Abstract:
Hydrogen peroxide (H
2O
2), as a green oxidizing agent and clean energy carrier, finds extensive applications in fields such as organic synthesis, environmental remediation, and medical disinfection. The traditional anthraquinone method suffers from drawbacks such as complex procedures, high energy consumption, and severe pollution. Conversely, photocatalytic technology only utilizes solar energy as its driving force and employs water and oxygen as raw materials to directly synthesize H
2O
2, making it a current research hotspot. Metal-organic frameworks (MOFs) possess high specific surface area, tunable pore structures, molecular-level adjustable bandgap structures, and dual-functional synergistic catalytic sites and have demonstrated immense potential in the field of photocatalytic H
2O
2 production. However, MOF-based photocatalysts currently face several challenges, such as rapid recombination of photogenerated charge carriers, insufficient selectivity for H
2O
2 generation, and poor long-term stability. Previous researchers have focused on three core enhancement strategies: ligand structure optimization, metal center regulation, and heterostructure construction. In terms of ligand engineering, the introduction of electron-donating or electron-withdrawing groups can effectively modulate the electronic structure of the MOF, and induce lattice distortion, thereby lowering the reaction energy barrier, and significantly enhancing the selectivity and yield of the two-electron oxygen reduction reaction (2e
−ORR). Regarding metal center engineering, constructing bimetallic nodes, cyclic trinuclear units, or introducing single-atom sites can facilitate highly active centers, metal-metal charge transfer, and transform the reaction pathway from an indirect single-electron pathway to a direct two-electron pathway. In terms of heterostructure formation, constructing Type-Ⅱ, Z-type, and S-type heterojunctions by compositing with other semiconductors represents a core strategy for inhibiting carrier recombination and strong redox activity. These heterojunctions generate an internal electric field at the interface to drive the spatial separation of photogenerated electrons and holes in opposite directions, which effectively improves carrier utilization efficiency and reaction kinetics. Future research should focus on strengthening coordination bonds at the molecular level to enhance stability and to develop unique MOFs with spatially separated redox sites to shorten charge transfer distances. Besides, the advancing advanced characterization techniques such as in-situ infrared spectroscopy and transient absorption spectroscopy should be used to monitor key intermediates in real time and elucidate the true reaction mechanism.