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.