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

HL Su and FC Hou and XH Wu and ZC Lin and Z Mei and CC She and LXS Du and J Sun and L Song, COMPUTATIONAL AND THEORETICAL CHEMISTRY, 1252, 115388 (2025).

DOI: 10.1016/j.comptc.2025.115388

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 C-C bonds adjacent to the head group and the breakage of C-S 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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