Intermetallic electrocatalysts have demonstrated significant potential in facilitating the cathodic oxygen reduction reaction (ORR) in fuel cells with enhanced activity and durability. However, it is still an enormous challenge to the facile synthesis of Pt-based intermetallic catalysts with uniform size and high ordering degree. Here, we innovatively fabricate the core-shell structured L1₀-PtFe intermetallics with Pt skins supported on N-doped porous carbon matrix through one-step pyrolysis of PtFe Hofmann-type metal-organic frameworks (denoted as L1₀-PtFe/NC). Under the constraints of the porous structure and cyano-ligand bonding, most Fe atoms are alloyed with Pt to form uniform-ordered PtFe intermetallics, while some Fe atoms are atomically dispersed in the carbon framework to form FeN_x moieties. Notably, a series of intermetallic PtFe catalysts with different ordering degrees are successfully constructed by adjusting the pyrolysis temperature, which verified that the increase of ordering degree is beneficial to promote the electrocatalytic performance. In particular, the ordered L1₀-PtFe/NC-800 exhibits superb ORR activity with both mass and specific activities, which are 2.7-folds higher than those of commercial Pt/C. Moreover, after an accelerated durability test, L1₀-PtFe/NC-800 retains over 90 % mass activity. This work provides a promising approach for the development of efficient Pt-based intermetallic electrocatalysts for fuel cells.

金属间电催化剂在促进燃料电池中的阴极氧还原反应（ORR）方面表现出巨大的潜力，并具有增强的活性和耐用性。然而，如何简便地合成尺寸均匀、高有序度的Pt基金属间催化剂仍然是一个巨大的挑战。在这里，我们通过一步热解PtFe Hofmann型金属有机骨架（表示为L1 0 -PtFe/NC），创新性地制备了核壳结构的L1 0 -PtFe金属间化合物，其负载于氮掺杂多孔碳基体上，并_具有Pt皮层_。。在多孔结构和氰基配体键合的约束下，大多数Fe原子与Pt形成合金，形成均匀有序的PtFe金属间化合物，而一些Fe原子原子分散在碳骨架中形成FeN x_部分。值得注意的是，通过调节热解温度成功构建了一系列不同有序度的金属间化合物PtFe催化剂，验证了有序度的提高有利于提升电催化性能。特别是，有序的L1 ₀ -PtFe/NC-800在质量和比活性方面均表现出优异的ORR活性，比商业Pt/C高2.7倍。此外，经过加速耐久性测试后，L1 ₀ -PtFe/NC-800 保留了超过 90% 的质量活性。这项工作为开发用于燃料电池的高效 Pt 基金属间电催化剂提供了一种有前途的方法。