团簇CrPS4催化析氢密度泛函研究

为了探究团簇CrPS₄的催化析氢能力，依据拓扑学原理，利用密度泛函理论，采用B3LYP泛函和def2-tzvp基组，运用Gaussian09量子化学软件对团簇CrPS₄的基础构型分别在二重态和四重态下进行优化运行，获得16种稳定构型，其中10种构型在吸附氢原子后能够稳定存在。从前线轨道理论、HOMO-LUMO轨道能级差以及键级方面对团簇CrPS₄的10种构型的吸附与解吸能力进行探究，结果表明：在团簇CrPS₄中，S原子为主要活性位点；在结合氢原子后，相对于二重态构型，四重态构型的稳定性较高，催化活性较强，更适合用于催化析氢；团簇CrPS₄的催化析氢能力因构型不同而异，在与水反应形成(CrPS₄)—H构型的过程中，构型4⁽(4))吸附氢原子的能力最强，而在解吸过程中，构型7⁽(2))更占优势；构型8⁽(4))的综合析氢能力在10种构型中最强，其次为构型5⁽(4))和6

Density functional study of catalytic hydrogen evolution with the CrPS4 cluster

In order to explore the catalytic hydrogen evolution ability of the CrPS₄ cluster, according to the principles of topology and density functional theory, the basic configurations of the CrPS₄ cluster have been optimized in doublet and quadruplet states by Gaussian09 quantum chemistry software using the B3LYP functional and the def2-tzvp basis set. Sixteen stable configurations were obtained, of which ten were stable after adsorbing hydrogen atoms. The adsorption and desorption abilities of the ten configurations of the CrPS₄ cluster were investigated from the aspects of frontier orbital theory, HOMO-LUMO orbital energy level differences and bond levels. The results show that the S atom is the main active site in the CrPS₄ cluster. After binding a hydrogen atom, the quadruplet state configuration has higher stability and stronger catalytic activity than the doublet state configuration, making it more suitable for catalytic hydrogen evolution. The catalytic hydrogen evolution ability of the CrPS₄ cluster varies for different configurations. In the process of reacting with water to form the (CrPS₄)-H configuration, configuration 4⁽⁴⁾ has the strongest ability to adsorb hydrogen atoms. In the process of desorption, configuration 7⁽²⁾ is more dominant. The comprehensive hydrogen evolution ability of configuration 8⁽⁴⁾ is the optimum among the ten configurations, followed by configurations 5⁽⁴⁾ and 6⁽⁴⁾.