Boron modulating electronic structure of FeN4C to initiate high-efficiency oxygen reduction reaction and high-performance zinc-air battery

The biggest challenge is to develop a low cost and readily available catalyst to replace expensive commercial Pt/C for efficient electrochemical oxygen reduction reaction (ORR). In this research, closo-[B12H12]2− and 1,10-phenanthroline-iron complexes were introduced into the porous metal-organic framework by impregnation method, and further annealing treatment achieved the successful anchoring of single-atom-Fe in B-doped CN Matrix (FeN4CB). The ORR activity of FeN4CB is comparable to the widely used commercial 20 wt% Pt/C. Where the half-wave potential (E1/2) in alkaline medium up to 0.84 V, and even in the face of challenging ORR in acidic medium, the E1/2 of ORR driven by FeN4CB is still as high as 0.81 V. When FeN4CB was used as air cathode, the open circuit voltage of Zn-air battery reaches 1.435 V, and the power density and specific capacity are as high as 177 mW cm−2 and 800 mAh gZn−1 (theoretical value: 820 mAh gZn−1), respectively. The dazzling point of FeN4CB also appears in the high ORR stability, whether in alkaline or acidic media, E1/2 and limiting current density are still close to the initial value after 5000 times cycles. After continuously running the charge-discharge test for 220 h, the charge voltage and discharge voltage of the rechargeable zinc-air battery with FeN4CB as the air cathode maintained the initial state. Density functional theory calculations reveals that introducing B atom to Fe–N4–C can adjust the electronic structure to easily break O = O bond and significantly reduce the energy barrier of the rate-determining step resulting in an improved ORR activity.