Hydrogen peroxide (H₂O₂) is a crucial energy carrier with growing significance in sustainable energy systems. Covalent organic frameworks (COFs) have recently emerged as promising materials for efficient H₂O₂ photosynthesis, while transition-metal complexes are recognized for their efficacy as molecular photocatalysts in H₂O₂ production. This study introduces a novel π–π interaction strategy to immobilize ruthenium complexes into COFs, using DaTp COF as a model system. This approach significantly enhances the photocatalytic activity for H₂O₂ production, achieving an initial rate of 3276 μmol g^–1 h^–1 without using scavengers under visible-light irradiation (λ > 420 nm). Notably, incorporating ruthenium complexes optimizes the oxygen reduction reaction pathways, shifting from a less efficient four-electron process to a more efficient two-electron process. Density functional theory calculations further reveal that ruthenium complexes not only broaden the light absorption spectrum of the COF but also increase water affinity, directly contributing to H₂O₂ generation. These findings offer a strategic framework for designing and enhancing COFs in H₂O₂ photosynthesis applications.

中文翻译：

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通过 π-π 相互作用制备含钌配合物的 DaTp COFs，用于可见光驱动的光催化过氧化氢生产


过氧化氢 （H₂O₂） 是一种重要的能源载体，在可持续能源系统中的重要性越来越大。共价有机框架 （COF） 最近已成为高效 H₂O₂ 光合作用的有前途的材料，而过渡金属络合物因其在 H₂O₂ 生产中作为分子光催化剂的功效而得到认可。本研究引入了一种新的 π-π 相互作用策略，使用 DaTp COF 作为模型系统，将钌配合物固定到 COF 中。这种方法显著提高了 H₂O₂ 产生的光催化活性，在可见光照射 （λ > 420 nm） 下无需使用清除剂即可达到 3276 μmol ^{g-1 h-1} 的初始速率。值得注意的是，掺入钌配合物优化了氧还原反应途径，从效率较低的四电子工艺转变为效率较高的双电子工艺。密度泛函理论计算进一步表明，钌配合物不仅拓宽了 COF 的光吸收光谱，还增加了水的亲和力，直接促进了 H₂O₂ 的产生。这些发现为设计和增强 H₂O₂ 光合作用应用中的 COF 提供了一个战略框架。