Electrocatalytic Deep Dehalogenation and Mineralization of Florfenicol: Synergy of Atomic Hydrogen Reduction and Hydroxyl Radical Oxidation over Bifunctional Cathode Catalyst.

Abstract

It is difficult to achieve deep dehalogenation or mineralization for halogenated antibiotics using traditional reduction or oxidation processes, posing the risk of microbial activity inhibition and bacterial resistance. Herein, an efficient electrocatalytic process coupling atomic hydrogen (H*) reduction with hydroxyl radical (•OH) oxidation on a bifunctional cathode catalyst is developed for the deep dehalogenation and mineralization of florfenicol (FLO). Atomically dispersed NiFe bimetallic catalyst on nitrogen-doped carbon as a bifunctional cathode catalyst can simultaneously generate H* and •OH through H2O/H+ reduction and O2 reduction, respectively. The H* performs nucleophilic hydro-dehalogenation, and the •OH performs electrophilic oxidization of the carbon skeleton. The experimental results and theoretical calculations indicate that reductive dehalogenation and oxidative mineralization processes can promote each other mutually, showing an effect of 1 + 1 > 2. 100% removal, 100% dechlorination, 70.8% defluorination, and 65.1% total organic carbon removal for FLO are achieved within 20 min (C0 = 20 mg·L-1, -0.5 V vs SCE, pH 7). The relative abundance of the FLO resistance gene can be significantly reduced in the subsequent biodegradation system. This study demonstrates that the synergy of reduction dehalogenation and oxidation degradation can achieve the deep removal of refractory halogenated organic contaminants.