Oxygen reduction and evolution reactions constitute the core process of many vital energy storage or conversion techniques. However, the kinetic sluggishness of the oxygen redox reactions and heavy reliance on noble-metal-based electrocatalysts strongly limit the energy efficiency of the related devices. Developing high-performance noble-metal-free bifunctional ORR and OER electrocatalysts has gained worldwide attention, where much important progress has been made during the last decade. This review systematically addresses the design principles to obtain high-performance noble-metal-free bifunctional oxygen electrocatalysts by emphasizing strategies of both intrinsic activity regulation and active site integration. A statistical analysis of the reported bifunctional electrocatalysts is further carried out to reveal the composition-performance relationship and guide further exploration of emerging candidates. Finally, perspectives for developing advanced bifunctional oxygen electrocatalysts and aqueous rechargeable metal-air batteries are proposed.
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