Effect of Sorbitol/Oxidizer Ratio on Microwave Assisted Solution Combustion Synthesis of Copper Based Nanocatalyst for Fuel Cell Grade Hydrogen Production

Document Type: Research Paper


1 Sahand University of Technology

2 Sahand University of Technology Reactor and Catalysis Research Center


Steam reforming of methanol is one of the promising processes for on-board hydrogen production used in fuel cell applications. Due to the time and energy consuming issues associated with conventional synthesis methods, in this paper a quick, facile, and effective microwave-assisted solution combustion method was applied for fabrication of copper-based nanocatalysts to convert methanol to hydrogen. For this purpose, a series of nanocatalysts with different sorbitol/nitrates ratios were synthesized by microwave-assisted combustion method. Their physicochemical properties were studied by XRD, FESEM, EDX, BET and FTIR analyses. It was found that enhancement of sorbitol/nitrates ratio led to increase of CuO dispersion and specific surface area, as well as smaller, nanometric and homogeneously dispersed particles. These significant characteristic properties especially achieved by CZA(S/N=3) nanocatalyst, resulted in high methanol conversion and hydrogen selectivity even at low temperatures. This effective performance was accompanied by negligible CO production as undesired by-product as well as poison in fuel cell applications.


Main Subjects

1.    McLarty, D., Brouwer, J., and Ainscough, C., "Economic analysis of fuel cell installations at commercial buildings including regional pricing and complementary technologies", Energy and Buildings, 2016, 113: 112.

2.    Wu, H.-W., "A review of recent development: Transport and performance modeling of PEM fuel cells", Applied Energy, 2016, 165: 81.

3.    Kim, J. and Kim, T., "Compact PEM fuel cell system combined with all-in-one hydrogen generator using chemical hydride as a hydrogen source", Applied Energy, 2015, 160: 945.

4.    Kim, D.H., Kim, S.H., and Byun, J.Y., "A microreactor with metallic catalyst support for hydrogen production by partial oxidation of dimethyl ether", Chemical Engineering Journal, 2015, 280: 468.

5.    Takeishi, K. and Akaike, Y., "Hydrogen production by dimethyl ether steam reforming over copper alumina catalysts prepared using the sol-gel method", Applied Catalysis A: General, 2016, 510: 20.

6.    Carvalho, F.L.S., Asencios, Y.J.O., Bellido, J.D.A., and Assaf, E.M., "Bio-ethanol steam reforming for hydrogen production over Co3O4/CeO2 catalysts synthesized by one-step polymerization method", Fuel Processing Technology, 2016, 142: 182.

7.    Ma, H., Zeng, L., Tian, H., Li, D., Wang, X., Li, X., and Gong, J., "Efficient hydrogen production from ethanol steam reforming over La-modified ordered mesoporous Ni-based catalysts", Applied Catalysis B: Environmental, 2016, 181: 321.

8.    Matsumura, Y., "Durable Cu composite catalyst for hydrogen production by high temperature methanol steam reforming", Journal of Power Sources, 2014, 272: 961.

9.    Mironova, E.Y., Lytkina, A.A., Ermilova, M.M., Efimov, M.N., Zemtsov, L.M., Orekhova, N.V., Karpacheva, G.P., Bondarenko, G.N., Muraviev, D.N., and Yaroslavtsev, A.B., "Ethanol and methanol steam reforming on transition metal catalysts supported on detonation synthesis nanodiamonds for hydrogen production", International Journal of Hydrogen Energy, 2015, 40: 3557.

10.  Shokrani, R., Haghighi, M., Jodeiri, N., Ajamein, H., and Abdollahifar, M., "Fuel cell grade hydrogen production via methanol steam reforming over CuO/ZnO/Al2O3 nanocatalyst with various oxide ratios synthesized via urea-nitrates combustion method", International Journal of Hydrogen Energy, 2014, 39: 13141.

11.  Baneshi, J., Haghighi, M., Jodeiri, N., Abdollahifar, M., and Ajamein, H., "Homogeneous precipitation synthesis of CuO-ZrO2-CeO2-Al2O3 nanocatalyst used in hydrogen production via methanol steam reforming for fuel cell applications", Energy Conversion and Management, 2014, 87: 928.

12.  Chen, W.-H. and Lin, B.-J., "Hydrogen production and thermal behavior of methanol autothermal reforming and steam reforming triggered by microwave heating", International Journal of Hydrogen Energy, 2013, 38: 9973.

13.  Katiyar, N., Kumar, S., and Kumar, S., "Comparative thermodynamic analysis of adsorption, membrane and adsorption-membrane hybrid reactor systems for methanol steam reforming", International Journal of Hydrogen Energy, 2013, 38: 1363.

14.  Matsumura, Y., "Stabilization of Cu/ZnO/ZrO2 catalyst for methanol steam reforming to hydrogen by coprecipitation on zirconia support", Journal of Power Sources, 2013, 238: 109.

15.  Zhang, L., Pan, L., Ni, C., Sun, T., Zhao, S., Wang, S., Wang, A., and Hu, Y., "CeO2-ZrO2-promoted CuO/ZnO catalyst for methanol steam reforming", International Journal of Hydrogen Energy, 2013, 38: 4397.

