基于第一性原理的二氧化铈完整和缺陷表面上氢气活化研究

doi:10.52396/JUST-2021-0084

摘要/Abstract

摘要： 氢气活化在过渡金属氧化物催化的加氢反应中起到至关重要的作用.二氧化铈(CeO₂)表面上氢气如何活化是乙炔加氢反应中的重要科学问题.本文利用密度泛函理论计算(DFT)的方法,系统研究了化学计量及有氧缺陷的CeO₂(111)、(110)和(100)表面上氢气活化机理.氢气在化学计量的CeO₂表面解离时仅形成羟基,而氧空位的存在可以有效促进氢气活化.CeO_2-x(111)和(100)缺陷表面上H⁺和H^-物种可以共存,而在CeO_2-x(110)缺陷表面上只能观察到H⁺物种.化学计量及有氧缺陷的CeO₂表面上氢气活化的结构敏感性与H⁺和H^-吸附能有关,并由氧空位形成能以及Ce、O离子的电荷分布决定.该理论工作深入理解了二氧化铈基催化剂上氢气活化过程,为优化和设计高效加氢催化剂提供了理论支撑.

关键词: 二氧化铈, 氢气活化, 表面敏感性, 密度泛函理论

Abstract: Hydrogen activation plays a pivotal role in hydrogenation reactions over transition metal oxide catalysts. Clarifying hydrogen activation over ceria oxide (CeO₂) is an important issue in the acetylene hydrogenation reaction. Employing density functional theory (DFT) calculations, we studied hydrogen activation over stoichiometric and defective CeO₂(111), (110), and (100) surfaces. Hydrogen dissociates on the stoichiometric CeO₂ surfaces only forming hydroxyl groups. The presence of oxygen vacancies can promote the H₂ activation over the defective CeO₂ surfaces. Both H⁺ and H^-species can be found on the defective CeO₂(111) and (100) surfaces, whereas only H⁺ species can be observed on the defective CeO₂(110) surface. The structure sensitivity of the H₂ activation over the stoichiometric and defective CeO₂ surfaces is correlated with H⁺ and H^- adsorption energies determined by the ability of the surface oxygen vacancy formation and charge distributions of Ce and O ions. Our work provides more insight into H₂ activation on CeO₂-based catalysts which will guide better catalyst design for hydrogenation reactions.

Key words: CeO₂, hydrogen activation, surface sensitivity, density functional theory

中图分类号:

O647.1

陈姊慧, 赵川林, 刘进勋, 李微雪. 基于第一性原理的二氧化铈完整和缺陷表面上氢气活化研究[J]. 中国科学技术大学学报, 2021, 51(6): 485-493.

CHEN Zihui, ZHAO Chuanlin, LIU Jinxun, LI Weixue. Hydrogen activation over stoichiometric and defective CeO₂ surfaces: A first-principles study[J]. Journal of University of Science and Technology of China, 2021, 51(6): 485-493.

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