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NiO支撑In2O3(110)表面CO2加氢合成甲醇的理论计算研究

张科文 陈毅飞 胡廷平 吕喜梅

张科文, 陈毅飞, 胡廷平, 吕喜梅. NiO支撑In2O3(110)表面CO2加氢合成甲醇的理论计算研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60139-1
引用本文: 张科文, 陈毅飞, 胡廷平, 吕喜梅. NiO支撑In2O3(110)表面CO2加氢合成甲醇的理论计算研究[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60139-1
ZHANG Ke-wen, CHEN Yi-fei, HU Ting-ping, LV Xi-mei. Theoretical study of methanol synthesis from CO2 hydrogenation on the surface of NiO supported In2O3(110) catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60139-1
Citation: ZHANG Ke-wen, CHEN Yi-fei, HU Ting-ping, LV Xi-mei. Theoretical study of methanol synthesis from CO2 hydrogenation on the surface of NiO supported In2O3(110) catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60139-1

NiO支撑In2O3(110)表面CO2加氢合成甲醇的理论计算研究

doi: 10.1016/S1872-5813(21)60139-1
基金项目: 国家自然科学基金(21536008)资助
详细信息
    作者简介:

    张科文(1994-),男,甘肃庄浪,硕士生,邮箱:1746085505@qq.com

    通讯作者:

    Tel: 027-83943956, E-mail: tingpinghu@163.com

Theoretical study of methanol synthesis from CO2 hydrogenation on the surface of NiO supported In2O3(110) catalyst

Funds: The proiect was supporteed by the National Natural Science Foundation of China (21536008)
  • 摘要: 本研究采用密度泛函理论(DFT),研究了NiO支撑对In2O3(110)缺陷表面上CO2加氢合成甲醇过程的影响,分析了两种甲醇合成路径,即HCOO路径和逆水煤气(RWGS)合成路径,计算了HCOO和RWGS路径中每个基元反应的反应能和活化能垒。结果表明,NiO支撑能够强化In2O3催化剂对CO2的吸附性能,促进甲醇通过HCOO反应路径的生成。在HCOO路径中,HCOO加氢生成H2COO是HCOO反应路径的速率控制步骤,活化能垒为1.66 eV。NiO支撑的In2O3(110)缺陷表面对CO2的加氢具有促进作用,有助于CO2沿着HCOO路径合成甲醇,从而提高CO2加氢合成甲醇的效率。
  • 图  1  (a) NiO支撑的In2O3(110)完美表面,(b) NiO支撑的In2O3(110)缺陷表面;侧视图(上),俯视图(下);其中,红色,O原子;棕色,In原子;绿色,Ni原子

    Figure  1  (a) NiO supported In2O3(110) perfect surface, (b) NiO supported In2O3(110) defect surface; side view (upper), top view (lower); Here, the red O atom; Brown, In atom; Green, Ni atom

    图  2  在D表面上CO2加氢合成甲醇中间体的优化结构,侧视图(上),俯视图(下)

    Figure  2  Optimized structures of CO2 hydrogenation to methanol intermediates on D surface, side view (upper), top view (lower)

    图  3  D表面CO2加氢合成甲醇的各个基元反应的初始、过渡和最终状态的优化结构;侧视图(上),俯视图(下)

    Figure  3  Optimized structure of the initial, transition and final states of the elementary reaction steps of the hydrogenation of CO2 to methanol on D surface; side view (upper), top view (lower)

    图  4  D面上HCOO路径合成甲醇的势能曲线,(a) NiO支撑的In2O3(110) D表面,(b) In2O3(110) D表面

    Figure  4  Potential energy curves for methanol synthesis through HCOO route on D surface, (a) NiO supported In2O3(110) D surface, (b) In2O3(110) D surface

    图  5  在D表面上CO加氢合成甲醇中间体的优化结构,侧视图(上),俯视图(下)

    Figure  5  Optimized structure of CO hydrogenation to methanol intermediates on D surface, side view (upper), top view (lower)

    图  6  D表面CO加氢合成甲醇的各个基元反应的初始、过渡和最终状态的优化结构;侧视图(上),俯视图(下)

    Figure  6  Optimized structure of the initial, transition and final states of the elementary reaction steps for the hydrogenation of surface CO to methanol; side view (upper), top view (lower)

