Comprehensive Mechanism of CO₂ Electroreduction on Non‐Noble Metal Single‐Atom Catalysts of Mo₂CS₂‐MXene

Abstract

Abstract In this work, a series of non‐noble metal single‐atom catalysts of Mo 2 CS 2 ‐MXene for CO 2 reduction were systematically investigated by well‐defined density‐functional‐theory (DFT) calculations. It is found that nine types of transitional metal (TM) supported Mo 2 CS 2 (TM‐Mo 2 CS 2 ) are very stable, while eight can effectively inhibit the competitive hydrogen evolution reaction (HER). After comprehensively comparing the changes of free energy for each pathway in CO 2 reduction reaction (CO 2 RR), it is found that the products of TM‐Mo 2 CS 2 are not completely CH 4 . Furthermore, Cr‐, Fe‐, Co‐ and Ni‐Mo 2 CS 2 are found to render excellent CO 2 RR catalytic activity, and their limiting potentials are in the range of 0.245–0.304 V. In particular, Fe‐Mo 2 CS 2 with a nitrogenase‐like structure has the lowest limiting potential and the highest electrocatalytic activity. Ab initio molecular dynamics (AIMD) simulations have also proven that these kinds of single‐atom catalysts with robust performance could exist stably at room temperature. Therefore, these single TM atoms anchored on the surface of MXenes can be profiled as a promising catalyst for the electrochemical reduction of CO 2 .