Mixed Copper States in Anodized Cu Electrocatalyst for Stable and Selective Ethylene Production from CO₂ Reduction

Oxygen-Cu (O-Cu) combination catalysts have recently achieved highly improved selectivity for ethylene production from the electrochemical CO₂ reduction reaction (CO₂RR). In this study, we developed anodized copper (AN-Cu) Cu(OH)₂ catalysts by a simple electrochemical synthesis method and achieved ∼40% Faradaic efficiency for ethylene production, and high stability over 40 h. Notably, the initial reduction conditions applied to AN-Cu were critical to achieving selective and stable ethylene production activity from the CO₂RR, as the initial reduction condition affects the structures and chemical states, crucial for highly selective and stable ethylene production over methane. A highly negative reduction potential produced a catalyst maintaining long-term stability for the selective production of ethylene over methane, and a small amount of Cu(OH)₂ was still observed on the catalyst surface. Meanwhile, when a mild reduction condition was applied to the AN-Cu, the Cu(OH)₂ crystal structure and mixed states disappeared on the catalyst, becoming more favorable to methane production after few hours. These results show the selectivity of ethylene to methane in O-Cu combination catalysts is influenced by the electrochemical reduction environment related to the mixed valences. This will provide new strategies to improve durability of O-Cu combination catalysts for C-C coupling products from electrochemical CO₂ conversion.