构建钌卟啉共价有机框架催化金刚烷C-H键空气氧化接力实现烯烃环氧化

doi:10.1016/S1872-2067(26)65132-7

催化学报 ›› 2026, Vol. 88: 442-456.DOI: 10.1016/S1872-2067(26)65132-7

构建钌卟啉共价有机框架催化金刚烷C-H键空气氧化接力实现烯烃环氧化

李东珀¹, 毛倩倩¹, 熊超^*(), 系璐颖, 聂宇, 徐啸天, 纪红兵^*()

浙江工业大学化学工程学院, 绿色石化与轻烃转化研究院, 绿色化学合成与转化技术国家重点实验室, 浙江杭州 310014

收稿日期:2025-12-20 接受日期:2026-02-23 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: xiongclh@zjut.edu.cn (熊超),
jihb@zjut.edu.cn (纪红兵).
基金资助:
国家自然科学基金(22508360);浙江省自然科学基金(QN26B060028);国家重点研发计划纳米科技专项(2020YFA0210900);广东省科技计划项目(STKJ2023015)

Constructing Ru-porphyrin COF for catalyzing air oxidation of adamantane C-H bonds to relay olefin epoxidation

Dongpo Li¹, Qianqian Mao¹, Chao Xiong^*(), Luying Xi, Yu Nie, Xiaotian Xu, Hongbing Ji^*()

State Key Laboratory of Green Chemical Synthesis and Conversion, Institute of Green Petroleum Processing and Light Hydrocarbon Conversion, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2025-12-20 Accepted:2026-02-23 Online:2026-09-18 Published:2026-09-05
About author:First author contact:1 共同第一作者.
1 Contributed equally to this work.
Supported by:
The National Natural Science Foundation of China(22508360);The Zhejiang Provincial Natural Science Foundation of China(QN26B060028);The National Key Research and Development Program Nanotechnology Specific Project(2020YFA0210900);The Science and Technology Planning Project of Guangdong Province(STKJ2023015)

摘要/Abstract

摘要：

环氧化物作为精细化工生产中的关键中间体, 在医药、材料、香料等领域具有广泛应用, 但其现有合成工艺普遍存在环境污染严重、反应流程冗长、操作安全风险较高等突出问题, 制约了其绿色高效生产. 以活性烃类化合物为桥梁介导分子氧活化与烯烃环氧化反应, 是解决上述问题的可行路径: 该路径通常通过高效活化C-H键生成活性自由基, 进而与分子氧耦合, 实现后续的选择性氧化转化. 然而, 如何设计能够高效调控C-H键氧化过程、定向生成烯烃环氧化关键中间体的催化剂, 仍是当前该领域面临的核心挑战.
本文设计并合成了一种金属卟啉基共价有机框架(COF)催化剂(Ru-COF-TPD), 以空气作为绿色氧化剂, 通过金刚烷氧化接力策略构建了高效的烯烃环氧化催化体系. Ru-COF-TPD催化剂具有金属活性位点分散均匀、结构稳定性优异及孔径可调等独特优势. 在空气氛围下, 该催化剂可高效活化金刚烷的C-H键, 原位生成过氧活性物种, 并精准调控活性氧物种的转移过程, 从而实现烯烃的高选择性环氧化. 以1-丁烯为模型底物时, 该催化体系可实现83%的底物转化率和81%的环氧化物选择性, 且对多种不同结构的烯烃底物均表现出良好的催化普适性. 反应后催化剂的金属活性位点仍保持高度分散状态, 证实其具备优异的结构稳定性. 动力学研究表明, 该反应体系为吸热且无序的反应过程, 其反应动力学行为符合拟一级动力学模型, 计算得到的表观活化能为108.08 kJ/mol. 机理研究进一步揭示, Ru-COF-TPD通过活化金刚烷的C-H键生成碳中心自由基, 该自由基与氧气结合形成过氧自由基, 随后通过高价钌氧(Ru=O)中间体调控环氧化反应的选择性.
综上, 本研究针对烯烃直接空气环氧化反应的技术瓶颈, 设计并合成了一种结构有序、性能稳定、催化位点均匀分散的Ru-COF-TPD催化剂. 该催化剂可在较温和的反应条件下, 有效活化金刚烷, 并与氧气原位生成烷基过氧自由基, 进而实现以丙烯、丁烯为代表的烯烃的高效环氧化反应. 所建立的催化体系兼具安全性、经济性与催化高效性, 为烯烃环氧化反应的绿色工业化应用提供了实验室规模的可行方案与理论支撑.

