Isolated Co Atoms Anchored on Defective Nitrogen‐doped Carbon Graphene as Efficient Oxygen Reduction Reaction Electrocatalysts

Oxygen reduction reaction (ORR) is the heart of many new energy conversions and storage devices, such as metal‐air batteries and fuel cells. However, ORR is currently facing the dilemma of sluggish intrinsic kinetics and the noble electrocatalysts of high price and low reserves. In this work, isolated Co atoms anchored on defective nitrogen‐doped carbon graphene single‐atom catalyst (Co‐SAC/NC) are synthesized via the proposed movable type printing method. The prepared Co‐SAC/NC catalyst demonstrates admirable ORR performance, with a high half‐wave potential of 0.884 V in alkaline electrolytes and outstanding durability. In addition, an assembled zinc–air battery with prepared Co‐SAC/NC as air‐cathode catalyst displays a high‐peak power density of 179 mW cm −2 and a high‐specific capacity (757 mAh g −1 ). Density functional theory calculations confirm that the true active sites of the prepared catalyst are Co‐N 4 moieties, and further reveal a significantly electronic structure evolution of Co sites in the ORR process, in which the project density of states and local magnetic moment of Co atom varies during its whole reaction process. This work not only paves a new avenue for synthesizing SACs as robust electrocatalysts, but also provides an electronic‐level insight into the evolution of the electronic structure of single‐atom catalysts.