Promotion of electrochemical CO2 reduction to ethylene on phosphorus-doped copper nanocrystals with stable Cuδ+ sites

Electrochemical reduction of CO 2 to C 2+ products is a sustainable energy-driven pursuit for high added-value hydrocarbons. Tremendous efforts have been made to copper based electrocatalysts, which are well-known for producing C 2+ products. However, being short of well-defined catalysts with stable Cu δ+ electronic structure hinders its practical application and in-depth understanding. Herein, we developed a facile one-pot approach to prepare Cu δ+ -rich catalyst by doping phosphorus. Enhanced performance and tunable product selectivities are achieved due to the electron donor–acceptor interaction based on phosphorus content in series. C 2 hydrocarbons and alcohols are produced with high (~44.9%) selectivity, in which C 2 H 4 (30.7 ± 0.9%) is dominant at −1.6 V vs reversible hydrogen electrode (RHE). This P-Cu catalyst shows a significantly higher current density (57.2 mA cm −2 ) compared to pristine Cu. In addition, the favorable Cu δ+ is reserved during CO 2 RR contributing to a long-term stability. Experimental results and DFT calculations demonstrate that the Cu δ+ moiety facilitates the adsorption of carbon intermediates, C-C coupling and hence promotes the generation of C 2 H 4 energetically. The well-designed catalyst indicates the profit of electronic structure engineering in designing catalysts for multiple-step chemical conversions.