• Vol 9, No 1 (2018)
  • Chemical Engineering

The Effect of Metal Loading on the Performance of Tri-metallic Supported Catalyst for Carbon Nanotubes Synthesis from Liquefied Petroleum Gas

Puguh Setyopratomo, Praswasti P.D.K. Wulan, Mahmud Sudibandriyo

Publish at : 27 Jan 2018 - 00:00
IJtech : IJtech Vol 9, No 1 (2018)
DOI : https://doi.org/10.14716/ijtech.v9i1.1165

Cite this article as:
Setyopratomo, P., Wulan, P.P.D.K., Sudibandriyo, M., 2018. The Effect of Metal Loading on the Performance of Tri-metallic Supported Catalyst for Carbon Nanotubes Synthesis from Liquefied Petroleum Gas. International Journal of Technology. Volume 9(1), pp. 120-129
Puguh Setyopratomo Universitas Indonesia
Praswasti P.D.K. Wulan Universitas Indonesia
Mahmud Sudibandriyo Universitas Indonesia
Email to Corresponding Author


Carbon nanotubes (CNT) were synthesized from liquefied petroleum gas by a chemical vapor deposition method using a Fe-Co-Mo/MgO supported catalyst. Metal loading was varied from 2.5 to 20 wt%. The catalyst with metal loading of 10 wt% produced the highest CNT yield, at 4.55 g CNT/g catalyst. This high CNT yield was attributed to the high pore volume of the catalyst. The diameter of the CNT was quite variable: the outer diameter ranged from about 4 to 12 nm, while the inner diameter ranged from about 2 to 5 nm. The catalyst with 10 wt% metal loading produced CNT with the highest surface area and the largest total pore volume. XRD analysis detected the existence of highly oriented pyrolytic graphite, C(002), at 2 theta ? 26o, which was attributed to the CNT.    

Carbon nanotubes; Chemical vapor deposition; Liquefied petroleum gas; Metal loading; Supported catalyst


Various methods are available for carbon nanotube (CNT) synthesis, but chemical vapor deposition (CVD) is viewed as having the most potential for use in large scale production. This is because CVD is easily controlled and less expensive than other CNT synthesis methods, and it can be operated at atmospheric pressure and a lower temperature (i.e., 500–1000°C) (Tapasztó et al., 2005).

In CNT production by CVD, the performance of the catalysts is often more efficient if mixtures of transition metals are used, rather than a single metal alone. The reaction temperature also can be lowered for mixtures of two or more metals (Dupuis, 2005). Ago et al. (2006) reported that catalyst activity increased in accordance with the metal used, in the order of Fe > Co > Ni. Although Fe is more active than Co, Co is superior to Fe for producing CNT with respect to the degree of graphitization and the CNT structure (Fonseca et al., 1996; Hernadi et al., 2000).

Molybdenum (Mo) is usually added to the Fe or Co catalyst to increase its activity. Mo does not play a role as an active catalyst; instead, it serves as a promoter or activator to enhance the catalyst performance. Mo also acts as an inhibitor to prevent rapid deactivation of the catalyst (Dupuis, 2005; Ago et al., 2006). Mo also improves dispersion and prevents the sintering of Fe nanoparticles (Zhang et al., 2011). An advantage of using MgO as a catalyst support is that it increases the CNT yield and it can be separated easily from the CNT product (Tsoufis et al., 2007) by a simple acid treatment, thereby facilitating the purification of CNT (Ago et al., 2006).

A significant factor for controlling catalyst performance is the level of metal loading (Tsoufis et al., 2007). The size of metal nanoparticles dispersed on a catalyst support is affected by the level of metal loading, as a lower metal loading results in a smaller size of the metal nanoparticles. By contrast, increased metal loading may result in sintering of the metal particles (Zhang et al., 2011). The metal loading also substantially affects the extent of dispersion of the metal nanoparticles on the support (Wei et al., 2008).

