Computational Screening of Doped Graphene Electrodes for Alkaline CO2 Reduction

The electrocatalytic CO₂ reduction reaction (CO₂RR) is considered as one of the most promising approaches to synthesizing carbonaceous fuels and chemicals without utilizing fossil resources. However, current technologies are still in the early phase focusing primarily on identifying optimal electrode materials and reaction conditions. Doped graphene-based materials are among the best CO₂RR electrocatalysts and in the present work we have performed a computational screening study to identify suitable graphene catalysts for CO₂RR to CO under alkaline conditions. Several types of modified-graphene frameworks doped with metallic and non-metallic elements were considered. After establishing thermodynamically stable electrodes, the electrochemical CO₂RR to CO is studied in the alkaline media. Both concerted proton-coupled electron transfer (PCET) and decoupled proton and electron transfer (ETPT) mechanisms were considered by developing and using a generalization of the computational hydrogen electrode approach. It is established that the CO₂ electrosorption and associated charge transfer along the ETPT pathway are of utmost importance and significantly impact the electrochemical thermodynamics of CO₂RR. Our study suggests an exceptional performance of metal-doped nitrogen-coordinated graphene electrodes, especially 3N-coordinated graphene electrodes.