Rational‐Designed Principles for Electrochemical and Photoelectrochemical Upgrading of CO2 to Value‐Added Chemicals

Abstract The chemical transformation of carbon dioxide (CO 2 ) has been considered as a promising strategy to utilize and further upgrade it to value‐added chemicals, aiming at alleviating global warming. In this regard, sustainable driving forces (i.e., electricity and sunlight) have been introduced to convert CO 2 into various chemical feedstocks. Electrocatalytic CO 2 reduction reaction (CO 2 RR) can generate carbonaceous molecules (e.g., formate, CO, hydrocarbons, and alcohols) via multiple‐electron transfer. With the assistance of extra light energy, photoelectrocatalysis effectively improve the kinetics of CO 2 conversion, which not only decreases the overpotentials for CO 2 RR but also enhances the lifespan of photo‐induced carriers for the consecutive catalytic process. Recently, rational‐designed catalysts and advanced characterization techniques have emerged in these fields, which make CO 2 ‐to‐chemicals conversion in a clean and highly‐efficient manner. Herein, this review timely and thoroughly discusses the recent advancements in the practical conversion of CO 2 through electro‐ and photoelectrocatalytic technologies in the past 5 years. Furthermore, the recent studies of operando analysis and theoretical calculations are highlighted to gain systematic insights into CO 2 RR. Finally, the challenges and perspectives in the fields of CO 2 (photo)electrocatalysis are outlined for their further development.