Electro-oxidation of persistent organic contaminants at graphene sponge electrodes using intermittent current

Abstract

Borophene (Bph) and hexagonal boron nitride (hBN)-modified graphene sponge anode coupled to N-doped graphene sponge cathode were applied for electrochemical degradation of persistent organic contaminants using intermittent current. Three different ON-OFF pulse cycles were tested using low-conductivity supporting electrolyte in flow-through mode. Functionalization of the reduced graphene oxide (RGO) with Bph and hBN improved the ability of the double layer to store electrical charge, thus maintaining the generation of H2O2, O3, and ·OH even during the OFF cycles. Both anodes tested showed enhanced contaminant removal during shorter OFF periods (e.g. 52.5 s/52.s and 75 s/30 s ON/OFF), due to the improved retention of anode charge during the shorter OFF stages. Electrochemical removal of the target contaminants required 24 kWh m−3 in continuous current mode for both hBN-RGO and Bph-RGO anodes at 231 A/m−2, which was lowered to 11.7 and 13.5 kWh m−3 respectively, using ON-OFF pulse cycles. Electrochemical degradation pathways were elucidated in both systems using carbamazepine as a representative persistent contaminant. Flow-through reactors with both Bph- and hBN-RGO anodes removed ≥60 % of the target contaminants in a single pass using continuous current, whereas intermittent current led to somewhat decreased removal efficiencies (43–58 %) due to the scavenging effect of the wastewater matrix. Thus, halving the current ON time led to less than 20 % decrease in the removal efficiencies due to the capacitive properties of RGO. Given that switching to intermittent current decreased the energy consumption from 9.3 kWh m−3 to 4.4 kWh m−3 (Bph-RGO anode) and from 6.9 kWh m−3 to 3.6 kWh m−3 (hBN-RGO anode), higher removal of the target contaminants can be achieved by coupling sequential reactors in the intermittent current mode.