Enhancing oxygen reduction reaction in air-cathode microbial fuel cells treating wastewater with cobalt and nitrogen...

The sluggish oxygen reduction reaction (ORR) on the cathode severely limits the energy conversion efficiency of microbial fuel cells (MFCs). In this study, cobalt and nitrogen co-doped ordered mesoporous carbon (Co_x-N-OMC) was prepared by heat-treating a mixture of cobalt nitrate, melamine and ordered mesoporous carbon (OMC). The addition of cobalt nitrate remarkably improved the ORR reactivity, compared to the nitrogen-doped OMC catalyst. By optimizing the dosage of cobalt nitrate (x = 0.6, 0.8 and 1.0 g), the Co_0.8-N-OMC catalyst displayed excellent ORR catalytic performances in neutral media with the onset potential of 0.79 V (vs. RHE), half-wave potential of 0.59 V and limiting current density of 5.43 mA/cm², which was comparable to the commercial Pt/C catalyst (0.86 V, 0.60 V and 4.76 mA/cm²). The high activity of Co_0.8-N-OMC catalyst was attributed to the high active surface area, higher total nitrogen amount, and higher relative distribution of graphitic nitrogen and pyrrolic nitrogen species. Furthermore, single chamber microbial fuel cell (SCMFC) with Co_0.8-N-OMC cathode exhibited the highest power density of 389 ± 24 mW/m², chemical oxygen demand (COD) removal of 81.1 ± 2.2% and coulombic efficiency (CE) of 17.2 ± 2.5%. On the other hand, in the Co_1.0-N-OMC catalyst, increasing the cobalt dosage from 0.8 to 1.0 g resulted in more oxidized-N species, and the reduced power generation in SCMFC (360 ± 8 mW/m²). The power generated by these catalysts and results of electrochemical evaluation were strongly correlated with the total nitrogen contents on the catalyst surface. This study demonstrated the feasibility of optimizing the dosage of metal to enhance wastewater treatment capacity.