Hydrogen‐Bonding‐Directed Assembly of COF/Nanocluster Hybrids With Synergistic Roles for Efficient Solar Hydrogen Production

Precise interfacial engineering and rational component synergy are critical for high‐performance photocatalysts but remain challenging to achieve. Here, we report a COF/nanocluster hybrid photocatalyst (NZT‐1) constructed by a hydrogen‐bonding‐directed assembly strategy. The catalyst comprises a photoactive TP‐TDS COF (a covalent organic framework built from 2,4,6‐triformylphloroglucinol and 3,7‐diaminodibenzo[b,d]thiophene‐5,5‐dioxide) and NiZnCo nanoclusters embedded in an N‐doped carbon matrix (NiZnCo‐NC). Unlike conventional physical mixing or random loading, this approach enables molecular‐level interfacial wiring between the COF and the nanoclusters. Within the ternary cocatalyst, a synergistic division of roles is inferred: Ni acts as a structural stabilizer, Zn fine‐tunes the Co d‐band center to optimize hydrogen adsorption, and Co serves as the active site. This architecture achieves a photocatalytic H 2 evolution rate of 439.8 mmol g −1 h −1 and an apparent quantum yield of 18.6% at 500 nm—competitive with the best noble‐metal‐free systems. This work demonstrates that molecular‐level interfacial control combined with rational multi‐metal synergy provides a new paradigm for efficient, earth‐abundant artificial photosynthesis.