Combined Effects of Functional Cation and Anion on the Reversible Dehydrogenation of LiBH4

doi:10.1021/jp200137n

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	Combined Effects of Functional Cation and Anion on the Reversible Dehydrogenation of LiBH4
	Fang, Zhan-Zhao 1; Kang, Xiang-Dong 1; Yang, Zhu-Xian 2; Walker, Gavin S.2; Wang, Ping 1
刊名	JOURNAL OF PHYSICAL CHEMISTRY C
	2011-06-16
卷号	115 期号:23 页码:11839-11845
ISSN号	1932-7447
DOI	10.1021/jp200137n
通讯作者	Wang, Ping(pingwang@imr.ac.cn)
英文摘要	Catalyst doping has been widely employed as an effective method for improving the H-exchange kinetics of complex hydrides. However, a viable hydrogen storage material requires favorable properties on both kinetic and thermodynamic aspects to allow dehydrogenation and rehydrogenation reactions to proceed at moderate temperatures. In the present study, titanium halides (TiCl3 or TiF3) were mechanically milled with LiBH4 and examined with respect to their effects on the hydrogen storage properties of LiBH4. Experimental study showed that both halides are effective promoters. In particular, TiF3 exhibits a superior promoting effect to its analogue, TiCl3, on the reversible dehydrogenation of LiBH4. Phase characterization and chemical state analysis results showed that both halides react with the host LiBH4, resulting in the in situ formation of the catalytically active Ti hydride. However, the two halogen anions differ substantially from each other in terms of state and function. Associated with the dissolution of LiCl into LiBH4, the Cl- anion can readily replace [BH4](-) and exerts a stabilizing effect on the hexagonal phase of LiBH4. By contrast, the F- anion may partially substitute the anionic H in both LiBH4 (hydrogenated state) and LiH (dehydrogenated state) lattices, resulting in a favorable modification of the hydrogen-exchange thermodynamics of LiBH4. The observed promoting effect of TiF3 on the reversible dehydrogenation of LiBH4 should be understood from the combined effects of functional cation and anion. In this regard, TiF3 provides a prototype catalyst that can simultaneously modify the H-exchange kinetics and thermodynamics of complex hydrides.
资助项目	National Basic Research Program of China (973 Program)[2010CB631305] ; National Natural Science Foundation of China[50771094] ; National Natural Science Foundation of China[50801059] ; Knowledge Innovation of CAS[KGCXZ-YW-342] ; CAS ; EPSRC through the U.K.-China initiative
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000291339000064
资助机构	National Basic Research Program of China (973 Program) ; National Natural Science Foundation of China ; Knowledge Innovation of CAS ; CAS ; EPSRC through the U.K.-China initiative
内容类型	期刊论文
源URL	[http://ir.imr.ac.cn/handle/321006/104991]
专题	金属研究所_中国科学院金属研究所
通讯作者	Wang, Ping
作者单位	1.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Peoples R China 2.Univ Nottingham, Fac Engn, Energy & Sustainabil Res Div, Nottingham NG7 2RD, England
推荐引用方式 GB/T 7714	Fang, Zhan-Zhao,Kang, Xiang-Dong,Yang, Zhu-Xian,et al. Combined Effects of Functional Cation and Anion on the Reversible Dehydrogenation of LiBH4[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2011,115(23):11839-11845.
APA	Fang, Zhan-Zhao,Kang, Xiang-Dong,Yang, Zhu-Xian,Walker, Gavin S.,&Wang, Ping.(2011).Combined Effects of Functional Cation and Anion on the Reversible Dehydrogenation of LiBH4.JOURNAL OF PHYSICAL CHEMISTRY C,115(23),11839-11845.
MLA	Fang, Zhan-Zhao,et al."Combined Effects of Functional Cation and Anion on the Reversible Dehydrogenation of LiBH4".JOURNAL OF PHYSICAL CHEMISTRY C 115.23(2011):11839-11845.