In Situ Assembly of Recyclable Polyoxometalate-Derived Photocatalysts for Sustainable Photocatalytic H2 Generation

Polyoxometalate-derived photocatalysts with unique semiconductor-like performance and abundant catalytic sites are promising in photocatalysis. However, the cumbersome synthesis steps and complex structures of polyoxometalate-based compound carriers for photocatalysis pose significant challenges. In this study, we report two isostructural polyoxometalate-derived photocatalysts [M(H 2 O) 4 (TeMo 6 O 24 )][M(Hpca)(H 2 O) 5 ] 2 · 6H 2 O [M = Co ( 1 ), Zn ( 2 )], in situ synthesized via iso-nicotinic acid (pca) as the organic ligand and Anderson-type polyoxometalate [TeMo 6 O 24 ] 6– as the inorganic block, which enable heterogeneous photocatalytic H 2 production (3207.1 μmol g –1 h –1 ), far superior to most reported polyoxometalate-based heterogeneous systems. Moreover, compound 1, as a photocatalyst, displays excellent photocatalytic recyclability and stability. Density functional theory calculation reveals that the presence of the cobalt(II) ligand facilitates the H2 evolution reactions process, and the incorporation of M(Hpca)(H 2 O) 5 further promotes the reaction. This work presents a versatile strategy for designing advanced polyoxometalate-based photocatalysts for sustainable photocatalytic H 2 generation.