Metal-Center Charge Redistribution in Co−MOF Induced by Room-Temperature Metallic Deposition for Industrial-Current Seawater Splitting

Metal−organic frameworks (MOFs) offer structural tunability for seawater electrolysis, but poor conductivity and limited active sites in chlorine-rich environments hinder their practical use. Here, cobalt−MOF nanosheets are decorated with various metal oxides to induce charge redistribution at Co centers, thereby increasing the cobalt oxidation state and active-site density. Theoretical calculations indicate strong Fe 2 O 3 /Co−MOF interfacial adhesion (bond distance: 1.95 Å) and significantly enhanced OH − adsorption (−6.76 eV). In contrast, Mo oxide (bond distance: 2.26 Å) weakens Cl − binding (−0.53 eV), mitigating chlorine corrosion. Under oxygen evolution reaction conditions, Fe−Mo@Co−MOF undergoes Mo surface reconstruction, forming MoO 4 2− species that selectively repel chloride. At the cathode, Ni−Mn@Co−MOF reduces Ca/Mg hydroxide precipitation via an electric double-layer effect. The Ni−Mn@Co−MOF||Fe−Mo@Co−MOF full cell exhibits impressive performance, requiring only 1.80 and 2.07 V to reach 500 and 1000 mA/cm 2, respectively, outperforming 20 wt % Pt/C||RuO 2 cell (2.07 and 2.35 V). Moreover, Ni−Mn@Co−MOF||Fe−Mo@Co−MOF operates continuously in alkaline seawater at 500 mA/cm 2 for 1500 h without performance decay, demonstrating a viable strategy for durable, high-current-density seawater electrolysis using MOF-based electrocatalysts.