Due to the fact that single chamber microbial fuel cells (SC-MFCs) generally require efficient, stable, and inexpensive cathode catalysts to promote bioelectricity generation performance, metal-free catalysts have attracted increasing attention in SC-MFCs. However, enhancing the electrocatalytic activity of the oxygen reduction reaction (ORR) using metal-free catalysts remains a challenge. This study introduces a metal-free porous catalyst by synchronously doping phosphorus (P) and nitrogen (N) atoms into the biomass-derived carbon skeleton (AB-N-P). The AB-N-P catalyst, displaying half-wave potentials (E1/2) of 0.89 (alkaline) and 0.832 V (neutral), exhibits superior ORR performances compared to most metal-free catalysts and is comparable to some non-precious metal catalysts. Remarkably, it (E1/2: 0.890 to 0.880 V) matches or even exceeds the stability of commercial Pt/C catalyst (E1/2: 0.864 to 0.849 V) after 3000 cyclic voltammetry cycles. Density functional theory (DFT) calculations demonstrate that P and N co-doping synergistically increases the sp3-hybridized carbon content and redistributes charge density, thereby enhancing the catalytic properties and altering the electronic properties of the active sites. In practical applications in SC-MFCs, the AB-N-P electrocatalyst shows exceptional performance, achieving a higher power density (896.4 mW m−2) than that of commercial Pt/C (538.2 mW m−2). This study offers insightful revelations into the modulation of carbon active-sites by doping heteroatoms to carbon skeleton as metal-free catalyst in bioenergy-generation systems.
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