Tailoring the Compositions and Nanostructures of Trimetallic Prussian Blue Analog‐Derived Carbides for Water Oxidation

Abstract The electrochemical splitting of water for hydrogen production faces a major challenge due to its anodic oxygen evolution reaction (OER), necessitating research on the rational design and facile synthesis of OER catalysts to enhance catalytic activity and stability. This study proposes a ligand‐induced MOF‐on‐MOF approach to fabricate various trimetallic MnFeCo‐based Prussian blue analog (PBA) nanostructures. The addition of [Fe(CN) 6 ] 3− transforms them from cuboids with protruding corners (MnFeCoPBA‐I) to core–shell configurations (MnFeCoPBA‐II), and finally to hollow structures (MnFeCoPBA‐III). After pyrolysis at 800 °C, they are converted into corresponding PBA‐derived carbon nanomaterials, featuring uniformly dispersed Mn 2 Co 2 C nanoparticles. A comparative analysis demonstrates that the Fe addition enhances catalytic activity, while Mn‐doped materials exhibit excellent stability. Specifically, the optimized MnFeCoNC‐I‐800 demonstrates outstanding OER performance in 1.0 m KOH solution, with an overpotential of 318 mV at 10 mA cm −2 , maintaining stability for up to 150 h. Theoretical calculations elucidate synergistic interactions between Fe dopants and the Mn 2 Co 2 C matrix, reducing barriers for oxygen intermediates and improving intrinsic OER activity. These findings offer valuable insights into the structure‐morphology relationships of MOF precursors, advancing the development of highly active and stable MOF‐derived OER catalysts for practical applications.