The main disadvantage of using a single metal as an active catalyst component is the low performance, as described above. The aim of the present study was to examine the use of a tri-metallic supported catalyst (Fe-Co-Mo/MgO) for CNT synthesis by the CVD method, focusing on the effect of metal loading on the catalyst performance. The main observed parameter of the catalyst performance was CNT yield, which was determined by the mass of CNT produced per unit mass of catalyst. The quality of the CNT produced was also analyzed.


We observed a significant influence of the catalyst composition and characteristics on the yield and properties of the produced CNT. The experimental results showed that the high CNT yield was attributed to the high pore volume of the catalyst. This confirmed that the pore volume of the catalyst plays an important role in the growth of CNT. Mesopores dominated the pore distribution of the CNT product. A high yield of CNT with high surface area and pore volume was produced with a 10 wt% metal loading. The Fe-Co-Mo/MgO catalyst successfully facilitated the formation and growth of multi-walled CNT with ordered structures and a high degree of graphitization. 


The authors wish to thank The Directorate Research and Community Services, Universitas Indonesia, for providing the financial support through The Research Cluster Grant 2015- contract number: 1875/UN2.R12/HKP.05.00/2015.


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, Volume 44(14), pp. 2912–2918

Awadallah, A.E., Gad, F.K., Aboul-Enein, A.A., Labib, M.R., Aboul-Gheit, A.K., 2013. Direct Conversion of Natural Gas into COx-free Hydrogen and MWCNTs over Commercial Ni–Mo/Al2O3 Catalyst: Effect of Reaction Parameters. Egyptian Journal of Petroleum, Volume 22(1), pp. 27–34

Dupuis, A., 2005. The Catalyst in the CCVD of Carbon Nanotubes—A Review. Progress in Materials Science, Volume 50(8), pp. 929–961

Fonseca, A., Hernadi, K., Nagya, B., Bernaerts, D., Lucas, A.A., 1996. Optimization of Catalytic Production and Purification of Buckytubes. Journal of Molecular Catalysis A: Chemical, Volume 107(1–3), pp. 159–168

Gangupomu, R.H., Sattler, M.L., Ramirez, D., 2016. Comparative Study of Carbon Nanotubes and Granular Activated Carbon: Physicochemical Properties and Adsorption Capacities. Journal of Hazardous Materials, 302, pp. 362–374

Groen, J.C., Peffer, L.A.A., Perez-Ram?rez, J., 2003. Review - Pore Size Determination in Modified Micro- and Mesoporous Materials. Pitfalls and Limitations in Gas Adsorption Data Analysis. Microporous and Mesoporous Materials, Volume 60(­1–3), pp. 1–17

Hernadi, K., Fonseca, A., Nagya, J.B., Siska, A., Kiricsi, I., 2000. Production of Nanotubes by the Catalytic Decomposition of Different Carbon-containing Compounds. Applied Catalysis A: General, Volume 199(2), pp. 245–255

Hordy, N., Mendoza-Gonzalez, N., Coulombe, S., Meunier, J., 2013. The Effect of Carbon Input on the Morphology and Attachment of Carbon Nanotubes Grown Directly from Stainless Steel. Carbon, Volume 63, pp. 348–357

Hsieh, C., Lin, Y., Lin, J., Wei, J., 2009. Synthesis of Carbon Nanotubes over Ni- and Co-supported CaCO3 Catalysts using Catalytic Chemical Vapor Deposition. Materials Chemistry and Physics, Volume 114(2–3), pp. 702–708

Huang, J., Zhang, Q., Wei, F., Qian, W., Wang, D., Hu, L., 2008. Liquefied Petroleum Gas Containing Sulfur as the Carbon Source for Carbon Nanotube Forests. Carbon, Volume 46(2), pp. 291–296

Kuo, C.Y., Wu, C.H., Wu, J.Y., 2008. Adsorption of Direct Dyes from Aqueous Solutions by Carbon Nanotubes: Determination of Equilibrium, Kinetics and Thermodynamics Parameters. Journal of Colloid and Interface Science, Volume 327(2), pp. 308–315

