Mass Spectrometry Monitoring of Water Dimer Radical Cations for Highly Efficient Dye Degradation

The practical application of advanced oxidation processes is often constrained by their high energy consumption and dependence on chemical additives. To overcome these limitations, this work harnesses the highly reactive species water dimer radical cation (H₂O)₂^+•, as a green oxidant for efficient dye degradation. A corona discharge setup was developed for the controlled, ambient generation of (H₂O)₂^+•, which was directly detected by in situ mass spectrometry. Electron paramagnetic resonance spectroscopy further verified its role as a precursor to hydroxyl radicals, elucidating the underlying radical cascade. Using model dyes (e.g., rhodamine B) as representative pollutants, degradation was quantitatively tracked via their characteristic UV-vis absorption. The (H₂O)₂^+•-based process achieved 99% removal of rhodamine B in 8 min without any external chemical inputs, representing a more than 1100-fold enhancement in processing rate over conventional Fenton oxidation. Scalability was demonstrated through an enlarged array device, which exhibited an energy consumption of 0.75 kJ/mg and a degradation efficiency ∼90 times higher than that of a standard Fenton system. This study establishes a practical route to utilize (H₂O)₂^+• for rapid, chemical-free water treatment, offering a scalable and energy-efficient strategy for green degradation technologies.