Although microbial fuel cells (MFCs) offer a promising avenue for clean power production, they are hindered by inefficient extracellular electron transfer (EET), thereby resulting in a low power output. This study focused on augmenting MFC power by boosting the EET rate using an exogenous electric field (EEF). By leveraging the dual benefits of microbial electrolysis cells (MECs) in organic waste treatment and energy recovery, we developed an MFC–MEC system that utilizes the EEF from MEC as a connecting link. Two configurations, EEF in the same direction (SD-MFC–MEC) and EEF in the reverse direction (RD-MFC–MEC), were used to examine the EET kinetic rate at the MFC anode in the EEF environment using various electrochemical methods for quantitative evaluation. Our findings revealed that EEF significantly enhanced MFC anode biofilm formation and electrochemical activity, leading to a prominent improvement in electrode reaction rates. The EET rate constants in the SD-MFC–MEC and RD-MFC–MEC were more than double those in the control R-MFC, with power density increases of 117.8% and 108.4%, respectively. The formation of electrochemically active sites within the biofilm induced by EEF has emerged as a crucial factor in amplifying the EET rate, and consequently, the MFC power output. Additionally, the variation in EET rate constants between the SD-MFC–MEC and RD-MFC–MEC was minimal, thereby indicating the negligible impact of the EEF orientation on the EET efficiency. This study provides a novel method for quantitatively examining EET rates, opens up new avenues for further facilitating microbe-to-electrode electron transfer, and promotes the application of MFC–MEC systems in energy recovery, CO2 emission reduction, and waste treatment.
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