Simultaneous CO ₂ and H ₂ O Activation via Integrated Cu Single Atom and N Vacancy Dual‐Site for Enhanced CO Photo‐Production

Abstract Photocatalytic conversion of CO 2 into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate‐change crisis and realizing a carbon‐neutral economy. Single‐atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single‐site features they are usually only amenable to activations involving single molecules. For CO 2 photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO 2 reduction and H 2 O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single‐atom centers and two‐coordinated N vacancies as dual active sites on CN (Cu 1 /N 2C V‐CN). Experimental and theoretical results show that Cu single‐atom centers promote CO 2 chemisorption and activation via accumulating photogenerated electrons, and the N 2C V sites enhance the dissociation of H 2 O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual‐functional sites, the Cu 1 /N 2C V‐CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g −1 h −1 . An ingenious atomic‐level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO 2 photoreduction process.