It is significant for the rational construction of the high–efficient bifunctional electrocatalysts for in–depth understandings of how to improve the electron transfer and ion/oxygen transport in catalyzing oxygen reduction reaction and oxygen evolution reaction (ORR and OER), but still full of vital challenges. Herein, we synthesize the novel “three–in–one” catalyst that engineers core–shell Mott–Schottky Co₉S₈/Co heterostructure on the defective reduced graphene oxide (Co₉S₈/Co–rGO). The Co₉S₈/Co–rGO catalyst exhibits abundant Mott–Schottky heterogeneous–interfaces, the well–defined core–shell nanostructure as well as the defective carbon architecture, which provide the multiple guarantees for enhancing the electron transfer and ion/oxygen transport, thus boosting the catalytic ORR and OER activities in neutral electrolyte. As expected, the integrated core–shell Mott–Schottky Co₉S₈/Co–rGO catalyst delivers the most robust and efficient rechargeable ZABs performance in neutral solution electrolytes accompanied with a power density of 59.5 mW cm⁻² and superior cycling stability at 5 mA cm⁻² over 200 h. This work not only emphasizes the rational designing of the high–efficient bifunctional oxygen catalysts from the fundamental understanding of accelerating the electron transfer and ion/oxygen transport, but also sheds light on the practical application prospects in more friendly environmentally neutral rechargeable ZABs.

对于深入理解如何在催化氧还原反应和析氧反应（ORR和OER）中提高电子转移和离子/氧传输的高效双功能电催化剂的合理构建具有重要意义，但仍然充满了至关重要的挑战。在此，我们合成了新型“三合一”催化剂，该催化剂在有缺陷的还原氧化石墨烯（Co ₉ S ₈ /Co-rGO）上设计了核壳莫特-肖特基 Co ₉ S ₈ /Co 异质结构。公司₉ S ₈/Co-rGO 催化剂表现出丰富的莫特-肖特基异质界面、明确定义的核-壳纳米结构以及有缺陷的碳结构，为增强电子转移和离子/氧传输提供多重保证，从而促进催化中性电解质中的 ORR 和 OER 活性。正如预期的那样，集成的核-壳 Mott-Schottky Co ₉ S ₈ /Co-rGO 催化剂在中性溶液电解质中提供了最强大和最有效的可充电 ZABs 性能，功率密度为 59.5 mW cm ^-2并在 5 ℃下具有出色的循环稳定性毫安厘米^-2超过 200 小时。这项工作不仅从加速电子转移和离子/氧传输的基本认识上强调了高效双功能氧催化剂的合理设计，而且揭示了更友好的环境中性可充电ZABs的实际应用前景。