Zeolite confined copper(0) nanoclusters as cost-effective and reusable catalyst in hydrogen generation from the hydrolysis of ammonia-borane

Zahmakiran, Mehmet
Durap, Feyyaz
Özkar, Saim
Herein we report the development of a cost-effective nanocluster catalyst for the hydrolytic dehydrogenation of ammonia-borane which is considered to be one among the new hydrogen storage materials. Zeolite confined copper(0) nanoclusters were prepared by the ion-exchange of Cu2+ ions with the extra framework Na+ ions in zeolite-Y followed by reduction of the Cu2+ ions within the cavities of zeolite with sodium borohydride in aqueous solution and characterized by HR-TEM, XRD, XPS, SEM, EDX, ICP-OES, Raman spectroscopy and N-2 adsorption-desorption technique. Zeolite confined copper(0) nanoclusters are found to be active catalysts in the hydrolysis of ammonia-borane even at low temperatures (<= 15 degrees C) and stable enough for being isolated as solid materials. They provide 1300 turnovers in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. The average value of turnover frequency is 46.5 h(-1) for the same reaction. More importantly, zeolite confined copper(0) nanoclusters were found to be isolable, bottleable and reusable catalysts in the hydrolytic dehydrogenation of ammonia-borane; even at fifth run the complete release of hydrogen from the hydrolysis of ammonia-borane at room temperature is achieved. The work reported here also includes the full experimental details for the collection of a wealth of kinetic data to determine the activation energy and the effect of catalyst concentration on the rate for the catalytic hydrolysis of ammonia-borane. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.


Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: Highly efficient and fast hydrogen generation system at room temperature
Karahan, Senem; Zahmakiran, Mehmet; Özkar, Saim (2011-04-01)
There has been rapidly growing interest for materials suitable to store hydrogen in solid state for transportation of hydrogen that requires materials with high volumetric and gravimetric storage capacity. B-N compounds such as ammonia-triborane, ammonia-borane and amine-borane adducts are well suited for this purpose due to their light weight, high gravimetric hydrogen storage capacity and inclination for bearing protic (N-H) and hydridic (B-H) hydrogens. In addition to them, more recent study [261 has sho...
Copper(0) Nanoparticles Supported on Silica-Coated Cobalt Ferrite Magnetic Particles: Cost Effective Catalyst in the Hydrolysis of Ammonia-Borane with an Exceptional Reusability Performance
KAYA, MURAT; Zahmakıran, Mehmet; Özkar, Saim; Volkan, Mürvet (2012-08-01)
Herein we report the development of a new and cost-effective nanocomposite catalyst for the hydrolysis of ammonia-borane (NH3BH3), which is considered to be one of the most promising solid hydrogen carriers because of its high gravimetric hydrogen storage capacity (19.6% wt) and low molecular weight. The new catalyst system consisting of copper nanoparticles supported on magnetic SiO2/CoFe2O4 particles was reproducibly prepared by wet-impregnation of Cu(II) ions on SiO2/CoFe2O4 followed by in situ reduction...
Dihydrogen Phosphate Stabilized Ruthenium(0) Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature
DURAP, FEYYAZ; Caliskan, Salim; Özkar, Saim; Karakas, Kadir; Zahmakıran, Mehmet (2015-07-01)
Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0) nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 +/- 0.9 n...
Poly(4-styrenesulfonic acid-co-maleic acid) stabilized cobalt(0) nanoparticles: A cost-effective and magnetically recoverable catalyst in hydrogen generation from the hydrolysis of hydrazine borane
Karahan, Senem; Özkar, Saim (2015-02-09)
Herein, we report the in situ generation, isolation and characterization of cobalt(0) nanoparticles, stabilized by poly(4-styrenesulfonic acid-co-maleic acid), PSSMA, and their catalytic activity in the hydrolysis of hydrazine borane (HB). Cobalt(0) nanoparticles having average particle size of 3.1 +/- 0.5 nm were prepared by in situ reduction of cobalt(II) chloride in aqueous solution of hydrazine borane in the presence of PSSMA, isolated magnetically from the catalytic reaction solution using a magnet, an...
Oleylamine-Stabilized Copper(0) Nanoparticles: An Efficient and Low-Cost Catalyst for the Dehydrogenation of Dimethylamine Borane
DUMAN, SİBEL; Özkar, Saim (2017-07-07)
Copper(0) nanoparticles, in situ generated from the reduction of copper(II) 2-ethylhexanoate during the dehydrogenation of dimethylamine borane (DMAB) at 50.0 +/- 0.1 degrees C in toluene solution, are active catalysts in hydrogen generation from DMAB, but not very stable against agglomeration. Addition of 5.0 equivalents of oleylamine (OAm) was found to stabilize copper(0) nanoparticles noticeably, while maintaining high catalytic activity. Oleylamine-stabilized copper(0) nanoparticles could be isolated fr...
Citation Formats
M. Zahmakiran, F. Durap, and S. Özkar, “Zeolite confined copper(0) nanoclusters as cost-effective and reusable catalyst in hydrogen generation from the hydrolysis of ammonia-borane,” INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, pp. 187–197, 2010, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/48380.