Mechanism of Bronsted-acid-promoted self-photosensitized [2+2] cycloaddition for synthesis of high-performance bio-spiral fuel  

作　　者：Ying Chen Yumei Shu Minhua Ai Wenbiao Chen Chengwen Liu Songyi Zhang Shaojie Wang Haopeng Shi Ji-Jun Zou Lun Pan 

机构地区：[1]Key Laboratory for Green Chemical Technology of the Ministry of Education,School of Chemical Engineering and Technology,Tianjin University,Tianjin,300072,China [2]Shandong Key Laboratory for Chemical Engineering and Processing,College of Chemistry&Chemical Engineering,Yantai University,Yantai,264005,China [3]Haihe Laboratory of Sustainable Chemical Transformations,Tianjin,300192,China [4]Zhejiang Institute of Tianjin University,Ningbo,Zhejiang,315201,China [5]Collaborative Innovative Center of Chemical Science and Engineering(Tianjin),Tianjin,300072,China [6]School of Future Technology,Tianjin University,Tianjin,300072,China

出　　处：《Green Energy & Environment》2025年第3期585-597,共13页绿色能源与环境(英文版)

基　　金：the support from National Key R&D Program of China (2021YFC2103704);the National Natural Science Foundation of China (22222808);the Natural Science Foundation of Shandong Province (ZR2023QB152);the Youth Innovation Team Plan of Shandong Province (2022KJ270);the China National Postdoctoral Program for Innovative Talents (BX20240251);the Aeronautical Science Foundation of China (2023Z073048003);the Haihe Laboratory of Sustainable Chemical Transformations。

摘　　要：Photoinduced[2+2]cycloaddition of biomass-derived cycloolefin is a promising approach to synthesize high-energy bio-fuels,however,the conversion efficiency and selectivity are still low.Herein,we provide an acid-promoted photocycloaddition approach to synthesize a new kind of spiral fuel from biomass-derived cyclohexanone (CHOE) and camphene (CPE).Bronsted acids show higher catalytic activity than Lewis acids,and acetic acid (HOAc) possesses the best catalytic performance,with CHOE conversion up to 99.1%.Meanwhile,the HOAc-catalytic effect has been confirmed for[2+2]photocycloaddition of other biomass-derived ketenes and olefins.The catalytic mechanism and dynamics have been investigated,and show that HOAc can bond with C=O groups of CHOE to form H–CHOE complex,which leads to higher light adsorption and longer triplet lifetime.Meanwhile,H–CHOE complex reduces the energy gap between CHOE LUMO and CPE HOMO,shortens the distance of ring-forming atoms,and then decreases the energy barrier (from 103.3 kcal mol^(-1)to 95.8 kcal mol^(-1)) of rate-limiting step.After hydrodeoxygenation,the targeted bio-spiral fuel shows high density of 0.992 g cm^(-3),high neat heat of combustion of 41.89 MJ L^(-1),low kinetic viscosity of 5.69 mm^(2)s^(-1)at 20℃,which is very promising to serve as high-performance aerospace fuel.

关 键 词：BIOFUEL Bronsted acid catalysis Spiral fuel [2+2]photocycloaddition 

分 类 号：O64[理学—物理化学]