基于炔丙基与丁二炔生成第一个碳环的反应机理研究  

Study of the reaction mechanism based on the formation of the first carbocyclic ring from propargyl and diacetylene

作　　者：张韦[1] 宁硕 毛仕迪 杨喜历 陈朝辉[1] 孟丽苹 ZHANG Wei;NING Shuo;MAO Shi-di;YANG Xi-li;CHEN Zhao-hui;MENG Li-ping(Yunnan Province Key Laboratory of Engines,Kunming University of Science and Technology,Kunming 650500,China)

机构地区：[1]昆明理工大学、云南省内燃机重点实验室,云南昆明650500

出　　处：《燃料化学学报（中英文）》2023年第4期492-501,共10页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(52166007)资助。

摘　　要：第一碳环的形成是多环芳烃(PAHs)生成的关键速率控制步,探明第一碳环的生成机理对抑制PAHs生成至关重要。为探究第一碳环的生长过程,本研究利用平均局部离子化能(ALIE)和静电势(ESP)预测反应发生的位点,基于密度泛函(DFT)方法和过渡态理论(TST),计算炔丙基(C_(3)H_(3))+丁二炔(C_(4)H_(2))生成第一碳环的反应路径与化学动力学参数。结果表明,C_(3)H_(3)与C_(4)H_(2)加成反应形成五、六和七元环分子,其中,五元环形成速率最快,六元环最慢。在第一碳环的生成过程中,H转移和闭环反应所需的活化能较大、反应速率缓慢,其决定了第一碳环的生长速率。各碳环上的H转移反应速率取决于碳环上的C原子数量,其中,五元环最快,六元环最慢。本研究完善了碳氢燃料燃烧过程中第一碳环生成的反应动力学和热力学数据,可为PAHs的生成及预测提供有力的理论依据。The formation of the first carbon ring is a crucial rate-controlling step in developing polycyclic aromatic hydrocarbons(PAHs).It is vital to investigate the mechanism of the creation of the first carbon ring to inhibit the formation of PAHs.To explore the growth process of the first carbocyclic ring,this work used the average localized ionization energy(ALIE)and electrostatic potential(ESP)to predict the reaction sites.Moreover,the reaction paths and chemical kinetic parameters for the generation of the first carbocyclic ring from propargyl(C_(3)H_(3))+diacetylene(C_(4)H_(2))are calculated based on the density functional theory(DFT)method and transition state theory(TST).The results showed that the addition reaction of C_(3)H_(3)+C_(4)H_(2)can form five-,six-and seven-membered ring molecules,in which the five-membered ring formation is fastest and the six-membered ring formation is slowest.During the formation of the first carbon ring,the activation energy required for the H transfer and cyclization reactions is large,and the reaction rate is slow,which determines the formation rate of the first carbon ring.The rate of H-transfer reaction on each carbon ring depends on the number of C atoms of the carbon ring,with the five-membered ring being the fastest and the six-membered ring the slowest.This paper improves the reaction kinetics and thermodynamic data of the first carbon ring formation during the combustion of hydrocarbon fuels,which offers a powerful theoretical basis for predicting the generation of PAHs.

关 键 词：第一碳环 炔丙基 丁二炔 密度泛函理论 过渡态理论 反应路径 

分 类 号：TQ517.1[化学工程]