Dipole Polarization Engineering Enables Ultrahigh One-Step Hydroxyl Radical Generation for Low-Chemical Water Decontamination

Abstract Hydroxyl radicals (•OH) were key radicals for the removal of organic contaminants from water. Peroxymonosulfate (PMS) activation had attracted broad interest as a route to •OH generation because of its asymmetric O–O bonds and ease of storage and transport. However, conventional Fenton-like activation of PMS typically produced •OH through a two-step pathway involving sulfate radicals (SO4•–), which incurred kinetic losses and limited •OH availability. Here, we reported a one-step •OH generation pathway from PMS enabled by synergistic polarization effects. This electronic regulation increased the O–O bond dipole moment from 0.45 to 3.86 D and produced a steady-state •OH concentration more than 2 orders of magnitude higher than those reported for representative state-of-the-art Fenton-like systems. Mechanistic analyses revealed that the amplified dipole promoted heterolytic O–O bond cleavage, thereby bypassing the SO4•– intermediate and enabling direct •OH generation. This system achieved efficient removal of diverse organic pollutants and increased rate constant of oxidant activation by 175–400% higher than the values reported for representative PMS/PDS-based Fenton-like systems. Life cycle assessment further revealed a lower environmental footprint, attributed to improved chemical utilization rates. This oxidant-centered strategy provided a promising route to utilize dipole polarization for efficient generation of •OH, with the potential to achieve scalable and low-carbon advanced oxidation water remediation.