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Title: A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride

Abstract

Solid-state mechanochemical synthesis of alane (AlH3) starting from sodium hydride (NaH) and aluminum chloride (AlCl3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction, which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl3 system presents some subtle differences compared to LiH–AlCl3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1374741
Report Number(s):
IS-J-9396
Journal ID: ISSN 0022-2461; PII: 1219
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Science
Additional Journal Information:
Journal Volume: 52; Journal Issue: 20; Journal ID: ISSN 0022-2461
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alane; ball milling; hydrogen storage; mechanochemistry; metathesis; solid-state NMR

Citation Formats

Hlova, Ihor, Goldston, Jennifer F., Gupta, Shalabh, Kobayashi, Takeshi, Pruski, Marek, and Pecharsky, Vitalij K. A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride. United States: N. p., 2017. Web. doi:10.1007/s10853-017-1219-y.
Hlova, Ihor, Goldston, Jennifer F., Gupta, Shalabh, Kobayashi, Takeshi, Pruski, Marek, & Pecharsky, Vitalij K. A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride. United States. doi:10.1007/s10853-017-1219-y.
Hlova, Ihor, Goldston, Jennifer F., Gupta, Shalabh, Kobayashi, Takeshi, Pruski, Marek, and Pecharsky, Vitalij K. Tue . "A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride". United States. doi:10.1007/s10853-017-1219-y. https://www.osti.gov/servlets/purl/1374741.
@article{osti_1374741,
title = {A benign synthesis of alane by the composition-controlled mechanochemical reaction of sodium hydride and aluminum chloride},
author = {Hlova, Ihor and Goldston, Jennifer F. and Gupta, Shalabh and Kobayashi, Takeshi and Pruski, Marek and Pecharsky, Vitalij K.},
abstractNote = {Solid-state mechanochemical synthesis of alane (AlH3) starting from sodium hydride (NaH) and aluminum chloride (AlCl3) has been achieved at room temperature. The transformation pathway of this solid-state reaction was controlled by a stepwise addition of AlCl3 to the initial reaction mixture that contained sodium hydride in excess of stoichiometric amount. As in the case of previously investigated LiH–AlCl3 system, complete selectivity was achieved whereby formation of unwanted elemental aluminum was fully suppressed, and AlH3 was obtained in quantitative yield. Reaction progress during each step was investigated by means of solid-state NMR and powder X-ray diffraction, which revealed that the overall reaction proceeds through a series of intermediate alanates that may be partially chlorinated. The NaH–AlCl3 system presents some subtle differences compared to LiH–AlCl3 system particularly with respect to optimal concentrations needed during one of the reaction stages. Based on the results, we postulate that high local concentrations of NaH may stabilize chlorine-containing derivatives and prevent decomposition into elemental aluminum with hydrogen evolution. As a result, complete conversion with quantitative yield of alane was confirmed by both SSNMR and hydrogen desorption analysis.},
doi = {10.1007/s10853-017-1219-y},
journal = {Journal of Materials Science},
number = 20,
volume = 52,
place = {United States},
year = {2017},
month = {5}
}

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