揭示四氢吡喃氧化中的冷火焰化学：SVUV-PEPICO光谱和对氧杂环依赖反应性的计算见解

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Combustion and Flame Pub Date : 2025-09-24 DOI:10.1016/j.combustflame.2025.114502

Jiabiao Zou , Caroline Smith Lewin , Olivier Herbinet , Philippe Arnoux , Gustavo A. Garcia , Laurent Nahon , Luc-Sy Tran , Guillaume Vanhove , Zhandong Wang , Frédérique Battin-Leclerc , Aamir Farooq , Jérémy Bourgalais

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引用次数: 0

摘要

环醚，如四氢吡喃（THP），是从木质纤维素-生物质中提取的有前途的生物燃料，是生物燃料和化石燃料氧化的关键中间体，但它们的低温氧化机制，特别是杂环构象在链分支途径中的作用，仍然知之甚少。在这项研究中，我们采用基于同步加速器的真空紫外光电子光离子重合（SVUV-PEPICO）光谱研究了射流搅拌反应器（JSR）中THP的氧化。这种独特的分子结构灵敏度技术能够区分异构体，特别是酮-氢过氧化物（KHPs）和烯-氢过氧化物（anhp），揭示了环构象如何影响反应性。除了同分异构体鉴定外，我们还检测了anhp衍生的分解产物（例如，二醛和烯醛），将它们的形成与杂环特异性链分支途径联系起来。基于质量选择阈值光电子能谱（TPES）和总离子产率（TIY）测量的过氧化氢形态定量分析为动力学建模提供了实验约束。我们构建了一个更新的THP氧化机制，以准确地再现我们的实验数据和先前的文献结果，解决预测的中间摩尔分数的差异。通过将异构体分辨光谱与动力学建模相结合，这项工作促进了对杂环构象如何控制低温反应性的理解，这是生物燃料燃烧效率和冷火焰化学的关键因素。

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Unraveling cool-flame chemistry in tetrahydropyran oxidation: SVUV-PEPICO spectroscopy and computational insights into oxygenated heterocycle-dependent reactivity

Cyclic ethers, such as tetrahydropyran (THP), are promising biofuels derived from lignocellulosic-biomass and serve as key intermediates in the oxidation of both biofuels and fossil fuels, yet their low-temperatures oxidation mechanism—particularly the role of heterocycle conformation in chain-branching pathways—remains poorly understood. In this study, we employed synchrotron-based vacuum ultraviolet photoelectron photoion coincidence (SVUV-PEPICO) spectroscopy to investigate THP oxidation in a jet-stirred reactor (JSR). The unique sensitivity technique to molecular structure enabled the discrimination of isomers, specifically keto-hydroperoxides (KHPs) and alkenal-hydroperoxides (AnHPs), revealing how ring conformation influences the reactivity. Beyond isomer identification, we detected AnHP-derived decomposition products (e.g., dialdehydes and enals), linking their formation to heterocycle-specific chain-branching pathways. Quantitative analysis of hydroperoxide speciation, based on mass-selected threshold photoelectron spectroscopy (TPES) and total ion yield (TIY) measurements, provided experimental constraints for kinetic modeling. An updated THP oxidation mechanism was constructed to accurately reproduce both our experimental data and prior literature results, resolving discrepancies in predicted intermediate mole fractions. By combining isomer-resolved spectroscopy with kinetic modeling, this work advances the understanding of how heterocycle ring conformation governs low-temperature reactivity, a critical factor in biofuel combustion efficiency and cool-flame chemistry.

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来源期刊

Combustion and Flame 工程技术-工程：化工

CiteScore

9.50

自引率

20.50%

发文量

631

审稿时长

3.8 months

期刊介绍： The mission of the journal is to publish high quality work from experimental, theoretical, and computational investigations on the fundamentals of combustion phenomena and closely allied matters. While submissions in all pertinent areas are welcomed, past and recent focus of the journal has been on: Development and validation of reaction kinetics, reduction of reaction mechanisms and modeling of combustion systems, including: Conventional, alternative and surrogate fuels; Pollutants; Particulate and aerosol formation and abatement; Heterogeneous processes. Experimental, theoretical, and computational studies of laminar and turbulent combustion phenomena, including: Premixed and non-premixed flames; Ignition and extinction phenomena; Flame propagation; Flame structure; Instabilities and swirl; Flame spread; Multi-phase reactants. Advances in diagnostic and computational methods in combustion, including: Measurement and simulation of scalar and vector properties; Novel techniques; State-of-the art applications. Fundamental investigations of combustion technologies and systems, including: Internal combustion engines; Gas turbines; Small- and large-scale stationary combustion and power generation; Catalytic combustion; Combustion synthesis; Combustion under extreme conditions; New concepts.