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γ-Fe2O3表面HCl对汞的吸附和氧化机理研究

周文波 牛胜利 王俊 李颖 韩奎华 王永征 路春美 朱英

周文波, 牛胜利, 王俊, 李颖, 韩奎华, 王永征, 路春美, 朱英. γ-Fe2O3表面HCl对汞的吸附和氧化机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60098-1
引用本文: 周文波, 牛胜利, 王俊, 李颖, 韩奎华, 王永征, 路春美, 朱英. γ-Fe2O3表面HCl对汞的吸附和氧化机理研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60098-1
ZHOU Wen-bo, NIU Sheng-li, WANG Jun, LI Ying, HAN Kui-hua, WANG Yong-zheng, LU Chun-mei, ZHU Ying. Study on the adsorption and oxidation mechanism of mercury by HCl over γ-Fe2O3 catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60098-1
Citation: ZHOU Wen-bo, NIU Sheng-li, WANG Jun, LI Ying, HAN Kui-hua, WANG Yong-zheng, LU Chun-mei, ZHU Ying. Study on the adsorption and oxidation mechanism of mercury by HCl over γ-Fe2O3 catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60098-1

γ-Fe2O3表面HCl对汞的吸附和氧化机理研究

doi: 10.1016/S1872-5813(21)60098-1
基金项目: 山东省重大科技创新工程(2019JZZY020305)资助
详细信息
    作者简介:

    周文波:514267024@qq.com

    通讯作者:

    E-mail:nsl@sdu.edu.cn

  • 中图分类号: TQ534

Study on the adsorption and oxidation mechanism of mercury by HCl over γ-Fe2O3 catalyst

Funds: The project was supported by the Important Project in the Scientific Innovation of Shandong Province (2019JZZY020305).
  • 摘要: 本研究采用密度泛函理论(DFT)研究了在γ-Fe2O3表面HCl对Hg0的吸附和催化氧化的作用机制。构建了Hg0、HCl、HgCl和HgCl2在γ-Fe2O3(001)表面的吸附模型,分析了HCl对γ-Fe2O3表面催化氧化Hg0的作用机理,并通过反应路径的能量分布测定,研究了γ-Fe2O3表面Hg0的氧化过程。结果表明,Hg0倾向于化学吸附在γ-Fe2O3(001)表面Feoct位。HCl在催化剂表面进行解离吸附,形成吸附态Cl和羟基,从而促进Hg0的吸附。HgCl以分子形式化学吸附在γ-Fe2O3(001)上,并作为Hg0氧化过程的中间体。HgCl2倾向在γ-Fe2O3表面上的平行吸附。同时,HCl在γ-Fe2O3(001)上氧化Hg0遵循L-H机理,即化学吸附的Hg0与解离吸附的HCl反应,且HCl对Hg0的非均相氧化通过两步反应途径进行,即Hg0 (ads)→HgCl(ads)→HgCl2(ads)。
  • 图  1  γ-Fe2O3的晶胞

    Figure  1  Conventional cell of γ-Fe2O3

    图  2  γ-Fe2O3表面结构

    Figure  2  Structure of the γ-Fe2O3 surface

    (a): front view; (b): top view

    图  3  Hg0在γ-Fe2O3表面的优化吸附模型

    Figure  3  Optimized models of Hg0 adsorbed on γ-Fe2O3

    图  4  HCl在γ-Fe2O3表面的优化吸附模型

    Figure  4  Optimized models of HCl adsorbed on γ-Fe2O3

    图  5  Hg0在氯化γ-Fe2O3表面的优化吸附模型

    Figure  5  Optimized models of Hg0 adsorbed on chlorinated γ-Fe2O3 surface

    图  6  HgCl在γ-Fe2O3表面的优化吸附模型

    Figure  6  Optimized models of HgCl adsorbed on γ-Fe2O3

    图  7  HgCl2在γ-Fe2O3表面的优化吸附模型

    Figure  7  Optimized models of HgCl2 adsorbed on γ-Fe2O3

    图  8  γ-Fe2O3上HCl氧化Hg0的中间体、过渡态和终态的优化结构

    Figure  8  Optimized structures of intermediate, transition states and final state of Hg0 oxidation by HCl on γ-Fe2O3

    图  9  γ-Fe2O3上HCl氧化Hg0的能量分布

    Figure  9  Energy profiles of Hg0 oxidation by HCl on γ-Fe2O3(001) surface

    表  1  键长的计算和文献值

    Table  1  Bond length of calculated values andliterature values

    SpecieBondBond length/ Å
    calculatedliterature
    HClr(H−Cl)1.2851.275[30]
    HgClr(Hg−Cl)2.4642.360−2.50[31]
    HgCl2r(Hg−Cl)2.2972.250−2.440[31]
    下载: 导出CSV

    表  2  Hg0在γ-Fe2O3表面吸附的优化参数

    Table  2  Optimized adsorption parameters of Hg0 adsorbed on γ-Fe2O3

    Eads/(kJ·mol−1)RHg-XΔQ/e
    1A−39.262.9190.14
    1B−24.473.1940.05
    1C−24.733.518/3.5350.08
    下载: 导出CSV

    表  3  HCl在γ-Fe2O3表面吸附的优化参数

    Table  3  Optimized adsorption parameters of HCl adsorbed on γ-Fe2O3

    Eads/(kJ·mol−1)RCl−FeRH−OΔQ/e
    2A−73.692.1920.9930.07
    2B−106.662.1690.9830.15
    下载: 导出CSV

    表  4  HgCl在γ-Fe2O3表面吸附的优化参数

    Table  4  Optimized adsorption parameters of HgCl adsorbed on γ-Fe2O3

    Eads/(kJ·mol−1)RHg−FeRCl−FeRHg−ClΔQ/e
    3A−136.922.5452.3830.03
    3B−141.252.1653.041−0.22
    3C−174.542.8852.1673.236−0.11
    3D−180.672.9262.1663.290−0.12
    下载: 导出CSV

    表  5  HgCl2在γ-Fe2O3表面吸附的优化参数

    Table  5  Optimized adsorption parameters of HgCl2 adsorbed on γ-Fe2O3

    Eads/(kJ·mol−1)RHg−FeRCl−FeΔQ/e
    4A−63.282.9562.942/2.9680.03
    4B−58.432.8812.159/2.161−0.26
    4C−27.132.7490.05
    下载: 导出CSV
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  • 收稿日期:  2021-03-26
  • 修回日期:  2021-04-28
  • 网络出版日期:  2021-05-18

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