Dynamic Interface Engineering via Mechanistic Understanding of Copper Reconstruction in Electrochemical CO 2 Reduction Reaction

Efforts to improve C2+ selectivity in CO2 electroreduction have increasingly focused on strategies that deliberately induce catalyst surface reconstruction to create and maintain active sites. Among these, approaches using anodic pulses have gained particular attention for their ability to modulate the copper catalyst surface in situ. However, the underlying Cu surface reconstruction mechanisms triggered by anodic polarization still remain unclear. Here, we show that applying anodic potentials to copper can lead to two distinct surface reconstructions: surface oxide formation or metal dissolution, each defining a different reconstruction pathway with contrasting impacts on product selectivity. Oxide-derived reconstruction transiently enhances C2 over C1 selectivity but gradually loses effectiveness during operation, while dissolution-redeposition reconstruction continuously forms C2-selective sites, resulting in a progressive increase in C2 selectivity over time. Leveraging this mechanistic understanding, we implement electrolyte engineering by introducing trace Cu2+ ions under cathodic conditions to directly activate the dissolution-redeposition pathway without anodic bias. This strategy drives a dynamic electrochemical interface that sustains active-site regeneration and enables controllable selectivity, offering an energy-efficient alternative.