Long-term operation of bio-catalyzed cathodes within continuous flow membrane-less microbial fuel cells

Microorganisms were observed to facilitate cathodic oxygen reduction and enhance cathode performance of microbial fuel cells (MFCs). However, the long-term activity and stability of bio-catalyzed cathode needs to be explored. This study evaluated the long-term performance of bio-catalyzed cathode and iron(II) phthalocyanine (FePc)-catalyzed cathode MFCs through effluent water quality, electricity production and electrochemical impedance spectroscopy (EIS) analysis under different scenarios, including conventional wastewater treatment and energy harvesting using a power management system (PMS). During the continuous operation, both systems demonstrated high chemical oxygen demand and ammonium removal, but bio-catalyzed cathode MFCs could achieve significantly better total nitrogen removal than FePc-catalyzed cathode MFCs. The FePc-coated cathode showed constant cathode potential during the entire operation period, but the biocathode showed varied but step-wise increased cathode potential to achieve more than 500 mV versus the standard hydrogen electrode, likely due to the gradual enrichment of biocathode biofilm. EIS analysis revealed that biocathode had higher ohmic resistance than bare carbon felt cathode but the microbial biofilm could largely decrease polarization resistance of cathode material. Microbial community analysis has shown the presence of nitrifying and denitrifying bacteria in the bio-catalyzed cathode biofilm. When connecting PMS, both bio-catalyzed cathode and FePc-catalyzed cathode MFCs successfully charged a capacitor, but the bio-catalyzed cathode MFC voltage significantly dropped to less than 100 mV after charging for 91 h, and gradually recovered when disconnecting PMS. This study has demonstrated the potential application of oxygen reduction bio-catalyzed cathode MFCs for continuous wastewater treatment and energy harvesting for long period of time.