Manipulating Precursor to Anchor Mo ₃ S ₉ Cluster onto Carbon Nitride for Photocatalytic H ₂ Production

Abstract Atom‐cluster catalysts (ACCs) have excellent prospects for various applications, yet designedly and mildly constructing ACCs remains challenging. Herein, an innovative structure‐match design strategy is proposed for anchoring Mo _x S _y cluster onto carbon nitride (CN) through triple Mo─N bonds, and developing a facile, mild, and controlled solution synthesis method through precursor‐engineering to fabricate a new C‐Mo ₃ S ₉ @CN photocatalyst (C represents cluster). The triple‐bonding in C‐Mo ₃ S ₉ @CN promotes photogenerated‐carriers separation/transfer of CN, and ensures cluster stability for 52 h, the best result in reported ACCs and single‐atom catalysts (SACs). Furthermore, the loading of Mo ₃ S ₉ clusters with abundant active sites improves hydrogen evolution reaction (HER), photoabsorption, and formic acid (FA) volume diffusion. Hence, C‐Mo ₃ S ₉ @CN exhibits a remarkable HER rate of 559 µmol h ⁻¹ under full‐spectrum illumination. The apparent quantum yield (AQY) reaches up to 88.6% at 380 nm, outperforming all reported CN‐based photocatalysts, including single‐atom Pt‐loaded CN (SA‐Pt/CN) photocatalysts. These findings offer new insights for designing and preparing cost‐effective, efficient, and stable ACCs.