Development of the C/F/S/O/H ReaxFF force field for the pyrolysis of PFHxS

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-07-22 DOI:10.1016/j.comptc.2025.115388

Hao-Long Su , Fang-Chao Hou , Xiao-Hong Wu , Ze-Chun Lin , Zheng Mei , Chong-Chong She , Li-Xiao-Song Du , Jing Sun , Liang Song

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Abstract

The pyrolysis mechanism of perfluorohexane sulfonic acid (PFHxS) is crucial for the harmless treatment of PFHxS. Herein, a ReaxFF reactive force field for PFHxS was developed, and ReaxFF molecular dynamics simulations were applied to study the pyrolysis behavior of PFHxS in the temperature range of 1500–3500 K. The homolytic cleavage of CC bonds adjacent to the head group and the breakage of CS bonds are predominant, accounting for 36 % and 27 % of the reactions, respectively. The final products of the pyrolysis of the tail group (-C₆F₁₃) are CF₂ and CF₃. As the temperature rises, the rate of defluorination increases, leading to higher yield of HF and CF₄. Higher temperatures promote the formation of CF₂O and CFO. CF₂ reacts with other intermediates in the free radical pool to form species such as CF₂O and CFO. Initially, HSO₃ and SO₂ are the main carriers of sulfur, and SO₃ contributes less.

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PFHxS热解C/F/S/O/H ReaxFF力场的建立

全氟己烷磺酸（PFHxS）的热解机理对PFHxS的无害化处理至关重要。为此，建立了PFHxS的ReaxFF反应力场，并应用ReaxFF分子动力学模拟研究了PFHxS在1500-3500 K温度范围内的热解行为。头基附近的CC键均裂和CS键断裂是主要的，分别占反应的36%和27%。尾基（-C6F13）热解的最终产物为CF2和CF3。随着温度的升高，脱氟速率加快，HF和CF4的收率提高。较高的温度促进了CF2O和CFO的形成。CF2与自由基池中的其他中间体反应生成CF2O和CFO等物质。初始阶段，HSO3和SO2是硫的主要载体，SO3的贡献较小。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.