Highly efficient photocatalytic generation of hydrogen peroxide via pyrene-anthraquinone structural covalent organic frameworks  

芘-蒽醌结构的共价有机框架高效光催化生成过氧化氢

作　　者：Xinyu Hao Yiying Lan Shuiying Gao Xue Yang Rong Cao 郝心宇;兰义营;高水英;杨雪;曹荣

机构地区：[1]College of Chemistry,Fuzhou University,Fuzhou,350002,China [2]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou,350002,China [3]University of Chinese Academy of Sciences,Beijing,100049,China [4]Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou,350108,China [5]Fujian College,University of Chinese Academy of Sciences,Fuzhou,350002,China

出　　处：《Science China Materials》2025年第4期1145-1153,共9页中国科学(材料科学)(英文版)

基　　金：supported by the National Key Research and Development Program of China(2021YFA1501500,2018YFA0208604);the National Natural Science Foundation of China(22033008,22220102005,22171265);the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ103);the Natural Science Foundation of Fujian Province(2023J05087)。

摘　　要：Covalent organic frameworks(COFs)constitute a novel category of porous materials that exhibit considerable promise for photocatalysis,particularly in the production of hydrogen peroxide(H_(2)O_(2)).A novel COF distinguished by a pyrene-anthraquinone architecture(denoted as Py-DQ-COF)was successfully prepared through a solvothermal process.The pyrene moiety acts as an electron-rich component,while the anthraquinone moiety serves as its electron-deficient counterpart.The strategic integration of these two moieties as essential building blocks in the formation of a donor-acceptor type Py-DQ-COF structure facilitates the efficient separation of electron-hole pairs.By employing benzylamine as a sacrificial reagent and utilizing water as the solvent,this study meticulously explores the photocatalytic efficiency in the production of H_(2)O_(2).Mechanistic investigations validate that the reaction proceeds through a two-step two-electron(2e-)oxygen reduction reaction pathway,culminating in an impressive H_(2)O_(2)yield of 15,207µmol g^(-1)h^(-1),significantly exceeding the yields associated with conventional sacrificial alcohols.Cyclic experiments further elucidate that the materials exhibit commendable stability and sustain high activity.This study introduces a new method for the identification of novel sacrificial agents,and integrates anthraquinone into COFs,thereby offering an efficient strategy to optimize the industrial anthraquinone process for H_(2)O_(2)production.Ultimately,it provides a valuable reference for the advancement of efficient and sustainable photocatalytic systems.共价有机框架(COFs)是一种新型的多孔材料,在光催化,特别是过氧化氢(H_(2)O_(2))的生产中表现出相当大的前景.采用溶剂热法成功制备了一种具有芘-蒽醌结构的新型COF(命名为Py-DQ-COF).芘基团作为富电子组分,而蒽醌基团作为缺电子组分.这两个部分的整合是形成供体-受体型Py-DQ-COF结构的重要组成部分,这促进了电子-空穴对的有效分离.本研究我们以苄胺为牺牲剂,水为溶剂,详细地探讨了PyDQ-COF光催化生产H_(2)O_(2)的性能和机制.机理研究证明了该反应是通过两步双电子氧还原反应(ORR)途径进行的,其产量达到惊人的15,207μmol g^(-1)h^(-1),大大超过了使用传统牺牲剂的产量.循环实验进一步表明,该材料具有良好的稳定性和持续的高活性.本研究提出了一种鉴定新型牺牲剂的新方法,并将蒽醌整合到COFs中,从而为优化工业蒽醌法生产H_(2)O_(2)提供了有效的策略,为开发高效、可持续的光催化系统提供了有价值的参考.

关 键 词：covalent organic framework H2O2 PYRENE ANTHRAQUINONE BENZYLAMINE 

分 类 号：O643.36[理学—物理化学]