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 H 2 and O 2 production, a high-nuclear {Cu I 24 (μ 3 -Cl) 8 (μ 4 -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 H 2 evolution (6614 μmol g –1 h –1 ) and O 2 evolution (1032 μmol g –1 calculated for the first 6 min). The {Cu I 24 (μ 3 -Cl) 8 (μ 4 -Cl) 6 } clusters and mixed POMs not only work as the active units for H 2 and O 2 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.