MgO catalyst. TGA and DTA analysis showed that the as-grown CNTs over both Ni-Mo and Ni-W/MgO catalysts exhibited higher thermal stability.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Aboul-Gheit, A. K., Awadallah, A. E., El-Kossy, S. M., & Mahmoud, A. L. H. (2008) Effect of Pd or Ir on the catalytic performance of Mo/H-ZSM-5 during the non-oxidative conversion of natural gas to petrochemicals. Journal of Natural Gas Chemistry, 17, 337–343. DOI: 10.1016/s1003-9953(09)60005-0.
Aboul-Gheit, A. K., & Awadallah, A. E. (2009) Effect of combining the metals of group VI supported on H-ZSM-5 zeolite as catalysts for non-oxidative conversion of natural gas to petrochemicals. Journal of Natural Gas Chemistry, 18, 71–77. DOI: 10.1016/s1003-9953(08)60080-8.
Aboul-Gheit, A. K., Awadallah, A. E., Aboul-Enein, A. A., & Mahmoud, A. L. H. (2011) Molybdenum substitution by copper or zinc in H-ZSM-5 zeolite for catalyzing the direct conversion of natural gas to petrochemicals under non-oxidative conditions. Fuel, 90, 3040–3046. DOI: 10.1016/j.fuel.2011.05.010.
Aboul-Gheit, A. K., El-Masry, M. S., & Awadallah, A. E. (2012) Oxygen free conversion of natural gas to useful hydrocarbons and hydrogen over monometallic Mo and bimetallic Mo-Fe, Mo-Co or Mo-Ni/HZSM-5 catalysts prepared by mechanical mixing. Fuel Processing Technology, 102, 24–29. DOI: 10.1016/j.fuproc.2012.04.017.
Ago, H., Uehara, N., Yoshihara, N., Tsuji, M., Yumura, M., Tomonaga, N., & Setoguchi, T. (2006) Gas analysis of the CVD process for high yield growth of carbon nanotubes over metal-supported catalysts. Carbon, 44, 2912–2918. DOI: 10.1016/j.carbon.2006.05.049.
Andersen, S. M., Borghei, M., Lund, P., Elina, Y. R., Pasanen, A., Kauppinen, E., Ruiz, V., Kauranen, P., & Skou, E. M. (2013) Durability of carbon nanofiber (CNF) & carbon nanotube (CNT) as catalyst support for Proton Exchange Membrane Fuel Cells. Solid State Ionics, 231, 94–101. DOI: 10.1016/j.ssi.2012.11.020.
Ashok, J., Kumar, S. N., Venugopal, A., Kumari, V. D., & Subrahmanyam, M. (2007) CO x -free H2 production via catalytic decomposition of CH4 over Ni supportedonzeolite catalysts. Journal of Power Sources, 164, 809–814. DOI: 10.1016/j.jpowsour.2006.11.029.
Awadallah, A. E., Aboul-Enein, A. A., & Aboul-Gheit, A. K. (2014) Effect of progressive Co loading on commercial Co-Mo/Al2O3 catalyst for natural gas decomposition to CO x -free hydrogen production and carbon nanotubes. Energy Conversion and Management, 77, 143–151. DOI: 10.1016/j.enconman.2013.09.017.
Cassell, A. M., Raymakers, J. A., Kong, J., & Dai, H. J. (1999) Large scale CVD synthesis of single-walled carbon nanotubes. The Journal of Physical Chemistry B, 103, 6484–6492. DOI: 10.1021/jp990957s.
Chai, S. P., Zein, S. H. S., & Mohamed, A. R. (2006) Preparation of carbon nanotubes over cobalt-containing catalysts via catalytic decomposition of methane. Chemical Physics Letter, 426, 345–350. DOI: 10.1016/j.cplett.2006.05.026.
