Unveiling the Underlying Mechanism of Transition Metal Atoms Anchored Square Tetracyanoquinodimethane Monolayers as Electrocatalysts for N_(2) Fixation  

作　　者：Shengyao Lv Chunxiang Huang Guoliang Li Liming Yang 

机构地区：[1]Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica,Key Laboratory of Material Chemistry for Energy Conversion and Storage,Ministry of Education,Hubei Key Laboratory of Materials Chemistry and Service Failure,Hubei Engineering Research Center for Biomaterials and Medical Protective Materials,School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan 430074,China [2]Key Laboratory of Theoretical Chemistry of Environment,Ministry of Education,Center for Computational Quantum Chemistry,School of Chemistry,South China Normal University,Guangzhou 510006,China

出　　处：《Energy & Environmental Materials》2022年第2期533-542,共10页能源与环境材料（英文）

基　　金：support from the National Natural Science Foundation of China(22073033,21873032,21673087,21903032);startup fund(2006013118 and 3004013105)from Huazhong University of Science and Technology;the Fundamental Research Funds for the Central Universities(2019kfyRCPY116);the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003);support from Guangdong Basic and Applied Basic Research Foundation(2021A1515010382);the computational resources from the computing cluster at the Key Laboratory of Theoretical Chemistry of Environment,Ministry of Education&School of Chemistry,South China Normal University;The work was carried out at the LvLiang Cloud Computing Center of China,and the calculations were performed on TianHe-2;The computing work in this paper is supported by the Public Service Platform of High Performance Computing by Network and Computing Center of HUST.

摘　　要：We for the first time systematically studied the structures and electrochemical nitrogen reduction reaction properties of two-dimensional single transition-metal anchored square tetracyanoquinodimethane monolayers(labeled as:TM-sTCNQ,TM=3d,4d,5d series transition metals)by employing density functional theory method.Through highthroughput screenings and full reaction path researches,two promising electrochemical nitrogen reduction reaction catalysts Nb-sTCNQ and MosTCNQ have been obtained.The nitrogen reduction reaction onset potential on Nb-sTCNQ is as low as−0.48 V.Furthermore,the Nb-sTCNQ catalyst can quickly desorb NH3 produced with a free energy of 0.65 eV,giving Nb-sTCNQ excellent catalytic cycle performance.The high catalytic activity of the two materials might be attributed to the effective charge transfer between the active center and adsorbed N_(2),which enables the active center to adsorb and activate inert N_(2) molecules well,and the reduction processes require small energy input(i.e.,the maximum free energy changes are small).This work provides insights for finding highly efficient,stable,and low-cost nitrogen reduction reaction electrocatalysts.We hope our results can promote further experimental and theoretical research of this field.

关 键 词：2D TM-sTCNQ monolayers density functional theory method electrochemical nitrogen reduction reaction high-throughput screening single-atom catalysts 

分 类 号：TQ113.2[化学工程—无机化工] TQ426