Lee, S.Y., Park, S.J., 2012. Influence of the Pore Size in Multi-walled Carbon Nanotubes on the Hydrogen Storage Behaviors. Journal of Solid State Chemistry, Volume 194, pp. 307–312

Liu, Q., Fang, Y., 2006. New Technique of Synthesizing Single-walled Carbon Nanotubes from Ethanol using Fluidized-bed over Fe–Mo/MgO Catalyst. Spectrochimica Acta Part A, Volume 64(2), pp. 296–300

Maccalini, E., Tsoufis, T., Policicchio, A., Rosa, S.L., Caruso, T., Chiarello, G., Colavita, E., Formoso, V., Gournis, D., Agostino, R.G., 2010. A Spectro-microscopic Investigation of Fe–Co Bimetallic Catalysts Supported on MgO for the Production of Thin Carbon Nanotubes. Carbon, Volume 48(12), pp. 3434–3445

Ni, L., Kuroda, K., Zhou, L., Kizuka, T., Ohta, K., Matsuishi, K., Nakamura, J., 2006. Kinetic Study of Carbon Nanotube Synthesis over Mo/Co/MgO Catalysts. Carbon, Volume 44(11), pp. 2265–2272

Ni, L., Kuroda, K., Zhou, L., Ohta, K., Matsuishi, K., Nakamura, J., 2009. Decomposition of Metal Carbides as an Elementary Step of Carbon Nanotube Synthesis. Carbon, Volume 47(13), pp. 3054–3062

Reyhani, A., Mortazavi, S.Z., Akhavan, O., Moshfegh, A.Z., Lahooti, S., 2007. Effect of Ni, Pd and Ni–Pd Nano-islands on Morphology and Structure of Multi-wall Carbon Nanotubes. Applied Surface Science, Volume 253(20), pp. 8458–8462

Tapasztó, L., Kertész, K., Vértesy, Z., Horváth, Z.E., Koós, A.A., Osváth, Z., Sárközi, Z., Darabont, A., Biró, L.P., 2005. Diameter and Morphology Dependence on Experimental Conditions of Carbon Nanotube Arrays Grown by Spray Pyrolysis. Carbon, Volume 43(5), pp. 970–977

Tsoufis, T., Xidas, P., Jankovic, L., Gournis, D., Saranti, A., Bakas, T., Karakassides, M.A. 2007. Catalytic Production of Carbon Nanotubes over Fe–Ni Bimetallic Catalysts Supported on MgO. Diamond & Related Materials, Volume 16(1), pp. 155–160

Wang, G., Wang, J., Wang, H., Bai, J., 2014. Preparation and Evaluation of Molybdenum Modified Fe/MgO Catalysts for the Production of Single-walled Carbon Nanotubes and Hydrogen-rich Gas by Ethanol Decomposition. Journal of Environmental Chemical Engineering, Volume 2(3), pp. 1588–1595

Wang, Z.M., Hoshinoo, K., Yamagishi, M. Yoshizawa, N., Kanoh, H., Hirotsu, T., 2006. Formation of Graphite-derived Layered Mesoporous Carbon Materials. Microporous and Mesoporous Materials, Volume 93(1–3), pp. 254–262

Wei, F., Zhang, Q., Qian, W., Yu, H., Wang, Y., Luo, G., Xu, G., Wang, D., 2008. The Mass Production of Carbon Nanotubes using a Nano-agglomerate Fluidized Bed Reactor: A Multiscale Space–time Analysis. Powder Technology, Volume 183(1), pp. 10–20

Xu, J., Ibrahim, A., Hu, X., Hong, Y., Su, Y., Wang, H., Li, J., 2016. Preparation of Large Pore Volume ?-Alumina and Its Performance as Catalyst Support in Phenol Hydroxylation. Microporous and Mesoporous Materials, Volume 231, pp. 1–8

Zhang, Q., Huang, J., Zhao, M., Qian, W., Wei, F., 2011. Carbon Nanotube Mass Production: Principles and Processes. ChemSusChem, Volume 4(7), pp. 864–889