Manipulating Precursor to Anchor Mo3S9 Cluster onto Carbon Nitride for Photocatalytic H2 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.