Deciphering Electrolyte Selection for Electrochemical Reduction of Carbon Dioxide and Nitrogen to High‐Value‐Added Chemicals

Abstract Electrochemical reduction of CO 2 (CO 2 RR) and nitrogen (NRR) constitute alternatives to fossil fuel‐based technologies for the production of high‐value‐added chemicals. Yet their practical application is still hampered by the low energy and Faradaic efficiencies although numerous efforts have been paid to overcome the fatal shortcomings. To date, most studies have focused on designing and developing advanced electrocatalysts, while the understanding of electrolyte, which would significantly influence the reaction microenvironment, are still not enough to provide insight to construct highly active and selective electrochemical systems. Here, a comprehensive review of the different electrolytes participating in the CO 2 RR and NRR is provided, including acidic, neutral, alkaline, and water‐in‐salt electrolyte as aqueous electrolytes, as well as organic electrolyte, ionic‐liquids electrolyte, and the mixture of the two as non‐aqueous electrolytes. Through the discussion of the roles of these various electrolytes, it is aimed to grasp their essential function during the electrochemical process and how these functions can be used as design parameters for improving electrocatalytic performance. Finally, priorities for future studies are suggested to support the in‐depth understanding of the electrolyte effects and thus guide efficient selection for next‐generation gas‐involving electrochemical reactions.