Coordination-Assisted Polymerization of Mesoporous Cobalt Sulfide/Heteroatom (N,S)-Doped Double-Layered Carbon Tubes as an Efficient Bifunctional Oxygen Electrocatalyst

It is a critical challenge to construct efficient precious-metal-free bifunctional oxygen electrocatalysts for fuel cell and metal–air batteries via structural and component engineering. Herein, a one-dimensional mesoporous double-layered tubular structure, where Co9S8 nanocrystals are incorporated into nitrogen, sulfur codoped carbon, is successfully synthesized via the coordinated-assisted polymerization and sacrificial template methods. The double-layered tubular structure provides for a large electrochemically active surface area and promotes fast mass transfer. Cobalt oxides/oxyhydroxides, which are evolved from the sulfides during the catalytic processes, as the main active sites efficiently catalyze the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), in cooperation with the Co–N–C and heteroatom-induced active sites. Hence, it demonstrates excellent bifunctional electrocatalytic activity with the overvoltage between the OER potential at 10 mA cm–2 (E10) and ORR half-wave potential (E1/2) of 0.707 V, which is superior to most of precious-metal-free bifunctional oxygen electrocatalysts reported recently, as well as the state-of-art Pt/C and RuO2 catalysts.