Hydrogen-Bonding-Directed Assembly of COF/Nanocluster Hybrids With Synergistic Roles for Efficient Solar Hydrogen...

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 H₂ 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.