Photocatalytic hydrogen evolution over a nickel complex anchoring to thiophene embedded g-C₃N₄

Evolution of hydrogen from water by utilizing solar energy and photocatalysts is one of the most promising ways to solve energy crisis. However, designing a cost-effective and stable photocatalyst without any noble metals is of vital importance for this process. Herein, an extremely active molecular complex cocatalyst NiL₂(Cl)₂ is successfully designed. After being covalently linked to thiophene-embedded polymeric carbon nitride (TPCN), the hybrid catalyst NiL₂(Cl)₂/TPCN exhibits extraordinary H₂ production activity of 95.8 μmol h^-1 without Pt (λ ≥ 420 nm), together with a remarkable apparent quantum yield of 6.68% at 450 nm. In such a composite catalyst, the embedded π-electron-rich thiophene-ring not only extends the π-conjugated system to enhance visible light absorption, but also promotes the charge separation through electron-withdrawing effect. It turns out that the CN covalent bonds formed between NiL₂(Cl)₂ and TPCN skeleton accelerate the transfer of electrons to the Ni active sites. Our finding reveals that the strategy of embedding π-electron-rich compounds to graphitic carbon nitride provides potentials to develop excellent photocatalysts. The strong covalent combination of molecular complexes cocatalyst onto organic semiconductors represents an important step towards designing noble-metal-free photocatalysts with superior activity and high stability for visible light driven hydrogen evolution.