Chen, M. H., Huang, Z. C., Wu, G. T., Zhu, G. M., You, J. K., & Lin, Z. G. (2003) Synthesis and characterization of SnO-carbon nanotube composite as anode material for lithiumion batteries. Materials Research Bulletin, 38, 831–836. DOI: 10.1016/s0025-5408(03)00063-1.
Chen, C. M., Dai, Y. M., Huang, J. G., & Jehng, J. M. (2006) Intermetallic catalyst for carbon nanotubes (CNTs) growth by thermal chemical vapor deposition method. Carbon, 44, 1808–1820. DOI: 10.1016/j.carbon.2005.12.043.
Chen, L., Liu, H. T., Yang, K., Wang, J. K., & Wang, X. L. (2009) Catalytic synthesis of carbon nanotubes from the decomposition of methane over a Ni-Co/La2O3 catalyst. Canadian Journal of Chemistry, 87, 47–53. DOI: 10.1139/v08-077.
de Lucas, A., Garrido, A., Sánchez, P., Romero, A., & Valverde, J. L. (2005) Growth of carbon nanofibers from Ni/Y zeolite based catalysts: Effects of Ni introduction method, reaction temperature, and reaction gas composition. Industrial & Engineering Chemistry Research, 44, 8225–8236. DOI: 10.1021/ie058027k.
Dresselhaus, M. S., Dresselhaus, G., Jorio, A., Souza Filho, A. G., & Saito, R. (2002) Raman spectroscopy on isolated single wall carbon nanotubes. Carbon, 40, 2043–2061. DOI: 10.1016/s0008-6223(02)00066-0.
Dupuis, A. C. (2005) The catalyst in the CCVD of carbon nanotubes—a review. Progress in Materials Science, 50, 929–961. DOI: 10.1016/j.pmatsci.2005.04.003.
Fan, S. S., Chapline, M. G., Franklin, N. R., Tombler, T. W., Cassell, A. M., & Dai, H. J. (1999) Self-oriented regular arrays of carbon nanotubes and their field emission properties. Science, 283, 512–514. DOI: 10.1126/science.283.5401.512.
Flahaut, E., Peigney, A., Bacsa, W. S., Bacsa, R. R., & Laurent. Ch. (2004) CCVD synthesis of carbon nanotubes from (Mh,Co,Mo)O catalysts: influence of the proportions of cobalt and molybdenum. Journal of Materials Chemistry, 14, 646–653. DOI: 10.1039/b312367g.
Fujiwara, A., Ishii, K., Suematsu, H., Kataura, H., Maniwa, Y., Suzuki, S., & Achiba, Y. (2001) Gas adsorption in the inside and outside of single-walled carbon nanotubes. Chemical Physics Letter, 336, 205–211. DOI: 10.1016/s0009-2614(01)00111-7.
Harutyunyan, A. R., Pradhan, B. K., Kim, U. J., Chen, G. G., & Eklund, P. C. (2002) CVD synthesis of single wall carbon nanotubes under “soft” conditions. Nano Letters, 2, 525–530. DOI: 10.1021/nl0255101.
Herrera, J. E., & Resasco, D. E. (2003) Role of Co-W interaction in the selective growth of single-walled carbon nanotubes from CO disproportionation. The Journal of Physical Chemistry B, 107, 3738–3746. DOI: 10.1021/jp027602k.
Jehng, J. M., Tung, W. C., & Kuo, C. H. (2008) The formation mechanisms of multi-wall carbon nanotubes over the Ni modified MCM-41 catalysts. Journal of Porous Materials, 15, 43–51. DOI: 10.1007/s10934-006-9050-x.
Kitiyanan, B., Alvarez, W. E., Harwell, J. H., & Resasco, D. E. (2000) Controlled production of single-wall carbon nanotubes by catalytic decomposition of CO on bimetallic Co-Mo catalysts. Chemical Physics Letter, 317, 497–503. DOI: 10.1016/s0009-2614(99)01379-2.
