团簇Ni_(4)P催化析氢性能研究

Study on the Catalytic Properties of Cluster Ni_(4)P for Hydrogen Evolution

为探究团簇Ni_(4)P催化析氢最强的结构,基于密度泛函理论,在B3LYP/Lan12dz水平下,对团簇Ni_(4)P的初始构型进行计算和优化,得到5种优化构型。从热力学稳定性、前线轨道图和前线轨道能级差对团簇Ni_(4)P的析氢性能分析发现,构型1^((4))和1^((2))的热力学稳定性较强;团簇Ni_(4)P各优化构型均易吸附水中的氢原子,Ni原子为团簇Ni_(4)P催化活性位点,且构型1^((4))、1^((2))和2^((4))催化析氢的活性更强。(1^((2)))-H、(2^((2)))-H在电化学脱附法和化学重组法中均具有较强的催化活性。以上说明构型1^((2))是团簇Ni_(4)P催化析氢最强的结构。

In order to investigate the strongest structure of cluster Ni_(4)P for catalytic hydrogen evolution,based on density functional theory,the initial configurations of cluster Ni_(4)P were calculated and optimized at B3 LYP/lan12 dz level,and five optimized configurations were obtained.After analyzing the catalytic hydrogen evolution of cluster Ni_(4)P from the point of view of the thermodynamic stability,frontier orbital diagram and frontier orbital energy level difference,it is found that configurations 1^((4)) and 1^((2)) have stronger thermodynamic stability.All the optimized configurations of cluster Ni_(4)P are easy to adsorb hydrogen atom in water,Ni atoms are the catalytic active site of cluster Ni_(4)P,and configurations 1^((4)),1^((2)) and 2^((4)) have stronger catalytic activity for hydrogen evolution.(1^((2)))-H and(2^((2)))-H have stronger catalytic activity in electrochemical desorption and chemical recombination methods.From the above results,configuration 1^((2)) is the strongest structure for catalytic hydrogen evolution of cluster Ni_(4)P.