The design of efficient electrocatalysts is limited by scaling relationships governing trade-offs between thermodynamic and kinetic performance metrics. This ″iron law″ of electrocatalysis arises from synthetic design strategies, where structural alterations to a catalyst must balance nucleophilic versus electrophilic character. Efforts to circumvent this fundamental impasse have focused on bioinspired applications of extended coordination spheres and charged sites proximal to a catalytic center. Herein, we report evidence for breaking a molecular scaling relationship involving electrocatalysis of the oxygen reduction reaction (ORR) by leveraging ligand design. We achieve this using a binuclear catalyst (a diiron porphyrin), featuring a macrocyclic ligand with extended electronic conjugation. This ligand motif delocalizes electrons across the molecular scaffold, improving the catalyst’s nucleophilic and electrophilic character. As a result, our binuclear catalyst exhibits low overpotential and high catalytic turnover frequency, breaking the traditional trade-off between these two metrics.

中文翻译：

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使用铁-铁熔融卟啉电催化剂打破分子尺度关系进行氧还原

高效电催化剂的设计受到控制热力学和动力学性能指标之间权衡的比例关系的限制。电催化的这一“铁律”源于合成设计策略，其中催化剂的结构改变必须平衡亲核与亲电特性。规避这一基本僵局的努力主要集中在扩展配位球和靠近催化中心的带电位点的生物启发应用上。在此，我们报告了通过利用配体设计打破涉及氧还原反应（ORR）电催化的分子尺度关系的证据。我们使用双核催化剂（二铁卟啉）实现了这一目标，该催化剂具有具有扩展电子共轭的大环配体。该配体基序使电子在分子支架上离域，从而改善催化剂的亲核和亲电特性。因此，我们的双核催化剂表现出低过电势和高催化周转频率，打破了这两个指标之间的传统权衡。