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

doi:10.6023/A25100352

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (3): 370-376.DOI: 10.6023/A25100352 Previous Articles Next Articles

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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^,^*()

^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 发布日期:2026-02-03
基金资助:
项目受国家自然科学基金(52322204); 项目受国家自然科学基金(52072374); 国家重点研发计划(2022YFA1205900); 以及中国科学院青年创新促进会(Y2022015)

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

Song Yupeng^a^,^c, Hua Zihui^b^,^c, Ge Jiechao^a^,^c, Wang Chunru^b^,^c, Wu Bo^b^,^c^,^d^,^*()

^a Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
^b Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
^c University of Chinese Academy of Sciences, Beijing 100049, China
^d Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2025-10-23 Published:2026-02-03
Contact: *E-mail: zkywubo@iccas.ac.cn
Supported by:
National Natural Science Foundation of China(52322204); National Natural Science Foundation of China(52072374); National Key Research and Development Program of China(2022YFA1205900); Youth Innovation Promotion Association of CAS(Y2022015)

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Abstract

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 ℃ for 72 h. After cooling, the product was filtered, washed with anhydrous THF, soaked in dry acetone for solvent exchange, and vacuum-dried at 120 ℃ for 12 h 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 ℃ for 3 d. After cooling, the composite was filtered, washed with warm o-DCB to remove physiosorbed C₆₀, and further washed with ethanol. The final product, C₆₀@TpPa-(CH₃)₂-COF, was vacuum-dried at 60 ℃ for 12 h. Comprehensive characterization confirms both framework formation and successful loading of C₆₀. Powder X-ray diffraction and Raman spectroscopy verify retention of the ordered lattice together with signatures of the guest fullerene. The IEF in C₆₀@TpPa-(CH₃)₂-COF is 4.32-fold higher than that of the pristine COF, which promotes spatial charge separation and transport. Complementary calculations indicate that pore-confined C₆₀ induces an uneven charge distribution and increase the polarity, thereby amplifying the IEF. Consequently, under AM 1.5 irradiation and loading 1% (w) of Pt, the optimized material delivers a hydrogen-evolution rate of 61.58 mmol•g^－1•h^－1. This performance represents a 5.63-fold enhancement compared to the pristine COF, and the apparent quantum efficiency (AQE) reaches 4.04% at 450 nm. At the same time, the photocatalyst demonstrated excellent cyclic stability and there had no obvious changes occurred in the structure after 24 h cyclic testing. In short, this approach utilizes the host-guest electronic interactions to enhance the strength of internal electric fields, offering a general and efficient route to high-performance COF-based photocatalysts for solar hydrogen production.

Key words: fullerenes, covalent organic framework, built-in electric field, charge separation, photocatalytic hydrogen production

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Song Yupeng, Hua Zihui, Ge Jiechao, Wang Chunru, Wu Bo. C₆₀@TpPa Covalent Organic Framework with Strong Built-In Electric Field Enables Efficient Photocatalytic Hydrogen Production[J]. Acta Chimica Sinica, 2026, 84(3): 370-376.

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Figure 1. (a) Schematic illustration for the synthesis of C60@TpPa-(CH3)2-COF. The TEM images of (b) TpPa-(CH3)2-COF and (c) C60@TpPa-(CH3)2- COF. (d) Comparison of powder XRD Patterns for TpPa-(CH3)2-COF, C60@TpPa-(CH3)2-COF and C60

Figure 2. (a) Adsorption-desorption isotherms (77 K) and (b) pore size distributions of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. (c) Fourier transform infrared spectra of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. (d) Raman spectra of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF and C60

Figure 3. (a) Comparison of UV-visible diffuse reflection spectra of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. Mott-Schottky plots of (b) TpPa- (CH3)2-COF and (c) C60@TpPa-(CH3)2-COF. (d) Valence and conduction band energy level diagrams for TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF

Figure 4. (a) Photocurrent density comparison of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. (b) Surface photovoltage (SPV) comparison of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. (c) The internal electric field intensity comparison of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. (d) Electrochemical impedance spectroscopy comparison of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. (e) The ESP of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF

Figure 5. (a) The photocatalytic hydrogen evolution of C60@TpPa-(CH3)2-COF with time under full-spectrum light. (b) Comparison of hydrogen-producing capacity of TpPa-(CH3)2-COF and C60@TpPa-(CH3)2-COF. (c) Overlayer curve of AQE and SPV of C60@TpPa-(CH3)2-COF and (d) hydrogen-producing cycle stability of C60@TpPa-(CH3)2-COF

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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

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

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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