Photocatalytic water splitting and carbon dioxide photoreduction are considered effective strategies for alleviating the energy crisis and environmental pollution. Polynuclear metal-oxo clusters possess excellent electron storage/release ability and unique catalytic properties via intermetallic synergy, which enables them with great potential in environmentally friendly photosynthesis. Importantly, metal-oxo clusters with precise structure can not only act as high-efficiency catalysts but also provide well-defined structural models for exploring structure–activity relationships. In this review, we systematically summarize recent progress in the catalytic application of polynuclear metal-oxo clusters, including polyoxometalate clusters, low-cost transition metal clusters, and metal-oxo-cluster-based metal–organic frameworks for water splitting and CO2 reduction. Furthermore, we discuss the challenges and solutions to the problems of polynuclear metal-oxo clusters in photocatalysis.

Transition metal-substituted polyoxometalates (POMs) were filled into a metal–organic framework (MOF) to construct a series of POM@MOF composites (PMo12O40@MIL-101, PMo11VO40@MIL-101, PMo10V2O40@MIL-101). The composite materials possess ultra-high adsorption ability, especially for PMo10V2O40@MIL-101, with an adsorption capacity of 912.5 mg·g−1 for cationic antibiotic tetracycline in wastewater, much higher than that of isolated MIL-101(Fe) and the commonly used adsorption materials, such as activated carbon and graphene oxide. In particular, they can be used as efficient photocatalysts for the photodegradation of antibiotics under visible light irradiation. The complete photodegradation of the adsorbed species can induce the facile reusability of these composites for multiple cycles. This work opens an avenue to introduce POMs into an MOF matrix for the simultaneous adsorption and photodegradation of antibiotics.

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