近日，武汉理工大学曹少文团队报道了分子工程水氧化位点的D-A共轭聚合物在纯水中有效的H₂O₂光合作用。相关论文发表在2026年3月23日出版的《科学通报》杂志上。

利用空气和水光催化生成过氧化氢，被视为生产这一重要化学品的可行策略。目前，过氧化氢的生成主要通过双电子氧还原反应，并与四电子水氧化反应相耦合。然而，多电子/质子耦合的水氧化反应动力学缓慢，严重制约了整体效率。

为解决这一局限，研究组以苯并噻二唑为电子受体单元，分别引入联苯、联噻吩和联吡啶单元作为不同的水氧化反应位点，设计了三种给体-受体型共轭聚合物（BP、TP和PD），以实现高效过氧化氢转化。值得注意的是，PD在环境条件下于纯水中表现出高达6687 μmol g^-1 h^-1的过氧化氢产率，显著优于BP（3200 μmol g^-1 h^-1）和TP（4650 μmol g^-1 h^-1）。

研究表明，PD的优异性能源于其增强的电荷分离和加速的水氧化反应动力学，后者促进了用于双电子氧还原反应的质子耦合电子转移，从而提高了过氧化氢的生成效率。此外，超氧自由基可通过与单线态氧发生环加成反应在PD上稳定存在，进一步促进了过氧化氢的生成。上述机理通过开尔文探针力显微镜和原位漫反射红外傅里叶变换光谱等技术得到了系统验证。这种精细的分子设计不仅促进了空间电荷分离，还加速了水氧化反应动力学，为高性能过氧化氢光合作用提供了一种有效的策略。

附：英文原文

Title: Molecularly engineered water oxidation sites in D-A conjugated polymers for efficient H2O2 photosynthesis in pure water

Author: Wang Wang a b, Shaowen Cao a b

Issue&Volume: 2026/03/23

Abstract: Photocatalytic generation of H2O2 from air and water has been regarded as a promising strategy to produce this vital chemical. Currently, H2O2 production primarily occurs via the two-electron oxygen reduction reaction (ORR), coupled with the four-electron water oxidation reaction (WOR). However, the overall efficiency is severely hampered by the sluggish kinetics of the multi-electron/proton-coupled WOR. To address this limitation, three donor-acceptor (D-A) conjugated polymers (BP, TP, and PD) were designed by integrating biphenyl, bithiophene, and bipyridine units as distinct water-oxidation sites, respectively, with benzodithiazole as the electron-accepting moiety to enable efficient H2O2 conversion. Impressively, PD exhibited a high H2O2 evolution rate of 6687 μmol g1 h1 in pure water under ambient conditions, significantly exceeding BP (3200 μmol g1 h1) and TP (4650 μmol g1 h1). It was revealed that the striking performance of PD stems from enhanced charge separation and accelerated WOR kinetics, which promote proton-coupled electron transfer for the 2e ORR, thereby enhancing H2O2 formation. Moreover, the superoxide radical (O2) can be stabilized over PD via cycloaddition with singlet oxygen (1O2), thus facilitating the H2O2 evolution. These mechanisms were systematically validated using techniques such as Kelvin probe force microscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy. This tailored molecular design not only promotes spatial charge separation but also accelerates WOR kinetics, offering a robust strategy for high-performance H2O2 photosynthesis.

DOI: 10.1016/j.scib.2026.03.051

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927326003191