Performance enhancement and mechanism of electroenhanced peroxymonosulfate activation by single-atom Fe catalyst modified electrodes

Abstract

Peroxymonosulfate-based electrochemical advanced oxidation processes (PMS-EAOPs) have great potential for sustainable water purification, so an in-depth understanding of its catalytic mechanism is imperative to facilitate its practical application. Herein, the performance enhancement and mechanism of electroenhanced PMS activation by single-atom Fe catalyst modified carbon felt was investigated. Compared with the anode, the cathode exhibited faster bisphenol A degradation ( k cathode = 0.073 vs. k anode = 0.015 min −1 ), increased PMS consumption (98.8 vs. 10.3%), and an order of magnitude reduction of Fe dissolution (0.068 vs. 0.787 mg L −1 ). Mass transfer is a key factor limiting PMS activation, while the electrostriction of water in the hydrophobic region caused by cathode electric field (CEF) significantly increased mass transfer coefficient ( k m, cathode = 1.49 × 10 −4 vs. k m, anode = 2.68 × 10 −5 m s −1 ). The enhanced activation of PMS is a synergistic result between electroactivation and catalyst-activation, which is controlled by the applied current density. 1 O 2 and direct electron transfer are the main active species and activation pathway, which achieve high degradation efficiency over pH 3 to 10. Density functional theory calculations prove CEF increases the adsorption energy, lengthens the O–O bond in PMS, and promotes charge transfer. A flow-through convection unit achieves sustainable operation with high removal efficiency (99.5% to 97.5%), low electrical energy consumption (0.15 kWh log –1 m –3 ), and low Fe leaching (0.81% of the total single atom Fe). This work reveals the critical role of electric fields in modulating Fenton-like catalytic activity, which may advance the development of advanced oxidation processes and other electrocatalytic applications.