Modulating the electronic structure of MoS3 catalyst via heteroatom doping for Electrocatalytic nitrogen reduction reaction: A theoretical study

Heteroatom doping is an effective strategy to enhance the catalytic activity of catalysts. In this study, we propose a series of heteroatom doping (P, O) MoS3 catalysts to investigate the effect of heteroatoms on the catalytic activity of these catalysts for electrocatalytic nitrogen reduction reaction (eNRR). In P doping catalysts, the electron-donating ability of the Mo1 active site is improved by raising the P atom content, and N2 is activated by the π*-acceptation effect. In O doping catalysts, the electron-accepting ability of the Mo1 active site is improved by raising the O atom content, meanwhile, the N2 activation process transforms from the π*-acceptation effect to the σ-donation effect. The reaction mechanism of the catalysts can be accurately depicted under the constant-potential method, the calculated results elucidate that the MoS8/3O1/3 catalyst with a tiny amount of O atom exhibits good catalytic activity for eNRR with the limiting potential of -0.43 V vs. RHE. Additionally, the Eads(*N2) and Eads(*NNH) can be served as the descriptors to understand the origins of catalytic activity for the catalysts.