In situ investigation of cathode and local biofilm microenvironments reveals important roles of OH- and oxygen transport in microbial fuel cells.

Mass transport within a cathode, including OH(-) transport and oxygen diffusion, is important for the performance of air-cathode microbial fuel cells (MFCs). However, little is known regarding how mass transport profiles are associated with MFC performance and how they are affected by biofilm that inevitably forms on the cathode surface. In this study, the OH(-) and oxygen profiles of a cathode biofilm were probed in situ in an MFC using microelectrodes. The pH of the catalyst layer interface increased from 7.0 ± 0.1 to 9.4 ± 0.3 in a buffered MFC with a bare cathode, which demonstrates significant accumulation of OH(-) in the cathode region. Furthermore, the pH of the interface increased to 10.0 ± 0.3 in the presence of the local biofilm, which indicates that OH(-) transport was severely blocked. As a result of the significant OH(-) accumulation, the maximum power density of the MFC decreased from 1.8 ± 0.1 W/m(2) to 1.5 ± 0.08 W/m(2). In contrast, oxygen crossover, which was significant under low current flow conditions, was limited by the cathode biofilm. As a result of the blocked oxygen crossover, higher MFC coulombic efficiency (CE) was achieved in the presence of the cathode biofilm. These results indicate that enhanced OH(-) transport and decreased oxygen crossover would be beneficial for high-performance MFC development.