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

Understanding the influence of local electric fields on electrochemical reactions is crucial for designing highly selective electrocatalysts for CO reduction reactions (CORR). 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 CORR on 2D hybrid metal/graphene electrocatalysts. Our findings reveal that the electronic structures of the CO molecule undergo substantial modification, resulting in the increased adsorption energy of CO on metal/graphene structures, thus reducing the initial barrier of the CORR mechanism. This field-assisted CORR mechanism promotes CO production while suppressing HCOOH production. Our findings highlight the potential of manipulating electric fields to tailor the pathways of CORR, providing new avenues designing selective electrocatalysts.