物理化学学报 >> 2013, Vol. 29 >> Issue (05): 937-945.doi: 10.3866/PKU.WHXB201303081

理论与计算化学 上一篇    下一篇

水在HfO2(111)和(110)表面的吸附与解离

李璐1, 李奕1, 郭欣2, 章永凡1, 陈文凯1,3   

  1. 1 福州大学化学系, 福州 350116;
    2 华中科技大学煤燃烧国家重点实验室, 武汉 410074;
    3 福州大学省部共建光催化国家重点实验室培育基地, 福州 350002
  • 收稿日期:2012-11-12 修回日期:2013-03-08 发布日期:2013-04-24
  • 通讯作者: 陈文凯 E-mail:qc2008@fzu.edu.cn
  • 基金资助:

    福建省自然科学基金(2012J01032, 2012J01041)和华中科技大学煤燃烧国家重点实验室开放基金(FSKLCC1110)资助项目

Adsorption and Dissociation of Water on HfO2(111) and (110) Surfaces

LI Lu1, LI Yi1, GUO Xin2, ZHANG Yong-Fan1, CHEN Wen-Kai1,3   

  1. 1 Department of Chemistry, Fuzhou University, Fuzhou 350116, P. R. China;
    2 States Key Laboratory of Coal combustion, Huazhong University of Science and Technology, Wuhan, Hubei, 410074, P. R. China;
    3 Fujian Provincial Key Laboratory of Photocatalysis-State Key Laboratory Breeding Base, Fuzhou University, Fuzhou 350002, P. R. China
  • Received:2012-11-12 Revised:2013-03-08 Published:2013-04-24
  • Supported by:

    The project was supported by the Natural Science Foundation of Fujian Province, China (2012J01032, 2012J01041) and Foundation of State Key Laboratory of Coal Combustion of Huazhong University of Science and Technology, China (FSKLCC1110).

摘要:

运用广义梯度近似密度泛函理论方法(GGA-PW91)结合周期平板模型, 研究水分子在二氧化铪(111)和(110)表面不同吸附位置在不同覆盖度下的吸附行为. 通过比较不同吸附位的吸附能和几何构型参数发现:(111)和(110)表面铪原子(top 位)是活性吸附位. 水分子与表面的吸附能值随覆盖度的变化影响较小. 在(111)和(110)表面, 水分子都倾向以氧端与表面铪原子相互作用. 同时也计算了羟基、氧和氢在表面的吸附, Mulliken 电荷布居, 态密度及部分频率. 结果表明, 在两种表面羟基以氧端与表面铪相互作用, 氧原子与表面铪和氧原子同时成键, 而氢原子直接与表面氧原子相互作用形成羟基. 通过过渡态搜索, 水分子在(111)和(110)表面发生解离, 反应能垒分别为9.7和17.3 kJ·mol-1, 且放热为59.9和47.6 kJ·mol-1.

关键词: 密度泛函理论, 二氧化铪, 水分子, 吸附, 解离

Abstract:

First-principles calculations based on density functional theory (DFT) with the generalized gradient approximation (GGA-PW91) have been used to investigate the adsorption and dissociation of H2O molecules on HfO2(111) and (110) surfaces at different sites with different coverages. It was found that the surface hafnium atom was the active adsorption position of the (111) and (110) surfaces when compared different adsorption energies and various geometrical parameters. Adsorption energies of water on the HfO2 (111) and (110) surfaces varied slightly as the coverage increased. It was shown that the most favorable configuration of H2O on the HfO2(111) and (110) surfaces corresponded to the coordination of H2O via its oxygen to a surface hafnium atom. Adsorption geometries, Mulliken population charges, density of states, and frequency calculations for HfO2-OH, HfO2-O, and HfO2-H at both surfaces were also carried out. The results showed that the hydroxyl group interacted with the surface by its oxygen atom to surface hafnium atoms. Isolated oxygen atoms bound to surface hafnium and oxygen atoms, while hydrogen atoms interact only with surface oxygen atoms to form hydroxyl groups. For the dissociation reaction, according to transition searching, H2O→H (ads)+OH (ads). The energy barriers were endothermic by 9.7 and 17.3 kJ· mol-1 for the (111) surfaces and exothermic by -59.9 and -47.6 kJ·mol-1 for the (110) surfaces.

Key words: Ddensity functional theory, HfO2, H2O molecule, Adsorption, Dissociation

MSC2000: 

  • O647