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Title: Understanding and Mitigating the Effects of Stable Dodecahydro- closo -dodecaborate Intermediates on Hydrogen-Storage Reactions

Abstract

Alkali metal borohydrides can reversibly store hydrogen; however, the materials display poor cyclability, often times linked to occurrence of stable closo-polyborate intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of metal borohydrides, several alkali metal dodecahydro-closo-dodecaborate salts were isolated in anhydrous form and characterized by diffraction and spectroscopic techniques. Mixtures of Li 2B 12H 12, Na 2B 12H 12, and K 2B 12H 12 with the corresponding alkali metal hydrides were subjected to hydrogenation conditions known to favor partial or full reversibility in metal borohydrides. The stoichiometric mixtures of MH and M 2B 12H 12 salts form the corresponding metal borohydrides MBH 4 (M=Li, Na, K) in almost quantitative yield at 100 MPa H 2 and 500 °C. In addition, stoichiometric mixtures of Li 2B 12H 12 and MgH 2 were found to form MgB 2 at 500 °C and above upon desorption in vacuum. The two destabilization strategies outlined above suggest that metal polyhydro-closo-polyborate species can be converted into the corresponding metal borohydrides or borides, albeit under rather harsh conditions of hydrogen pressure and temperature.

Authors:
 [1];  [2];  [3];  [4];  [1]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of California, Santa Cruz, CA (United States)
  3. Univ. of California, Santa Cruz, CA (United States)
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1338335
Report Number(s):
SAND-2016-10142J
Journal ID: ISSN 1932-7447; 648158
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 45; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

White, James L., Newhouse, Rebecca J., Zhang, Jin Z., Udovic, Terrence J., and Stavila, Vitalie. Understanding and Mitigating the Effects of Stable Dodecahydro- closo -dodecaborate Intermediates on Hydrogen-Storage Reactions. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b09789.
White, James L., Newhouse, Rebecca J., Zhang, Jin Z., Udovic, Terrence J., & Stavila, Vitalie. Understanding and Mitigating the Effects of Stable Dodecahydro- closo -dodecaborate Intermediates on Hydrogen-Storage Reactions. United States. doi:10.1021/acs.jpcc.6b09789.
White, James L., Newhouse, Rebecca J., Zhang, Jin Z., Udovic, Terrence J., and Stavila, Vitalie. Tue . "Understanding and Mitigating the Effects of Stable Dodecahydro- closo -dodecaborate Intermediates on Hydrogen-Storage Reactions". United States. doi:10.1021/acs.jpcc.6b09789. https://www.osti.gov/servlets/purl/1338335.
@article{osti_1338335,
title = {Understanding and Mitigating the Effects of Stable Dodecahydro- closo -dodecaborate Intermediates on Hydrogen-Storage Reactions},
author = {White, James L. and Newhouse, Rebecca J. and Zhang, Jin Z. and Udovic, Terrence J. and Stavila, Vitalie},
abstractNote = {Alkali metal borohydrides can reversibly store hydrogen; however, the materials display poor cyclability, often times linked to occurrence of stable closo-polyborate intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of metal borohydrides, several alkali metal dodecahydro-closo-dodecaborate salts were isolated in anhydrous form and characterized by diffraction and spectroscopic techniques. Mixtures of Li2B12H12, Na2B12H12, and K2B12H12 with the corresponding alkali metal hydrides were subjected to hydrogenation conditions known to favor partial or full reversibility in metal borohydrides. The stoichiometric mixtures of MH and M2B12H12 salts form the corresponding metal borohydrides MBH4 (M=Li, Na, K) in almost quantitative yield at 100 MPa H2 and 500 °C. In addition, stoichiometric mixtures of Li2B12H12 and MgH2 were found to form MgB2 at 500 °C and above upon desorption in vacuum. The two destabilization strategies outlined above suggest that metal polyhydro-closo-polyborate species can be converted into the corresponding metal borohydrides or borides, albeit under rather harsh conditions of hydrogen pressure and temperature.},
doi = {10.1021/acs.jpcc.6b09789},
journal = {Journal of Physical Chemistry. C},
number = 45,
volume = 120,
place = {United States},
year = {2016},
month = {10}
}

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