Zhou Shiyuan, Chen Wenwen, Kan Lixuan, Zhu Lei, Zhao Wuzi, Wang Danfeng, Gu Qianfeng, Liu Guangfeng, Zhang Qichun, Gu Peiyang
Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University, Changzhou, 213164, P. R. China.
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
Angew Chem Int Ed Engl. 2025 Jul 7;64(28):e202508436. doi: 10.1002/anie.202508436. Epub 2025 May 15.
Hydrogen peroxide (HO) production utilizing conjugated microporous polymers (CMPs)-based photocatalysts represents a crucial green technology for achieving solar-to-chemical energy conversion. Proper material design is paramount to improve the dispersity and charge transfer of CMPs for enhanced HO production performance. Herein, a post-modification strategy employing chloromethylation reaction was proposed to enhance HO production. The simple one-step chloromethylation reaction simultaneously achieved two objectives: One is enhanced hydrophilicity through the hydrolysis of cyanogen groups in the pyranonitrile unit to carboxyl groups, the other is the improved O adsorption and charge transfer by incorporating chloromethyl groups. The two objectives synergistically enhanced the HO production rate of the chloromethylated CMP named DCM-TPA-Cl, reaching 5.01 mmol g h in air, 6.7-fold of the unmodified photocatalyst. Moreover, the rate achieved at an O atmosphere increased by only 1.8%, highlighting its superior O utilization efficiency in air. An exceptional 38.02 mmol g h rate was further achieved in water/benzyl alcohol mixtures, exceeding most reported polymer photocatalysts. Experimental and theoretical results corroborated the predominant role of the one-step two-electron O reduction pathway in the HO generation. This work demonstrates the potential of a post-modification method to significantly enhance HO production performance directly from water and air.
利用基于共轭微孔聚合物（CMPs）的光催化剂生产过氧化氢（HO）是实现太阳能到化学能转换的一项关键绿色技术。合理的材料设计对于提高CMPs的分散性和电荷转移以增强HO生产性能至关重要。在此，提出了一种采用氯甲基化反应的后修饰策略来提高HO的产量。简单的一步氯甲基化反应同时实现了两个目标：一是通过将吡喃腈单元中的氰基水解为羧基来增强亲水性，另一个是通过引入氯甲基来改善氧吸附和电荷转移。这两个目标协同提高了名为DCM-TPA-Cl的氯甲基化CMP的HO产率，在空气中达到5.01 mmol g h，是未修饰光催化剂的6.7倍。此外，在氧气氛下实现的速率仅增加了1.8%，突出了其在空气中卓越的氧利用效率。在水/苯甲醇混合物中进一步实现了38.02 mmol g h的优异速率，超过了大多数报道的聚合物光催化剂。实验和理论结果证实了一步双电子氧还原途径在HO生成中的主导作用。这项工作证明了一种后修饰方法直接从水和空气中显著提高HO生产性能的潜力。