    图  7  在D面上RWGS路径合成甲醇的势能曲线,(a) NiO支撑In2O3(110) D表面,(b) In2O3(110) D表面

    Figure  7  Potential energy curves for methanol synthesis by RWGS route on D surface, (a) NiO supported In2O3(110) D surface, (b) In2O3(110) D surface

    表  1  在D表面CO2加氢合成甲醇中间体的吸附能Eads(eV)和几何参数

    Table  1  Adsorption energies and geometric parameters of the intermediates of CO2 hydrogenation to synthesize methanol on the D surface

    SpeciesSitesEads/eVBond length/Å
    CO2 D −0.85 d(In2−Oa) = 2.25, d(In2−Ob) = 2.31, d(C−Oa) = 1.30, d(C−Ob) = 1.26, d(In3−C) = 2.19
    HCOO D −2.59 d(In2−Oa) = 2.26, d(In2−Ob) = 2.32, d(C−Oa) = 1.36, d(C−Ob) = 1.26, d(In3−C) = 2.20
    H2COO D −3.88 d(In2−Oa) = 2.26, d(In2−Ob) = 2.32, d(C−Oa) = 1.30, d(C−Ob) = 1.26, d(In3−C) = 2.20
    H2CO P −2.45 d(In2−Ob) = 2.32, d(C−Ob) = 1.30, d(C−H2) = 1.26
    H3CO P −1.40 d(In2−Ob) = 2.32, d(C−Ob) = 1.26, d(C−H3) = 1.30
    H3COH P −0.85 d(In2−Ob) = 2.32, d(C−Ob) = 1.30, d(C−H4) = 1.26
    下载: 导出CSV

    表  2  D表面上CO2加氢合成甲醇的各个基元反应的反应能Er和活化能垒Ea

    Table  2  Reaction energy and activation energy barrier for the hydrogenation of CO2 to methanol on D surface

    Elementary reaction stepEr/eVEa/eV
    CO2 + H → HCOO−1.401.61
    HCOO + H → H2COO0.171.66
    H2COO + H → H3CO + Os−0.160.68
    H2CO + H → H3CO−0.641.33
    H3CO + H→ H3COH0.300.71
    下载: 导出CSV

    表  3  D表面CO加氢合成甲醇中间体的吸附能Eads和几何参数

    Table  3  Adsorption energy and geometric parameters of methanol intermediates synthesized by hydrogenation of CO on D surface

    SpeciesEads/eVBond length/Å
    CO−0.77d(In2−C) = 2.44, d(C−O) = 1.19,
    d(In3−C) = 2.42
    HCO−1.48d(In3−C) = 2.26, d(C−O) = 1.20,
    d(C−H) = 1.17
    H2CO−1.14d(In3−C) = 2.27, d(In2−O) = 2.08,
    d(C−O) = 1.37, d(C−H2) = 1.11
    H3CO−2.23d(In3−O) = 2.29, d(In2−O) = 2.23,
    d(C−O) = 1.47, d(C−H3) = 1.10
    H3COH−0.73d(In2−O) = 2.31, d(C−O) = 1.47,
    d(O−H4) = 1.20
    下载: 导出CSV

    表  4  D表面CO加氢合成甲醇的各个基元反应的反应能Er和活化能垒Eb

    Table  4  Reaction energy and activation energy barrier for the hydrogenation of CO on D surface to methanol

    Elementary reaction stepEr/eVEa/eV
    CO2 → CO+O1.01.42
    CO + H → HCO−0.980.19
    HCO + H → H2CO−0.951.84
    H2CO + H → H3CO−0.970.11
    H3CO + H → H3COH−0.550.36
    下载: 导出CSV

    表  5  CO2在In2O3(110)D表面,NiO支撑In2O3(110)D表面吸附的Mulliken电荷布局

    Table  5  Mulliken atomic charge populations for CO2 adsorption on the D surface,NiO supported In2O3(110)D surface

    Atom
    Charge/e
    CO2In2O3(110)NiO/In2O3(110)
    C0.4820.4830.490
    O1−0.241−0.443−0.446
    O2−0.241−0.494−0.501
    下载: 导出CSV
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  • 收稿日期:  2021-05-31
  • 修回日期:  2021-07-20
  • 网络出版日期:  2021-08-10

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