Pseudomorphic Reaction: A New Approach to Produce Bulk Mesoporous Silica as Catalyst Support in Methane Reforming


1 Energy, Materials and Energy Research Center

2 Dept. of Energy, Materials and Energy Research Centre

3 Chemical Engineering, School of Chemical and petroleum Engineering, Shiraz

4 Nano-Technology and Advanced Materials, Materials and Energy Research Center


Pseudomorphism is known as a suitable technique for producing mesoscale pore in silica powders keeping their original morphologies. Herein, silica discs with several millimeter dimensions have been prepared using the same method. This method has been utilized through application of pseudomorphism reaction of preshaped bodies by immersion in a solution containing surfactant and swelling reagents. The pseudomorphism reactions were performed on time and temperature controlled condition. Large surface area of mesoporous silica discs have been considered here for investigation in methane steam reforming as catalyst support. The silica support has been utilized for preparation Ni-silica catalyst through impregnation method.  The physical properties of synthesized mesoporous support and nanocatalysts have been characterized by nitrogen adsorption-desorption surface measurement (BET- BJH method) and Archemideous immersion analysis as well as field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), inductively coupled plasma (ICP) analyses techniques. Investigation on catalytic behavior of prepared samples in steam reforming of methane resulted improving of methane conversion in addition to hydrogen production yield.


