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Cu13、Cu12Zr和Cu12Zn团簇上CO2还原反应的密度泛函理论研究

李杰 李慧

李杰, 李慧. Cu13、Cu12Zr和Cu12Zn团簇上CO2还原反应的密度泛函理论研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022051
引用本文: 李杰, 李慧. Cu13、Cu12Zr和Cu12Zn团簇上CO2还原反应的密度泛函理论研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022051
LI Jie, LI Hui. Density Functional Theory Study of CO2 Reduction on Cu13, Cu12Zr and Cu12Zn Clusters[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022051
Citation: LI Jie, LI Hui. Density Functional Theory Study of CO2 Reduction on Cu13, Cu12Zr and Cu12Zn Clusters[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022051

Cu13、Cu12Zr和Cu12Zn团簇上CO2还原反应的密度泛函理论研究

doi: 10.19906/j.cnki.JFCT.2022051
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  • 中图分类号: O643.32

Density Functional Theory Study of CO2 Reduction on Cu13, Cu12Zr and Cu12Zn Clusters

  • 摘要: 从社会和技术的角度来看,在可再生能源储存的背景下,了解CO2还原反应的机理非常重要。在各种催化剂中,Cu基催化剂因其在化学工业中的显着催化性能而广为人知。在本研究中,我们采用密度泛函理论来研究了Cu13、Cu12Zn和Cu12Zr团簇的CO2还原反应的吸附和活化能力,计算结果表明相比于Cu13团簇,Cu12Zr增强了对反应物和中间体的吸附能力,而Cu12Zn团簇降低了对反应物和中间体的吸附能力。我们计算了Cu13、Cu12Zr和Cu12Zn团簇上CO2还原为CO的能垒为分别为0.65 eV、0.35 eV和0.58 eV,CO2加氢生成HCOO的能垒为0.87 eV、0.77 eV和0.49 eV,而CO2加氢生成COOH的能垒为1.67 eV、1.89 eV和0.99 eV。Zn和Zr元素的掺杂提高了铜团簇的CO2催化还原能力,其中表现为Cu12Zr团簇有利于CO2解离生成CO,Cu12Zn团簇有利于CO2加氢生成HCOO
  • 图  1  三类团簇的结构模型图

    Figure  1  Structural model diagram of three types of clusters (a):Cu13;(b):Cu12Zr;(c):Cu12Zn

    图  2  (a)、(b)和(c)分别表示CO2分子在Cu13、Cu12Zr和Cu12Zn簇上的吸附构型

    Figure  2  (a), (b) and (c) represent the adsorption configurations of CO2 molecules on Cu13, Cu12Zr and Cu12Zn clusters, respectively

    图  3  CO2*解离成CO和O势能图及(a)Cu13、(b)Cu12Zr和(c)Cu12Zn团簇表面过渡态结构的对应描述。C、O和H原子以灰色、红色和白色显示

    Figure  3  CO2* dissociation into CO and O potential energy diagrams and corresponding descriptions of the surface transition state structures of (a)Cu13, (b)Cu12Zr and (c)Cu12Zn clusters. C, O and H atoms are shown in grey, red and white

    图  4  CO2*加氢生成HCOO*势能图以及(a)Cu13、(b)Cu12Zr和(c)Cu12Zn团簇表面过渡态结构的相应描述。C、O和H原子以灰色、红色和白色显示

    Figure  4  Hydrogenation of CO2* to HCOO* potential energy diagram and corresponding descriptions of the surface transition state structures of (a)Cu13, (b)Cu12Zr and (c)Cu12Zn clusters. C, O and H atoms are shown in grey, red and white

    图  5  CO2*加氢生成COOH*势能图以及(a)Cu13、(b)Cu12Zr和(c)Cu12Zn团簇表面过渡态结构的相应描述。C、O和H原子以灰色、红色和白色显示

    Figure  5  Hydrogenation of CO2* to COOH* potential energy diagram and corresponding descriptions of the surface transition state structures of (a)Cu13, (b)Cu12Zr and (c)Cu12Zn clusters. C, O and H atoms are shown in grey, red and white

    图  6  (a)Cu13、(b)Cu12Zr和(c)Cu12Zn团簇表面原子的电荷分布。负值表示得电子,正值表示失电子

    Figure  6  Charge distribution of surface atoms of (a)Cu13, (b)Cu12Zr and (c)Cu12Zn clusters. Negative values indicate electron gain, positive values indicate electron loss

    图  7  黑色、蓝色和红色分别表示Cu13表面的Cu原子、Cu12Zn表面的Zn原子和Cu12Zr表面的Zr原子的d电子轨道态密度图。0 eV处的虚线表示费米能级

    Figure  7  Black, red and blue represent the d electron orbital density of states of Cu atoms on the surface of Cu13, Zn atoms on the surface of Cu12Zn, and Zr atoms on the surface of Cu12Zr, respectively.The dashed line at 0 eV represents the Fermi level

    表  1  Zr和Zn掺杂在Cu13团簇表面的偏析能SE和CO2吸附参数

    Table  1  Segregation energy SE and CO2 adsorption parameters of Zr and Zn doping on the surface of Cu13 cluster

    SpeciesSE(eV)EadsCO2(eV)Charge(e)dc = o(Å)∠OCO(°)
    Cu13−0.39−0.0181.246137
    Cu12Zr−2.4−1.950.4321.345127
    Cu12Zn−0.86−0.170.0671.182178
    下载: 导出CSV

    表  2  中间产物在Cu13、Cu12Zr和 Cu12Zn 簇上的吸附构型和吸附能(以eV为单位)

    Table  2  Adsorption configuration and adsorption energy (in eV) of intermediates on Cu13, Cu12Zr and Cu12Zn clusters

    SpeciesCu12Cu12ZrCu12Zn
    CO
    Eads(eV)−1.84−2.10−1.72
    HCOO
    Eads(eV)−4.11−4.83−3.82
    COOH
    Eads(eV)−2.85−3.97−2.42
    O
    Eads(eV)−2.20−4.23−1.98
    H
    Eads(eV)−0.67−0.86−0.41
    下载: 导出CSV

    表  3  Cu13、Cu12Zr和Cu12Zn团簇CO2还原的活化能Ea和反应能ΔE(in eV)

    Table  3  Activation energy Ea and reaction energy ΔE(in eV) of CO2 reduction on Cu13, Cu12Zr and Cu12Zn clusters

    Elementary stepCu13Cu12ZrCu12Zn
    EaΔEEaΔEEaΔE
    CO2*→CO* + O*0.65−0.670.35−0.820.58−0.66
    CO2* + H*→HCOO*0.87−0.710.770.180.49−0.52
    CO2* + H*→COOH*1.670.411.890.630.990.47
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-05-05
  • 录用日期:  2022-06-07
  • 修回日期:  2022-06-07
  • 网络出版日期:  2022-07-06

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