B, N Codoped and Defect‐Rich Nanocarbon Material as a Metal‐Free Bifunctional Electrocatalyst for Oxygen Reduction and Evolution Reactions

The development of highly active, inexpensive, and stable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts to replace noble metal Pt and RuO2 catalysts remains a considerable challenge for highly demanded reversible fuel cells and metal–air batteries. Here, a simple approach for the facile construction of a defective nanocarbon material is reported with B and N dopants (B,N‐carbon) as a superior bifunctional metal‐free catalyst for both ORR and OER. The catalyst is prepared by pyrolyzing the composites of ethyl cellulose and high‐boiling point 4‐(1‐naphthyl)benzeneboronic acid in NH3 atmosphere with an inexpensive Zn‐based template. The obtained porous B,N‐carbon with rich carbon defects exhibits excellent ORR and OER performances, including high activity and stability. In alkaline medium, B,N‐carbon material shows high ORR activity with an onset potential (Eonset) reaching 0.98 V versus reversible hydrogen electrode (RHE), very close to that of Pt/C, a high electron transfer number and excellent stability. This catalyst also presents the admirable ORR activity in acidic medium with a high Eonset of 0.81 V versus RHE and a four‐electron process. The OER activity of B,N‐carbon is superior to that of the precious metal RuO2 and Pt/C catalysts. A Zn–air battery using B,N‐carbon as the air cathode exhibits a low voltage gap between charge and discharge and long‐term stability. The excellent electrocatalytic performance of this porous nanocarbon material is attributed to the combined positive effects of the abundant carbon defects and the heteroatom codopants. A defective nanocarbon with B, N codopants is constructed using the precursors for heteroatom doping and creating carbon defects simultaneously. This results in multiple types of pores, abundant carbon defects, and fine graphitization. As an electrocatalyst, this unique carbon material performs a superior bifunctional electrocatalytic performance for both oxygen reduction reaction and oxygen evolution reaction.