Regulating the Electronic Structure of Cu–Nx Active Sites for Efficient and Durable Oxygen Reduction Catalysis to Improve Microbial Fuel Cell Performance

The efficient and durable oxygen reduction reaction (ORR) catalyst is of great significance to boost power generation and pollutant degradation in microbial fuel cells (MFCs). Although transition metal–nitrogen-codoped carbon materials are an important class of ORR catalysts, copper–nitrogen-codoped carbon is not considered a suitable MFC cathode catalyst due to the insufficient performance and especially instability. Herein, we report a three-dimensional (3D) hierarchical porous copper, nitrogen, and boron codoped carbon (3DHP Cu–N/B–C) catalyst synthesized by the dual template method. The introduced B atom as an electron donor increases the electron density around the Cu–Nx active site, which significantly promotes the efficiency of the ORR process and stabilizes the active site by preventing demetallization. Thus, the 3DHP Cu–N/B–C catalyst exhibited excellent ORR performance with the half-wave potential of 0.83 V (vs reversible hydrogen electrode (RHE)) in a 0.1 M KOH electrolyte and 0.68 V (vs RHE) in a 50 mM PBS electrolyte. Meanwhile, 3DHP Cu–N/B–C had satisfactory stability with 94.16% current retention after 24 h of chronoamperometry test, which is better than that of 20% Pt/C. The MFCs using 3DHP Cu–N/B–C not only showed a maximum power density of up to 760.14 ± 19.03 mW m–2 but also operating durability of more than 50 days. Moreover, the 16S rDNA sequencing results presented that the 3DHP Cu–N/B–C catalyst had a positive effect on the microbial community of the MFC with more anaerobic electroactive bacteria in the anode biofilm and fewer aerobic bacteria in the cathode biofilm. This study provides a new approach for the development of Cu-based ORR electrocatalysts as well as guidance for the rational design of high-performance MFCs.