16.  Das, D., Llorca, J., Dominguez, M., Colussi, S., Trovarelli, A., and Gayen, A., "Methanol steam reforming behavior of copper impregnated over CeO2-ZrO2 derived from a surfactant assisted coprecipitation route", International Journal of Hydrogen Energy, 2015, 40: 10463.

17.  Zhang, L., Pan, L.-w., Ni, C.-j., Sun, T.-j., Wang, S.-d., Hu, Y.-k., Wang, A.-j., and Zhao, S.-s., "Effects of precipitation aging time on the performance of CuO/ZnO/CeO2-ZrO2 for methanol steam reforming", Journal of Fuel Chemistry and Technology, 2013, 41: 883.

18.  Behrens, M., "Coprecipitation: An excellent tool for the synthesis of supported metal catalysts - From the understanding of the well known recipes to new materials", Catalysis Today, 2015, 246: 46.

19.  Aruna, S.T. and Mukasyan, A.S., "Combustion synthesis and nanomaterials", Current Opinion in Solid State and Materials Science, 2008, 12: 44.

20.  Mukasyan, A.S., Rogachev, A.S., and Aruna, S.T., "Combustion synthesis in nanostructured reactive systems", Advanced Powder Technology, 2015, 26: 954.

21.  González-Cortés, S.L. and Imbert, F.E., "Fundamentals, properties and applications of solid catalysts prepared by solution combustion synthesis (SCS)", Applied Catalysis A: General, 2013, 452: 117.

22.  Liu, G., Li, J., and Chen, K., "Combustion synthesis of refractory and hard materials: A review", International Journal of Refractory Metals and Hard Materials, 2013, 39: 90.

23.  Baneshi, J., Haghighi, M., Jodeiri, N., Abdollahifar, M., and Ajamein, H., "Urea-nitrate combustion synthesis of ZrO2 and CeO2 doped CuO/Al2O3 nanocatalyst used in steam reforming of biomethanol for hydrogen production", Ceramics International, 2014, 40: 14177.

24.  Srinatha, N., Dinesh Kumar, V., Nair, K.G.M., and Angadi, B., "The effect of fuel and fuel-oxidizer combinations on ZnO nanoparticles synthesized by solution combustion technique", Advanced Powder Technology, 2015, 26: 1355.

25.  Tarragó, D.P., Malfatti, C.d.F., and de Sousa, V.C., "Influence of fuel on morphology of LSM powders obtained by solution combustion synthesis", Powder Technology, 2015, 269: 481.

26.  Esmaeili, E., Khodadadi, A., and Mortazavi, Y., "Microwave-induced combustion process variables for MgO nanoparticle synthesis using polyethylene glycol and sorbitol", Journal of the European Ceramic Society, 2009, 29: 1061.

27.  Gao, Y., Meng, F., Ji, K., Song, Y., and Li, Z., "Slurry phase methanation of carbon monoxide over nanosized Ni-Al2O3 catalysts prepared by microwave-assisted solution combustion", Applied Catalysis A: General, 2016, 510: 74.

28.  Li, F.-t., Zhao, Y., Liu, Y., Hao, Y.-j., Liu, R.-h., and Zhao, D.-s., "Solution combustion synthesis and visible light-induced photocatalytic activity of mixed amorphous and crystalline MgAl2O4 nanopowders", Chemical Engineering Journal, 2011, 173: 750.

29.  Nassar, M.Y., Ahmed, I.S., and Samir, I., "A novel synthetic route for magnesium aluminate (MgAl2O4) nanoparticles using sol-gel auto combustion method and their photocatalytic properties", Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, 131: 329.

30.  Ruiz-Gómez, M.A., Gómez-Solís, C., Zarazúa-Morín, M.E., Torres-Martínez, L.M., Juárez-Ramírez, I., Sánchez-Martínez, D., and Figueroa-Torres, M.Z., "Innovative solvo-combustion route for the rapid synthesis of MoO3 and Sm2O3 materials", Ceramics International, 2014, 40: 1893.

31.  Scherrer, P., "Bestimmung der Grösse und der inneren Struktur von Kolloidteilchen mittels Röntgenstrahlen", Nachrichten von der Gesellschaft der Wissenschaften zu Gottingen, 1918, 26: 98.

32.  Allahyari, S., Haghighi, M., Ebadi, A., and Qavam Saeedi, H., "Direct synthesis of dimethyl ether as a green fuel from syngas over nanostructured CuO-ZnO-Al2O3/HZSM-5 catalyst: Influence of irradiation time on nanocatalyst properties and catalytic performance", Journal of Power Sources, 2014, 272: 929.

33.  Allahyari, S., Haghighi, M., and Ebadi, A., "Direct synthesis of DME over nanostructured CuO-ZnO-Al2O3/HZSM-5 catalyst washcoated on high pressure microreactor: Effect of catalyst loading and process condition on reactor performance", Chemical Engineering Journal, 2015, 262: 1175.

34.  Abramoff, M.D., Magalhaes, P.J., and Ram, S.J., "Image Processing with ImageJ", Biophotonics International, 2004, 11: 36−42.

