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.