Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual‐Site for Enhanced CO Photo‐Production

Photocatalytic conversion of CO2 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 CO2 photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO2 reduction and H2O 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 (Cu1/N2CV‐CN). Experimental and theoretical results show that Cu single‐atom centers promote CO2 chemisorption and activation via accumulating photogenerated electrons, and the N2CV sites enhance the dissociation of H2O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual‐functional sites, the Cu1/N2CV‐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 CO2 photoreduction process. Herein, it is delicately constructed Cu single‐atoms anchored CN with N2C vacancies (Cu1/N2CV‐CN) as dual active sites for photocatalytic CO2 reduction. The Cu single‐atoms are identified as the active centers to accumulate photogenerated electrons for promoting CO2 chemisorption, while the N2C vacancy sites are proven to enhance the activation of H2O.