Designing non-precious electrocatalysts to synergistically achieve a facilitated mass/electron transfer and exposure of abundant active sites is highly desired but remains a significant challenge. Herein, a composite electrocatalyst consisting of highly dispersed Co/CoP heterojunction embedded within a hierarchically ordered macroporous-mesoporous-microporous carbon matrix (Co/CoP@HOMC) is rationally designed through the pyrolysis of polystyrene sphere-templated zeolite imidazolate framework-67 (ZIF-67) assemblies. The combined experimental and theoretical calculations reveal that Co/CoP interfaces not only provide richly exposed active sites but also optimize hydrogen/water absorption free energy via electronic coupling, while the interconnected macroporous structure enables a superior mass transfer to all accessible active sites. As a result, the as-developed Co/CoP@HOMC composites exhibit outstanding catalytic activity with overpotentials of only 120 and 260 mV at 10 mA cm⁻² for the hydrogen evolution reaction and oxygen evolution reaction in 1.0 m KOH, respectively. Moreover, an alkaline electrolyzer constructed by Co/CoP@HOMC requires an ultralow cell voltage of 1.54 V to achieve 10 mA cm⁻², outperforming that of the Pt@C||IrO₂@C couple (1.64 V).

中文翻译：

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分层有序多孔碳上的 Co/CoP 异质结作为一种高效的析氢和析氧电催化剂

设计非贵重的电催化剂以协同实现促进质量/电子转移和丰富活性位点的暴露是非常需要的，但仍然是一个重大挑战。在此，通过聚苯乙烯球模板沸石咪唑酯骨架-67（ZIF -67) 组件。结合实验和理论计算表明，Co/CoP 界面不仅提供了丰富的暴露活性位点，而且还通过电子耦合优化了氢/水吸收自由能，而互连的大孔结构能够实现向所有可接近的活性位点的卓越传质。其结果，^{-2 分别}用于 1.0 m KOH 中的析氢反应和析氧反应。此外，由 Co/CoP@HOMC 构建的碱性电解槽需要 1.54 V 的超低电池电压才能实现 10 mA cm ^-2，性能优于 Pt@C||IrO ₂ @C 对（1.64 V）。