基于sp2-碳连接具有D-A结构共价有机框架的构筑及其光催化产双氧水性能研究

doi:10.6023/A25030077

化学学报 ›› 2025, Vol. 83 ›› Issue (7): 685-693.DOI: 10.6023/A25030077 上一篇下一篇

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基于sp²-碳连接具有D-A结构共价有机框架的构筑及其光催化产双氧水性能研究

闫生荣^a^,^b, 刘文浩^a, 段芳^a^,^*(), 陈明清^a^,^*(), 东为富^a, 陆双龙^a, 杜明亮^a

^a 江南大学化学与材料工程学院合成与生物胶体教育部重点实验室无锡 214122
^b 南通科技职业学院环境与生物工程学院江苏省环境功能材料与污染治理工程技术研究开发中心南通 226007

投稿日期:2025-03-12 发布日期:2025-07-28
基金资助:
国家重点研发计划(2023YFF1105200); 国家自然科学基金(52173201); 江苏省研究生科研与实践创新计划项目(KYCX18_1808); 江苏省高职院校教师专业带头人高端研修项目(2023GRFX045)

Constructing of sp²-Carbon Linked Covalent Organic Frameworks with D-A Structure and Evaluating Their Photocatalytic Performance towards Hydrogen Peroxide Production

Shengrong Yan^a^,^b, Wenhao Liu^a, Fang Duan^a^,^*(), Mingqing Chen^a^,^*(), Weifu Dong^a, Shuanglong Lu^a, Mingliang Du^a

^a School of Chemical and Material Engineering, Jiangnan University, Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, Wuxi 214122, China
^b School of Environmental and Biological Engineering, Nantong College of Science and Technology, Jiangsu Engineering Research Center of Environmental Functional Materials and Pollution Control, Nantong 226007, China

Received:2025-03-12 Published:2025-07-28
Contact: *E-mail: duanfang@jiangnan.edu.cn;E-mail: mqchen@jiangnan.edu.cn
Supported by:
National Key Research and Development Program of China(2023YFF1105200); National Natural Science Foundation of China(52173201); Postgraduate Research & Practice Innovation Program of Jiangsu Province(KYCX18_1808); High-end Training Program for Teachers' Professional Leaders in Higher Vocational Colleges of Jiangsu Province in 2023(2023GRFX045)

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摘要/Abstract

设计高度共轭和电子给体-受体(D-A)结构是提升共价有机框架(COFs)电荷分离和转移的有效手段. 鉴于此, 通过Knoevenagel缩合反应构筑了两种sp²-碳连接的BBpy-COF和BBph-COF光催化剂, 并系统研究了其光催化产双氧水(H₂O₂)性能. 实验结果表明, BBpy-COF光催化H₂O₂生成速率可达1394.7 µmol•g⁻¹•h⁻¹, 为BBph-COF (656.5 µmol•g⁻¹•h⁻¹)的2.12倍, 其性能提升归因于苯并三噻吩(Btt)电子给体与联吡啶(Bpy)电子受体间的强D-A作用和C=C双键连接的共轭增强效应调控优化了光生载流子的分离效率, 最后依靠氧还原反应(ORR)活性位点Bpy, 高效通过两步单电子ORR路径实现光催化产H₂O₂. 本项工作为合理设计和构筑高效COFs光催化材料提供了一定的参考.

关键词: sp²-碳连接, D-A结构, 共价有机框架, 光催化产双氧水

Covalent organic frameworks (COFs) are crystalline organic materials connected by covalent bonds. Due to their pre-designed structures similar to the modular assembly of Lego bricks, adjustable optical and electronic properties, high chemical and thermal stability and so on, COFs have been proved to be promising photocatalysts for the production of hydrogen peroxide (H₂O₂). However, similar to other photocatalysts, COFs also suffer from the common challenge of inefficient separation of photogenerated charge carriers. Constructing COFs with high conjugation and electron donor-acceptor (D-A) structure is an effective strategy to improve the separation and transfer capacity of photogenerated charges. Herein, through a simple yet effective one-step solvothermal synthesis approach, two kinds of sp²-carbon conjugated COFs with D-A structure (designated as BBpy-COF and BBph-COF) were successfully fabricated by the Knoevenagel condensation reaction, and their photocatalytic performance towards H₂O₂ production was evaluated. BBpy-COF with the linker of 2,2'-([2,2'-bipyridine]- 5,5'-diyl) diacetonitrile (Bpy-2CN) displayed a high photocatalytic H₂O₂ production rate of 1394.7 µmol•g⁻¹•h⁻¹, with 2.12-fold enhancement compared to BBph-COF with the linker of 4,4'-biphenyldiacetonitrile (Bph-2CN). Through a series of experiments such as the electron paramagnetic resonance (EPR) spectroscopy and rotating disk electrode (RDE) measurements as well as density functional theory (DFT) calculations, the photocatalytic mechanism was revealed that compared with BBph-COF, by virtue of the D-A structure constructed by the strong electron donor benzo[1,2-b:3,4-b':5,6-b'']trithiophene- 2,5,8-tricarbaldehyde (Btt) with the strong electron acceptor bipyridine (Bpy) and the C=C double bond connection to enhance the conjugation of the framework, BBpy-COF possessed a stronger electron push-pull effect to enhance the visible-light absorption capacity and accelerate the separation and migration of photogenerated e⁻-h⁺ pairs. Ultimately, leveraging Bpy as active sites of oxygen reduction reaction (ORR), BBpy-COF achieved efficient photocatalytic H₂O₂ production via a two-step single-electron ORR pathway. This work employs an innovative ‘triple-in-one’ integration strategy that combines D-A structure construction, the C=C double bond linkages and embedding Bpy as ORR active sites into the skeleton of COFs, offering valuable insights and references for the rational design and fabrication of high-performance COFs-based photocatalytic materials.

