高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (11(1)): 83.

• 研究论文 • 上一篇    下一篇

As(Ⅴ)/TiO2、Zn(Ⅱ)/TiO2体系电子结构的密度泛函研究

马骁楠1,2, 夏树伟1, 于良民1, 潘纲2   

  1. 1. 中国海洋大学海洋化学理论与工程技术教育部重点实验室, 青岛 266003;
    2. 中国科学院生态环境研究中心环境水质学国家重点实验室, 北京 100085
  • 收稿日期:2009-07-28 出版日期:2009-11-30 发布日期:2009-11-30
  • 通讯作者: 潘纲, 男, 教授, 主要从事分子环境化学研究. E-mail: gpan@mail.rcees.ac.cn
  • 基金资助:

    国家自然科学基金(批准号: 20677053)和新世纪优秀人才支持计划(批准号: 070783)资助.

DFT Study of the Electronic Structure in As(Ⅴ), Zn(Ⅱ)/TiO2 System

XIA Shu-Wei1, MA Xiao-Nan1,2, YU Liang-Min1, PAN Gang2*   

  1. 1. Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Ocean University of China, Qingdao 26600, China;
    2. State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Science, Chinese Academy of Science, Beijing 100085, China
  • Received:2009-07-28 Online:2009-11-30 Published:2009-11-30
  • Contact: PAN Gang. E-mail: gpan@mail.rcees.ac.cn
  • Supported by:

    国家自然科学基金(批准号: 20677053)和新世纪优秀人才支持计划(批准号: 070783)资助.

摘要:

用密度泛函方法对As(Ⅴ)和Zn(Ⅱ)在TiO2表面以双角、单角和单边方式化学吸附物种的电子结构特征进行了研究. 发现As(Ⅴ)和Zn(Ⅱ)在TiO2表面发生吸附时具有不同的微观机制: As(Ⅴ)与表面氧原子通过As—O σ键形成较为紧密的结合, Zn(Ⅱ)仅通过孤对电子和外层空轨道与表面进行电子交换形成较弱的结合, As-TiO2吸附体系的电子离域程度高于Zn-TiO2体系. 这种微观结合机制上的不同导致了两个体系在振动光谱、电荷分布和前线轨道组成等方面的差异.

关键词: As(Ⅴ); Zn(Ⅱ); 电子结构; 密度泛函

Abstract:

Adsorbed species(DC double corner, SC single corner and SE single edge) in As(Ⅴ)-TiO2 and Zn(Ⅱ)-TiO2 system were calculated with DFT method to describe their electronic structural characters. The natural bond orbital analysis indicate that some obvious differences of the adsorption bonding mechanism were existed between As(Ⅴ) and Zn(Ⅱ) species on TiO2 surface. For As(Ⅴ), it tend to form stable As—O σ bond with O atom of TiO2 surface, but Zn(Ⅱ) always link with surface in a incompact style. The differences make the electronic delocalized degree of As(Ⅴ) adsorbed species being higher than Zn(Ⅱ), and it further results in a series differences with two system: vibrational spectra, charge distribution and the component of frontier orbital, etc.

Key words: As(Ⅴ); Zn(Ⅱ); Electronic structure; Density functional theory

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