In this contribution, a high-performance bifunctional electrocatalyst composed of Co/Co₂P nanoparticles encapsulated in nitrogen and phosphorus co-doped carbon nanotubes (NPCNTs) has been synthesized via a mechanochemistry-pyrolysis approach. The Schottky effect of metal-semiconductor heterojunction affords a built-in electric field at the interfaces to enhance electron transport, whereas the intertwined structure of one-dimensional (1D) NPCNTs facilitates the mass transfer of reactants and intermediates. Therefore, the as-prepared Co/Co₂P@NPCNTs catalyst exhibits outstanding bifunctional ORR/OER activities, which are superior to those of commercial Pt/C and RuO₂. It can also deliver a high power density and cycling life when used as the cathode for rechargeable ZABs. Theoretical calculation confirms that the spontaneous electron transport from Co to Co₂P enables an up-shifted d-band center of Co/Co₂P heterojunctions, which is beneficial for the intermediate adsorption in electrocatalytic process.

在这一贡献中，通过机械化学-热解方法合成了一种由封装在氮和磷共掺杂碳纳米管 (NPCNT) 中的 Co/Co ₂ P 纳米颗粒组成的高性能双功能电催化剂。金属-半导体异质结的肖特基效应在界面处提供了内置电场以增强电子传输，而一维 (1D) NPCNT 的交织结构促进了反应物和中间体的传质。因此，所制备的 Co/Co ₂ P@NPCNTs 催化剂表现出优异的双功能 ORR/OER 活性，优于商业 Pt/C 和 RuO ₂. 当用作可充电 ZAB 的阴极时，它还可以提供高功率密度和循环寿命。理论计算证实，从 Co 到 Co ₂ P的自发电子传输使Co/Co ₂ P 异质结的d 带中心上移，这有利于电催化过程中的中间吸附。