Lin Xiuhua, Qin Peng, Ni Shaofei, Yang Tilong, Li Mingde, Dang Li
Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou, Guangdong 515063, P. R. China.
Department of Chemistry, The Hong Kong University of Science and Technology, Kowloon, Hong Kong.
Inorg Chem. 2021 May 3;60(9):6688-6695. doi: 10.1021/acs.inorgchem.1c00483. Epub 2021 Apr 16.
Redox non-innocent metal dithiolene or diamine complexes are potential alternative catalysts in hydrogen evolution reaction and have been incorporated into 2D metal-organic frameworks to obtain unexpected electrocatalytic activity. According to an experimental study, Co-bis(dithiolene), Co-bis(diamine), and Co-dithiolene-diamine portions are considered as active sites where the generation of H occurs and a diamine ligand is necessary for high catalytic efficiency. We are interested in the difference between these catalytic active sites, and mechanistic studies on extracted Co-bis(dithiolene), Co-bis(diamine), and Co-dithiolene-diamine complex-catalyzed hydrogen evolution reactions are carried out by using density functional methods. Our calculated results indicate that the priority of ligand mixed complexes resulted from the readily occurring protonation of diamine ligands and large electron affinity of dithiolene ligands as well as the lowest overall barrier for H evolution.
氧化还原非惰性金属二硫纶或二胺配合物是析氢反应中潜在的替代催化剂，并且已被纳入二维金属有机框架中以获得意外的电催化活性。根据一项实验研究，钴双（二硫纶）、钴双（二胺）和钴二硫纶-二胺部分被认为是氢气产生的活性位点，并且二胺配体对于高催化效率是必需的。我们对这些催化活性位点之间的差异感兴趣，并通过使用密度泛函方法对提取的钴双（二硫纶）、钴双（二胺）和钴二硫纶-二胺配合物催化的析氢反应进行了机理研究。我们的计算结果表明，配体混合配合物的优先顺序源于二胺配体容易发生的质子化、二硫纶配体的大电子亲和力以及析氢的最低总势垒。
