Light-induced hydrogen production from water using nickel(ii) catalysts and N-doped carbon-dot photosensitizers: catalytic efficiency enhancement by increase of catalyst nuclearity

Abstract

Solar energy conversion to chemical energy via light-induced H₂O splitting to O₂ and H₂ is considered to be a promising solution to meet the growing global energy demands. To make this transformation economically viable, it is necessary to develop sustainable photocatalytic systems. Herein, we present an efficient photocatalytic H₂ production system which relies on components comprised of low-cost and high-abundance elements. In particular, a series of mononuclear complexes [Ni(L^NS)₃]⁻ and [Ni(N^{^}N)(L^NS)₂] and a hexanuclear complex [Ni(L^NS)₂]₆ (N^{^}N = diimine and L^NS⁻ = heterocyclic thioamidate with different group-substituents) were synthesized and utilized as catalysts, in combination with N-doped carbon dots as photosensitizer, for efficient H₂ evolution from aqueous protons. Differences in H₂ production efficiency were observed among the studied Ni(II) catalysts, with complexes bearing ligands with stronger electron-donating ability exhibiting higher catalytic activity. A remarkable catalytic efficiency enhancement was observed for the hexanuclear complex, with catalyst loadings lower than those of the mononuclear Ni(II) complexes, affording TONs >1550 (among the highest values reported for photocatalytic systems of similar type operating in H₂O). These data provide an indication of catalytic cooperativity between the metal centers of the hexanuclear complex, and demonstrate the crucial role of atomically precise polynuclear Ni(II) catalysts in light-induced H₂ production, a result that can guide future catalyst design towards the development of highly efficient, low-cost and environmentally benign photocatalytic systems.