Key words: sp²-carbon linkage, D-A structure, covalent organic frameworks, photocatalytic hydrogen peroxide production

引用此文

闫生荣, 刘文浩, 段芳, 陈明清, 东为富, 陆双龙, 杜明亮. 基于sp²-碳连接具有D-A结构共价有机框架的构筑及其光催化产双氧水性能研究[J]. 化学学报, 2025, 83(7): 685-693.

Shengrong Yan, Wenhao Liu, Fang Duan, Mingqing Chen, Weifu Dong, Shuanglong Lu, Mingliang Du. Constructing of sp²-Carbon Linked Covalent Organic Frameworks with D-A Structure and Evaluating Their Photocatalytic Performance towards Hydrogen Peroxide Production[J]. Acta Chimica Sinica, 2025, 83(7): 685-693.

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图/表 8

图式1. BBph-COF和BBpy-COF合成示意图

Scheme 1. Schematic illustration for the synthesis of BBph-COF and BBpy-COF

图1. BBpy-COF (a)和BBph-COF (d)的PXRD图谱; Btt, Bpy-2CN, BBpy-COF (b)和Btt, Bph-2CN, BBph-COF (e)的FT-IR谱图; BBpy-COF (c)和BBph-COF (f)的固体13C NMR谱图

Figure 1. The PXRD patterns of BBpy-COF (a) and BBph-COF (d); FT-IR spectra of Btt, Bpy-2CN, BBpy-COF (b) and Btt, Bph-2CN, BBph-COF (e); solid-state 13C NMR spectra of BBpy-COF (c) and BBph-COF (f)

图2. BBpy-COF (a)和BBph-COF (c) N 1s的XPS能谱; BBpy-COF (b)和BBph-COF (d) S 2p的XPS能谱

Figure 2. N 1s XPS spectra of BBpy-COF (a) and BBph-COF (c); S 2p XPS spectra of BBpy-COF (b) and BBph-COF (d)

图3. BBpy-COF (a)和BBph-COF (b)的SEM图像; BBpy-COF (c)和BBph-COF (d)的TEM图像

Figure 3. The SEM images of BBpy-COF (a) and BBph-COF (b); the TEM images of BBpy-COF (c) and BBph-COF (d)

图4. BBpy-COF和BBph-COF的紫外-可见吸收光谱(a)和Tauc图(b); BBpy-COF的HOMO和LUMO轨道分布(c)

Figure 4. UV-Vis absorption spectra (a) and Tauc plots (b) of BBpy-COF and BBph-COF; distribution of HOMO and LUMO orbits over BBpy-COF (c)

图5. BBpy-COF和BBph-COF瞬态光电流响应图谱(a), 电化学阻抗谱Nyquist图(b), 光致发光光谱图(c)和时间分辨荧光衰减光谱图(d)

Figure 5. Transient photocurrent responses (a), EIS Nyquist plots (b), photoluminescence spectra (c), the fluorescence decay curves (d) of BBpy-COF and BBph-COF

图6. BBpy-COF和BBph-COF光催化产H2O2的动力学分析(a); BBpy-COF光催化产H2O2循环实验(b); 不同实验条件下BBpy-COF光催化产H2O2 (c); BBpy-COF自由基淬灭实验(d); BBpy-COF的DMPO- EPR谱(e); 对BBpy-COF进行RDE测试所得到的Koutecky-Levich图(f)

Figure 6. Kinetic profile of photocatalytic H2O2 production over BBpy-COF and BBph-COF (a); cyclic experiments of photocatalytic H2O2 production for BBpy-COF (b); photocatalytic H2O2 production over BBpy-COF under various conditions (c); the free radical quenching experiments of BBpy-COF (d); EPR spectra of DMPO- by BBpy-COF (e); Koutecky-Levich plots obtained from RDE measurement of BBpy-COF (f)

图7. BBpy-COF光催化产H2O2机理示意图

Figure 7. The proposed photocatalytic mechanism of H2O2 production over BBpy-COF

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基于sp²-碳连接具有D-A结构共价有机框架的构筑及其光催化产双氧水性能研究

Constructing of sp²-Carbon Linked Covalent Organic Frameworks with D-A Structure and Evaluating Their Photocatalytic Performance towards Hydrogen Peroxide Production

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