Sustained Solar H₂ Evolution from a Thiazolo[5,4-d]thiazole-Bridged Covalent Organic Framework and Nickel-Thiolate...

Solar hydrogen (H₂) evolution from water utilizing covalent organic frameworks (COFs) as heterogeneous photosensitizers has gathered significant momentum by virtue of the COFs' predictive structural design, long-range ordering, tunable porosity, and excellent light-harvesting ability. However, most photocatalytic systems involve rare and expensive platinum as the co-catalyst for water reduction, which appears to be the bottleneck in the development of economical and environmentally benign solar H₂ production systems. Herein, we report a simple, efficient, and low-cost all-in-one photocatalytic H₂ evolution system composed of a thiazolo[5,4-d]thiazole-linked COF (TpDTz) as the photoabsorber and an earth-abundant, noble-metal-free nickel-thiolate hexameric cluster co-catalyst assembled in situ in water, together with triethanolamine (TEoA) as the sacrificial electron donor. The high crystallinity, porosity, photochemical stability, and light absorption ability of the TpDTz COF enables excellent long-term H₂ production over 70 h with a maximum rate of 941 μmol h^-1 g^-1, turnover number TON_Ni > 103, and total projected TON_Ni > 443 until complete catalyst depletion. The high H₂ evolution rate and TON, coupled with long-term photocatalytic operation of this hybrid system in water, surpass those of many previously known organic dyes, carbon nitride, and COF-sensitized photocatalytic H₂O reduction systems. Furthermore, we gather unique insights into the reaction mechanism, enabled by a specifically designed continuous-flow system for non-invasive, direct H₂ production rate monitoring, providing higher accuracy in quantification compared to the existing batch measurement methods. Overall, the results presented here open the door toward the rational design of robust and efficient earth-abundant COF-molecular co-catalyst hybrid systems for sustainable solar H₂ production in water.