Hollow nitrogen-doped carbon nanospheres as cathode catalysts to enhance oxygen reduction reaction in microbial fuel cells treating wastewater

Hollow nanospheres play a pivotal role in the electro-catalytic oxygen reduction reaction (ORR), which is a crucial step in microbial fuel cell (MFC) device. Herein, the hollow nitrogen-doped carbon nanospheres (HNCNS) were synthesized with the sacrifice of silica coated carbon nanospheres (CNS@SiO 2 ) as template. HNCNS remarkably enhanced the ORR activity compared to the solid carbon and solid silica spheres. By tuning calcination temperature (800–1100 °C), the surface chemistry properties of HNCNS were effectively regulated. The optimal HNCNS-1000 catalyst which was calcined at 1000 °C exhibited the highest ORR activity in neutral media with the onset potential of 0.255 V and half-wave potential of −0.006 V (vs. Ag/AgCl). Single chamber MFC (SCMFC) assembled with HNCNS-1000 cathode unveiled comparable activity to a conventional Pt/C reference. It showed the highest maximum power density of 1307 ± 26 mW/m 2 , excellent output stability of 5.8% decline within 680 h, chemical oxygen demand (COD) removal of 94.0 ± 0.3% and coulombic efficiency (CE) of 7.9 ± 0.9%. These excellent results were attributed to a cooperative effect of the optimized surface properties (e.g., structural defects, relative content of pyrrolic nitrogen and specific surface area) and the formation of hollow nanosphere structure. Furthermore, the positive linear relationship of the structural defects and pyrrolic nitrogen species with the maximum power generation in SCMFC were clearly elucidated. This study demonstrated that the cost effective HNCNS-1000 was a promising alternative to commercial Pt/C catalyst for practical application in MFCs treating wastewater. Our result revealed the effectiveness of MFC fabricated with HNCNS-1000 cathode catalyst in terms of power generation and wastewater treatment . • Hollow carbon nanospheres synthesized using core-shell silica coated carbon as template. • Hollow morphology surpassing the solid analogue in oxygen reduction reaction. • Microbial fuel cell fabricated with hollow nitrogen-doped carbon as catalyst. • Pyrrolic-nitrogen linearly correlated with power density in microbial fuel cell.