Structural regulation of imine-linked benzothiadiazole-based covalent organic frameworks for efficient photocatalysis

IF 9.7 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2025-03-19 DOI:10.1007/s11426-024-2507-5

Xin Zhao, Yuancheng Wang, Guangchao Han, Guoye Yu, Guanshi Ren, Xiang Li, Tongyang Zhang, Lishui Sun, Yingjie Zhao

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Abstract

Slightly structural variation often leads to huge changes in the properties of the covalent organic frameworks (COFs). The atom-level precisely arranged structures of COFs make it possible to understand the structure-performance relationship. Here, four highly crystalline imine-linked benzothiadiazole-based COFs were constructed from precisely designed monomers. The effects of imine linkage orientation, the π bridge between the benzothiadiazole unit and imine linkage on the photocatalysis performance were systematically studied. It is noted that photocatalytic performance can be dramatically improved when the imine carbon atoms are attached to the pyrene-based unit. In addition, the extension of the π bridge in the benzothiadiazole units could obviously enhance the photocatalytic hydrogen evolution and weaken the hydrogen peroxide generation. The PC-NPB containing the diphenylbenzothiadiazole building block exhibited the highest hydrogen evolution rate of 15.7 mmol h⁻¹ g⁻¹, 4.4 times higher than that of non-phenyl-substituted benzothiadiazole-containing PC-NB. Interestingly, PC-NB displayed the highest hydrogen peroxide generation rate of 1376 µmol h⁻¹ g⁻¹, 2.8 times higher than that of PC-NPB.

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用于高效光催化的亚胺连接苯并噻唑基共价有机框架的结构调控

微小的结构变化往往导致共价有机框架（COFs）性质的巨大变化。COFs的原子级精确排列结构使理解结构-性能关系成为可能。在这里，用精确设计的单体构建了四种高结晶亚胺连接的苯并噻二唑基COFs。系统地研究了亚胺键取向、苯并噻唑基团与亚胺键间的π桥对光催化性能的影响。我们注意到，当亚胺碳原子附着在芘基单元上时，光催化性能可以显著提高。此外，苯并噻唑基上π桥的延伸可以明显增强光催化析氢，减弱过氧化氢的生成。含二苯基苯并噻唑的PC-NB的析氢速率最高，为15.7 mmol h−1 g−1，是含非苯基取代苯并噻唑的PC-NB的4.4倍。有趣的是，PC-NB的过氧化氢生成速率最高，为1376µmol h−1 g−1，是PC-NPB的2.8倍。

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.