IF 2.7 2区 化学 Q3 CHEMISTRY, PHYSICAL
Zhengyan Guo, Hongqing Wu, Ruoyue Tang, Xinrui Ren, Ting Zhang, Mingrui Wang, Guojie Liang, Hengjie Guo, Song Cheng
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引用次数: 0

摘要

充分了解氮氧化物的相互作用化学性质是更顺利地过渡到无碳和无碳燃料(如氨和氢)的先决条件。为此,本研究全面研究了 NO2 从 C3 至 C7 烯烃、二烯烃和三烯烃中抽取 H 原子形成 3 种 HNO2 异构体(即 TRANS_HONO、HNO2 和 CIS_HONO)的过程,包括 8 种碳氢化合物和 24 个反应。通过结合高水平量子化学计算,在 DLPNO-CCSD(T)/cc-pVDZ//M06-2X/6-311++g(d,p)确定了每个反应所涉及的反应物、过渡态 (TS)、配合物和产物的电子结构、单点能量、C-H 键解离能和一维受阻转子势,并由此确定了每个反应的势能面和能垒。随后,基于 TS 理论,使用主方程系统求解程序,考虑非对称隧道修正,计算出所有研究反应在 298 至 2000 K 温度范围内的速率系数。对支化率的综合分析阐明了不同物种、不同 HNO2 异构体和不同抽取位点之间的多样性和相似性。将计算出的速率参数纳入最新的化学模型,可以发现这类反应对模型性能的重大影响,在预测自燃特性时,更新后的模型对所有炔烃、二烯烃和三烯烃的反应性都更强。我们还进一步进行了敏感性和通量分析,通过分析突出了二氧化氮抽取 H 原子的重要性。随着速率参数的更新,燃料消耗中的分支比率明显转向由二氧化氮抽取 H 原子,而不是由ȮH 抽取 H 原子。所获得的结果强调了在利用本研究确定的速率参数开发新的炔烃、二烯和三烯化学模型时充分反映这些动力学的必要性,并呼吁今后努力通过实验研究二氧化氮对炔烃、二烯和三烯的掺混效应。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Key Kinetic Interactions between NOX and Unsaturated Hydrocarbons: H Atom Abstraction from C3-C7 Alkynes, Dienes, and Trienes by NO2.

An adequate understanding of the NOx interacting chemistry is a prerequisite for a smoother transition to carbon-lean and carbon-free fuels such as ammonia and hydrogen. In this regard, this study presents a comprehensive study on the H atom abstraction by NO2 from C3 to C7 alkynes, dienes, and trienes forming 3 HNO2 isomers (i.e., TRANS_HONO, HNO2, and CIS_HONO), encompassing 8 hydrocarbons and 24 reactions. Through a combination of high-level quantum chemistry computation, electronic structures, single-point energies, C-H bond dissociation energies, and 1-D hindered rotor potentials of the reactants, transition state (TS), complexes, and products involved in each reaction are determined at DLPNO-CCSD(T)/cc-pVDZ//M06-2X/6-311++g(d,p), from which potential energy surfaces and energy barriers for each reaction are determined. Following this, the rate coefficients for all studied reactions, over a temperature range from 298 to 2000 K, are computed based on TS theory using the Master Equation System Solver program by considering unsymmetric tunneling corrections. Comprehensive analysis of branching ratios elucidates the diversity and similarities between different species, different HNO2 isomers, and different abstraction sites. Incorporating the calculated rate parameters into a recent chemistry model reveals the significant influences of this type of reaction on model performance, where the updated model is consistently more reactive for all the alkynes, dienes, and trienes studied in predicting autoignition characteristics. Sensitivity and flux analyses are further conducted, through which the importance of H atom abstractions by NO2 is highlighted. With the updated rate parameters, the branching ratios in fuel consumption clearly shift toward H atom abstractions by NO2 while away from H atom abstractions by ȮH. The obtained results emphasize the need for adequately representing these kinetics in new alkyne, diene, and triene chemistry models to be developed by using the rate parameters determined in this study, and call for future efforts to experimentally investigate NO2 blending effects on alkynes, dienes, and trienes.

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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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