Steering surface reconstruction of copper with electrolyte additives for CO2 electroreduction.

Electrocatalytic CO2 reduction to value-added hydrocarbon products using metallic copper (Cu) catalysts is a potentially sustainable approach to facilitate carbon neutrality. However, Cu metal suffers from unavoidable and uncontrollable surface reconstruction during electrocatalysis, which can have either adverse or beneficial effects on its electrocatalytic performance. In a break from the current catalyst design path, we propose a strategy guiding the reconstruction process in a favorable direction to improve the performance. Typically, the controlled surface reconstruction is facilely realized using an electrolyte additive, ethylenediamine tetramethylenephosphonic acid, to substantially promote CO2 electroreduction to CH4 for commercial polycrystalline Cu. As a result, a stable CH4 Faradaic efficiency of 64% with a partial current density of 192 mA cm-2, thus enabling an impressive CO2-to-CH4 conversion rate of 0.25 µmol cm-2 s-1, is achieved in an alkaline flow cell. We believe our study will promote the exploration of electrochemical reconstruction and provide a promising route for the discovery of high-performance electrocatalysts.