Main Subjects

1. Yuganov, I., Meckler, P., Suvorov, E., Buffet, P., Kiwi-Minster, L. and Rankin, A., "Pd/SiO2 catalysts: synthesis of Pd nanoparticles with the controlled size in mesoporous silicas", Journal of Molecular Catalysis A: Chemical, Vol. 192, (2003), 239-251.
2. Kailas, K. and Muller, K., "Physico- chemical characterization of MCM-41 silica spheres made by the pseudomorphic route and grafted with octadecyl chains", Journal of Chromatography. A, Vol. 1191, (2008), 125-135.
3. Galarneau, A., Desplantier-Giscard, D., Di Renzo, F. and Facula, F., "Thermal and mechanical stability of micelletemplated silica support for catalysis", Catalysis Today, Vol. 68, (2001), 191-200.
4. Liu, X., Sun, H., Chen, Y., Yang, Y. and Brogan, A., "Preparation of spherical large-particle MCM-41 with a broad particle-size distribution by a modified pseudomorphic transformation", Microporous and Mesoporous Materials, Vol. 121, (2009), 73-78.
5. Wang, X., Zhang, X., Wang, Y., Liu, H., Qi, J., Wang, J., Han, W. and Yeung, K.L., "Investigation the role of zeolite nanocrystal seeds in the synthesis of mesoporous catalysts with wall structure", Chemistry of Materials, Vol. 23, (2011), 4469- 4479.
6. Taguchi, A. and Shut, F., "ordered mesoporous materials in catalysis", Microporous and Mesoporous Materials, Vol. 77, (2005), 1-45.
7. Kim, P., Kim, Y., Kim, C., Kim, H., Park, Y., Lee, J.H., Song, I. K. and Yi, J., "Synthesis and characterization of mesoporous alumina as a catalyst support for hydrodechlorination of 1,2- dichloropropane: Effect of catalyst preparation method", Catalysis Letter, Vol. 89, (2003), 185-193.
8. Moue, C.Y. and Lin, H.P., "control of morphology in synthesizing mesoporous silica", Pure and Applied Chemistry, Vol. 72, (2000), 137-146.
9. Iapichella, J., Menses, J.M., Beurroies, I., Denoyel, R., Bayram- Hahn, Z., Unger, K. and Galarneau, A., "Characterization of mesoporous silica and its pseudomorphically transformed derivative by gas and liquid adsorption", Microporous and Mesoporous Materials, Vol. 102, (2007), 111-121.
10. Galarneau, A., Calin, N., Iapichella, J., Barrande, M., Denote, R., Coasne, B. and Facula, F., "Optimization of the properties of mesoporous chromatography silica supports through surface roughness control", Chemistry of Materials, Vol. 21, (2009), 1884-1892.
11. Yasmin, T. and muller, K., "Synthesis and modification of mesoporous mcm-41 silica materials", Journal of Chromatography. A, Vol. 1217, (2010), 3362-3374.
12. Yoo, W.C. and Stein, A., "Solvent effect of morphologies of mesoporous silica spheres prepared by pseudomorphic transformation", Chemistry of Materials, Vol. 23, (2011), 1761- 1767.
13. Nagata, H. Takimura, M. Yamasaki, Y. and Nakahira, A., "Syntheses and characterization of bulky mesoporous silica MCM-41 by hydrothermal hot-pressing method", Materials Transaction, Vol. 47, (2006), 2103-2105.
14. Fajula, F., "Engineering mesostructured silicas by pseudomorphism", Dalton Transaction, (2007), 291-294.
15. Lebeau, B., Galarneau, A. and Linden, M., "Introduction for 20 years of ordered mesoporous materials", Chemical Society Reviews, Vol. 42, (2013), 3661-3662.
16. Choi, M., Na, K. and Ryoo, R., "The synthesis of hierarchically porous BEA zeolite via pseudomorphic crystallization", Chemical Communications, (2009), 2845-2847.
17. Galarneau, A., Iapichella, J., Bonhomme, K., Di Renzo, F., Kooyman, P., Terasaki, O. and Facula, F., "Controlling the morphology of mesostructured silica by pseudomorphic transformation: A rout towards applications", Advanced Functional Materials, Vol. 16, (2006), 1657-1667.
18. Einicke, W.D., Enke, D., Dvoyashkin, M., Valiullin, R. and Glaser, R., "The mechanism of pseudomorphic transformation of spherical silica gel into MCM-41 studied by PFG NMR diffusometry", Materials, Vol. 6, (2013), 3688-3709.
19. Galarneau, A., Cangiotti, M., Di Renzo, F., Sartori, F. and Ottaviani, M.F., "Synthesis of large-pore micelle-templated silico-aluminas at different alumina contents", The Journal of Physical Chemistry B, Vol. 110, (2006), 20202-20210.
20. Corma, A., "from microporous to mesoporous molecular sieve material and their use in catalysis", Chemical Reviews, Vol. 97, (1997), 2373-2419.
21. Inayat, A., Reinhardt, B., Uhlig, H., Einicke, W.D. and Enke, D., "silica monolith with hierarchical porosity obtained from glasses", Chemical Society Reviews, Vol. 47, (2013), 3753- 3765.
22. Lovell, E.C., Scott, J. and Amal, R., "Ni-SiO2 catalysts for the carbon dioxide reforming of the methane: Varying support properties by flame spray pyrolysis", Molecules, Vol. 20, (2015), 4594-4609.
23. Wang, Z. and Navarrete, J., "production of carbon nanotubes and hydrogen catalyzed with Ni/MCM-41 catalysts", Green and Sustainable Chemistry, Vol. 2, (2012), 91-96.
24. Guevara, J.C., et al., "Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of hydrogen and nanocarbon via methane decomposition", Hydrogen Enregy, Vol. 35, (2010), 3509- 3521.
25. Liu, D., Quek, X.Y., Cheo, Y.N.E., Lau, R., Borgna, A. and Yang, Y., "MCM-41 supported nickel- based bimetallic catalysts with superior stability during carbon dioxide reforming of methane: Effect of strong metal- support interaction", Journal of Catalysis, Vol. 266, (2009), 380-90.
26. Wu, H. Parola, V.L., Pantaleo, G., Puleo, F., Venezia, A.M. and Liotta, L.F., "Ni- based catalysts for low temperature methane steam reforming reforming: Recent results on Ni- Au and comparison with other bi- metallic systems", Vol. 3, Catalysts 3, (2013) 563-583.
27. Zhang, Y., Wang, W., Wang, Z., Zhou, X., Wang, Z. and Liu, C.J., "Steam reforming of methane over Ni/SiO2 catalyst with enhanced coke resistance at low steam to methane ratio", Catalysis Today, Vol. 256, (2015), 130-136.
28. Matsumura, Y. and Nakamori, T., "Steam reforming of methane over nickel catalysts at low reaction temperature", Applied Catalysis A, Vol. 258, (2004), 107–114.
29. Soltan Mohammadzadeh, J. S. and Zamaniyan, A., "Catalyst shape as a design parameter-optimum shape for methane – steam reforming catalyst", Chemical Engineering Research and Design, Vol. 80, (2002), 383-391.
30. Mortazavi, A., Razavi, M., Ebadzadeh, T. and Sedaghat Ahangari, A., "Effect of milling time on the microstructure of Al2O3-Mo nanocomposite", ACERP, Vol. 2, (2016) 12-16.
31. Shojaeepour, F., Kazemzad, M., Rahimpour, M.R., Khanlarkhani, A. and Hafizi, A., "Physico- chemical characterization of shaped mesoporous silica prepared by pseudomorphic transformation as catalyst support in methane steam reforming", Reaction Kinetics, Mechanisms and Catalysis, Vol. 124, (2018), 229–245.
32. Rer. Nat, "Catalytic reforming of methane in presence of CO2 and H2O at high pressure", Faculty of Chemistry and Biosciences, Karlsruhe Institute of Technology (KIT) University, (2013).