Dual-Functionalized Mixed Keggin- and Lindqvist-Type Cu24-Based POM@MOF for Visible-Light-Driven H2 and O2 Evolution.

The development of logical visible-light-driven heterogeneous photosystems for water splitting is a subject of new research. As the first example of a noble-metal-free photocatalyst for both H2 and O2 production, a high-nuclear {CuI24(μ3-Cl)8(μ4-Cl)6}-based polyoxometalate (POM)@metal-organic framework (MOF) (ZZULI-1) is rationally designed to serve as a robust dual-functionalized photocatalyst. ZZULI-1 exhibits highly efficient photocatalytic H2 evolution (6614 μmol g-1 h-1) and O2 evolution (1032 μmol g-1 calculated for the first 6 min). The {CuI24(μ3-Cl)8(μ4-Cl)6} clusters and mixed POMs not only work as the active units for H2 and O2 production, respectively, but also improve the effective electron transfer between the photosensitizer and ZZULI-1. The highly stable dual-functionalized ZZULI-1 affords new penetrations into the development of cost-effective high-nuclear cluster-based POM@MOFs for efficient solar-to-fuel generation.