Linkage engineering in covalent organic frameworks for overall photocatalytic H_(2)O_(2) synthesis from water and air  

共价有机框架中的连接工程用于在水和空气中光催化全合成H_(2)0_(2)

作　　者：Jian-Zhou Xiao Zhi-Hao Zhao Nan-Nan Zhang Hong-Tu Che Xiu Qiao Guang-Ying Zhang Xiaoyu Chu Ya Wang Hong Dong Feng-Ming Zhang 肖建洲;赵致灏;张楠楠;车宏途;乔秀;张光颖;初小宇;王雅;董鸿;张凤鸣(哈尔滨理工大学材料科学与化学工程学院,黑龙江省CO_(2)资源化利用与能源催化材料重点实验室,黑龙江哈尔滨150080)

机构地区：[1]Heilongjiang Provincial Key Laboratory of CO_(2)Resource Utilization and Energy Catalytic Materials,School of Material Science and Chemical Engineering,Harbin University of Science and Technology,Harbin 150080,Heilongjiang,China

出　　处：《Chinese Journal of Catalysis》2025年第2期219-229,共11页催化学报(英文)

基　　金：国家自然科学基金(22178077,22102178);中国博士后科学基金(2021M693119);山东省自然科学基金(ZR2022MB126);黑龙江省省属本科院校基本科研业务费(2024-KYYWF-0928,2020-KYYWF-0337).

摘　　要：Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))using covalent organic frameworks(COFs)as photocatalysts holds promise for future applications.However,the influence of linkage chemistry on the photoelectrochemical properties and photocatalytic performance of COFs remains a significant challenge.Herein,we designed and synthesized a model system with different linkages,including imine-,amine-,azo-linked COFs,then investigated their photocatalytic activity of overall H_(2)O_(2)production.The photocatalytic results revealed varying activities for H_(2)O_(2)synthesis among these COFs,with the azo-linked TTA-Azo-COF(COF synthesized by 4,4’,4’’-(1,3,5-triazine-2,4,6-triyl)-trianiline and terephthalaldehyde)demonstrating the highest overall H2O2 photosynthesis activity of 2516μmol g^(–1)h^(–1)in an O2 atmosphere without any sacrificial agents,which is 6.72 and 2.85 times higher than that of imine-linked TTA-COF and amine-linked TTA-COF-AR,respectively.Furthermore,TTA-Azo-COF maintained a high photosynthesis H2O2 activity of 2116μmol g^(–1)h^(–1)under an air atmosphere,outperforming most COF-based photocatalytic systems under similar reaction conditions.Further characterizations and density functional theory calculations reveal these various linkages in different COFs result in distinct visible-light absorption,charge transfer capacities and formation energy barriers of key intermediates.This work revealed the significant impact of linkages on COFs and provided comprehensive guidance for the rational design of COFs with tailored linkages to fulfill specific requirements for future applications.过氧化氢(H_(2)0_(2))已经被认为是一种极具价值的化学品,具有极其广泛的应用,特别是在废水处理、医疗消毒和化学合成方面。传统的生产双氧水方法包括葱醌法、电解法、异丙醇法和氢氧化合法等,但是以上方法均伴随着大量能源或有机溶剂的消耗,并产生有毒的副产品.近年来,利用半导体催化剂光催化合成H_(2)0_(2)被广泛关注,其中利用共价有机框架(COFs)作为光催化剂用于人工光合作用合成H_(2)0_(2)的策略具有广泛的应用前景.然而,研究COFs中的连接化学对催化材料的光电化学性质和光催化性能的影响仍然是一个重大的挑战.本文设计并合成了一个具有不同连接方式的模型COFs体系,包括亚胺、仲胺和偶氮连接的三种COFs.表征结果表明,三种不同连接的COFs亚胺连接COF(TTA-COF)、仲胺连接COF(TTA-COF-Ar)和偶氮连接COF(TTA-AZo-COF)在光电化学性质上表现出显著的差异,其中偶氮连接的TTA-AzO-COF显示了更强的可见光吸收能力和较窄的带隙.随后研究了三种COFs的光催化全合成H_(2)0_(2)活性,光催化结果表明,这些不同连接的COFs显示了不同的H_(2)0_(2)光合成活性,其中偶氮连接的TTA-Azo-COF显示了最高的全H_(2)0_(2)光合作用活性,在没有任何牺牲剂存在的O_(2)气氛中活性为2516μmolg^(-1)h^(-1),分别是亚胺连接的TTA-COF和仲胺连接的TTA-COF-AR的6.72和2.85倍。此外,TTA-Azo-COF在空气气氛下保持了2116μmolg^(-1) h^(-1)的高光合作用连接工程;过氧化氢;共价有机框架;光催化过氧化氢合成;偶氮合成活性,在类似的反应条件下优于大多数COFs光催化体系.稳态荧光光谱、瞬态荧光光谱、电化学交流阻抗、光电流响应曲线和电子顺磁共振光谱等表征结果证实了在偶氮连接的TTA-AZO-COF上显示了更快的电荷分离和转移速率,原位漫反射红外光谱结果表明,三个COFs中碳位点均是氧还原的主要活性位点,并有过氧化物中

关 键 词：Linkage engineering Hydrogen peroxide COFs Photocatalytic H_(2)O_(2)synthesis Azo 

分 类 号：O643.32[理学—物理化学]