Density functional theory study of CO2 reduction on Cu13, Cu12Zr and Cu12Zn clusters
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摘要: 本研究采用密度泛函理论研究了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。计算了Cu13、Cu12Zr和Cu12Zn团簇上CO2还原为CO的能垒为分别为0.65、0.35和0.58 eV,CO2加氢生成HCOO的能垒为0.87、0.77和0.49 eV,而CO2加氢生成COOH的能垒为1.67、1.89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。Abstract: In this study, we used density functional theory to study the adsorption and activation capacity of Cu13, Cu12Zn, and Cu12Zr clusters for CO2 reduction. The calculated results showed that Cu12Zr enhanced the adsorption capacity of reactants and intermediates compared with Cu13 clusters, while Cu12Zn clusters decreased the adsorption capacity of reactants and intermediates. We calculated that the energy barriers for CO2 reduction to CO on Cu13, Cu12Zr, and Cu12Zn clusters were 0.65, 0.35 and 0.58 eV, respectively, and the energy barriers for CO2 plus H to generate HCOO were 0.87, 0.77 and 0.49 eV, while the energy barriers of CO2 hydrogenation to COOH were 1.67, 1.89 and 0.99 eV. The doping of Zn and Zr elements improved the CO2 catalytic reduction ability of the Cu clusters, which showed that the Cu12Zr clusters were favorable for the dissociation of CO2 to form CO, and the Cu12Zn clusters were favorable for the hydrogenation of CO2 to HCOO.
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Key words:
- density functional theory /
- CO2 reaction /
- copper-based alloy /
- adsorption and activation
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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 7 Cu13表面的Cu原子(黑色)、Cu12Zn表面的Zn原子(蓝色)和Cu12Zr表面的Zr原子(红色)的d电子轨道态密度图
Figure 7 The d electron orbital density of states of Cu atoms (black) on the surface of Cu13, Zn atoms (blue) on the surface of Cu12Zn, and Zr atoms (red) 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
Species SE/eV EadsCO2/eV Charge/e d(C=O)/Å ∠OCO(°) Cu13 − −0.39 −0.018 1.246 137 Cu12Zr −2.4 −1.95 0.432 1.345 127 Cu12Zn −0.86 −0.17 0.067 1.182 178 表 2 中间产物在Cu13、Cu12Zr和 Cu12Zn 簇上的吸附构型和吸附能
Table 2 Adsorption configuration and adsorption energy (in eV) of intermediates on Cu13, Cu12Zr and Cu12Zn clusters
Species Cu13 Cu12Zr Cu12Zn 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 表 3 Cu13、Cu12Zr和Cu12Zn团簇CO2还原的活化能Ea和反应能ΔE
Table 3 Activation energy Ea and reaction energy ΔE of CO2 reduction on Cu13, Cu12Zr and Cu12Zn clusters
Elementary step Cu13/eV Cu12Zr/eV Cu12Zn/eV Ea ΔE Ea ΔE Ea ΔE CO2*→CO* + O* 0.65 −0.67 0.35 −0.82 0.58 −0.66 CO2* + H*→HCOO* 0.87 −0.71 0.77 0.18 0.49 −0.52 CO2* + H*→COOH* 1.67 0.41 1.89 0.63 0.99 0.47 -
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