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研究论文

具有强大内建电场的C60@TpPa共价有机框架材料高效光催化产氢

宋玉朋a,c, 华紫辉b,c, 葛介超a,c, 王春儒b,c, 吴波*,b,c,d   

  1. a中国科学院理化技术研究所 中国科学院光化学转化与功能器件重点实验室 北京 100190;
    b中国科学院化学研究所 北京分子科学国家研究中心 分子纳米结构与纳米技术重点实验室 北京 100190;
    c中国科学院大学 北京 100049;
    d中国科学院化学研究所 碳中和化学中心 北京 100190
  • 投稿日期:2025-10-23
  • 基金资助:
    国家自然科学基金（Nos. 52322204、52072374）、国家重点研发计划（No. 2022YFA1205900）以及中国科学院青年创新促进会（No. Y2022015）资助.

C60@TpPa Covalent Organic Framework with Strong Built-In Electric Field Enables Efficient Photocatalytic Hydrogen Production

Song Yupenga,c, Hua Zihuib,c, Ge Jiechaoa,c, Wang Chunrub,c, Wu Bo*,b,c,d   

  1. aKey Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China;
    bBeijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;
    cUniversity of Chinese Academy of Sciences, Beijing 100049, China;
    dCenter for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
  • Received:2025-10-23
  • Contact: *E-mail: zkywubo@iccas.ac.cn
  • Supported by:
    National Natural Science Foundation of China (Nos. 52322204, 52072374), the National Key Research and Development Program of China (Grant No. 2022YFA1205900), and the Youth Innovation Promotion Association of CAS (No. Y2022015).

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补充材料

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共价有机框架COFs,兼具可设计性、比表面积大和能带可调性,近年来逐渐受到了研究者的青睐。但其COFs存在光生电荷快速复合以及电子传递路径受限的问题,限制了其光催化产氢的应用。构建强大内建电场促进高效电荷分离与传输是提升光催化剂性能的关键。本工作通过利用一种具有β-酮烯胺连接的甲基COFs孔内嵌入富勒烯C60成功制备了一种C60@TpPa-(CH3)2-COF光催化剂。结果表明,与未封装C60的COF相比,封装C60后内建电场强度提升了4.32倍,极大促进了电荷分离与传输。优化后的C60@TpPa-(CH3)2-COF 在全光谱条件下的产氢速率高达61.58 mmol·g-1·h-1。本研究为构筑高效COF基光催化剂的提供了新策略。

关键词: 富勒烯, 共价有机框架, 内建电场, 电荷分离, 光催化产氢

Photocatalytic hydrogen evolution has emerged as a promising strategy for generating clean fuel. Covalent organic framework (COFs), which possess designability, large specific surface area and adjustable energy band, have gradually gained favor among researchers in recent years. However, their hydrogen-evolution activity is often restricted by rapid carrier recombination and limited electron transfer pathways. Although various strategies such as heterojunction construction or skeletal functionalization have been explored, they often involve complex chemical modifications that may compromise the crystallinity. In contrast, the host-guest assembly strategy offers a mild route to modulate optoelectronic properties without destroying the intrinsic porous structure. Here we report a C60@TpPa-(CH3)2-COF composite with a markedly reinforced internal electric field (IEF) to increase the hydrogen-evolution rate. C60 was selected as the guest due to its high electron affinity and size compatibility with the COF pores, acting as an ideal electron acceptor. The TpPa-(CH3)2-COF was synthesized via Schiff-base polycondensation between 2,4,6-triformylphloroglucinol (Tp) and 2,5-dimethyl-p-phenylenediamine (Pa-(CH3)2) in a 1:1.5 molar ratio, using mesitylene and benzyl alcohol as solvents, with anhydrous acetic acid as a catalyst. The reaction mixture underwent freeze-pump-thaw cycles under vacuum before being sealed and heated at 120°C for 72 hours. After cooling, the product was filtered, washed with anhydrous THF, soaked in dry acetone for solvent exchange, and vacuum-dried at 120°C for 12 hours to obtain TpPa-(CH3)2-COF. For C60 encapsulation, 20 mg of the COF was added to a 5 mL saturated C60 solution in o-dichlorobenzene and heated at 60°C for 3 days.

Key words: Fullerenes, Covalent organic framework, Built-in electric field, Charge separation, Photocatalytic hydrogen