Landois, P., Peigney, A., Laurent, Ch., Frin, L., Datas, L., & Flahaut, E. (2009) CCVD synthesis of carbon nanotubes with W/Co-MgO catalysts. Carbon, 47, 789–794. DOI: 10.1016/j.carbon.2008.11.018.
Lee, C. J., Park, J. H., Kim, J. M., Huh, Y., Lee, J. Y., & No, K. S. (2000) Low-temperature growth of carbon nanotubes by thermal chemical vapor deposition using Pd, Cr, and Pt as co-catalyst. Chemical Physics Letter, 327, 277–283. DOI: 10.1016/s0009-2614(00)00877-0.
Li, Y., Zhang, B. C., Tang, X. L., Xu, Y. D., & Shen, W. J. (2006) Hydrogen production from methane decomposition over Ni/CeO2 catalysts. Catalysis Communications, 7, 380–386. DOI: 10.1016/j.catcom.2005.12.002.
Li, Y. D., Li, D. X., & Wang, G. W. (2011) Methane decomposition to CO x -free hydrogen and nano-carbon material on group 8–10 base metal catalysts: A review. Catalysis Today, 162, 1–48. DOI: 10.1016/j.cattod.2010.12.042.
Loebick, C. Z., Derrouiche, S., Fang, F., Li, N., Haller, G. L., & Pfefferle, L. D. (2009) Effect of chromium addition to the Co-MCM-41 catalyst in the synthesis of single wall carbon nanotubes. Applied Catalysis A: General, 368, 40–49. DOI: 10.1016/j.apcata.2009.08.004.
Loebick, C. Z., Lee, S. C., Derrouiche, S., Schwab, M., Chen, Y., Haller, G. L., & Pfefferle, L. (2010) A novel synthesis route for bimetallic CoCr-MCM-41 catalysts with higher metal loadings. Their application in the high yield, selective synthesis of Single-Wall Carbon Nanotubes. Journal of Catalysis, 271, 358–369. DOI: 10.1016/j.jcat.2010.02.021.
Ni, L., Kuroda, K., Zhou, L. P., Kizuka, T., Ohta, K., Matsuishi, K., & Nakamura, J. (2006) Kinetic study of carbon nanotube synthesis over Mo/Co/MgO catalysts. Carbon, 44, 2265–2272. DOI: 10.1016/j.carbon.2006.02.031.
Pasha, M. A., Shafiekhani, A., & Vesaghi, M. A. (2009) Hot filament CVD of Fe-Cr catalyst for thermal CVD carbon nanotube growth from liquid petroleum gas. Applied Surface Science, 256, 1365–1371. DOI: 10.1016/j.apsusc.2009.08.090.
Pour, A. N., Zamani Kheirolah, Y., Jozani, J., & Mehr, J. Y. (2005) The influence of La2O3 and TiO2 on NiO/MgO/α-Al2O3. Reaction Kinetics and Catalysis Letters, 86, 157–162. DOI: 10.1007/s11144-005-0307-1.
Sinnott, S. B., Andrews, R., Qian, D., Rao, A. M., Mao, Z., Dickey, E. C., & Derbyshire, F. (1999) Model of carbon nanotube growth through chemical vapor deposition. Chemical Physics Letter, 315, 25–30. DOI: 10.1016/s0009-2614(99)01216-6.
Song, C. S., & Pan, W. (2004) Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios. Catalysis Today, 98, 463–484. DOI: 10.1016/j.cattod.2004.09.054.
Takenaka, S., Kobayashi, S., Ogihara, H., & Otsuka, K. (2003) Ni/SiO2 catalyst effective for methane decomposition into hydrogen and carbon nanofiber. Journal of Catalysis, 217, 79–87. DOI: 10.1016/s0021-9517(02)00185-9.
