Formate‐Anion‐Induced Water Network Reshaping Enables Concurrent Hydrogen and Magnesium Hydroxide Production From Seawater

Abstract

ABSTRACT The key challenges in direct seawater electrolysis for hydrogen evolution reaction (HER) are the substantially high energy demands for water dissociation and preventing catalyst surface precipitation. By grafting formate groups onto the NiFe 2 O 4 spinel surface (NiFe 2 O 4 ─HCOO ─ ), the rigid hydrogen‐bond network at the outer Helmholtz plane (OHP) are disrupted, which facilitates direct interaction with free water molecules and enhances water dissociation for HER. Especially, hydrogen‐bond network disruption reduces gas–liquid interfacial tension, enabling self‐cleaning by releasing dense bubbles to remove Ca 2+ /Mg 2+ precipitates, along with enhanced bubble separation. This dual function preserves the active sites of NiFe 2 O 4 ─HCOO ─ for sustained seawater electrolysis. Benefiting from above, the synthesized NiFe 2 O 4 ─HCOO ─ delivers −1.0 A cm −2 at just 435 mV in alkaline seawater while maintaining exceptional stability over 1000 h and can be deployed in anion exchange membrane (AEM) electrolyzers with the technical and economic analysis (TEA) indicating the low cost of hydrogen production. Furthermore, this study confirms the technical feasibility of the simultaneous electrosynthesis of high‐value magnesium hydroxide and hydrogen from natural seawater.