燃料化学学报（中英文）2026，Vol.54Issue(4)：96-106,11.DOI:10.1016/S1872-5813(25)60627-X
碳烟前驱体形成中C4H3自由基和乙炔成环机理
Ring formation mechanism of C4H3 radical and acetylene in soot precursor formation
摘要
Abstract
This study systematically investigates the cyclization reaction mechanisms between n-C4H3(1-buten-3-yn-1-yl)and i-C4H3(2-buten-3-yn-1-yl)radicals with acetylene(C2H2)using density functional theory(DFT)and transition state theory(TST).The results reveal that the reaction of n-C4H3 with acetylene proceeds via a radical chain mechanism through an addition-cyclization pathway,yielding phenyl(six-membered ring),fulvenyl(five-membered ring),and four-membered ring intermediates.The product formation rates follow the order:fulvenyl(five-membered ring)＞phenyl(six-membered ring)＞four-membered ring.For i-C4H3,the intermediate structures depend on the carbon position of i-C4H3 where acetylene addition occurs:addition at the C2 position predominantly generates fulvenyl(five-membered ring)as the primary product,whereas addition at the C4 position may lead to phenyl(six-membered ring),fulvenyl(five-membered ring),or four-membered ring intermediates,with the four-membered ring forming most rapidly and the six-membered ring the slowest.Theoretical analyses demonstrate that the selectivity of reaction pathways is primarily governed by structural differences between the isomers.This work provides atomic-scale insights into the cyclization processes between acetylene and C4H3 species,establishing a foundation for refining models of soot precursor formation.关键词
密度泛函理论/过渡态理论/n-C4H3/i-C4H3/乙炔/碳烟前驱体Key words
density functional theory(DFT)/transition state theory(TST)/n-C4H3/i-C4H3/acetylene(C2H2)/soot precursors分类
化学化工引用本文复制引用
杨宏彬,张春昌,夏文文,姚丽..碳烟前驱体形成中C4H3自由基和乙炔成环机理[J].燃料化学学报（中英文）,2026,54(4):96-106,11.基金项目
Supported by the National Key Research and Development Program of China(2022YFB4301400),the Basic Science(Natural Science)Research Project for Higher Education Institutions in Jiangsu Province(24KJD580001). （2022YFB4301400）