Tang, S., Zhong, Z., Xiong, Z., Sun, L., Liu, L., Lin, J., Shen, Z. X., & Tan, K. L. (2001) Controlled growth of single-walled carbon nanotubes by catalytic decomposition of CH4 over Mo/Co/MgO catalysts. Chemical Physics Letters, 350, 19–26. DOI: 10.1016/s0009-2614(01)01183-6.
Tans, S. J., Verschueren, A. R. M., & Dekker, C. (1998) Room-temperature transistor based on a single carbon nanotube. Nature, 393, 49–52. DOI: 10.1038/29954.
Tauster, S. T., Fung, S. C., Baker, R. T. K., & Horsley, J. A. (1981) Strong interactions in supported-metal catalysts. Science, 211, 1121–1125. DOI: 10.1126/science.211.4487.1121.
Tauster, S. J. (1987) Strong metal-support interactions. Accounts of Chemical Research, 20, 389–394. DOI: 10.1021/ar00143a001.
Toebes, M. L., Zhang, Y. H., Hájek, J., Nijhuis, T. A., Bitter, J. H., van Dillen, A. J., Murzin, D. Yu., Koningsberger, D. C., & de Jong, K. P. (2004) Support effects in the hydrogenation of cinnamaldehyde over carbon nanofiber-supported platinum catalysts: characterization and catalysis. Journal of Catalysis, 226, 215–225. DOI: 10.1016/j.jcat.2004.05.026.
Wang, L. S., Tao, L. X., Xie, M. S., Xu, G. F., Huang, J. S., & Xu, Y. D. (1993) Dehydrogenation and aromatization of methane under non-oxidizing conditions. Catalysis Letters, 21, 35–41. DOI: 10.1007/bf00767368.
Willems, I., Kónya, Z., Fonseca, A., & Nagy, J. B. (2002) Heterogeneous catalytic production and mechanical resistance of nanotubes prepared on magnesium oxide supported Co-based catalysts. Applied Catalysis A: General, 229, 229–233. DOI: 10.1016/s0926-860x(02)00030-3.
Yeoh, W. M., Lee, K. Y., Chai, S. P., Lee, K. T., & Mohamed, A. R. (2010) The role of molybdenum in Co-Mo/MgO for large-scale production of high quality carbon nanotubes. Journal of Alloys and Compounds, 493, 539–543. DOI: 10.1016/j.jallcom.2009.12.151.
Yoshida, A., Kaburagi, Y., & Hishiyama, Y. (2006) Full width at half maximum intensity of the G band in the first order Raman spectrum of carbon material as a parameter for graphitization. Carbon, 44, 2333–2335. DOI: 10.1016/j.carbon.2006.05.020.
Zheng, G. B., Kouda, K., Sano, H., Uchiyama, Y., Shi, Y. F., & Quan, H. J. (2004) A model for the structure and growth of carbon nanofibers synthesized by the CVD method using nickel as a catalyst. Carbon, 42, 635–640. DOI: 10.1016/j.carbon.2003.12.077.
Zhou, L. P., Ohta, K., Kuroda, K., Lei, N., Matsuishi, K., Gao, L. Z., Matsumoto, T., & Nakamura, J. (2005) Catalytic functions of Mo/Ni/MgO in the synthesis of thin carbon nanotubes. The Journal of Physical Chemistry B, 109, 4439–4447. DOI: 10.1021/jp045284e.
Zhou, W. W., Han, Z. Y., Wang, J. Y., Zhang, Y., Jin, Z., Sun, X., Zhang, Y. W., Yan, C. H., & Li, Y. (2006) Copper catalyzing growth of single-walled carbon nanotubes on substrates. Nano Letters, 6, 2987–2990. DOI: 10.1021/nl061871v.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Awadallah, A.E. Promoting effect of group VI metals on Ni/MgO for catalytic growth of carbon nanotubes by ethylene chemical vapour deposition. Chem. Pap. 69, 316–324 (2015). https://doi.org/10.1515/chempap-2015-0029
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1515/chempap-2015-0029