Hydroxylated Rh Single‐Atom Antennas Assembled on Carbon Nitride Toward Stable Photocatalytic Hydrogen Evolution

Abstract Polymeric carbon nitride (PCN)‐based single‐atom catalysts represent the most promising catalysts for photocatalytic hydrogen evolution (PHE), which, however, still suffer from reduced thermodynamic stability because of the metal‐induced heptazine skeleton distortion. Herein, hydroxylated Rh single‐atom antennas (Rh‐SAAs) connected by dual oxygen‐bridges are constructed on the surface of PCN matrix, which brings great structural advantages in avoiding skeleton distortion and increasing stability compared to the traditional direct coordination of metal atoms onto PCN. The optimal PCN‐Rh‐0.5 delivers an average PHE rate of 3409 µmol g ⁻¹ h ⁻¹ , 32.5 times that of the PCN/Pt benchmark. More importantly, it achieves an ultralong stable operation time (192 h) with a higher amount of hydrogen production per unit mass than those of the state‐of‐the‐art single‐atom catalysts and other high‐stability catalysts (≥50 h) under the same conditions. Insights into the mechanism reveal the key role of the electron pump effect induced by interband trap states composed of hybridized Rh 4d/O 2p orbitals that can propel the directed electron transfer toward Rh‐SAAs. As a result, the improved charge separation efficiency and lifetime, along with the strong protonation capability with dual oxygen‐bridges, trigger a dual‐cycle reaction path, thereby achieving high PHE activity and stability.