Phosphorus‐Doped Graphene Aerogel as Self‐Supported Electrocatalyst for CO2‐to‐Ethanol Conversion

Abstract Electrochemical reduction of carbon dioxide (CO 2 ) to ethanol is a promising strategy for global warming mitigation and resource utilization. However, due to the intricacy of C─C coupling and multiple proton–electron transfers, CO 2 ‐to‐ethanol conversion remains a great challenge with low activity and selectivity. Herein, it is reported a P‐doped graphene aerogel as a self‐supporting electrocatalyst for CO 2 reduction to ethanol. High ethanol Faradaic efficiency (FE) of 48.7% and long stability of 70 h are achieved at −0.8 V RHE . Meanwhile, an outstanding ethanol yield of 14.62 µmol h −1 cm −2 can be obtained, outperforming most reported electrocatalysts. In situ Raman spectra indicate the important role of adsorbed *CO intermediates in CO 2 ‐to‐ethanol conversion. Furthermore, the possible active sites and optimal pathway for ethanol formation are revealed by density functional theory calculations. The graphene zigzag edges with P doping enhance the adsorption of *CO intermediate and increase the coverage of *CO on the catalyst surface, which facilitates the *CO dimerization and boosts the EtOH formation. In addition, the hierarchical pore structure of P‐doped graphene aerogels exposes abundant active sites and facilitates mass/charge transfer. This work provides inventive insight into designing metal‐free catalysts for liquid products from CO 2 electroreduction.