Design of Single Atom Transition Metal‐Doped and N/P/S‐Modified Graphene <scp>TM</scp> ‐ <scp> N ₃ S </scp> ‐ <scp>PC</scp> Catalysts for Efficient <scp> CO ₂ </scp> Electrocatalytic Reduction: A <scp>DFT</scp> Study

ABSTRACT The catalytic reduction of CO 2 into high‐value carbon‐based compounds presents a promising strategy for sustainable energy supply and industrial applications. In this work, inspired by the experimentally synthesized Ga‐N 3 S‐PC catalyst, a catalyst for single‐atom Ga doped graphene and modified with N/P/S atoms, which demonstrates outstanding performance in CO 2 reduction reactions (CO 2 RR), we constructed 27 transition metal‐doped TM‐N 3 S‐PC (TM = transition metal) catalysts to systematically explore their catalytic properties. Through first‐principles calculations, we evaluated the structural stability of the catalysts, CO 2 adsorption configurations, reaction mechanisms for four C 1 products (CO, HCOOH, CH 3 OH, and CH 4 ), and the competing hydrogen evolution reaction (HER). Among the designed catalysts, 23 exhibit high stability, while 22 demonstrate effective CO 2 adsorption; the adsorption energy varies periodically with properties of transition metals: electronegativity and d‐band center. Notably, Pt‐N 3 S‐PC may have selectivity for HCOOH production at a low limiting potential ( U L = −0.21 V), while Mo‐N 3 S‐PC may selectively yield CH 4 at U L = −0.29 V. Additionally, Fe‐N 3 S‐PC catalyzes the formation of HCOOH, CH 3 OH, and CH 4 at U L = −0.15 V, and Cd‐N 3 S‐PC facilitates CO, CH 3 OH, and CH 4 generation at U L = −0.38 V. Their catalytic performance is superior to that of the experimentally synthesized Ga‐N 3 S‐PC catalyst. These findings provide valuable insights for the rational design and synthesis of graphene‐supported single‐atom catalysts for efficient CO 2 conversion.