INVESTIGATION ON ACTIVITIES OF METAL OXIDES CATALYZED AMMONIA BORANE HYDROLYSIS

In the present study, the activities of metal oxide - catalyzed ammonia borane (NH3BH3, AB) hydrolysis were investigated. Two non-noble metal oxide catalysts, cobalt oxide (Co3O4) and copper oxide (CuO), were synthesized by sol-gel method and catalytic activity tests were performed. The comparative kinetic analyses were investigated via Power Law and Bimolecular kinetic models. Hydrogen generation rates were achieved 4381.20 ml H2.g-1cat.min-1 and 835.04 ml H2.g-1cat.min-1 for Co3O4 and CuO metal oxides catalysts, respectively. Despite the different hydrogen generation rates of metal oxides catalysts, both metal oxides had similar apparent activation energy as 46.28 kJ.mol-1 for Co3O4 and 45.64 kJ.mol-1 for CuO with free of reactant concentration behaviors. According to the bimolecular kinetic model investigations, Co3O4 had stronger relationship with NH3BH3. Co3O4 metal oxide catalyst was found to be more active for NH3BH3 hydrolysis in order to generate hydrogen gas for practical energy applications.

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  • [1] Ramachandran, P. V.,Mistry, H., Kulkarni, A. S., &Gagare, P. D. (2014) Ammonia-mediated, large-scalesynthesis of ammoniaborane. DaltonTransactions, 43:44:16580-16583.
  • [2] Jiang, Hai-Long, and Qiang Xu. (2011) “Catalytic hydrolysis of ammonia borane for chemical hydrogen storage” Catalysis Today 170: 1: 56-63.
  • [3] Yoon, Chang Won, and Larry G. Sneddon. (2006) Ammonia triborane: a promising new candidate for amineborane-based chemical hydrogen storage. Journal of the American Chemical Society 128: 43:13992-13993.
  • [4] Moussa, G.,Moury, R., Demirci, U. B., &Miele, P. (2013) Borates in hydrolysis of ammoniaborane. İnternational Journal of Hydrogen Energy, 38:19: 7888-7895.
  • [5] Xi, Pinxian, Fengjuan Chen, Guoqiang Xie, Cai Ma, Hongyan Liu, Changwei Shao, Jun Wang, Zhihong Xu, Ximing Xu, and Zhengzhi Zeng. (2012) Surfactant free RGO/Pd nanocomposites as highly active heterogeneous catalysts for the hydrolytic dehydrogenation of ammonia borane for chemical hydrogen storage. Nanoscale 4:185597-5601.
  • [6] Cao, Nan, Wei Luo, and Gongzhen Cheng. (2013) One-step synthesis of graphene supported Ru nanoparticles as efficient catalysts for hydrolytic dehydrogenation of ammonia borane. International Journal of Hydrogen Energy 38: 27: 11964-11972.
  • [7] Barakat, Nasser AM. (2013) Effective Co–Mn–O nanofibers for ammonia borane hydrolysis. Materials Letters 106: 229-232.
  • [8] Wang, Hong-Li, Jun-Min Yan, Zhi-Li Wang, and Qing Jiang. “One-step synthesis of Cu@ FeNi core–shell nanoparticles: Highly active catalyst for hydrolytic dehydrogenation of ammonia borane”. International journal of hydrogen energy 37, no. 13 (2012): 10229-10235.
  • [9] Kelly, Henry C., and Vic B. Marriott. (1979) Reexamination of the mechanism of acid-catalyzed amine-borane hydrolysis. The hydrolysis of ammonia-borane. Inorganic Chemistry 18:10: 2875-2878.
  • [10] Chandra, Manish, and Qiang Xu. (2006) Dissociation and hydrolysis of ammonia-borane with solid acids and carbon dioxide: an efficient hydrogen generation system. Journal of Power Sources 159: 2: 855-860.
  • [11] Rachiero, Giovanni P., Umit B. Demirci, and Philippe Miele. (2011) Bimetallic RuCo and RuCu catalysts supported on γ-Al 2 O 3. A comparative study of their activity in hydrolysis of ammonia-borane. International Journal of Hydrogen Energy 36:12: 7051-7065.
  • [12] Liang, Hongyan, Guozhu Chen, Stefano Desinan, Renzo Rosei, Federico Rosei, and Dongling Ma. (2012) In situ facile synthesis of ruthenium nanocluster catalyst supported on carbon black for hydrogen generation from the hydrolysis of ammonia-borane. International Journal of Hydrogen Energy 37: 23: 17921-17927.
  • [13] Wang, Hong-Li, Jun-Min Yan, Zhi-Li Wang, and Qing Jiang. (2012) One-step synthesis of Cu@ FeNi core–shell nanoparticles: Highly active catalyst for hydrolytic dehydrogenation of ammonia borane. International Journal of Hydrogen Energy 37:13: 10229-10235.
  • [14] Li, Pei‐Zhou, Arshad Aijaz, and Qiang Xu. (2012) Highly Dispersed Surfactant‐Free Nickel Nanoparticles and Their Remarkable Catalytic Activity in the Hydrolysis of Ammonia Borane for Hydrogen Generation. Angewandte Chemie International Edition 51: 27: 6753-6756.
  • [15] Du, Jing, Fangyi Cheng, Meng Si, Jing Liang, Zhanliang Tao, and Jun Chen. (2013) Nanoporous Ni-based catalysts for hydrogen generation from hydrolysis of ammonia borane. International Journal of Hydrogen Energy 38:14: 5768-5774.
  • [16] Yan, Jun-Min, Xin-Bo Zhang, Hiroshi Shioyama, and Qiang Xu. (2010) Room temperature hydrolytic dehydrogenation of ammonia borane catalyzed by Co nanoparticles. Journal of Power Sources 195: 4: 1091-1094.
  • [17] Kalidindi, Suresh Babu, M. Indirani, and Balaji R. Jagirdar. (2008) First row transition metal ion-assisted ammonia− borane hydrolysis for hydrogen generation. Organic Chemistry 47:16: 7424-7429.
  • [18] Kalidindi, Suresh Babu, Udishnu Sanyal, and Balaji R. Jagirdar. (2008) Nanostructured Cu and Cu@Cu2O core shell catalysts for hydrogen generation from ammonia–borane. Physical Chemistry Chemical Physics 10:38: 5870-5874.
  • [19] Wu Z, Mao X, Zi Q, Zhang R, Dou T, Yip ACK. (2014) Mechanism and kinetics of sodium borohydride hydrolysis over crystalline nickel and nickel boride and amorphous nickel-boron nanoparticles. Journal of Power Sources.268:596-603.
  • [20] Basu S, Brockman A, Gagare P, Zheng Y, Ramachandran PV, Delgass WN, Gore JP (2009) Chemical kinetics of Ru-catalyzed ammonia borane hydrolysis. Journal of Power Sources. 188:238-43.
  • [21] Demirci UB, Miele P. (2014) Reaction mechanisms of the hydrolysis of sodium borohydride: A discussion focusing on cobalt-based catalysts. Comptes Rendus Chimie.17:707-16.
  • [22] Levenspiel O. Chemical reaction engineering: Wiley New York etc.; 1972.
  • [23] Fogler HS. Elements of chemical reaction engineering. 1999.
  • [24] Ozerova AM, Simagina VI, Komova OV, Netskina OV, Odegova GV, Bulavchenko OA, Rudina NA (2012) Cobalt borate catalysts for hydrogen production via hydrolysis of sodium borohydride. Journal of Alloys and Compounds.513:266-72.