The rapid upsurge of metal–organic frameworks (MOFs) as well as MOF‐derived materials has stimulated profound interest to capitalize on their many potential untapped benefits in electrocatalysis for energy applications. The possibility of tuning the metal–ligand junctions of the MOF architecture opens new avenues to design robust, extended heterostructures for addressing the present‐day energy challenges. Interestingly, despite having detailed crystallographic information, it is often difficult to envisage the interplay of charge transport (electrons and ions), mass transport (pore system) together with the specific effects of the molecularly defined reaction center of MOFs for a given electrocatalytic reaction. Here, guidelines are offered for judiciously engineering the electronic structure of MOFs to deliver targeted electrocatalytic function. Some of the pivotal works on MOF‐based materials for electrocatalysis are discussed, which can be correlated to the biological models in terms of their structural resemblance and an instructive insight is provided about the “new chemistry” that can be explored based on the lessons learned from nature in combination with the theoretical understanding of the energetics of the reactions.

中文翻译：

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用于电催化的MOF：从偶然性到设计策略

金属有机骨架（MOF）以及源自MOF的材料的迅速兴起，激发了人们极大的兴趣，希望利用它们在能源应用中的许多潜在未开发的益处。调整MOF体系结构的金属-配体结的可能性为解决当前的能源挑战提供了设计坚固耐用的异质结构的新途径。有趣的是，尽管具有详细的晶体学信息，但通常很难设想电荷传输（电子和离子），质量传输（孔系统）以及对于给定的电催化反应而言，MOF分子定义的反应中心的特定作用之间的相互作用。在这里，提供了一些指导原则，以明智地设计MOF的电子结构，以提供目标化的电催化功能。