Effect of cobalt doping on H2 generation mechanism of Mo-edge from density functional theory

• Published in: Theoretical chemistry accounts Vol. 140; no. 6
• Main Authors: Han, Yan-Xia, Kong, Chao, Hou, Li-jie, Yan, Pen-Ji
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.06.2021; Springer Nature B.V
• Subjects: Atomic/Molecular Structure and Spectra; Chemical reactions; Chemistry; Chemistry and Materials Science; Constraining; Density functional theory; Doping; Hydrogen evolution; Hydrogen production; Inorganic Chemistry; Molybdenum disulfide; Organic Chemistry; Physical Chemistry; Reaction mechanisms; Regular Article; Theoretical and Computational Chemistry; generation; H; Co doping; DFT; Mo-edge; 2H-MoS
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-021-02785-2

In this paper, the stable CoMo 6 S 16 clusters are built as the models of catalyst to research the H 2 production reaction mechanism of Co-doped Mo-edge by density functional theory (DFT) calculations. The results show that Co and Mo on Co-doped Mo-edge are the main active sites for catalyzing H 2 evolution reaction. In H 2 evolution process, S including Co-activated S atoms and the S atoms on Mo-edge first gain H atoms, which can accelerate the H 2 evolution on Co and Mo. Subsequently, Co and Mo at the edges efficiently catalyze the H 2 evolution reactions following the Volmer–Heyrovsky mechanism, and the Volmer reactions are proved to be the rate-limiting steps. The activation barriers of the rate-limiting steps are 15.5 and 16.2 kcal mol −1 , respectively, which are lower than that on Mo-edge. This implies that doping Co in 2H-MoS 2 can activate S atoms on the slab of 2H-MoS 2 and simultaneously enhance the H 2 evolution activity of Mo-edge.