PFAS-Free Carbon Electrodes for Efficient Micropollutants Removal through Heterogeneous Electro-Fenton: From Material Synthesis to Module Design

Abstract

Emerging micropollutants (MPs) in water bodies such as pharmaceuticals, pesticides, personal care products, and per-and poly-fluoroalkyl substances (PFAS) have posed environmental, ecological, and anthropological issues since MPs are too persistent to be degraded by conventional biological treatment. On the other hand, electrochemical advanced oxidation processes (EAOPs) have proved themselves as efficient and robust techniques to unselectively degrade MPs by forming OH radicals (•OH). Among EAOPs, electro-Fenton, or more specifically heterogeneous electro-Fenton (HEF), suggests an eco-friendly and energy-efficient treatment technique with a wide pH range for removing persistent MPs. In HEF, hydrogen peroxide (H2O2) is electrochemically produced on the cathode surface, which can react with immobilized, adjacent Fe catalysts for •OH generation. Yet, one challenge for HEF is that most of the studies have primarily focused on synthesizing Fe-containing carbons as a catalyst that suffers from several delicate preparation steps, which are time-, chemical-, and energy-consuming and lack reusability over consecutive runs [1].Additionally, these catalysts are usually powders, entailing adding polymeric binders for the immobilization of the catalyst layer on electrodes. The presence of polymeric binders, e.g., polytetrafluoroethylene (PTFE)—as PFAS-containing compounds on the electrode surface—enhances the risk of PFAS contamination during the HEF process due to mechanical wear-off or degradation under the harsh oxidative condition caused by the formation of unselective •OH. Therefore, developing PFAS-free carbon electrodes for the HEF process offering facile fabrication and good reusability with a scaling-up perspective is imperative to enable decentralized solutions for MPs removal, especially highly recalcitrant PFAS. In this work, freestanding carbons made of bio-based precursors, chitosan and sucrose, serve as electrodes for the HEF process. Chitosan is the backbone for the self-standing feature and a nitrogen-rich biopolymer, while sucrose serves as a carbon-rich compound. The mixture of chitosan and sucrose undergoes silica- and ice-templating to make a hierarchically porous carbon [2]. Bio-based carbons illustrated their capability for oxygen reduction reactions, particularly the electro-generation H2O2 [3]. As-synthesized carbons proved to remove carbamazepine and sulfamethoxazole as two persistent MPs at pH 3 and pH 7 [3]. Moreover, a novel flow-through electrolysis module equipped with as-synthesized carbons has been designed and operated to remove 20 mg/L CBZ solution at a current density of 20 mA/cm2. This module design demonstrates the ease of scaleup for a decentralized water/wastewater treatment unit to remove highly recalcitrant MPs.