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Ligand-Directed Nitrate Incorporation Into Reconstructed Oxyhydroxides for Durable Seawater Electrolysis
Huangcong Tang1, Jieting Ding1, Zemin Feng1
1Guangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China.
Abstract:
Chloride ions (Cl-)-induced corrosion severely limits the practical implementation of direct seawater electrolysis. Although oxyanion incorporation can mitigate Cl- poisoning, existing approaches offer limited control over oxyanion generation and retention during catalyst reconstruction. Herein, we report a MOF-based ligand-engineering strategy that enables defined oxyanion incorporation into reconstructed metal oxyhydroxides for active and durable seawater electrolysis. Nitro- (NO2) functionalized ligands are incorporated into a NiFe-MOF precursor, where the NO2 group undergo a simple and direct oxidation to nitrate (NO3 -) during electrochemical reconstruction, enabling well-defined NO3 - regulation of the reconstructed γ-NiFeOOH phase. The anchored NO3 - not only forms a robust Cl--repelling interface but also activates lattice oxygen to drive a mechanistic transition from an adsorbate evolution mechanism to a more efficient lattice-oxygen-mediated pathway. The designed catalyst achieves excellent oxygen evolution reaction performance in alkaline seawater, requiring an overpotential of only 230 mV to reach a current density of 500 mA cm-2, outperforming its NO3 --free counterpart. It also exhibits high durability, operating for over 4000 h at 1.5 A cm-2 with an ultralow degradation rate of 1.8 µV h-1. Furthermore, a kilowatt-level alkaline seawater electrolyzer equipped with the designed electrode operates stably for over 1100 h under industrially relevant conditions.
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