Artificial Photosynthesis with Polymeric Carbon Nitride: When Meeting Metal Nanoparticles, Single Atoms, and Molecular Complexes

Artificial photosynthesis for solar water splitting and CO₂ reduction to produce hydrogen and hydrocarbon fuels has been considered as one of the most promising ways to solve increasingly serious energy and environmental problems. As a well-documented metal-free semiconductor, polymeric carbon nitride (PCN) has been widely used and intensively investigated for photocatalytic water splitting and CO₂ reduction, owing to its physicochemical stability, visible-light response, and facile synthesis. However, PCN as a photocatalyst still suffers from the fast recombination of electron-hole pairs and poor water redox reaction kinetics, greatly restricting its activity for artificial photosynthesis. Among the various modification approaches developed so far, decorating PCN with metals in different existences of nanoparticles, single atoms and molecular complexes, has been evidently very effective to overcome these limitations to improve photocatalytic performances. In this Review article, a systematic introduction to the state-of-the-art metal/PCN photocatalyst systems is given, with metals in versatility of nanoparticles, single atoms, and molecular complexes. Then, the recent processes of the metal/PCN photocatalyst systems in the applications of artificial photosynthesis, e.g., water splitting and CO₂ reduction, are reviewed. Finally, the remaining challenges and opportunities for the development of high efficiency metal/PCN photocatalyst systems are presented and prospected.