Exo,exo-Tetracyclo[3.3.1.0^2,4.0^6,8]nonane (exo-TCN), a kind of cyclopropanated fuel with high tension three-membered ring, which has the characteristics of high density, high net heat of combustion and good low-temperature performance, is a potential high-energy-density liquid fuel. To deeply understand its combustion behavior, and lay a foundation for practical application, detailed experimental and theoretical study is necessary. The pyrolysis of exo-TCN was investigated in a jet-stirred reactor at a temperature range of 500–1010 K under atmospheric pressure with a residence time of 2 s. 54 products and intermediates ranging from m/z = 2–204 were identified and quantified by synchrotron vacuum ultraviolet photoionization mass spectrometry and online gas chromatography, the major products were hydrogen, ethylene, benzene, methane, propene, toluene and styrene. The potential energy surfaces of exo-TCN unimolecular decomposition reactions were calculated by quantum chemistry at CBS-QB3 level. It is found that the pyrolysis of exo-TCN experiences three stages. In the first stage, exo-TCN isomerizes into Tricyclo[3.3.1.0^2,4]non-6-ene (TCN-6) by ring expansion of the three-membered ring. In the second stage, TCN-6 generates two main isomers through ring expansion reactions, and decomposes into pyrolysis products. The third stage is the secondary reaction of the intermediate products. Finally, combined with the experimental results and theoretical calculation, the possible reaction mechanism of exo-TCN pyrolysis was proposed, and the related reaction rate constants were calculated.

Exo,exo-四环[3.3.1.0 ^2,4 .0 ^6,8 ]壬烷（exo-TCN），一种高张力三元环的环丙烷燃料，具有高密度、高净热的特点燃烧性能和低温性能良好，是一种有潜力的高能量密度液体燃料。为了深入了解其燃烧行为，为实际应用奠定基础，需要进行详细的实验和理论研究。在喷射搅拌反应器中研究了 exo-TCN 的热解，温度范围为 500-1010 K，大气压力，停留时间为 2 s。采用同步加速器真空紫外光电离质谱和在线气相色谱对m / z =2~204范围内的54种产物和中间体 进行了鉴定和定量，主要产物为氢气、乙烯、苯、甲烷、丙烯、甲苯和苯乙烯。通过量子化学在CBS-QB3水平上计算了exo-TCN单分子分解反应的势能面。研究发现exo-TCN的热解经历了三个阶段。在第一阶段，外型TCN通过三元环的扩环异构化为三环[3.3.1.0 ^{2,4 ]non-6-烯（TCN-6）。}第二阶段，TCN-6通过扩环反应生成两种主要异构体，并分解为热解产物。第三阶段是中间产物的二次反应。最后，结合实验结果和理论计算，提出了exo-TCN热解可能的反应机理，并计算了相关的反应速率常数。