Abstract
High-energy-density fuels are important for volume-limited aerospace vehicles,but the increase in fuel energy density always leads to poor cryogenic performance.Herein,we investigated the transposed Paternò-Büchi reaction of biomass cyclic ketone and cyclic alkene to synthesize a new kind of alkyl-substituted polycyclic hydrocarbon fuel with high energy density and good cryogenic performance.The triplet-energy-quenching results and phosphorescent emission spectra reveal the sensitization mechanism of the reaction,including photosensitizer excitation,triplet-triplet energy transfer,cyclization,and relaxation,and the possible reaction path was revealed by the density functional theory(DFT)calculations.The reaction conditions of photosensitizer type and addition,molar ratio of substrates,reaction temperature,and incident light intensity were opti-mized,with the target product yield achieving 65.5％.Moreover,the reaction dynamics of the re-action rate versus the light intensity are established.After the hydrogenation-deoxygenation reaction,three fuels with a high density of 0.864-0.938 g·ml-1 and a low freezing point of＜-55 ℃ are obtained.This work provides a benign and effective approach to synthesize high-performance fuels.
基金项目
国家重点研发计划(2021YFC2103704)
国家自然科学基金(22222808)
国家自然科学基金(21978200)
Haihe Laboratory of Sustainable Chemical Transformations()
万方数据