A First-Principles Study of Regulating Spin States of MoSi2N4 Supported Single-Atom Catalysts Via Doping Strategy for Enhancing Electrochemical Nitrogen Fixation Activity

Mingqi He; Xing Chen; Yanan Zhou; Chang Xu; Xingxing Li; Qiquan Luo; Jinlong Yang

doi:10.1021/acs.jpclett.3c01576

A First-Principles Study of Regulating Spin States of MoSi₂N₄ Supported Single-Atom Catalysts Via Doping Strategy for Enhancing Electrochemical Nitrogen Fixation Activity

J Phys Chem Lett. 2023 Aug 10;14(31):7100-7107. doi: 10.1021/acs.jpclett.3c01576. Epub 2023 Aug 2.

Authors

Mingqi He¹, Xing Chen², Yanan Zhou³, Chang Xu², Xingxing Li¹, Qiquan Luo², Jinlong Yang¹

Affiliations

¹ Department of Chemical Physics, Key Laboratory of Precision and Intelligent Chemistry, Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, Anhui, China.
² Institutes of Physical Science and Information Technology, Department of Chemistry, Anhui University, Hefei 230601, Anhui, China.
³ School of Material Science and Chemical Engineering, Ningbo University, Ningbo 315211, China.

PMID: 37530607
DOI: 10.1021/acs.jpclett.3c01576

Abstract

Regulating the spin states of catalysts to enhance activity is fascinating but challenging. Herein, by using first-principles calculations, single transition-metal (TM) atoms Mo, Re, and Os embedded in nitrogen vacancy of the MoSi₂N₄ monolayer (TM₁/V_N-MoSi₂N₄) were screened out as potential catalysts for electrochemical nitrogen reduction reaction to ammonia. Our findings suggest that the spin states of these active centers can be precisely and gradually tuned through a simple doping strategy. Additionally, doping one O atom into the Mo₁/V_N-MoSi₂N₄ system as an example significantly improves catalytic activity. The spin state of Mo₁ transitions from high to intermediate while simultaneously breaking the C_3v symmetry of the supported atom. These factors synergistically lead to better orbital overlap between the catalyst and intermediates, facilitating subsequent protonation processes and overall catalytic activity. This work provides novel insight into designing, precisely controlling, and revisiting the spin-related catalytic performance in heterogeneous catalysis.