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Title: Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes

Abstract

Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100%more » which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum mediated hydrogenation process leading to reversibility. The Al-AB complexes have comparable hydrogen capacity with other M-AB and have potential to meet DOE’s 2010 and 2015 targets for system wt%.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
University of Missouri, Columbia, MO
Sponsoring Org.:
USDOE Assistant Secretary for Energy Efficiency and Renewable Energy (EE); USDOE Office of Hydrogen, Fuel Cells, and Infrastructure Technologies Program (EE-2H)
OSTI Identifier:
990217
Report Number(s):
DOE/GO/15058
TRN: US201020%%517
DOE Contract Number:  
FC36-05GO15058
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 25 ENERGY STORAGE; ALUMINIUM; AMMONIA; ANIONS; BORANES; BOROHYDRIDES; CATALYSTS; COBALT; DEHYDROGENATION; HYDROGEN; HYDROGEN STORAGE; HYDROGENATION; HYDROLYSIS; KINETICS; NICKEL; PALLADIUM; REGENERATION; RESIDUES; RHODIUM; STABILITY; SURFACE AREA; SYNTHESIS; TRANSITION ELEMENTS; Polyhedral Boranes; Aluminum Amido-boranes; Hydrogen storage

Citation Formats

Hawthorne, M Frederick, Jalisatgi, Satish S, Safronov, Alexander V, Lee, Han Beak, and Wu, Jianguo. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes. United States: N. p., 2010. Web. doi:10.2172/990217.
Hawthorne, M Frederick, Jalisatgi, Satish S, Safronov, Alexander V, Lee, Han Beak, & Wu, Jianguo. Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes. United States. doi:10.2172/990217.
Hawthorne, M Frederick, Jalisatgi, Satish S, Safronov, Alexander V, Lee, Han Beak, and Wu, Jianguo. Fri . "Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes". United States. doi:10.2172/990217. https://www.osti.gov/servlets/purl/990217.
@article{osti_990217,
title = {Chemical Hydrogen Storage Using Polyhedral Borane Anions and Aluminum-Ammonia-Borane Complexes},
author = {Hawthorne, M Frederick and Jalisatgi, Satish S and Safronov, Alexander V and Lee, Han Beak and Wu, Jianguo},
abstractNote = {Phase 1. Hydrolysis of borohydride compounds offer the potential for significant hydrogen storage capacity, but most work to date has focused on one particular anion, BH4-, which requires high pH for stability. Other borohydride compounds, in particular polyhedral borane anions offer comparable hydrogen storage capacity without requiring high pH media and their long term thermal and hydrolytic stability coupled with non-toxic nature make them a very attractive alternative to NaBH4. The University of Missouri project provided the overall program focal point for the investigation of catalytic hydrolysis of polyhedral borane anions for hydrogen release. Due to their inherent stability, a transition metal catalyst was necessary for the hydrolysis of polyhedral borane anions. Transition metal ions such as cobalt, nickel, palladium and rhodium were investigated for their catalytic activity in the hydrolysis of nido-KB11H14, closo-K2B10H10, and closo-K2B12H12. The rate of hydrolysis follows first-order kinetics with respect to the concentration of the polyhedral borane anion and surface area of the rhodium catalyst. The rate of hydrolysis depends upon a) choice of polyhedral borane anion, c) concentration of polyhedral borane anion, d) surface area of the rhodium catalyst and e) temperature of the reaction. In all cases the yield of hydrogen was 100% which corresponds to ~7 wt% of hydrogen (based on material wt%). Phase 2. The phase 2 of program at the University of Missouri was focused upon developing aluminum ammonia-boranes (Al-AB) as chemical hydrogen storage materials, specifically their synthesis and studies of their dehydrogenation. The ammonia borane molecule (AB) is a demonstrated source of chemically stored hydrogen (19.6 wt%) which meets DOE performance parameters except for its regeneration from spent AB and elemental hydrogen. The presence of an aluminum center bonded to multiple AB residues might combine the efficiency of AB dehydrogenation with an aluminum mediated hydrogenation process leading to reversibility. The Al-AB complexes have comparable hydrogen capacity with other M-AB and have potential to meet DOE’s 2010 and 2015 targets for system wt%.},
doi = {10.2172/990217},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2010},
month = {10}
}