并四苯(A4)氢提取及表面生长动力学特性研究.docxVIP

国家自然科学基金支助: （基金51506128 中国工程热物理学会 燃烧学 学术会议论文 编号：184293 并四苯(A4)氢提取及表面生长动力学特性研究 陈萍，卢坤，陈金超，顾明言*，林郁郁 安徽工业大学能源与环境学院，安徽马鞍山 243002 Tel Email： gumy@ahut.edu.cn 摘要：基于量子化学密度泛函理论和过渡态理论研究了并四苯(A4)氢提取及表面生长动力学特性。分析了A4氢提取及表面生长的路径、过程中能量变化以及动力学分析。研究结果表明，反应的第一步为H自由基在A4表面的化学吸附(△Eads=-193.76kJ/mol)。A4生长的过程分为两个阶段：氢提取及新活性位点的形成；C2H2在新活性位点的加成。动力学分析表明，氢提取过程表现为较强的温度依赖性。在温度大于1200K时，乙炔加成为五环过程成为A4长大过程的决速步。A5形成后可继续发生氢提取，形成的新活性位点可继续为乙炔加成所用，如此反复过程形成更大的PAHs。 关键词：A4，量子化学，氢提取，乙炔加成，动力学分析 The study on the kinetic characteristics of hydrogen extraction and surface growth of four benzene (A4) Abstract: Based on the density functional theory of quantum chemistry and transition state theory, this paper studies the kinetic characteristics of hydrogen extraction and surface growth of four benzene (A4). Meanwhile, hydrogen extraction and the surface growth path of A4, the energy changes and kinetic analysis were conducted. Research results show that the first step in the process of A4 growth is the chemical adsorption of H radicals (△Eads?=-193.76kJ/mol). The process of A4 growth is divided into two phases: Hydrogen extraction and formation of new active sites; Addition of C2H2 at new active sites. Kinetic analysis showed that the hydrogen extraction process has a strong dependence on the temperature. When the temperature is higher than 1200K, acetylene addition is the?rate-limiting step for the A4 growth process. Hydrogen extraction can continue after the formation of A5, and the new active sites formed can continue to be used for the addition of acetylene, so that repeated processes form larger PAHs. Keywords:A4; quantum chemistry; hydrogen extraction; acetylene addition; kinetic analysis 1 引言 碳烟（soot）是大气主要污染物之一，对环境和人体健康造成严重的危害[1-2]。对于碳氢燃烧，其碳烟生成过程十分复杂，许多现象尚未得到很好的解释。目前一般认为碳烟生成包括气相小分子形成碳烟前驱物多环芳烃（PAH），经成核、团聚、表面生长和氧化、凝并等过程[3-6]，如HACA机理。在该机理中， H原子或者OH自由基