大连理工大学叶莉莉团队报道了通过吸氢-苯乙炔加成机理形成碳质纳米结构。相关研究成果发表在2021年11月16日出版的《美国化学会杂志》。

大量实验证据表明，多环芳烃是富碳恒星燃烧和星周包壳中含碳纳米结构的组成部分，但其基本形成机制仍不清楚。

通过探索苯乙炔与1-萘基/4-苯基自由基的反应动力学，研究人员为一种新的自洽吸氢苯乙炔加成（HAPaA）机理提供了令人信服的理论和实验证据。HAPaA在低温和高温下都能高效运行，导致高缩合芳烃（PCAH）的形成、膨胀和成核，否则很难通过传统的吸氢-乙炔/乙烯基乙炔加成途径合成。HAPaA机制可推广到其他α-炔基PCAH，从而通过乙炔连接剂为PCAH组合提供了一种替代共价键桥。提出的HAPaA机制可能有助于全面了解碳烟的形成、含碳纳米材料的合成以及星系中碳的起源和演化。

附：英文原文

Title: Inception of Carbonaceous Nanostructures via Hydrogen-Abstraction Phenylacetylene-Addition Mechanism

Author: Hanfeng Jin, Lili Ye, Jiuzhong Yang, Yu Jiang, Long Zhao, Aamir Farooq

Issue&Volume: November 16, 2021

Abstract: Sufficient experimental evidence has suggested that polycyclic aromatic hydrocarbons are the building blocks of carbonaceous nanostructures in combustion and circumstellar envelops of carbon-rich stars, but their fundamental formation mechanisms remain elusive. By exploring the reaction kinetics of phenylacetylene with 1-naphthyl/4-phenanthryl radicals, we provide compelling theoretical and experimental evidence for a novel and self-consistent hydrogen-abstraction phenylacetylene-addition (HAPaA) mechanism. HAPaA operates efficiently at both low and high temperatures, leading to the formation, expansion, and nucleation of peri-condensed aromatic hydrocarbons (PCAHs), which are otherwise difficult to synthesis via traditional hydrogen-abstraction acetylene/vinylacetylene-addition pathways. The HAPaA mechanism can be generalized to other α-alkynyl PCAHs and thus provides an alternative covalent bond bridge for PCAH combination via an acetylene linker. The proposed HAPaA mechanism may contribute toward a comprehensive understanding of soot formation, carbonaceous nanomaterials synthesis, and the origin and evolution of carbon in our galaxy.

DOI: 10.1021/jacs.1c08230

Source: https://pubs.acs.org/doi/10.1021/jacs.1c08230