Cu_(13)、Cu_(12)Zr和Cu_(12)Zn团簇上CO_(2)还原反应的密度泛函理论研究  

Density functional theory study of CO_(2) reduction on Cu_(13), Cu_(12)Zr and Cu_(12)Zn clusters

作　　者：李杰 李慧[1] LI Jie;LI Hui(School of Material Science and Engineering,Taiyuan University of Technology,Taiyuan 030024,China)

机构地区：[1]太原理工大学材料科学与工程学院,山西太原030024

出　　处：《燃料化学学报（中英文）》2023年第3期314-319,共6页Journal of Fuel Chemistry and Technology

摘　　要：本研究采用密度泛函理论研究了Cu_(13)、Cu_(12)Zn和Cu_(12)Zr团簇的CO_(2)还原反应的吸附和活化能力,计算结果表明相比于Cu_(13)团簇,Cu_(12)Zr增强了对反应物和中间体的吸附能力,而Cu_(12)Zn团簇降低了对反应物和中间体的吸附能力。计算了Cu_(13)、Cu_(12)Zr和Cu_(12)Zn团簇上CO_(2)还原为CO的能垒为分别为0.65、0.35和0.58 eV,CO_(2)加氢生成HCOO的能垒为0.87、0.77和0.49 eV,而CO_(2)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CO_(2)催化还原能力,其中,表现为Cu_(12)Zr团簇有利于CO_(2)解离生成CO,Cu_(12)Zn团簇有利于CO_(2)加氢生成HCOO。In this study, we used density functional theory to study the adsorption and activation capacity of Cu_(13),Cu_(12)Zn, and Cu_(12)Zr clusters for CO_(2)reduction. The calculated results showed that Cu_(12)Zr enhanced the adsorption capacity of reactants and intermediates compared with Cu_(13)clusters, while Cu_(12)Zn clusters decreased the adsorption capacity of reactants and intermediates. We calculated that the energy barriers for CO_(2)reduction to CO on Cu_(13),Cu_(12)Zr, and Cu_(12)Zn clusters were 0.65, 0.35 and 0.58 eV, respectively, and the energy barriers for CO_(2)plus H to generate HCOO were 0.87, 0.77 and 0.49 eV, while the energy barriers of CO_(2)hydrogenation to COOH were 1.67,1.89 and 0.99 eV. The doping of Zn and Zr elements improved the CO_(2)catalytic reduction ability of the Cu clusters,which showed that the Cu_(12)Zr clusters were favorable for the dissociation of CO_(2)to form CO, and the Cu_(12)Zn clusters were favorable for the hydrogenation of CO_(2)to HCOO.

关 键 词：密度泛函理论 二氧化碳还原反应 铜基合金 吸附和活化 

分 类 号：O643.32[理学—物理化学]