A novel electrochemical oxidation-methanogenesis system for simultaneously degrading antibiotics and reducing CO2 to CH4 with low energy costs

Abstract

A novel electrochemical oxidation-methanogenesis (EO-M) system was proposed for the first time to simultaneously achieve antibiotic degradation and a bioelectrochemical conversion of CO₂ to CH₄ with low energy costs. A dual-chamber system was installed with an antimony-doped tin oxide anode (Ti/SnO₂-Sb) for the electrocatalytic generation of hydroxyl radicals to degrade ciprofloxacin (CIP), and a CO₂-reducing methanogenic biocathode was enriched based on a three-dimensional (3D) graphitized granular activated carbon (GGAC) for microbial electromethanogenesis. The anode achieved removal efficiencies as high as 99.99% and 90.53% for CIP (14 mL, 50 mg L^-1) and the chemical oxygen demand (COD, 89 mg L^-1), respectively. The biocathode was rapidly enriched within 15 days and exhibited a methane production rate that stabilized at 15.12 ± 1.82 m³ m^-3 d^-1; additionally, the cathodic coulombic efficiency reached 71.76 ± 17.24%. The energy consumption of CIP degradation was reduced by 3.03 Wh L^-1 compared to that of a single electrochemical oxidation system due to the lower cathodic overpotential of CO₂ bioelectrochemical reduction in the EO-M system. A detailed analysis of the biofilm evolution in the 3D biocathode during the start-up process demonstrated that the enhanced absorption of extracellular polymeric substances by the GGAC cathode accelerated the enrichment of methanogens and induced the formation of methanogens with a large number of flagella. An analysis of the microbial community showed that a high relative abundance of Methanobacterium movens could promote a flagella-mediated direct electron transfer of the biocathode, eventually reducing the cathodic overpotential and energy costs of the EO-M system.

Keywords: Antibiotics; Biocathode; CO(2) reduction; Electrochemical degradation; Energy costs.