Gas Phase Oxidation of Resonance-Stabilized Radicals

共振稳定自由基的气相氧化

• 批准号: 1764178
• 负责人: Fabien Goulay
• 金额: $ 46.26万
• 依托单位: West Virginia University Research Corporation
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-08-01 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764178&HistoricalAwards=false
• 关键词: Gas; Phase; Oxidation; Resonance; Stabilized

In this project, funded by the Chemical Structure, Dynamics and Mechanisms B Program of the Chemistry Division and by NSF EPSCoR, Professor Fabien Goulay from the Department of Chemistry at West Virginia University investigates combustion reaction mechanisms. The central focus is on the oxidation of large, stable free radicals which can accumulate in combustion environments. These intermediates are known to play a major role during the formation of pollutants such as polycyclic aromatic hydrocarbons (PAHs) and particulate matter. Gas phase and high temperature reactions are investigated both experimentally and computationally. Experimental studies employ spectroscopic methods to characterize intermediates and their chemical behavior. This research provides critical information on reaction mechanisms that will be used to develop more efficient combustion processes for transportation and power generation. This project also provides training opportunities for undergraduate and graduate students, including first generation college students and students from the Appalachian region, who have been traditionally underrepresented in the sciences. The project investigates the oxidation of resonance-stabilized radicals in the gas phase. These radicals can build up in appreciable concentrations and have recently been hypothesized as precursors to polycyclic aromatic hydrocarbons and soot. The concentration of these radicals in the gas phase is depleted mostly by oxidation reactions with very reactive species, such as the hydroxyl radical. Although theoretical studies have been performed to predict their reactivity toward the hydroxyl radicals, no experimental data are available to validate these predictions. The experimental study of radical - radical reactions is difficult because both radicals need to be formed simultaneously at sufficient concentrations. Professor Goulay and his Group produce both radicals in a flow reactor using laser photolysis, and detect their concentrations using laser spectroscopy and mass spectrometry. Theoretical calculations are used to analyze the reaction mechanisms. This work also contributes to the career development of future scientists by providing training at state-of-the-art experimental resources, including synchrotron facilities.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在这个项目中，由化学部化学结构、动力学和机制B计划和NSF EPSCoR资助，西弗吉尼亚大学化学系的Fabien Goulay教授研究燃烧反应机理。重点放在燃烧环境中积累的大而稳定的自由基的氧化上。众所周知，这些中间体在多环芳烃(PAHs)和颗粒物等污染物的形成过程中发挥着重要作用。对气相反应和高温反应进行了实验和计算研究。实验研究使用光谱方法来表征中间体及其化学行为。这项研究提供了有关反应机理的关键信息，将用于开发更有效的运输和发电燃烧过程。该项目还为本科生和研究生提供培训机会，包括第一代大学生和来自阿巴拉契亚地区的学生，他们传统上在科学界的代表性不足。该项目研究气相中共振稳定的自由基的氧化。这些自由基可以在可察觉的浓度下积累，最近被假设为多环芳烃和烟尘的前体。这些自由基在气相中的浓度主要通过与非常活跃的物种的氧化反应而耗尽，例如羟基自由基。虽然已经进行了理论研究来预测它们对羟基自由基的反应性，但没有实验数据来验证这些预测。自由基-自由基反应的实验研究是困难的，因为这两个自由基需要在足够的浓度下同时形成。Goulay教授和他的团队在流动反应器中使用激光光解产生这两种自由基，并使用激光光谱和质谱分析来检测它们的浓度。用理论计算对反应机理进行了分析。这项工作还通过在最先进的实验资源(包括同步加速器设施)中提供培训，为未来科学家的职业发展做出贡献。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Kinetic study of the CN radical reaction with 2‐methylfuran

CN自由基与2-甲基呋喃反应的动力学研究

• DOI: 10.1002/kin.21403
• 发表时间: 2020
• 期刊: International Journal of Chemical Kinetics
• 影响因子: 1.5
• 作者: Lee, James;Caster, Kacee;Maddaleno, Trey;Donnellan, Zachery;Selby, Talitha M.;Goulay, Fabien
• 通讯作者: Goulay, Fabien

Formation of a Resonance-Stabilized Radical Intermediate by Hydroxyl Radical Addition to Cyclopentadiene

通过羟基自由基加成环戊二烯形成共振稳定的自由基中间体

• DOI: 10.1021/acs.jpca.2c06934
• 发表时间: 2022
• 期刊: The Journal of Physical Chemistry A
• 作者: Caster, Kacee L.;Lee, James;Donnellan, Zachery;Selby, Talitha M.;Osborn, David L.;Goulay, Fabien
• 通讯作者: Goulay, Fabien