V_(2)CN_(2)负载过渡金属双原子电催化固氮的第一性原理研究  

First-principles study of V_(2)CN_(2)-supported transition metal dimers for electrocatalytic nitrogen fixation

作　　者：曹勇 朱雪婷 盛威 许英[1,2] CAO Yong;ZHU Xue-Ting;SHENG Wei;XU Ying(School of Physics and Electronic Science,Hunan University of Science and Technology,Xiangtan 411201,China;Hunan Provincial Key Laboratory of Intelligent Sensors and Advanced Sensor Materials,Xiangtan 411201,China)

机构地区：[1]湖南科技大学物理与电子科学学院,湘潭411201 [2]湖南省智能传感器与先进传感器材料重点实验室,湘潭411201

出　　处：《原子与分子物理学报》2023年第6期95-103,共9页Journal of Atomic and Molecular Physics

基　　金：湖南省自然科学基金(2022JJ30237);湖南省研究生科研资助创新基金(CX20211003,CX20211004);国家自然科学基金(11204076);湖南省教育局研究基金(批准号:15B083)资助的课题.

摘　　要：电催化剂固氮能够在温和条件下催化氮气还原制氨.本工作基于第一性原理计算,系统地探究了分散在二维V_(2)CN_(2)上过渡金属二聚体(Fe,Mo,Ru)形成的双原子催化剂用于电催化固氮的可行性.双原子的协同作用使氮气得到较好的活化.吉布斯自由能计算表明,在V_(2)CN_(2)负载双铁原子(Fe_(2)@V_(2)CN_(2))体系进行的催化反应过电位最低,仅为0.25 eV.进一步的分子动力学计算表明Fe_(2)@V_(2)CN_(2)具有较好的结构稳定性,并且该体系能很好的抑制HER反应的发生.通过与Mo_(2)@V_(2)CN_(2),Ru 2@V_(2)CN_(2)体系的比较可知,氮气分子的吸附构型以及HER反应的竞争对催化剂的选择影响很大.我们的计算能够为双原子催化剂的设计提供更多的依据.Electrocatalyst nitrogen fixation can catalyze nitrogen reduction to ammonia under mild conditions.Based on first-principles calculations,this work systematically explores the feasibility of diatomic catalysts formed by transition metal dimers(Fe,Mo,Ru)dispersed on 2D V_(2)CN_(2) for electrocatalytic nitrogen fixation.The synergistic effect of the diatoms enables the nitrogen to be better activated.The Gibbs free energy calculation shows that the catalytic reaction carried out in the V_(2)CN_(2) supported double iron atom(Fe_(2)@V_(2)CN_(2)) system has the lowest overpotential,which is only 0.25 eV.Further molecular dynamics calculations showed that Fe_(2)@V_(2)CN_(2) has better structural stability,and the system could well inhibit the HER reaction.Compared with Mo_(2)@V_(2)CN_(2)and Ru_(2)@V_(2)CN_(2) systems,it can be seen that the adsorption configuration of nitrogen molecules and the competition of HER reaction have a great influence on the selection of catalysts.Our calculations can provide more evidence for the design of diatomic catalysts.

关 键 词：第一性原理计算 固氮 双原子催化 电催化 

分 类 号：O64[理学—物理化学]