基于量子化学的团簇Co_(4)P非晶态合金析氢反应研究  

The Study on Hydrogen Evolution Reaction of Cluster Co_(4)P Amorphous Alloy Based on Quantum Chemistry

作　　者：方志刚[1] 许友 王智瑶 毛智龙 郑新喜 曾鑫渔 吴庭慧 FANG Zhigang;XU You;WANG Zhiyao;MAO Zhilong;ZHENG Xinxi;ZENG Xinyu;WU Tinghui(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan Liaoning 114051,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051

出　　处：《江西师范大学学报（自然科学版）》2022年第3期221-226,共6页Journal of Jiangxi Normal University(Natural Science Edition)

基　　金：国家自然科学基金(51634004);国家级大学生创新创业训练计划(202110146027,202010146009,202010146016);辽宁省大学生创新创业训练计划(S202110146030,S202110146056,S202110146052,S202110146055,S202110146040,S202110146049)资助项目.

摘　　要：为寻找在团簇Co_(4)P中具有最优催化析氢性能的构型,该文根据密度泛函理论于B3LYP/lanl2dz水平下对团簇Co_(4)P分别进行在二、四重态下的计算,根据前线轨道理论对优化后团簇Co_(4)P的HOMO图、水分子的LUMO图以及能级差进行分析,发现构型1^((2))、2^((2))的β电子与构型1^((4))、2^((4))的α电子的HOMO负相位对催化析氢反应的第1步提供了较大的贡献.此外,综合分析析氢反应的各步骤发现:构型2^((2))具有较好的吸附能力,且该构型在吸附1个氢原子后在电化学解吸和化学重组解吸中均具有最优解析性质.因此,构型2^((2))是在团簇Co_(4)P各优化构型中最优的催化析氢构型.In order to find the configuration with the optimal catalytic hydrogen evolution performance in the cluster Co_(4)P,according to the density functional theory at the B3LYP/lanl2dz level,the cluster Co_(4)P is calculated in the double and quartet states,and then the optimized cluster is calculated according to the frontier orbit theory.The HOMO diagram of cluster Co_(4)P,the LUMO diagram of water molecules and the energy level difference are analyzed,and it is found that the HOMO is generated by the β electrons of configuration 1^((2))and 2^((2))andαelectrons of configuration 1^((4))and 2^((4)).The negative phase provides a greater contribution to the first step of the catalytic hydrogen evolution reaction.In addition,comprehensive analysis of the various steps of the hydrogen evolution reaction finds that configuration 2^((2))has better adsorption capacity,and this configuration has the best desorption properties in both electrochemical desorption and chemical recombination desorption after adsorbing a hydrogen atom.Therefore,configuration 2^((2))is the optimal catalytic hydrogen evolution configuration among the optimized configurations of cluster Co_(4)P.

关 键 词：团簇Co_(4)P 催化析氢 密度泛函理论 前线轨道理论 

分 类 号：O641.12[理学—物理化学]