35.  Estifaee, P., Haghighi, M., Mohammadi, N., and Rahmani, F., "CO oxidation over sonochemically synthesized Pd-Cu/Al2O3 nanocatalyst used in hydrogen purification: Effect of Pd loading and ultrasound irradiation time", Ultrasonics Sonochemistry, 2014, 21: 1155.

36.  Khoshbin, R., Haghighi, M., and Asgari, N., "Direct synthesis of dimethyl ether on the admixed nanocatalystsof CuO-ZnO-Al2O3 and HNO3-modified clinoptilolite at high pressures: Surface properties and catalytic performance", Materials Research Bulletin, 2013, 48: 767.

37.  Allahyari, S., Haghighi, M., Ebadi, A., and Hosseinzadeh, S., "Effect of irradiation power and time on ultrasound assisted co-precipitation of nanostructured CuO-ZnO-Al2O3 over HZSM-5 used for direct conversion of syngas to DME as a green fuel", Energy Conversion and Management, 2014, 83: 212.

38.  Allahyari, S., Haghighi, M., and Ebadi, A., "Direct conversion of syngas to DME as a green fuel in a high pressure microreactor: Influence of slurry solid content on characteristics and reactivity of washcoated CuO-ZnO-Al2O3/HZSM-5 nanocatalyst", Chemical Engineering and Processing: Process Intensification, 2014, 86: 53.

39.  Charghand, M., Haghighi, M., and Aghamohammadi, S., "The Beneficial Use of Ultrasound in Synthesis of Nanostructured Ce-Doped SAPO-34 Used in Methanol Conversion to Light Olefins", Ultrasonics Sonochemistry, 2014, 21: 1827.

40.  Sajjadi, S.M., Haghighi, M., and Rahmani, F., "Dry Reforming of Greenhouse Gases CH4/CO2 over MgO-Promoted Ni-Co/Al2O3-ZrO2 Nanocatalyst: Effect of MgO Addition via Sol-Gel Method on Catalytic Properties and Hydrogen Yield", J Sol-Gel Sci Technol, 2014, 70: 111.

41.  Khoshbin, R. and Haghighi, M., "Urea-Nitrate Combustion Synthesis and Physicochemical Characterization of CuO-ZnO-Al2O3 Nanoparticles over HZSM-5", Chinese Journal of Inorganic Chemistry, 2012, 28: 1967.

42.  Aghaei, E. and Haghighi, M., "Effect of Crystallization Time on Properties and Catalytic Performance of Nanostructured SAPO-34 Molecular Sieve Synthesized at High Temperatures for Conversion of Methanol to Light Olefins", Powder Technology, 2015, 269: 358.

43.  Asgari, N., Haghighi, M., and Shafiei, S., "Synthesis and Physicochemical Characterization of Nanostructured CeO2/Clinoptilolite for Catalytic Total Oxidation of Xylene at Low Temperature", Environmental Progress and Sustainable Energy, 2013, 32: 587.

44.  Saedy, S., Haghighi, M., and Amirkhosrow, M., "Hydrothermal synthesis and physicochemical characterization of CuO/ZnO/Al2O3 nanopowder. Part I: Effect of crystallization time", Particuology, 2012, 10: 729.

45.  Rahmani, F., Haghighi, M., Vafaeian, Y., and Estifaee, P., "Hydrogen Production via CO2 Reforming of Methane over ZrO2-Doped Ni/ZSM-5 Nanostructured Catalyst Prepared by Ultrasound Assisted Sequential Impregnation Method", Journal of Power Sources, 2014, 272: 816.

46.  Sharifi, M., Haghighi, M., and Abdollahifar, M., "Hydrogen Production via Reforming of Biogas over Nanostructured Ni/Y Catalyst: Effect of Ultrasound Irradiation and Ni-Content on Catalyst Properties and Performance", Materials Research Bulletin, 2014, 60: 328.

47.  Wang, C., Liu, C., Fu, W., Bao, Z., Zhang, J., Ding, W., Chou, K., and Li, Q., "The water-gas shift reaction for hydrogen production from coke oven gas over Cu/ZnO/Al2O3 catalyst", Catalysis Today, 2016, 263: 46.

48.  Wilkinson, S.K., van de Water, L.G.A., Miller, B., Simmons, M.J.H., Stitt, E.H., and Watson, M.J., "Understanding the generation of methanol synthesis and water gas shift activity over copper-based catalysts – A spatially resolved experimental kinetic study using steady and non-steady state operation under CO/CO2/H2 feeds", Journal of Catalysis, 2016, 337: 208.

49.  Lin, S., Johnson, R.S., Smith, G.K., Xie, D., and Guo, H., "Pathways for methanol steam reforming involving adsorbed formaldehyde and hydroxyl intermediates on Cu (111): density functional theory studies", Physical Chemistry Chemical Physics, 2011, 13: 9622.

50.       Karelovic, A. and Ruiz, P., "The role of copper particle size in low pressure methanol synthesis via CO2 hydrogenation over Cu/ZnO catalysts", Catalysis Science & Technology, 2015, 5: 869.