Hydrogen generation mechanism of BH4- spontaneous hydrolysis: A sight from ab initio calculation

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	Hydrogen generation mechanism of BH4- spontaneous hydrolysis: A sight from ab initio calculation
	Zhou, Yongquan1 ; Fang, Chunhui1 ; Fang, Yan1 ; Zhu, Fayan1 ; Liu, Hongyan1,2 ; Ge, Haiwen1
	2016-12-28
发表期刊	INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
卷号	41 期号:48 页码:22668-22676
关键词	Bh4- Reaction Mechanism Ab Initio Hydrolysis Dihydrogen Bonding
摘要	Recognition of the reaction mechanism of hydrogen generation by borohydrides hydrolysis can provide effective help for optimizing the reaction condition and catalyst design. In the present work, the underlying mechanisms of BH4- spontaneous hydrolysis under water deficiency (2 water molecules) and water-rich (4 water molecules) condition were elaborated by the second-order Moller-Plesset perturbation theory (MP2) at MP2/6-311++G(3df, 3pd) level of theory. The present theoretical calculations predicted that dihydrogen bonding plays an extremely important role in the process of BH4- hydrolysis, and H-2 is formed by a hydridic B-H hydrogen and a protic O-H hydrogen. The hydrogen generation mechanism of BH4- hydrolysis in water-rich condition may experience BH4- -> BH3(OH)(-), BH3(OH)(-) -> BH2(OH)(2)(-), BH2(OH)(2)(-) -> BH(OH)(3)(-) and BH(OH)(3)(-) -> B(OH)(4)(-) four steps. BH4- hydrolysis mechanism in water-deficiency condition includes four steps in two possible reaction pathways as the water molecules participate with the reaction in different steps. All those reaction pathways with the same first step (BH4- -> BH3(OH)(-)) and its the Rate Determining Step (RDS) of the whole reaction. BH4- spontaneous hydrolysis at neutral or weak alkaline should be in the acid-catalyzed mechanism. (C) 2016 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.
语种	英语
引用统计
文献类型	期刊论文
条目标识符	http://ir.isl.ac.cn/handle/363002/6185
专题	盐湖资源与化学实验室中国科学院青海盐湖研究所
作者单位	1.Chinese Acad Sci, Inst Salt Lakes, Xining 810008, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Zhou, Yongquan,Fang, Chunhui,Fang, Yan,et al. Hydrogen generation mechanism of BH4- spontaneous hydrolysis: A sight from ab initio calculation[J]. INTERNATIONAL JOURNAL OF HYDROGEN ENERGY,2016,41(48):22668-22676.
APA	Zhou, Yongquan,Fang, Chunhui,Fang, Yan,Zhu, Fayan,Liu, Hongyan,&Ge, Haiwen.(2016).Hydrogen generation mechanism of BH4- spontaneous hydrolysis: A sight from ab initio calculation.INTERNATIONAL JOURNAL OF HYDROGEN ENERGY,41(48),22668-22676.
MLA	Zhou, Yongquan,et al."Hydrogen generation mechanism of BH4- spontaneous hydrolysis: A sight from ab initio calculation".INTERNATIONAL JOURNAL OF HYDROGEN ENERGY 41.48(2016):22668-22676.