Leveraging Metal Nodes in Metal–Organic Frameworks for Advanced Anodic Hydrazine Oxidation Assisted Seawater Splitting

Metal–organic frameworks (MOFs) show great promise for electrocatalysis owing to their tunable ligand structures. However, the poor stability of MOFs impedes their practical applications. Unlike the general pathway for engineering ligands, we report herein an innovative strategy for leveraging metal nodes to improve both the catalytic activity and the stability. Our electrolysis cell with a NiRh-MOF||NiRh-MOF configuration exhibited 10 mA cm^–2 at an ultralow cell voltage of 0.06 V in alkaline seawater (with 0.3 M N₂H₄), outperforming its counterpart benchmark Pt/C||Pt/C cell (0.12 V). Impressively, the incorporation of Rh into a MOF secured a robust stability of over 60 h even when working in the seawater electrolyte. Experimental results and theoretical calculations revealed that Rh atoms serve as the active sites for hydrogen evolution while Ni nodes are responsible for the hydrazine oxidation during the hydrazine oxidation assisted seawater splitting. This work provides a paradigm for green hydrogen generation from seawater. © 2023 American Chemical Society.