Adding Fe/dicyandiamide to Co-MOF to greatly improve its ORR/OER bifunctional electrocatalytic activity

Exploring efficient non-precious metal oxygen electrocatalysts for oxygen reduction/evolution reactions (ORR/OER) is of great importance in electrochemical energy conversion devices like metal-air battery. Among them, carbon-based composites derived from metal-organic framework (MOF) exhibit excellent catalytic performance in ORR/OER. In this paper, Co-MOF-67 was firstly prepared, and then mixed with FeCl3·6 H2O and dicyandiamide, followed by a one-step pyrolysis to obtain bamboo-like nitrogen-doped carbon nanotubes. For the samples, Fe and Co nanoparticles were encapsulated in the front end of the carbon nanotubes and the presence of new (n)-diamond carbon was unexpectedly found. The obtained catalyst (FeCo@CNTs-60) has an onset potential of 1.04 V for ORR in alkaline solution, which is close to the commercial Pt/C (40 wt% Pt) of 1.05 V. The onset potential of 1.02 V in quasi-neutral solution exceeds that of Pt/C of 0.99 V. In addition, FeCo@CNTs-60 exhibited a low potential difference of 0.81 V between OER and ORR potentials. The alkaline zinc-air batteries, fabricated with the sample as the electrocatalyst of air electrode, exhibit higher peak power density and stability than Pt/C, while the rechargeable batteries present superior cycling discharge/charge stability at 5 mA·cm−2 and 10 mA·cm−2. In particular, the battery with FeCo@CNTs-60 was conducted for continuous over 1300 h of ultra long-term cycle charging / discharging test at a current density of 5 mA·cm−2, and it reveals excellent stability with high voltage efficiency and also presents superior cycle charging / discharging stability after replacing the Zn plates and electrolyte.