首页|调控三芴酮基共价有机框架中的局域极化促进光催化析氢活性

调控三芴酮基共价有机框架中的局域极化促进光催化析氢活性

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局部电荷的强离域和强偶极矩是影响共价有机框架(COFs)基光催化剂催化析氢性能的两个关键因素.然而,基于精确的调控结构模型来系统研究这种构效关系的报告相对较少.本研究提出了一种新的策略,通过合理的设计,制备了三种三芴酮基COFs,通过在分子水平上调控单体的结构和偶极来提高局部电荷离域指数.我们重点研究这三种三芴酮基COF的局部电荷离域与光催化性能之间的构效关系.在不同三芴酮基COF中,1,3,5-三(对甲酰基苯基)苯基COF(TeTpb-COF)展现出21.6 mmol g-1 h-1的最高析氢速率,与2,4,6-三(4-醛基苯基-1,3,5-三嗪基COF(TeTt-COF,0.2 mmol g-1 h-1)相比,光催化析氢性能提高了108倍.这种性能的增强可归因于其强大的分子内置电场提高了供体-受体嵌段单元中光生电荷的有效分离效率.这项工作证实了调整构建块可以极大增强三芴酮基COFs中的局部偶极矩,从而显著改善光催化析氢性能.构建模块的调控策略为创建高效的新型COF基光催化析氢平台提供了新机会.
Regulating local polarization in truxenone-based covalent organic frameworks for boosting photocatalytic hydrogen evolution
The high local charge delocalization and strong dipole moment are two key factors that affect the photo-catalytic hydrogen evolution over covalent organic frame-works(COFs)-based photocatalysts.However,there is a scarcity of reports that systematically investigate the struc-ture-function relationship of these factors based on precise structural models.Herein,this study proposes a novel strategy for evaluating local charge delocalization using three ration-ally designed truxenone-based COFs.By controlling the structure and dipole of the monomers at the molecular level,we aim to investigate the structure-function relationship of these COFs concerning local charge delocalization.Among the different truxenone-based COFs evaluated,1,3,5-tris(p-for-myl phenyl)benzene-based COF(TeTpb-COF)exhibits the highest hydrogen evolution rate of 21.6 mmol g-1 h-1,result-ing in a 108-fold improvement in photocatalytic hydrogen evolution performance compared with that of 2,4,6-tris(4-formylphenyl)-1,3,5-triazine-based COF(TeTt-COF,0.2 mmol g-1 h-1).This enhancement can be attributed to the strong intramolecular built-in electric field,which facilitates the efficient separation of photogenerated charges in the do-nor-acceptor(D-A)block units and increases the photo-induced charge migration distance and separation efficiency.This work highlights the strategy of adjusting the building blocks to enhance the local dipole moment in truxenone-based COFs,thereby significantly improving photocatalytic hydro-gen evolution.The regulation of building blocks offers an opportunity to create a novel COF platform for high-efficiency photocatalytic hydrogen evolution.

covalent organic frameworksphotocatalytic hydro-gen evolutiontruxenonedipole momentlocal charge deloca-lization

郝磊、沈荣晨、秦朝超、李能、胡浩斌、梁桂杰、李鑫

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Institute of Biomass Engineering,Key Laboratory of Energy Plants Resource and Utilization,Ministry of Agriculture and Rural Affairs,South China Agricultural University,Guangzhou 510642,China

Henan Key Laboratory of Infrared Materials and Spectrum Measures and Applications,School of Physics,Henan Normal University,Xinxiang 453007,China

State Key Laboratory of Silicate Materials for Architectures,Wuhan University of Technology,Wuhan 430070,China

Key Laboratory of Efficient Utilization of Oil and Gas Resources in Longdong,College of Petroleum and Chemical Engineering,Longdong University,Qingyang 745000,China

Hubei Key Lab Low Dimens Optoelect Mat & Devices,Hubei University of Arts and Science,Xiangyang 441053,China

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covalent organic frameworks photocatalytic hydro-gen evolution truxenone dipole moment local charge deloca-lization

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNatural Science Foundation of Guangdong Province

2237814821975084516720892021A1515010075

2024

10.1007/s40843-023-2747-6

中国科学:材料科学(英文)

中国科学:材料科学(英文)

CSTPCD
ISSN：
年,卷(期)：2024.67(2)
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