Cu metal embedded in oxidized matrix catalyst to promote CO2 activation and CO dimerization for electrochemical reduction of CO2 [Applied Physical Sciences]

We propose and validate with quantum mechanics methods a unique catalyst for electrochemical reduction of CO₂ (CO₂RR) in which selectivity and activity of CO and C₂ products are both enhanced at the borders of oxidized and metallic surface regions. This Cu metal embedded in oxidized matrix (MEOM) catalyst is consistent with observations that Cu₂O-based electrodes improve performance. However, we show that a fully oxidized matrix (FOM) model would not explain the experimentally observed performance boost, and we show that the FOM is not stable under CO₂ reduction conditions. This electrostatic tension between the Cu⁺ and Cu⁰ surface sites responsible for the MEOM mechanism suggests a unique strategy for designing more efficient and selective electrocatalysts for CO₂RR to valuable chemicals (HCO_x), a critical need for practical environmental and energy applications.