Metal–Organic Frameworks for Photocatalytic Hydrogen Production Coupled with Selective Oxidation Reactions

Excessive fossil fuel combustion has accelerated renewable energy development, with hydrogen energy emerging as a promising alternative due to its high energy density and environmental compatibility. Photocatalytic hydrogen production through solar energy conversion represents a viable approach for sustainable development. Metal-organic frameworks (MOFs) have garnered significant research interest owing to their structural tunability, well-defined catalytic sites, and post-synthetic modification capabilities. Recent advances demonstrate that rationally designed MOF-based photocatalysts can achieve photocatalytic hydrogen production without requiring external photosensitizers or sacrificial agents. A systematic analysis of these optimization strategies is crucial for guiding the development of next-generation catalytic materials. This review examines the mechanistic principles underlying photocatalytic hydrogen production coupled with selective oxidation reactions, and focuses on recent key progress in MOF-based photocatalytic hydrogen production coupled with selective oxidation reactions, encompassing overall water splitting, benzyl alcohol oxidation, benzylamine coupling, 5-hydroxymethylfurfural oxidation, selective microplastics conversion, and so on. Key factors influencing reaction kinetics are analyzed, followed by a comprehensive evaluation of performance-enhancement strategies including 1) construction of single-component MOF photocatalysts, 2) introduction of the second metal, 3) loading oxidation/reduction cocatalyst, and 4) construction of heterojunctions. The discussion concludes with an assessment of current challenges and potential solutions for advancing MOF-based photocatalytic systems.