Copper (Cu) oxides with various oxidation states are known to be extremely active for oxygen reduction/evolution reactions (ORR/OER). Here, Cu₂O-based composites by combining with Co₃O₄ are designed as non-noble catalysts for ORR/OER by using density-functional-theory (DFT) calculations. Cu-sites in Cu₂O-Co₃O₄ (1 1 1) structure are the main active-sites for ORR/OER, which can obtain desirable interfacial charge transfer through favorable energy band arrangements. As inspired by calculation results, Cu₂O nanoparticles (20–30 nm) coated on hollow zeolitic imidazolate framework-67 (ZIF-67)-derived nitrogen (N)-doped carbon-cube (HZCNC) with skeleton Co₃O₄ are prepared as a hollowly-wrapped structure (Cu₂O/HZCNC) for boosting ORR/OER, which makes it have the fast electron/mass transfer characteristics. Catalyst marked as Cu₂O/HZCNC-0.425 (mass ratio of copper chloride to HZCNC is 0.425) exhibits better ORR activity (E_1/2 of 0.90 V) and methanol tolerance than Pt/C, a lower overpotential (350 mV) than RuO₂ for OER, and a stable cell voltage gap (0.941 V, average) in a primary zinc-air battery even after 200 h. As indicated by density functional theory results, Cu₂O can energetically supply the electrons to the closely-contacted HZCNC (Co₃O₄) to enhance ORR/OER activities and stabilities. It highlights the excellent functions of Cu-oxides in oxygen electrocatalysis, and provides new insights for development of highly-efficient electrocatalysts with hollow structure.

已知具有各种氧化态的铜 (Cu) 氧化物对氧还原/析出反应 (ORR/OER) 非常活跃。在这里，通过使用密度泛函理论 (DFT) 计算，将与 Co ₃ O ₄结合的Cu ₂ O 基复合材料设计为用于 ORR/OER 的非贵金属催化剂。Cu ₂ O-Co ₃ O ₄ (1 1 1)结构中的Cu位点是ORR/OER的主要活性位点，可以通过有利的能带排列获得理想的界面电荷转移。受计算结果启发，Cu _{2  将O纳米粒子（20-30 nm）包覆在中空沸石咪唑酯骨架67（ZIF-67）衍生的具有Co 3} O ₄骨架的氮（N）掺杂碳立方体（HZCNC）上，制备成中空包裹结构（ Cu ₂ O/HZCNC) 用于提高ORR/OER，使其具有快速电子/传质特性。标记为 Cu ₂ O/HZCNC-0.425（氯化铜与 HZCNC 的质量比为 0.425）的催化剂表现出比 Pt/C 更好的 ORR 活性（E _1/2 of 0.90 V）和甲醇耐受性，比 Pt/C 更低的过电势（350 mV）用于 OER 的RuO ₂，​​即使在 200 小时后，一次锌空气电池中的稳定电池电压间隙（平均为 0.941 V）。如密度泛函理论结果所示，Cu ₂O可以为紧密接触的HZCNC（Co ₃ O ₄）提供电子以增强ORR/OER活性和稳定性。突出了铜氧化物在氧电催化中的优异功能，为开发高效空心结构电催化剂提供了新的思路。