The manipulation of rectifying contact of Co and nitrogen‐doped carbon hierarchical superstructures toward high‐performance oxygen reduction reaction

Abstract Rational design and construction of oxygen reduction reaction (ORR) electrocatalysts with high activity, good stability, and low price are essential for the practical applications of renewable energy conversion devices, such as metal‐air batteries. Electronic modification through constructing metal/semiconductor Schottky heterointerface represents a powerful strategy to enhance the electrochemical performance. Herein, we demonstrate a concept of Schottky electrocatalyst composed of uniform Co nanoparticles in situ anchored on the carbon nanotubes aligned on the carbon nanosheets (denoted as Co@N‐CNTs/NSs hereafter) toward ORR. Both experimental findings and theoretical simulation testify that the rectifying contact could impel the voluntary electron flow from Co to N‐CNTs/NSs and create an internal electric field, thereby boosting the electron transfer rate and improving the intrinsic activity. As a consequence, the Co@N‐CNTs/NSs deliver outstanding ORR activity, impressive long‐term durability, excellent methanol tolerance, and good performance as the air‐cathode in the Zn‐air batteries. The design concept of Schottky contact may provide the innovational inspirations for the synthesis of advanced catalysts in sustainable energy conversion fields.