高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

Zn(Ⅱ)/γ-MnOOH体系化学吸附的密度泛函理论研究

夏树伟1, 马骁楠1,2, 于良民1, 潘纲2   

    1. 中国海洋大学化学化工学院, 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, 环境水质化学国家重点实验室, 北京 100085
  • 收稿日期:2007-11-22 修回日期:1900-01-01 出版日期:2008-09-10 发布日期:2008-09-10
  • 通讯作者: 夏树伟

DFT Study of Chemisorption of Zn(Ⅱ)/γ-MnOOH System

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

    1. Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, Chemistry and Chemical Engineering College, Ocean University of China, Qingdao 266003, China;
    2. State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Science, Chinese Academy of Sciences, Beijing 100085, China
  • Received:2007-11-22 Revised:1900-01-01 Online:2008-09-10 Published:2008-09-10
  • Contact: XIA Shu-Wei

PDF (PC)

摘要： 采用密度泛函B3LYP方法对Zn(Ⅱ)在水锰矿(MnOOH)2(H2O)6簇模型表面的水合、一级和二级水解三类共11种吸附构型进行了理论研究. 计算结果表明, 水合吸附构型的稳定性顺序为DC(双角)>SE-B(单边-B)>SE-A(单边-A)>DE(双边), 水解吸附构型的稳定性顺序为DC>SE-A>SE-B>DE, 均符合鲍林第三规则; 热化学分析结果说明, 其吸附和水解是相互制约的两个过程, 这一结论通过前线轨道理论分析得到了证明; 自然布居分析结果表明, 吸附过程中电子由簇模型向吸附质迁移; 结合电子供体-受体相互作用和前线轨道组成分析了吸附产物的稳定性.

关键词: 密度泛函理论, Zn(Ⅱ), 水锰矿, 吸附构型

Abstract: Three kinds of adsorption species(hydrated, 1st hydrolysis and 2nd hydrolysis) in Zn(Ⅱ)/γ-MnOOH system were calculated with DFT-B3LYP method. The thermochemistry analysis indicate that the stability order of the adsorption species was DC>SE-B>SE-A>DE for the hydrated species, and DC>SE-A>SE-B>DE for hydrolysis species, which obeyed the 3rd law of Pauling. The adsorptive process and hydrolytic process always show an inter-antagonistic relationship in this system, which is also consistent with the frontier molecular orbital analysis. Natural population analysis indicate that electronic transfer from cluster model to Zn—O unit was occurred clearly during adsorptive process, which give a reasonable explanation for the stabilization of adsorption species combining with electronic donor-acceptor and frontier molecular orbital analysis.

Key words: Density functional theory, Zn(Ⅱ), γ-MnOOH, Adsorption configuration

中图分类号: 

TrendMD: