水助催化氢分子在金纳米粒子上解离的理论研究

doi:10.13208/j.electrochem.170918

电化学（中英文） ›› 2018, Vol. 24 ›› Issue (3): 199-206. doi: 10.13208/j.electrochem.170918

水助催化氢分子在金纳米粒子上解离的理论研究

陈家丽，张霞光，吴德印^*，田中群

厦门大学化学化工学院，固体表面物理化学国家重点实验室，福建厦门，361005

收稿日期:2017-09-18 修回日期:2017-11-02 出版日期:2018-06-28 发布日期:2017-11-06
通讯作者: 吴德印 E-mail:dywu@xmu. edu. cn
基金资助:
国家自然科学基金项目（No. 21373172, No. 21533006, No. 21621091）、国家科技部(No. 2015CB932303)和固体物理化学国家重点实验室资助

DFT Study of Water Assisted Hydrogen Dissociation on Gold Nanoparticles

CHEN Jia-li, ZHANG Xia-guang, WU De-yin^*, TIAN Zhong-qun

Department of Chemistry,College of Chemistry and Chemical Engineering, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, Fujian, China

Received:2017-09-18 Revised:2017-11-02 Published:2018-06-28 Online:2017-11-06
Contact: WU De-yin E-mail:dywu@xmu. edu. cn

摘要/Abstract

摘要：

金纳米粒子（GNPs）对氢分子（H₂）的解离具有良好的催化活性. 本文研究了水分子对 GNPs 催化 H₂解离的影响. 对于H₂在中性和带正电的金簇（Au_n^δ，n=3~5；δ = 0，1）上的反应，考虑当水簇（(H₂O)_m，m = 1, 2, 3, 7）参与反应时 GNPs 催化H₂的解离过程的热力学和动力学. 研究结果表明，水对 H₂在GNPs上的解离有助催化的作用，且水簇大小不同，水助催化 H₂在金簇上解离的机理也有所不同，其由氢氢键的均裂解离转化为氧化解离. 对两种机理所得的产物，作者计算了它们的 Raman 和 IR 光谱.

关键词: 金纳米粒子, 氢解离机理, 水助催化, Raman光谱

Abstract: The gold nanoparticles (GNPs) show special activity toward hydrogen (H₂) dissociation, comparing with bulk gold. Such activity is significantly affected by the existence of water. To inspect the influence of water on GNPs catalyzed H₂ dissociation, we carried out density functional theory (DFT) calculations along the reaction paths for water clusters (H₂O)_m (m = 1, 2, 3, 7) assisted H₂ dissociation on gold clusters (Au_n^δ, n = 3 ~ 5; δ = 0, 1). Our calculated results show that water benefits to the H₂ dissociation. The dissociation mechanism varies with the size of water clusters, from the homolytic cleavage of the H-H bond to the oxidation dissociation mechanism on the small gold clusters. We also suggest Raman and IR spectroscopies can be used to characterize the products of those two mechanisms.

Key words: gold nanoparticles, hydrogen dissociation, water assisted reaction, density functional theory, Raman spectroscopy.

中图分类号:

O646.54

陈家丽，张霞光，吴德印，田中群. 水助催化氢分子在金纳米粒子上解离的理论研究[J]. 电化学（中英文）, 2018, 24(3): 199-206.

CHEN Jia-li, ZHANG Xia-guang, WU De-yin, TIAN Zhong-qun. DFT Study of Water Assisted Hydrogen Dissociation on Gold Nanoparticles[J]. Journal of Electrochemistry, 2018, 24(3): 199-206.

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水助催化氢分子在金纳米粒子上解离的理论研究

DFT Study of Water Assisted Hydrogen Dissociation on Gold Nanoparticles

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