Effect of Interfacial Electric Field on 2D Metal/Graphene Electrocatalysts for CO2 Reduction Reaction

Understanding the influence of local electric fields on electrochemical reactions is crucial for designing highly selective electrocatalysts for CO2 reduction reactions (CO2RR). In this study, we provide a theoretical investigation of the effect of the local electric field induced by the negative‐biased electrode and cations in the electrolyte on the energetics and reaction kinetics of CO2RR on 2D hybrid metal/graphene electrocatalysts. Our findings reveal that the electronic structures of the CO2 molecule undergo substantial modification, resulting in the increased adsorption energy of CO2 on metal/graphene structures, thus reducing the initial barrier of the CO2RR mechanism. This field‐assisted CO2RR mechanism promotes CO production while suppressing HCOOH production. Our findings highlight the potential of manipulating electric fields to tailor the pathways of CO2RR, providing new avenues designing selective electrocatalysts. Understanding the influence of local electric fields on electrochemical reactions is crucial for designing selective electrocatalysts for CO2 reduction. This study investigates how negative‐biased electrodes and electrolyte cations affect CO2 reduction on 2D hybrid metal/graphene catalysts. Our findings show the electric field can modify the electronic structures, adsorption energies, and overpotential required for various reactions, opening new possibilities for creating selective electrocatalysts.