团簇Co_(3)MoP的催化析氢反应机理  

Mechanism of hydrogen evolution reaction catalyzed by cluster Co_3MoP

作　　者：吴庭慧 方志刚[1] WU Tinghui;FANG Zhigang(School of Chemical Engineering,Liaoning University of Science and Technology,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：《贵州师范大学学报（自然科学版）》2024年第6期52-58,共7页Journal of Guizhou Normal University：Natural Sciences

基　　金：国家自然科学基金重点项目(51634004);国家级大学生创新创业训练计划(202310146025、202310146026、202310146027、202210146008、202110146027)。

摘　　要：为探究团簇Co_(3)MoP与水分子催化析氢反应的活性,采用量子化学方法和密度泛函理论(DFT)进行分析研究。使用B3LYP泛函和def2-TZVP基组,在单、三重态下优化团簇的构型结构,并进行理论计算,重点分析校正能、结合能、吉布斯自由能变化及电子密度差异等参数。结果显示,构型1^((3))、3^((3))表现出较高的稳定性,其原子间结合紧密,Co原子为潜在的活性位点,周围的电子密度显著增加,氢原子因从团簇获得了更多的电子(加强了与Co_(3)MoP之间的相互作用),故不利于H_(2)的释放。To investigate the catalytic activity of the cluster Co_(3MoP) with water molecules in the hydrogen evolution reaction(HER),we conducted an in-depth analysis by using quantum chemical methods and density functional theory(DFT).Employing the B3LYP functional and def2-TZVP basis set,we optimized the cluster configurations in both singlet and triplet states and performed theoretical calculations.Key parameters such as correction energy,binding energy,Gibbs free energy changes,and electronic density differences were analyzed.The results indicate that configurations 1~((3)) and 3~((3)) exhibit high stability with tight atomic bonding.The Co atom is identified as a potential active site,with a significant increase in the surrounding electronic density.The hydrogen atom gains more electrons from the cluster,strengthening the interaction with Co_3MoP,which is unfavorable for H_(2) release.

关 键 词：析氢反应 吉布斯自由能变 电子密度 

分 类 号：O641.12[理学—物理化学]