Rational design of a hydrophilic nanoarray-structured electro-Fenton membrane for antibiotics removal and fouling mitigation: An intensified catalysis process in an oxygen vacancy‐mediated cathodic microreactor

Electro-Fenton membranes (EFMs) can synchronously realize organic micropollutants destruction and fouling mitigation in a single filtration process with the assistance of hydroxyl radicals (•OH). Herein, a nanoarray-structured EFM (NS-EFM) was designed by assembling Fenton reactive CoFe-LDH nanowires using a low-temperature hydrothermal method. Combined with a defect-engineering strategy, the oxygen vacancies (O_Vac) in the CoFe-LDH nanoarrays were tailored by manipulating the stoichiometry of cations to optimize the Fenton reactivity of NS-EFMs. The optimized NS-EFM demonstrated exceptional sulfamethoxazole (SMX) removal (99.4%) and fast degradation kinetics (0.0846 min⁻¹), but lower energy consumption (0.22 kWh m⁻³ per log removal of SMX). In-depth mechanism analysis revealed that the intrinsic electronic properties of O_Vac endowed NS-EFM with enhanced reactivity and charge transferability at metallic active sites of CoFe-LDH, thereby intensifying •OH generation. Besides, the nanoarray-structured NS-EFM built a confined microreactor space, leading to expedited •OH microflow to SMX. Meanwhile, the hydrophilic nature of CoFe-LDH nanoarrays synergistically contributed to the high flux recovery (95.0%) and minimal irreversible membrane fouling (5.0%), effectively alleviating membrane fouling within pores and on surfaces. This study offers insights into the potential of defect engineering as a foundational strategy in the design of EFMs, significantly advancing the treatment of organic pollutants and control of membrane fouling.