Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: Highly efficient and fast hydrogen generation system at room temperature

Date

2011-04-01

Author

Karahan, Senem
Zahmakiran, Mehmet
Özkar, Saim

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

185
views

0
downloads

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 showed that hydrazine borane with a gravimetric hydrogen storage capacity of 15.4% wt needs to be considered as another B-N compound that can be used for the storage of hydrogen. Herein we report for the first time, metal catalyzed hydrolysis of hydrazine borane (N2H4BH3, HB) under air at room temperature. Among the catalyst systems tested, rhodium(III) chloride was found to provide the highest catalytic activity in this reaction. In the presence of rhodium(III) chloride, the aqueous solution of hydrazine borane undergoes fast hydrolysis to release nearly 3.0 equivalent of H-2 at room temperature with previously unprecedented H-2 generation rate TOF = 12000 h(-1). More importantly, it was found that in the catalytic hydrolysis of hydrazine borane the reaction between hydrazine borane and water proceeds almost in stoichiometric proportion indicating that the efficient hydrogen generation can be achieved even from the highly concentrated solution of hydrazine borane or in the solid state when water added to the solid hydrazine borane. This finding is crucial especially for on-board application of the existing system. The work reported here also includes (i) finding the solubility of hydrazine borane plus its stability against self-hydrolysis in water, (ii) the definition of reaction stoichiometry and the identification of reaction products for the catalytic hydrolysis of hydrazine borane, (iii) the collection of wealthy kinetic data to demonstrate the effect of substrate and catalyst concentrations on the hydrogen generation rate and to determine the rate law for the catalytic hydrolysis of hydrazine borane, (iv) the investigation of the effect of temperature on the rate of hydrogen generation and determination of activation parameters (E-a, Delta H-#, and Delta S-#) for the catalytic hydrolysis of hydrazine borane. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Subject Keywords

Hydrogen storage, Hydrogen generation, Hydrazine borane, Hydrolysis, Catalysts

URI

https://hdl.handle.net/11511/62793

Journal

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY

DOI

https://doi.org/10.1016/j.ijhydene.2010.12.129

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Water soluble laurate-stabilized ruthenium(0) nanoclusters catalyst for hydrogen generation from the hydrolysis of ammonia-borane: High activity and long lifetime DURAP, FEYYAZ; Zahmakiran, Mehmet; Özkar, Saim (2009-09-01) The simplest amine-borane, considered as solid hydrogen storage material, ammonia-borane (H(3)NBH(3)) can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, we report the preparation of a novel catalyst, water dispersible laurate-stabilized ruthenium(0) nanoclusters from the dimethylamine-borane reduction of ruthenium(III) chloride in sodium laurate solution at room temperature. The ruthenium nanoclusters in average size of 2.6 +/- 1.2 nm were isolated from the solution and well c...
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 (2010-01-01) 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 s...
Catalytic methanolysis of hydrazine borane: a new and efficient hydrogen generation system under mild conditions Karahan, Senem; Zahmakıran, Mehmet; Özkar, Saim (2012-01-01) Safe and efficient hydrogen storage is a major obstacle for using hydrogen as an energy carrier. Therefore, intensive efforts have been focused on the development of new materials for chemical hydrogen storage. Of particular importance, hydrazine borane (N2H4BH3) is emerging as one of the most promising solid hydrogen carriers due to its high gravimetric hydrogen storage capacity (15.4 wt%) and low molecular weight. Herein, we report metal catalyzed methanolysis of hydrazine borane (N2H4BH3, HB) as a fast h...
Cobalt-nickel-phosphorus supported on Pd-activated TiO2 (Co-Ni-P/Pd-TiO2) as cost-effective and reusable catalyst for hydrogen generation from hydrolysis of alkaline sodium borohydride solution Rakap, Murat; Kalu, Egwu Eric; Özkar, Saim (2011-06-23) Catalytically active, low-cost, and reusable transition metal catalysts are desired to develop on-demand hydrogen generation system for practical onboard applications. Electrolessly deposited Pd-activated TiO2-supported Co-Ni-P ternary alloy catalyst (Co-Ni-P/Pd-TiO2) is employed as catalyst in the hydrolysis of alkaline sodium borohydride solution. The catalyst is found to be isolable, redispersible, and reusable in the hydrolysis of alkaline NaBH4. The reported work also includes the full experimental det...
Deposition and testing of thin film hydrogen separation membranes Pişkin, Fatih; Öztürk, Tayfur; Department of Metallurgical and Materials Engineering (2013) Industrial production of hydrogen from the syngas, generated from steam reformation of natural gas or coal gasification, sets conditions for hydrogen separation membranes in terms of operating conditions. An alternative source for hydrogen is a syngas generated by gasification of municipal solid wastes which are likely to set more stringent conditions for the separation membranes. There is therefore, a growing demand for separation membranes with improved permeability and particularly of low cost. Among var...

Citation Formats

S. Karahan, M. Zahmakiran, and S. Özkar, “Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: Highly efficient and fast hydrogen generation system at room temperature,” INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, pp. 4958–4966, 2011, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/62793.