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<p>The UV/sulfite system is currently regarded as the most effective method for degrading and defluorinating per- and poly-fluoroalkyl substances (PFAS), operating via hydrated electrons (e<sub>aq</sub><sup>−</sup>). Previous studies largely concentrate on PFAS molecular structure, overlooking the critical influence of e<sub>aq</sub><sup>−</sup> microstructure. By integrating ab initio molecular dynamics simulations with experiments, we reveal strong correlations between cavity radius and PFAS removal efficiency (R<sup>2</sup> = 0.99) and defluorination reaction (R<sup>2</sup> = 0.89). Expanding the cavity radius enhances spin density at its centre (R<sup>2</sup> = 0.83), increasing the availability of solvated electrons for interaction with PFAS active sites and facilitating diffusion-controlled electron transfer that drives defluorination. Under alkaline conditions, an increase in cavity radius from 1.52 to 1.82 Å enhances spin-density delocalisation within the e<sub>aq</sub><sup>−</sup> cavity, improving degradation efficiency. These findings are supported by experimental results revealing &gt;97% degradation of hexafluoropropylene oxide dimer acid (or its ammonium salt ‘GenX’) at pH 12. Concentrated e<sub>aq</sub><sup>−</sup> enables cooperative multi-site attack on PFAS molecules, accounting for the enhanced defluorination. Overall, this study reveals an atomic-scale correlation between e<sub>aq</sub><sup>−</sup> microstructure and defluorination dynamics. Beyond conventional approaches of modifying PFAS structures, we propose that regulating the solvation structure of e<sub>aq</sub><sup>−</sup> offers a strategy for efficient degradation.</p>

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Solvation structure of hydrated electrons overlooked in the degradation of PFAS by UV/sulfite

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月8日

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  • Xu Liu,
  • Fang Li,
  • Zhicheng Zhang,
  • Tong Guan,
  • Boxue Pang,
  • Delin Qi,
  • Wei Wang,
  • Yang Wu,
  • Shubo Deng

摘要

The UV/sulfite system is currently regarded as the most effective method for degrading and defluorinating per- and poly-fluoroalkyl substances (PFAS), operating via hydrated electrons (eaq−). Previous studies largely concentrate on PFAS molecular structure, overlooking the critical influence of eaq− microstructure. By integrating ab initio molecular dynamics simulations with experiments, we reveal strong correlations between cavity radius and PFAS removal efficiency (R2 = 0.99) and defluorination reaction (R2 = 0.89). Expanding the cavity radius enhances spin density at its centre (R2 = 0.83), increasing the availability of solvated electrons for interaction with PFAS active sites and facilitating diffusion-controlled electron transfer that drives defluorination. Under alkaline conditions, an increase in cavity radius from 1.52 to 1.82 Å enhances spin-density delocalisation within the eaq− cavity, improving degradation efficiency. These findings are supported by experimental results revealing >97% degradation of hexafluoropropylene oxide dimer acid (or its ammonium salt ‘GenX’) at pH 12. Concentrated eaq− enables cooperative multi-site attack on PFAS molecules, accounting for the enhanced defluorination. Overall, this study reveals an atomic-scale correlation between eaq− microstructure and defluorination dynamics. Beyond conventional approaches of modifying PFAS structures, we propose that regulating the solvation structure of eaq− offers a strategy for efficient degradation.