Oxygen reduction/evolution reactions (ORR/OER) play the vital roles in energy-conversion devices, especially for Zn-air batteries (ZABs). However, it is always a challenge to explore a stable bifunctional catalyst. Here, WO₃-anchored ZIF-67-derived CoO@graphitized carbon is wrapped by a thin carbon-layer to obtain CoO@GC/WO₃@CL catalysts. The well-crystallized WO₃ nanospheres are evolved from WO₃ microrods via an intra-particle maturation. For ORR, the peak-potential of CoO@GC/WO₃@CL-800 (800 ℃) (0.81 V vs. RHE) is higher than that of Pt/C (0.79 V). Synergies between WO₃ (oxygen vacancies) and CoO (Co²⁺) improve mass/charge transfer to boost the 4e⁻ pathway. For OER, CoO@GC/WO₃@CL-800 has a lower overpotential (330 mV) than RuO₂ (490 mV) at 10 mA cm⁻². The O₂ evolution rate can reach 0.125 mmol s⁻¹ with a high Faraday efficiency of 96.7 %. Cooperation between CoOOH and oxygen vacancies promotes the H₂O-oxidation to boost the O₂-generation. A relatively low ΔE [E_j=10(OER)-E_1/2(ORR)] of 0.72 V confirms the highly-stable ORR/OER activities of CoO@GC/WO₃@CL-800, which obtains a higher power density (138 mW cm⁻²) than Pt/C + RuO₂ cathode in primary ZABs. This study indicates a new direction to build a multilayer-structured ORR/OER catalyst by using ZIFs as templates.

氧还原/析出反应 (ORR/OER) 在能量转换装置中发挥着至关重要的作用，特别是对于锌空气电池 (ZABs)。然而，探索稳定的双功能催化剂始终是一个挑战。在这里，WO ₃锚定的 ZIF-67 衍生的 CoO@石墨化碳被一层薄碳层包裹以获得 CoO@GC/WO ₃ @CL 催化剂。结晶良好的WO ₃纳米球是由WO ₃微棒通过颗粒内成熟演化而来的。对于 ORR，CoO@GC/WO ₃ @CL-800 (800 ℃) (0.81 V vs. RHE) 的峰电位高于 Pt/C (0.79 V)。WO ₃（氧空位）和CoO（Co ²⁺）之间的协同作用改善了质量/电荷转移以促进4e^-途径。对于 OER，CoO@GC/WO ₃ @CL-800在 10 mA cm ^-2下的过电位 (330 mV) 低于 RuO ₂ (490 mV) 。O ₂释放速率可达0.125 mmol s ^-1，法拉第效率高达96.7 %。CoOOH和氧空位之间的合作促进了H ₂ O的氧化，从而促进了O ₂的生成。0.72 V的相对较低的 ΔE [E _j=10 (OER)-E _{1/2 (ORR)] 证实了 CoO@GC/WO 3} @CL-800高度稳定的 ORR/OER 活性，获得了更高的功率密度 (138 mW cm ^-2 ) 比 Pt/C + RuO ₂初级 ZAB 中的阴极。本研究为以 ZIFs 为模板构建多层结构的 ORR/OER 催化剂指明了新方向。