A first-principles study of the catalytic mechanism of the dehydriding reaction of LiNH2 through adding Ti catalysts

doi:10.1088/1674-1056/19/4/048601

Abstract Experiments on a ball milled mixture with a 1:1 molar ratio of LiNH₂ and LiH with a small amount (1 mol %) of Ti^nano, TiCl₃ and TiO₂^nano have revealed a superior catalytic effect on Li--N--H hydrogen storage materials. In the x-ray diffraction profiles, no trace of Ti^nano, TiCl₃ and TiO₂^nano was found in these doped composites, by which we deduced that Ti atoms enter LiNH₂ by partial element substitution. A first-principles plane-wave pseudopotential method based on density functional theory has been used to investigate the catalytic effects of Ti catalysts on the dehydrogenating properties of LiNH₂ system. The results show that Ti substitution can reduce the dehydrogenation reaction activation energy of LiNH₂ and improve the dehydrogenating properties of LiNH₂. Based on the analysis of the density of states and overlap populations for LiNH₂ before and after Ti substitution, it was found that the stability of the system of LiNH₂ is reduced, which originates from the increase of the valence electrons at the Fermi level (E_F) and the decrease of the highest occupied molecular orbital (HOMO)--lowest unoccupied molecular orbital (LUMO) gap ($\Delta E_{\rm H-L})$ near E_F. The catalytic effect of Ti on the dehydrogenating kinetics of LiNH₂ may be attributed to the reduction of average populations between N--H per unit bond length (nm$^{ - 1})$, which leads to the reduction of the chemical bond strength of N--H.

Keywords: LiNH₂ first-principles calculation dehydrogenating properties Ti catalytic mechanism

Received: 28 April 2009
Revised: 26 September 2009
Accepted manuscript online:

PACS:	82.65.+r	(Surface and interface chemistry; heterogeneous catalysis at surfaces)
	84.60.-h	(Direct energy conversion and storage)
	71.20.Ps	(Other inorganic compounds)
	82.30.-b	(Specific chemical reactions; reaction mechanisms)

Fund: Project supported by the National High Technology Research $\&$ Development of China (Grant No.~2009AA05Z105), the National Natural Science Foundation of China (Grant No.~50671069), the Science Research Program of the Education Bureau of Liaoning Province

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Zhang Hui(张辉), Liu Gui-Li(刘贵立), Qi Ke-Zhen(戚克振), Zhang Guo-Ying(张国英), Xiao Ming-Zhu(肖明珠), and Zhu Sheng-Long(朱圣龙) A first-principles study of the catalytic mechanism of the dehydriding reaction of LiNH₂ through adding Ti catalysts 2010 Chin. Phys. B 19 048601

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A first-principles study of the catalytic mechanism of the dehydriding reaction of LiNH2 through adding Ti catalysts

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A first-principles study of the catalytic mechanism of the dehydriding reaction of LiNH₂ through adding Ti catalysts