高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

D-A型共价有机框架纳米棒用于可见光催化苄胺偶联反应

张小会,赵冬冬,张俊杰,庄金亮   

  1. 贵州师范大学化学与材料科学学院，贵州省功能材料化学重点实验室
  • 收稿日期:2025-01-20 修回日期:2025-03-11 出版日期:2025-03-26 发布日期:2025-03-26
  • 通讯作者: 庄金亮 E-mail:jizhuang@xmu.edu.cn
  • 基金资助:
    国家自然科学基金面上项目(批准号：22372045)、贵州省科技厅基础研究重点基金项目(批准号：黔科合基础-ZK[2022]重点034)、新能源材料和绿色催化贵州省科技创新领军人才工作站(批准号：黔科合平台KXJZ[2024]029)和贵州省教育厅自然科学研究项目(青年科技人才成长项目)(批准号：黔教技〔2022〕141号)资助

D-A type covalent organic framework nanorods for visible light catalyzed benzylamine coupling reaction

ZHANG xiaohui, ZHAO Dongdong, ZHANG Junjie, ZHUANG Jinliang   

  1. School of Chemistry and Materials Science, Guizhou Normal University, Key Laboratory of Functional Materials Chemistry of Guizhou Province
  • Received:2025-01-20 Revised:2025-03-11 Online:2025-03-26 Published:2025-03-26
  • Contact: Jin-Liang ZHUANG E-mail:jizhuang@xmu.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China (No. 22372045), the Science and Technology Foundation of Guizhou Province, China (No.ZK[2022]corefund034, KXJZ[2024]029), Guizhou Science and Technology Innovation Leading Talent Workstation of New Energy Materials and Green Catalysis(No. KXJZ[2024]029), and the Youth Scientific Research Project of Guzhou Provincial Education Department, China (Qian Jiao Ji [2022] No.141)

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摘要： 共价有机框架(Covalent Organic Frameworks，COFs)是一种新型的共价连接晶体材料，具有结构可预测性和永久孔隙度，被广泛应用于异相催化。本文以光活性芘基团的有机单体(TFPPy)和含苯并噻二唑(BTz)的有机单体作为构筑单元，通过溶剂热法成功合成一种D-A型(donor-acceptor)TFPPy-BTz-COF纳米棒光催化剂。利用扫描电子显微镜(SEM)高分辨率显微镜(HRTEM)、X射线衍射仪(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、傅里叶变换红外光谱(FT-IR)和氮气吸附-脱附等技术手段，研究了TFPPy-BTz-COF的形貌、结构和组成。得益于D-A型TFPPy-BTz-COF纳米棒优异的光生电子分离性能，在室温、氧气氛围及可见光照射条件下，TFPPy-BTz-COF纳米棒可将各种苄胺高效、高选择性催化氧化成相应的偶联产物。结合电子顺磁共振波谱(EPR)和活性物种捕获实验, 发现单线态氧(1O2)和超氧自由基(O2??)是关键活性氧物种，并提出了TFPPy-BTz-COF可见光催化氧化苄胺偶联反应的催化机理。

关键词: D-A共价有机框架, 可见光催化, 纳米棒, 苄胺偶联

Abstract: Covalent Organic Frameworks (COFs) are a new type of covalently bonded crystalline materials with predictable structures and permanent porosity. COFs have found extensive applications in heterogeneous catalysts. In this study, organic monomers containing photoactive pyrene groups (TFPPy) and benzothiadiazole (BTz) were used as building units for the construction of COFs. The D-A type (donor-acceptor) TFPPy-BTz-COF nanorods photocatalysts were successfully synthesized via a solvent-thermal method. The morphology, structure, and composition of TFPPy-BTz-COF were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), Fourier-transform infrared spectroscopy (FT-IR), and N2 adsorption-desorption measurements. The as-synthesized TFPPy-BTz-COF nanorods exhibited a rod-like morphology with high degree of crystallinity, a specific surface area (BET) of 118.86 m2/g, and a band gap (Eg) of 2.22 eV. Benefiting from their efficient photogenerated photo-electron pair ability, the TFPPy-BTz-COF nanorods enable the coupling reaction of various amines with high efficiency and selectivity under conditions of room temperature, oxygen atmosphere, and visible light irradiation. Electron paramagnetic resonance spectroscopy (EPR) and active species trapping experiments suggested that the singlet oxygen (1O2) and superoxide radical (O2??) are key intermediates, and a catalytic mechanism for the visible light mediated photocatalytic oxidation coupling of benzylamines catalyzed by TFPPy-BTz-COF was proposed.

Key words: D-A covalent organic frameworks, visible light mediated photocatalysis, nanorods, benzylamine coupling

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