Reaction Pathway‐Steered Dynamic Reconstruction of MOFs in Oxygen Evolution

Abstract The surface reconstruction of Metal‐Organic Framework (MOF) catalysts play a critical role in governing the distribution of active sites, modulating surface energy and controlling the way catalysts engage with reactants, but the origins during the oxygen evolution reaction (OER) remain unclear. It is demonstrated for the first time that the shift of the OER pathways from adsorbate evolution mechanism (AEM) to lattice oxygen mechanism (LOM), induced by specific metal doping (Fe and Co) can be the driving force for surface reconstruction of MOF‐based catalysts, overturning the conventional view of reconstruction. Combined differential electrochemical mass spectrometry (DEMS) and in‐situ Raman spectroscopy (in‐situ Raman) show that Fe or Co doping in ZIF‐8 shifts the OER mechanism from AEM to LOM. This shift prompts the surface reconstruction of ZIF‐8‐Fe and ZIF‐8‐Co, which subsequently generate FeOOH and CoOOH active species. In contrast, the introduction of Ni, Mn, and Cu fails to alter the reaction pathway, and no surface reconstruction is observed. ZIF‐8‐Fe exhibits superior OER performance with exceptionally low overpotential (overpotential as low as 243 mV@20 mA cm ⁻² ) and ultra‐stable performance, outperforming most reported catalysts. This finding fills the key knowledge gap, offering essential insights for understanding MOF reconstruction and designing OER catalysts.