Heterometallic cluster-based organic frameworks as highly active electrocatalysts for oxygen reduction and oxygen evolution reaction:a density functional theory study  

作　　者：Xin Chen Liang Luo Shihong Huang Xingbo Ge Xiuyun Zhao 

机构地区：[1]Center for Computational Chemistry and Molecular Simulation,College of Chemistry and Chemical Engineering,Southwest Petroleum University,Chengdu 610500,China [2]State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation,Southwest Petroleum University,Chengdu 610500,China [3]Oil&Gas Field Applied Chemistry Key Laboratory of Sichuan Province,College of Chemistry and Chemical Engineering,Southwest Petroleum University,Chengdu 610500,China [4]Department of Applied Physics,University of Eastern Finland,Kuopio 70211,Finland

出　　处：《Frontiers of Chemical Science and Engineering》2023年第5期570-580,共11页化学科学与工程前沿（英文版）

基　　金：supported by the Science and Technology Project of Sichuan Province(Grant No.2022YFS0447);the Local Science and Technology Development Fund Projects Guided by the Central Government of China(Grant No.2021ZYD0060);the Science and Technology Project of Southwest Petroleum University(Grant No.2021JBGS03);the Special Project of Science and Technology Strategic Cooperation between Nanchong City and Southwest Petroleum University(Grant No.SXQHJH064);the Postgraduate Research and Innovation Fund of Southwest Petroleum University(Grant No.2021CXYB14).

摘　　要：Recently,metal–organic frameworks are one of the potential catalytic materials for electrocatalytic applications.The oxygen reduction reaction and oxygen evolution reaction catalytic activities of heterometallic cluster-based organic frameworks are investigated using density functional theory.Firstly,the catalytic activities of heterometallic clusters are investigated.Among all heterometallic clusters,Fe_(2)Mn–Mn has a minimum overpotential of 0.35 V for oxygen reduction reaction,and Fe_(2)Co–Co possesses the smallest overpotential of 0.32 V for oxygen evolution reaction,respectively 100 and 50 mV lower than those of Pt(111)and RuO_(2)(110)catalysts.The analysis of the potential gap of Fe_(2)M clusters indicates that Fe_(2)Mn,Fe_(2)Co,and Fe_(2)Ni clusters possess good bifunctional catalytic activity.Additionally,the catalytic activity of Fe_(2)Mn and Fe_(2)Co connected through 3,3′,5,5′-azobenzenetetracarboxylate linker to form Fe_(2)M–PCN–Fe_(2)M is explored.Compared with Fe_(2)Mn–PCN–Fe_(2)Mn,Fe_(2)Co–PCN–Fe_(2)Co,and isolated Fe_(2)M clusters,the mixed-metal Fe_(2)Co–PCN–Fe_(2)Mn possesses excellent bifunctional catalytic activity,and the values of potential gap on the Mn and Co sites of Fe_(2)Co–PCN–Fe_(2)Mn are 0.69 and 0.70 V,respectively.Furthermore,the analysis of the electron structure indicates that constructing a mixed-metal cluster can efficiently enhance the electronic properties of the catalyst.In conclusion,the mixed-metal cluster strategy provides a new approach to further design and synthesize high-efficiency bifunctional electrocatalysts.

关 键 词：bimetallic metal–organic frameworks bifunctional electrocatalyst density functional theory oxygen reduction reaction oxygen evolution reaction 

分 类 号：TQ426[化学工程]