基于Povarov环化的共价有机框架孔道与电荷动力学调控及其光催化产氢增强

doi:10.1016/S1872-2067(26)65053-X

催化学报

基于Povarov环化的共价有机框架孔道与电荷动力学调控及其光催化产氢增强

李晗溪^a,b,1, 罗振东^b,1, 薛强^b, 支云飞^a,*, 杜骏^b, 周旭凯^b,c,*

^a昆明理工大学化学工程学院, 云南昆明 650500;
^b中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023;
^c中国科学院大学, 北京 100049

收稿日期:2025-10-29 接受日期:2025-10-29
通讯作者: *电子信箱: xkzhou@dicp.ac.cn (周旭凯), zyf891123@163.com (支云飞).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22301298); 辽宁省兴辽英才计划(XLYC2403136); 云南省昆明理工大学"双一流"建设联合专项(202201BE070001-060).

Engineering channel microenvironment and charge dynamics in covalent organic frameworks through linkage-specific povarov cyclization for enhanced photocatalytic hydrogen evolution

Hanxi Li^a,b, Zhendong Luo^b,1, Qiang Xue^b, Yunfei Zhi^a,*, Jun Du^b, Xukai Zhou^b,c,*

^aFaculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, Yunan, China;
^bState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-10-29 Accepted:2025-10-29
Contact: *E-mail: xkzhou@dicp.ac.cn (X. Zhou), zyf891123@163.com (Y. Zhi).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China (22301298), the Open Fund of State Key Laboratory of Catalysis (2024SKL-A-007), the Liaoning Revitalizing Talents Program (XLYC2403136), the Yunnan Province Joint Special Project for ‘Double First-Class’ Construction of Kunming University of Science and Technology (202201BE070001-060), and the startup funds from Dalian Institute of Chemical Physics and Chinese Academy of Sciences.

摘要/Abstract

摘要： 光催化制氢(PHE)作为一种将太阳能直接转化为化学燃料的清洁能源技术, 对实现碳中和目标具有重要意义. 共价有机框架(COFs)因其周期性结构、可编程拓扑和精确定义的孔道微环境, 成为理想的光催化剂平台. 然而, 当前研究多聚焦于表面电荷动力学, 忽视了孔道结构的空间微环境及其与给体-受体异构化的相互作用对光催化性能的深层影响. 这导致催化效率难以预测, 机制理解不完整, 阻碍了高性能光催化剂的设计. 本文通过连接特异性Povarov环化策略, 构建了两种异构COFs, 系统研究了连接拓扑对孔道微环境和电荷动力学的调控作用, 旨在揭示其光催化制氢的增强机制, 为理性设计COF光催化剂提供新思路.
本文的创新性在于通过一锅三组分Povarov环化反应, 精确合成了两种给体-受体异构COFs(COF-PQ和COF-DPPQ), 它们具有相同的建筑单元但不同的连接方向, 从而实现了孔道微环境和电子结构的差异化调控. 实验上, 首先通过溶剂热法合成亚胺连接的中间体, 再经Povarov环化获得最终喹啉连接的COFs. 结构表征结果表明, 两种COFs均具有高结晶度和微孔结构, 但COF-DPPQ表现出更高的对称性和更优的孔道有序性. 光电性能测试表明, COF-DPPQ具有更窄的光学带隙(2.38 eV)和更负的导带位置(-0.23 V vs. NHE), 利于质子还原; 其光电流密度是COF-PQ的近两倍, 且电荷转移电阻显著更低, 具有更高效的电荷分离能力. 光催化性能评估显示, COF-DPPQ在可见光(λ > 420 nm)下的制氢速率高达37.82 mmol g^-1 h^-1, 是COF-PQ(0.38 mmol g^-1 h^-1)的近100倍, 且表现出优异的稳定性和表观量子效率(500 nm处为8.9%). 机理研究表明, 这种性能差异源于连接拓扑对电荷动力学和质量传输的协同调控: 密度泛函理论(DFT)计算揭示COF-DPPQ具有更低的电子有效质量(0.574 vs. 1.046)、更强的给体-受体极化(电荷转移量~0.95|e| vs. ~0.24|e|)和更优的Pt吸附位点偏好(氮锚定为主); TD-DFT和飞秒瞬态吸收光谱进一步表明, COF-DPPQ的载流子寿命显著延长(平均37.28 vs. 1.26 ps), 激子分离效率更高. 同时, 分子动力学模拟和ζ电位测量证实, COF-DPPQ的孔道微环境能促进质子吸附(吸附容量提高2.2倍)和扩散(扩散系数为0.916 × 10^-3 vs. 0.660 × 10^-3 cm² s^-1), 因其负表面电荷(ζ电位-26.6 mV)能富集质子, 降低界面反应能垒.
综上, 本文通过多尺度实验与理论结合, 阐明了连接异构通过调控电子结构和质子传输路径, 协同增强光催化制氢的机制. 未来, COF光催化剂的设计将更加注重孔道微环境与电子结构的精准协同, 通过连接工程和多功能化进一步提升太阳能转换效率. 本文通过Povarov环化策略, 实现了连接拓扑对电荷动力学和质量传输的有效调控, 不仅为COF光催化剂提供了新的设计原则, 也为多孔材料在能源转换领域的应用开辟了新途径. 本结果有望推动高性能光催化材料的开发, 助力清洁能源技术的发展.

关键词: 共价有机框架, 孔道微环境调控, 电荷动力学调控, 质子传输机理, 光催化析氢

Abstract: Covalent organic frameworks (COFs) offer a modular platform for photocatalytic hydrogen evolution (PHE), where linkage topology and channel architecture dictate charge separation and mass transport. However, the role of linkage isomerism in coupling pore microenvironments with photocatalytic function remains unclear. We synthesized COF-PQ and COF-DPPQ via in-situ Povarov cyclization of pyrene-based imine direction distinct intermediates, creating frameworks with identical building blocks but distinct donor-acceptor arrangements and pore microenvironments that underpin their contrasting catalytic behaviors. This structural divergence drives profound functional differences: COF-DPPQ achieves a PHE rate of 37.82 mmol g^-1 h^-1, nearly 100-fold higher than COF-PQ. Mechanistically, COF-DPPQ exhibits lower electron effective mass (0.574 vs. 1.046), stronger donor-acceptor polarization (~0.95 |e| vs. ~0.24 |e|), prolonged carrier lifetimes (37.28 vs. 1.26 ps), and superior proton adsorption and diffusion (2.2-fold capacity; 0.916 × 10^-3 vs. 0.660 × 10^-3 cm² s^-1). These results identify linkage topology as an effective lever to regulate exciton dynamics and mass transport, guiding the design of next-generation COF photocatalysts.

Key words: Covalent organic frameworks, Channel microenvironment regulation, Charge dynamics tuning, Proton transport mechanism, Photocatalytic hydrogen evolution

李晗溪, 罗振东, 薛强, 支云飞, 杜骏, 周旭凯. 基于Povarov环化的共价有机框架孔道与电荷动力学调控及其光催化产氢增强[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65053-X.

Hanxi Li, Zhendong Luo, Qiang Xue, Yunfei Zhi, Jun Du, Xukai Zhou. Engineering channel microenvironment and charge dynamics in covalent organic frameworks through linkage-specific povarov cyclization for enhanced photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65053-X.

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