摘要
Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)to obtain C_(2) products has drawn widespread attentions.Copper-based materials are the most reported catalysts for CO_(2) reduction to C_(2) products.Design of high-efficiency pseudo-copper catalysts according to the key characteristics of copper(Cu)is an important strategy to understand the reaction mechanism of C_(2) products.In this work,density function theory(DFT)calculations are used to predict nickel–zinc(NiZn)alloy catalysts with the criteria similar structure and intermediate adsorption property to Cu catalyst.The calculated tops of 3d states of NiZn3(001)catalysts are the same as Cu(100),which is the key parameter affecting the adsorption of intermediate products.As a result,NiZn3(001)exhibits similar adsorption properties with Cu(100)on the crucial intermediates*CO_(2),*CO and*H.Moreover,we further studied CO formation,CO hydrogenation and C–C coupling process on Ni–Zn alloys.The free energy profile of C_(2) products formation shows that the energy barrier of C_(2) products formation on NiZn3(001)is even lower than Cu(100).These results indicate that NiZn3 alloy as pseudo-copper catalyst can exhibit a higher catalytic activity and selectivity of C_(2) products during CO_(2)RR.This work proposes a feasible pseudo-copper catalyst and provides guidance to design high-efficiency catalysts for CO_(2)RR to C_(2) or multi-carbon products.
基金
The authors gratefully thank the National Natural Science Foundation of China(Grant Nos.21872174,22002189,and U1932148)
the International Science and Technology Cooperation Program(Grant Nos.2017YFE0127800 and 2018YFE0203402)
the Hunan Provincial Science and Technology Program(No.2017XK2026)
the Hunan Provincial Natural Science Foundation(Grant Nos.2020JJ2041 and 2020JJ5691)
the Hunan Provincial Science and Technology Plan Project(No.2017TP1001)
the Shenzhen Science and Technology Innovation Project(No.JCYJ20180307151313532)
the Key R&D Program of Hunan Province(No.2020WK2002).
