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A graphene oxide film was formed on the PEO coatings of magnesium alloys via an electrostatic self-assembly method, which functioned as a physical separation with inhibiting effects between the protected metal and reactants.

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Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in energy conversion and storage devices. Particularly, the bifunctional ORR/OER catalysts are core components in rechargeable metal–air batteries, which have shown great promise in achieving "carbon emissions peak and carbon neutrality" goals. However, the sluggish ORR and OER kinetics at the oxygen cathode significantly hinder the performance of metal–air batteries. Although noble metal-based catalysts have been widely employed in accelerating the kinetics and improving the bifunctionality, their scarcity and high cost have limited their deployment in the market. In this review, we will discuss the ORR and OER mechanisms, propose the principles for bifunctional electrocatalysts design, and present the recent progress of the state-of-the-art bifunctional catalysts, with the focus on non-noble metal-based materials to replace the noble metal catalysts in Zn–air batteries. The perspectives for the future R&D of bifunctional electrocatalysts will be provided toward high-performance Zn–air batteries at the end of this paper.