期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 116, 期 22, 页码 11900-11906出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp301986k
关键词
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资金
- Ministry of Science and Technology of China [2010CB631302]
- National Natural Science Foundation of China [51071047]
- Ph.D. Programs Foundation of Ministry of Education of China [20110071110009]
- Science and Technology Commission of Shanghai Municipality [11JC1400700, 11520701100]
The electronic structure and initial dehydrogenation mechanism of M(BH4)(2)center dot 2NH(3) (M = Mg, Ca, and Zn) have been systematically studied using first-principles calculations. A detailed study of the electronic structure reveals that the metal cations in M(BH4)(2)center dot 2NH(3) play a crucial role in both suppressing ammonia emission and destabilizing the N-H/B-H bonds. The calculation results of hydrogen removal energies are in agreement with the tendency of dehydrogenation temperatures of these ammoniates, i.e., Zn(BH4)(2)center dot 2NH(3) < Mg(BH4)(2)center dot 2NH(3) < Ca(BH4)(2)center dot 2NH(3). The initial dehydrogenation of M(BH4)(2)center dot 2NH(3) is achieved by the dissociation of (N)H delta+ from NH3 and (B)H delta- atoms from BH4 groups, resulting in the formation of N-B dative bonds and the reduction of the neighboring (N)H delta+center dot center dot center dot(B)H delta- dihydrogen bonds, which accelerate the subsequent dehydrogenation.
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