关键词: 空气氧化, 卟啉基共价有机框架, 金刚烷C-H键活化, 接力催化, 烯烃环氧化

Abstract:

Epoxides are crucial intermediates in fine chemical production, but existing synthesis processes suffer from issues such as pollution, long process flows, or safety risks. Linking molecular oxygen activation and olefin epoxidation through active hydrocarbons as a bridge is a feasible pathway; this method typically involves effective C-H dehydrogenation to form active free radicals, which then couple with molecular oxygen to achieve subsequent selective oxidation. However, the design of catalysts capable of efficiently regulating the oxidative activation of C-H bonds to generate key intermediates for olefin epoxidation remains challenging. Herein, we designed a metal porphyrin-based COF catalyst (Ru-COF-TPD) and, using air as the oxidant, constructed a catalytic system for olefin epoxidation via the oxidation relay of adamantane. Ru-COF-TPD features highly dispersed metal atoms, excellent stability, and tunable pore sizes. Under an air atmosphere, it can activate the C-H bonds of adamantane to in-situ generate peroxy species and regulate active oxygen transfer, thereby enabling selective olefin epoxidation. It achieves 83% conversion for 1-butylene with 81% selectivity to the corresponding epoxide, and exhibits good activity towards various olefins. After the reaction, the metal sites remain dispersed, indicating good structural stability of the catalyst. This tandem system is an endothermic and disordered, following a pseudo-first-order model with an apparent activation energy of 108.08 kJ/mol. It was further found that Ru-COF-TPD generates carbon-centered radicals by activating the C-H bonds of adamantane, which then combine with oxygen to form peroxy radicals, and regulates the epoxidation process high-valence Ru=O intermediates. The catalytic system established in this study is safe, economical, and efficient, providing a lab-scale protocol for olefin oxidation with air.

Key words: Air oxidation, Porphyrin-based COF, Adamantane C-H activation, Relay catalysis, Olefins epoxidation

李东珀, 毛倩倩, 熊超, 系璐颖, 聂宇, 徐啸天, 纪红兵. 构建钌卟啉共价有机框架催化金刚烷C-H键空气氧化接力实现烯烃环氧化[J]. 催化学报, 2026, 88: 442-456.

Dongpo Li, Qianqian Mao, Chao Xiong, Luying Xi, Yu Nie, Xiaotian Xu, Hongbing Ji. Constructing Ru-porphyrin COF for catalyzing air oxidation of adamantane C-H bonds to relay olefin epoxidation[J]. Chinese Journal of Catalysis, 2026, 88: 442-456.

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Fig. 1. Preparation and characterization of the catalyst. (a) Synthetic diagram of Ru-COF-TPD. (b) XRD spectra of Ru-COF-TPD. (c) FT-IR spectra of Ru-COF-TPD. (d) 13C-SSNMR spectrum of Ru-COF-TPD, (e) N2 adsorption-desorption isotherms (inset: pore size distribution) of Ru-COF-TPD. (f) TGA/DTG curve.

Fig. 2. (a-c) SEM images of Ru-COF-TPD. (d-f) TEM images of Ru-COF-TPD. (g) EDS analysis of Ru-COF-TPD.

Fig. 3. (a) XPS full-scan survey spectra of Ru-COF-TPD. XPS core-level spectra of C 1s and Ru 3d (b), Ru 3p (c), and N 1s (d) for Ru-COF-TPD.

Fig. 4. The catalytic performance of the Ru-COF-TPD in 1-butylene epoxidation. (a) Effect of different metals. (b) Different solvents. (c) Catalyst dosage. (d) Reaction temperature. (e) Reaction time. (f) Air usage.

Fig. 5. (a) Thermodynamic linear fitting of 1-butylene epoxidation system via Van’t Hoof equation. Catalytic kinetic studies via the fitting of linear zero-order (b), linear pseudo-first-order (c), and linear pseudo-second-order (d).

Fig. 6. The catalytic performance of Ru-COF-TPD for various olefins. a Conditions: olefins amount (8 mmol), Ru-COF-TPD (10 mg), adamantane (20 mmol), ACN (20 mL), reaction time (8 h), reaction temperature (125 °C) and biphenyl (50 mg). b 6 h. c 115 °C. d 115 °C, 6 h.

Fig. 7. FT-IR spectra (a), 13C-SSNMR spectrum (b), and N2 adsorption-desorption isotherms (c) the catalyst before and after the epoxidation reaction. XPS core-level spectra of C 1s and Ru 3d (d), Ru 3p (e), and N 1s (f) for Ru-COF-TPD after the epoxidation reaction.

Fig. 8. (a-d) In-situ IR surface trend spectra. (e-g) In-situ IR spectra of 1-butylene epoxidation over Ru-COF-TPD with different reaction time.

Fig. 9. (a) ESR spectra under different conditions by using DMPO as the free-radical spin trapping agent. ESR spectra under different conditions with different times: standard condition (b), no 1-butylene (c), no catalyst (d) and no adamantane (e). (f) High-resolution ESR simulation analysis of the peroxy radical.

Scheme 1. The feasible epoxidation mechanism of 1-butylene over Ru-COF-TPD with air as oxidant.

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构建钌卟啉共价有机框架催化金刚烷C-H键空气氧化接力实现烯烃环氧化

Constructing Ru-porphyrin COF for catalyzing air oxidation of adamantane C-H bonds to relay olefin epoxidation

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