福州大学王心晨团队报道了用于光催化合成H₂O₂的腙键共价有机框架孔化学微环境的变化。相关研究成果发表在2024年7月2日出版的《德国应用化学》。

光催化合成H₂O₂是传统蒽醌工艺的一种有利且生态可持续的替代方法。然而，在没有牺牲剂的情况下实现高转化效率仍然是一个挑战。

该研究中，研究人员制备了两种具有相同框架结构但孔壁锚定在不同烷基链上的共价有机框架（COF-O和COF-C）。它们用于研究孔的化学微环境对光催化H₂O₂产生的影响。

实验结果表明，COF-O中的亲水性发生了变化，导致电荷复合受到抑制，电荷转移电阻降低，界面电子转移加速。H₂O和O₂通过氧还原反应可以获得高达10.3%（λ=420nm）的表观量子产率。这是聚合物光催化剂有史以来报道的最高值之一。

该项研究可能为优化H₂O₂生成中的光催化活性和选择性提供一条新的途径。

附：英文原文

Title: Variation of Chemical Microenvironment of Pores in Hydrazone-Linked Covalent Organic Frameworks for Photosynthesis of H2O2

Author: Zhipeng Xie, Xiong Chen, Wenbin Wang, Xiating Ke, Xirui Zhang, Sibo Wang, Xiaofeng Wu, Jimmy C. Yu, Xinchen Wang

Issue&Volume: 2024-07-02

Abstract: Photocatalytic synthesis of H2O2 is an advantageous and ecologically sustainable alternative to the conventional anthraquinone process. However, achieving high conversion efficiency without sacrificial agents remains a challenge. In this study, two covalent organic frameworks (COF-O and COF-C) were prepared with identical skeletal structures but with their pore walls anchored to different alkyl chains. They were used to investigate the effect of the chemical microenvironment of pores on photocatalytic H2O2 production. Experimental results reveal a change of hydrophilicity in COF-O, leading to suppressed charge recombination, diminished charge transfer resistance, and accelerated interfacial electron transfer. An apparent quantum yield as high as 10.3% (λ = 420 nm) can be achieved with H2O and O2 through oxygen reduction reaction. This is among the highest ever reported for polymer photocatalysts. This study may provide a novel avenue for optimizing photocatalytic activity and selectivity in H2O2 generation.

DOI: 10.1002/anie.202410179

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202410179