A Class of PAH Polymerization Reactions Featured by Radical Growth from Reactants to Products.

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
Bingjie Chen, Peng Liu, Hong Wang, Vasilios Samaras, Huajie Lyu, Jiwen Guan, Linghong Chen, Chenghang Zheng, Zhandong Wang, Xingcai Lu, Xiang Gao, Heinz Pitsch, William L Roberts
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Abstract

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic molecules and fundamental building blocks of carbonaceous nanoparticles in material synthesis, flames, and extraterrestrial environments, yet their formation reactions remain elusive. Here, we propose a unique PAH growth reaction of ethynyl-substituted aryl radical addition to ethynyl-substituted peri-condensed aromatic hydrocarbons (AEPAH mechanism) by exploring the exemplary reactions of the 2-ethynyl-phenyl radical with phenylacetylene, 1-ethynylnaphthalene, and 9-ethynylphenanthrene. Instead of stable molecules and small radicals as reaction intermediates in conventional mechanisms, the AEPAH mechanism synthesizes PAH radicals, which further grow to large PAHs and incipient carbonaceous nanoparticles. High-level quantum chemistry calculation, particle composition analysis by matrix-assisted laser desorption/ionization mass spectrometry, and product analysis of the elementary reaction by gas chromatography-mass spectrometry and synchrotron radiation photoionization mass spectrometry evidenced the AEPAH mechanism as a direct and efficient PAH growth reaction class under the temperature range of 800-1500 K. The unraveled AEPAH mechanism may help understand the evolution of organic and prebiotic molecules on Earth and in deep space.

一类以自由基从反应物到产物生长为特征的多环芳烃聚合反应。
多环芳烃(PAHs)是一种普遍存在的有机分子,是碳质纳米颗粒在材料合成、火焰和地外环境中的基本组成部分,但它们的形成反应仍然难以捉摸。本研究通过探索2-乙基苯基自由基与苯乙炔、1-乙基萘和9-乙基菲的典型反应,提出了一种独特的乙基取代芳基自由基加成乙基取代近缩合芳烃的多环芳烃生长反应(AEPAH机制)。AEPAH机制不以稳定分子和小自由基作为反应中间体,而是合成多环芳烃自由基,这些自由基进一步生长为大的多环芳烃和早期的碳质纳米颗粒。高阶量子化学计算、基质辅助激光解吸/电离质谱法粒子组成分析以及气相色谱-质谱法和同步辐射光电离质谱法对元素反应产物的分析,证明了在800-1500 K温度范围内,AEPAH是一种直接、高效的PAH生长反应类。解开AEPAH机制可能有助于了解地球和外太空中有机和益生元分子的进化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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