One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene

doi:10.1016/j.cjche.2025.02.005

Chinese Journal of Chemical Engineering ›› 2025, Vol. 80 ›› Issue (4): 61-69.DOI: 10.1016/j.cjche.2025.02.005

One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene

Zhengyang Liu^1,2,3, Xianlong Liu^1,2,3,4, Shuang Ma^1,2, Xiaolei Guo^1,4, Minhua Ai^1,2,3,4, Chengxiang Shi^1,2,3,4, Zhenfeng Huang^1,2,3,4, Xiangwen Zhang^1,2,3,4, Jijun Zou^1,2,3,4, Lun Pan^1,2,3,4

1 Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300072, China;
2 Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China;
3 Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China;
4 Zhejiang Institute of Tianjin University, Ningbo 315201, China

Received:2024-11-25 Revised:2025-01-16 Accepted:2025-02-06 Online:2025-03-05 Published:2025-04-28
Contact: Minhua Ai,E-mail:aiminhua@tju.edu.cn;Lun Pan,E-mail:panlun76@tju.edu.cn
Supported by:
The authors appreciate the support from the National Natural Science Foundation of China (22408272, 22222808, U24A20547), the Aeronautical Science Foundation of China (2023Z073048003), the China National Postdoctoral Program for Innovative Talents (BX20240251), the China Postdoctoral Science Foundation (2023M742592).

One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene

1 Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, National Industry-Education Platform for Energy Storage, Tianjin University, Tianjin 300072, China;
2 Collaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China;
3 Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China;
4 Zhejiang Institute of Tianjin University, Ningbo 315201, China

通讯作者: Minhua Ai,E-mail:aiminhua@tju.edu.cn;Lun Pan,E-mail:panlun76@tju.edu.cn
基金资助:
The authors appreciate the support from the National Natural Science Foundation of China (22408272, 22222808, U24A20547), the Aeronautical Science Foundation of China (2023Z073048003), the China National Postdoctoral Program for Innovative Talents (BX20240251), the China Postdoctoral Science Foundation (2023M742592).

Abstract

Abstract: Photocycloaddition affords opportunities to engage in advanced fuels with high-strained cyclobutyl-containing structures. Herein, the one-step route for the synthesis of high-energy-density caged fuel, tetracyclo [4.2.1.0^2,5.0^3,7]nonane (TCN) with high-strained four-membered structure, has been developed via photosensitized [2 + 2] cycloaddition of 5-vinyl-2-norbornene (VNB). The reaction conditions are optimized to obtain a high conversion of VNB of 91.9%. The triplet quenching and Stern-Volmer quenching studies indicate that [2 + 2] photocycloaddition follows the triplet-triplet energy transfer process, and a kinetic model is expressed as a reaction rate equation correlated with the incident light flux. Importantly, the obtained TCN shows a high density of 1.003 g·cm^-3 and volumetric net heat of combustion of 42.31 MJ·L^-1, which can serve as an excellent high-energy additive for blending with liquid fuels.

Key words: High-energy-density fuels, [2+2] photocycloaddition, Caged fuel, 5-Vinyl-2-norbornene, Reaction kinetics

摘要： Photocycloaddition affords opportunities to engage in advanced fuels with high-strained cyclobutyl-containing structures. Herein, the one-step route for the synthesis of high-energy-density caged fuel, tetracyclo [4.2.1.0^2,5.0^3,7]nonane (TCN) with high-strained four-membered structure, has been developed via photosensitized [2 + 2] cycloaddition of 5-vinyl-2-norbornene (VNB). The reaction conditions are optimized to obtain a high conversion of VNB of 91.9%. The triplet quenching and Stern-Volmer quenching studies indicate that [2 + 2] photocycloaddition follows the triplet-triplet energy transfer process, and a kinetic model is expressed as a reaction rate equation correlated with the incident light flux. Importantly, the obtained TCN shows a high density of 1.003 g·cm^-3 and volumetric net heat of combustion of 42.31 MJ·L^-1, which can serve as an excellent high-energy additive for blending with liquid fuels.

关键词: High-energy-density fuels, [2+2] photocycloaddition, Caged fuel, 5-Vinyl-2-norbornene, Reaction kinetics

Zhengyang Liu, Xianlong Liu, Shuang Ma, Xiaolei Guo, Minhua Ai, Chengxiang Shi, Zhenfeng Huang, Xiangwen Zhang, Jijun Zou, Lun Pan. One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene[J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 61-69.

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One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene

One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene

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