Frustrated Lewis-Pair Catalyst Based on Re Single Atoms for Efficient Solar-Driven CO₂ Conversion

Owing to the highly efficient activation ability of frustrated Lewis-pair (FLP) sites for small molecules, the development of FLP-based materials is a fascinating route to convert CO2 to value-added chemicals using solar energy. Herein, rhenium (Re) single atoms are introduced into the frame of graphitic carbon nitride (Re1/gCN) to construct unique N···Re1 FLP sites, where Re single atoms and neighboring N atoms serve as acidic and basic sites, respectively. The N···Re1 FLP sites can interact with CO2 molecules to form a Re–O–C-N structure (acid site–basic site–acid site–basic site) via the dramatic d–p orbital interactions, thus inducing an unusual push–push electronic effect to effectively break the C═O bond for CO2 activation and conversion. As a result, Re1/gCN achieves a high photocatalytic CO2-to-CO generation rate of 123.4 μmol g–1 h–1 (a CO selectivity of 95.6%) without any sacrificial agents, exceeding the majority of state-of-the-art catalysts under similar test conditions.