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The development and synthesis of cathode electrocatalysts with high activity and durable stability for metal-air batteries is an important challenge in the area of electrocatalysis. Herein, we introduce a novel in-situ nitriding and phosphating strategy for producing W3N4 and WP from phosphotungstic acid (HPW)-polyaniline-phytic acid-Fe3+ organic–inorganic hybrid material. The final material has a three-dimensional porous framework with W3N4-WP heterostructures embedded in the carbon matrix (W3N4-WP@NPC). As-made materials exhibit exceptional electrocatalytic performance for the oxygen reduction reaction (ORR), with a diffusion-limiting current density of 6.9 mA·cm−2 and a half-wave potential of 0.82 V. As a Zn-air primary cathode, the W3N4-WP@NPC assembled battery can provide a relatively high peak power density (194.2 mW·cm−2). As a Zn-air secondary air-cathode, it has great cycling stability over 500 h. This work provides a simple and efficient method for rationally designing high-performance air cathodes from copolymer-anchored polyoxometalates.
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