Yu Zhiwu, Yu Fengtao, Xu Mei, Feng Shufan, Qiu Jianding, Hua Jianli
Key Laboratory for Advanced Materials and Joint International Research Laboratory for Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai, 200237, China.
State Key Laboratory of Nuclear Resources and Environment, East China University of Technology, GuangLan Avenue 418, Nanchang, 330013, China.
Adv Sci (Weinh). 2025 Apr;12(14):e2415194. doi: 10.1002/advs.202415194. Epub 2025 Feb 18.
Cyano-functionalized sp-carbon-conjugated covalent organic frameworks (CN-COFs) have been considered as promising candidates for artificial photosynthesis of hydrogen peroxide (HO). Nevertheless, the performance of CN-COFs is inherently limited by constrained oxygen capture capacity, insufficient charge separation, and rapid carrier recombination. Herein, the study rationally reports a strategy for integrating amidoxime groups (AO) into a COF through one-step cyano hydrolysis process to increase photocatalytic HO production. Combined simulations and characterizations reveal that introducing AO groups enhances hydrophilicity, stabilizes adsorbed Oxygen (O) via hydrogen bonding, accelerates the charge separation and transfer, as well as lowers the energy barrier for oxygen reduction reaction pathway, thus achieving an unmatched HO production rate of 6024 µmol h g. Importantly, the solar-to-chemical conversion (SCC) efficiency of PTTN-AO reaches 0.61%, significantly surpassing that of natural plants (≈0.1%) and most COF-based photocatalysts. The current findings are encouraging for the molecular design of polymers for green and efficient HO production.
氰基功能化的sp-碳共轭共价有机框架（CN-COFs）被认为是用于过氧化氢（HO）人工光合作用的有前途的候选材料。然而，CN-COFs的性能本质上受到氧气捕获能力受限、电荷分离不足和载流子快速复合的限制。在此，该研究合理地报道了一种通过一步氰基水解过程将偕胺肟基团（AO）整合到COF中的策略，以提高光催化HO的产生。结合模拟和表征表明，引入AO基团增强了亲水性，通过氢键稳定吸附的氧（O），加速电荷分离和转移，并降低氧还原反应途径的能垒，从而实现了6024 μmol h g的无与伦比的HO产生速率。重要的是，PTTN-AO的太阳能到化学能转换（SCC）效率达到0.61%，显著超过天然植物（≈0.1%）和大多数基于COF的光催化剂。目前的研究结果对于绿色高效HO生产的聚合物分子设计具有鼓舞作用。
