Molecular Dynamics Simulations for Electrocatalytic CO₂ Reduction: Bridging Macroscopic Experimental Observations and Microscopic Explanatory Mechanisms

Abstract Electrocatalytic carbon dioxide reduction reaction (CO 2 RR) has been recognized as a promising route to convert carbon emissions to high‐value chemicals and fuels. Significant breakthroughs are usually inseparable from deeper understanding of reaction mechanisms. To this end, molecular dynamics (MD) simulations have been invaluable in providing detailed insights into elucidation of complex reaction pathways and prediction of overall electrochemical performance, thus bridging macroscopic experimental observations and microscopic explanatory mechanisms. Directed by MD simulations, tremendous efforts have been devoted toward enhancing the CO 2 RR with rational design of electrocatalyst and efficient construction of electrode/electrolyte interface. Herein, a comprehensive review of applications of MD simulations in CO 2 RR is emerged. To begin with, specific fundamentals along with familiar methods such as algorithm and force fields of various MD simulations have been summed up. Followed, employment of MD simulations in optimization of CO 2 RR is introduced, encompassing interpretation of electrocatalyst activity, explanation of electrolyte effect, and investigation of electrode microenvironment. Definitively, imminent challenges and avenues for optimization in future MD simulations are contemplated, envisioning this review as a guiding beacon for future endeavors aimed at harnessing MD simulations to propel CO 2 RR toward a realm of heightened efficiency, economic viability, and practical utility.