Proton‐Affinitive Interfaces Enable Pollutant‐Triggered Alkaline Fenton‐like Oxidation

Functional interfacial materials that regulate local proton availability offer a promising route to overcome the pH dependence of peroxide‐based oxidation without altering the bulk solution. Here, we introduce proton‐affinitive interfacial sites as a design principle for adaptive alkaline Fenton‐like oxidation. In this strategy, hydroxyl‐containing phenolic pollutants are not merely passive oxidation targets but act as in situ proton–electron donors. Upon adsorption, phenolic O–H dehydrogenation releases interfacial protons, while proton‐affinitive interfacial sites favor their retention near the catalytic centers, creating a localized proton‐enriched microenvironment that promotes peroxymonosulfate activation and reactive oxygen species generation under bulk alkaline conditions. Using fluorinated Fe‐NC as a representative functional interface, we show that fluorination promotes phenolic dehydrogenation, favors local proton retention, and lowers the energetic requirements for proton release, oxidant activation, and pollutant oxidation. The optimized catalyst achieves > 99% bisphenol A removal at pH 9, markedly outperforming the non‐fluorinated analog, while reducing operational and ecological costs by ∼85% and ∼98%, respectively. The enhancement was also observed in preliminary tests across several hydroxyl‐containing pollutants and fluorinated catalytic platforms, suggesting potential broader applicability of proton‐affinitive interface engineering. This work establishes adaptive functional interfaces for self‐regulated oxidant activation beyond conventional bulk pH control.