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    金属有机框架材料用于光催化产过氧化氢的研究进展

    Research progress on metal-organic frameworks in photocatalytic production of hydrogen peroxide

    • 摘要: 过氧化氢(H2O2)作为一种绿色氧化剂和清洁能源载体,在有机合成、环境治理及医疗消毒等领域应用广泛。传统的蒽醌法存在工艺复杂、能耗高、污染严重等弊端,光催化技术以太阳能为驱动力,以水和氧气为原料直接合成H2O2,工艺简单且环保,成为目前的研究热点。金属有机框架(MOFs)因其高比表面积、可调孔道结构、分子级可调的能带结构以及双功能协同催化位点等优势,在光催化产H2O2领域展现出巨大潜力。但当前MOFs基光催化剂面临着光生载流子复合快、H2O2生成选择性不足及长期稳定性差等难题。目前,开发高效稳定的光催化材料聚焦于三大核心策略:配体结构优化、金属中心调控以及异质结构建。在配体工程方面,通过引入给电子或吸电子基团可有效调控MOF的电子结构,诱导晶格畸变,从而改变关键氧还原中间体的质子化路径,降低反应能垒,显著提升两电子氧还原反应(2eORR)的选择性与产率。在金属中心调控方面,构建双金属节点、环状三核单元或引入单原子位点,能够创造高活性中心,促进金属−金属电荷转移,延长载流子寿命,并将反应路径从间接单电子路径转变为直接双电子路径,从而高效抑制H2O2的二次分解,提升产物累积浓度。在异质结构建方面,通过与半导体、其他MOF或功能材料复合,构建Type-Ⅱ、Z型与S型异质结,是抑制载流子复合、保留强氧化还原能力的核心策略,异质结在界面处形成内建电场,驱动光生电子与空穴向相反方向空间分离,从而在保留高氧化还原电位的同时,有效提升载流子的利用效率与反应动力学。未来的研究可从分子层面强化配位键以提升稳定性,开发具有空间分离氧化还原位点的二维MOF纳米片以缩短电荷传输距离,并大力发展原位红外、瞬态吸收光谱等先进表征技术,以实时监测关键中间体,揭示真实反应机理。

       

      Abstract: Hydrogen peroxide (H2O2), 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 H2O2, 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 H2O2 production. However, MOF-based photocatalysts currently face several challenges, such as rapid recombination of photogenerated charge carriers, insufficient selectivity for H2O2 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 (2eORR). 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.

       

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