团簇Ni4P催化析氢性能研究

为探究团簇Ni₄P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Ni₄P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Ni₄P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Ni₄P各优化构型均易吸附水中的氢原子，Ni原子为团簇Ni₄P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Ni₄P催化析氢最强的结构。

Study on the Catalytic Properties of Cluster Ni4P for Hydrogen Evolution

In order to investigate the strongest structure of cluster Ni4P for catalytic hydrogen evolution. Based on density functional theory, the initial configurations of cluster Ni4P were calculated and optimized at B3LYP/lan12dz level, and five optimized configurations were obtained. After analyzing the catalytic hydrogen evolution of cluster Ni4P from the point of view of the thermodynamic stability, frontier orbital diagram and frontier orbital energy level difference. These results indicated that configurations 1(4) and 1(2) have stronger thermodynamic stability. All the optimized configurations of cluster Ni4P are easy to adsorb hydrogen atom in water, Ni atoms are the catalytic active site of cluster Ni4P, 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 Ni4P.