The exploration of efficient bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction is pivotal for the development of rechargeable metal—air batteries. Transition metal phosphides are emerging as promising catalyst candidates because of their superb activity and low cost. Herein, a novel metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrid was developed by a carbothermal reduction of cobalt/nickel phosphonate hybrids with different Co/Ni molar ratios. The metal phosphonate derivation method achieved an intimately coupled interaction between metal phosphides and a heteroatom-doped carbon substrate. The resultant Co₂P/Ni₃P@NC-0.2 enables an impressive electrocatalytic oxygen reduction reaction activity, comparable with those of state-of-the-art Pt/C catalysts in terms of onset potential (0.88 V), 4e⁻ selectivity, methanol tolerance, and long-term durability. Moreover, remarkable oxygen evolution reaction activity was also observed in alkaline conditions. The high activity is ascribed to the N-doping, abundant accessible catalytic active sites, and the synergistic effect among the components. This work not only describes a high-efficiency electrocatalyst for both oxygen reduction reaction and oxygen evolution reaction, but also highlights the application of metal phosphonate hybrids in fabricating metal phosphides with tunable structures, which is of great significance in the energy conversion field.

探索用于氧还原反应和析氧反应的高效双功能电催化剂是开发可充电金属空气电池的关键。过渡金属磷化物因其优异的活性和低成本而成为有前景的催化剂候选者。在此，通过碳热还原具有不同 Co/Ni 摩尔比的钴/膦酸镍杂化物，开发了一种新型金属膦酸盐衍生的钴/镍磷化物@N 掺杂碳杂化物。金属膦酸盐衍生方法实现了金属磷化物和杂原子掺杂碳底物之间的紧密耦合相互作用。生成的 Co ₂ P/Ni ₃^{P@NC-0.2 具有令人印象深刻的电催化氧还原反应活性，在起始电位 (0.88 V)、4e -}选择性、甲醇耐受性和长期使用方面与最先进的 Pt/C 催化剂相当耐用性。此外，在碱性条件下也观察到显着的析氧反应活性。高活性归因于 N 掺杂、丰富的可及催化活性位点以及组分之间的协同效应。该工作不仅描述了一种用于氧还原反应和析氧反应的高效电催化剂，而且突出了金属膦酸盐杂化物在制备结构可调的金属磷化物中的应用，在能量转换领域具有重要意义。