Document Detail

Diborane release and structure distortion in borohydrides.
MedLine Citation:
PMID:  23047162     Owner:  NLM     Status:  Publisher    
Hydrogen desorption from borohydrides is often accompanied by the release of diborane. The amount of diborane released as a byproduct during the decomposition of borohydrides scales inversely with the borohydride stability, which in turn depends on the electronegativity of the corresponding cation. We present a model based on the difference between the symmetric and asymmetric assembly of B(2)H(6) units at the surface. The origin of this reaction is the degree of distortion of the BH(4)(-) anions in the bulk, hitherto depending on the degree of ionization of the cation. A practical measure of the distortion is the range in which the stretching vibration modes appear, which is the difference in the energy of the stretching vibrations of hydrogen atoms with maximum different bonding lengths (Badger's rule). We propose from this relation that the diborane released from the surface of the relatively unstable LiZn(2)(BH(4))(5) is formed from a recombination of BH(2)(δ+) and BH(4)(δ-) units. Ultra high vacuum mass spectroscopy measurements support the presented model and clarify the decomposition of stable borohydrides, such as LiBH(4). The sublimation of borohydrides in UHV competes with their decomposition.
Elsa Callini; Andreas Borgschulte; Anibal Javier Ramirez-Cuesta; Andreas Züttel
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-10-9
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-10     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Empa, Swiss Federal Laboratories for Materials Testing and Research, Hydrogen & Energy, CH-8600 Dübendorf, Switzerland.
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