Shu Chang, Yang Xiaoju, Liu Lunjie, Hu Xunliang, Sun Ruixue, Yang Xuan, Cooper Andrew I, Tan Bien, Wang Xiaoyan
Key Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Luoyu Road No. 1037, 430074, Wuhan, China.
Department of Chemistry and Materials Innovation Factory, University of Liverpool, 51 Oxford Street, Liverpool, L7 3NY, United Kingdom.
Angew Chem Int Ed Engl. 2024 May 27;63(22):e202403926. doi: 10.1002/anie.202403926. Epub 2024 Mar 14.
The solar-driven photocatalytic production of hydrogen peroxide (HO) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic HO production is often restricted by the low photo-generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed-linker strategy to build a donor-acceptor-acceptor (D-A-A) type covalent organic framework (COF) photocatalyst, FS-OHOMe-COF. The FS-OHOMe-COF structure features extended π-π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS-OHOMe-COF has a low exciton binding energy, long excited-state lifetime and high photo-stability that leads to high performance for photocatalytic HO production (up to 1.0 mM h) with an HO output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment.
利用半导体催化剂通过太阳能驱动从水和氧气中光催化生产过氧化氢（HO），为将太阳能转化为可储存的化学能提供了一种很有前景的方法。然而，光催化生产HO的效率常常受到光生电荷分离效率低、表面反应缓慢以及稳定性不足的限制。在此，我们开发了一种混合连接体策略来构建供体-受体-受体（D-A-A）型共价有机框架（COF）光催化剂FS-OHOMe-COF。FS-OHOMe-COF结构具有扩展的π-π共轭，可提高电荷迁移率，而砜单元的引入不仅作为活性位点促进与水的表面反应，还通过增加层间作用力增强稳定性。所得的FS-OHOMe-COF具有低激子结合能、长激发态寿命和高光稳定性，从而在光催化生产HO方面表现出高性能（高达1.0 mM·h），照射72小时后HO产量达到19 mM。此外，该催化剂表现出高稳定性，在192小时的光催化实验中保持活性。
