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

Solar hydrogen (H-2) 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 H-2 production systems. Herein, we report a simple, efficient, and low-cost allin-one photocatalytic H-2 evolution system composed of a thiazolo[5,4-d]thiazole-linked COF (TpDTz) as the photoabsorber and an earth-abundant, noble-metal-free nickelthiolate 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 H-2 production over 70 h with a maximum rate of 941 mu mol h(-1) g(-1), turnover number TONNi > 103, and total projected TONNi > 443 until complete catalyst depletion. The high H-2 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 H-2 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 H-2 production in water.