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 {Cu^I₂₄(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 {Cu^I₂₄(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.