Developing low-cost and high-efficiency bifunctional catalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is critical to expedite the widespread implementation of rechargeable zinc-air batteries. Herein, a unique Mg-decorated three-dimensionally ordered mesoporous (3DOM) Co₃O₄ electrocatalyst is engineered and evaluated as cathodic material for zinc-air batteries. The modulation of electronic structure and bonding configuration of Co sites through coordination with substituted Mg atoms effectively enhance the interaction with oxygen species and, therefore, the ORR/OER activity. Meanwhile, the substitution of Co²⁺ with Mg²⁺ creates abundant, more catalytically active octahedral sites (Co³⁺) in 3DOM-Mg_xCo_3−xO₄. Moreover, the tailored 3D interpenetrating porous structure endows the electrocatalyst with large diffusion channels for oxygen species and highly accessible active sites. The as-prepared catalyst retains 99% and 98% of its initial ORR and OER current, respectively, after 16 h under chronoamperometric measurement. The zinc-air battery assembled with 3DOM-Mg_xCo_3−xO₄ exhibits a high power density of 253 mW cm⁻² and long-term cyclability over 236 h, outperforming the commercial noble-metal based catalysts in terms of performance and stability. This work offers a straightforward and promising design strategy for development of robust bifunctional electrocatalysts toward practical applications of zinc-air batteries.

开发用于氧还原反应 (ORR) 和析氧反应 (OER) 的低成本和高效双功能催化剂对于加快可充电锌空气电池的广泛应用至关重要。在此，一种独特的 Mg 装饰的三维有序介孔 (3DOM) Co ₃ O ₄电催化剂被设计并评估为锌空气电池的阴极材料。通过与取代的 Mg 原子配位来调节 Co 位点的电子结构和键合配置，有效地增强了与氧物质的相互作用，从而提高了 ORR/OER 活性。同时，用Mg ²⁺取代Co ²⁺产生了丰富的、更具催化活性的八面体位点（Co³⁺ ) 在 3DOM-Mg _x Co _3−x O ₄中。此外，定制的 3D 互穿多孔结构赋予电催化剂大的氧扩散通道和高度可及的活性位点。在计时电流测量下 16 小时后，所制备的催化剂分别保留了 99% 和 98% 的初始 ORR 和 OER 电流。_{用 3DOM-Mg x} Co _3−x O ₄组装的锌空气电池具有253 mW cm ^-2的高功率密度和超过 236 小时的长期循环性能，在性能和稳定性方面优于商业贵金属基催化剂。这项工作为开发用于锌空气电池实际应用的稳健双功能电催化剂提供了一种直接且有前景的设计策略。