Unlocking lattice oxygen mechanism via Fe-doping-accelerated surface reconstruction in CoNiMn-MOF heterojunction for superior OER performance in alkaline seawater.
Fang Taiping T, Zhang Xiaolin X, Li Hai H, Long Lingyun L et al.
Seawater electrolysis for hydrogen production is challenged by the competing chlorine evolution reaction (ClER) and chloride-induced corrosion at the anode. Herein, we report an Fe-CoNiMn-MOF heterojunction, (FeCoNi)OOH/Fe-CoNiMn-MOF, which undergoes in-situ reconstruction into a MOF/(oxy)hydroxide interface. Unlike conventional binary or ternary Fe-doped systems that merely optimize metal site activity, the quaternary metal centers (Fe, Co, Ni, Mn) in this work exhibit a unique synergistic electronic redistribution where Co becomes electron-enriched as the primary active site while Ni and Mn act as electron donors. This configuration not only lowers the reconstruction energy barrier but also transforms the OER pathway from the AEM to the LOM, reducing the energy barrier to 1.47 eV, as confirmed by pH-dependence, TMA+ probe, and DFT calculations. Moreover, Fe doping weakens Cl- adsorption, effectively suppressing ClER. The catalyst delivers overpotentials of 216 and 264 mV at 10 and 100 mA cm-2, respectively, with a Tafel slope of 32.61 mV dec-1, near-unity Faradaic efficiency, and 100 h stability in alkaline seawater. This work demonstrates the simultaneous triple function of Fe doping in a multimetallic MOF heterojunction promoting reconstruction, switching reaction pathway, and repelling chloride, offering a new paradigm for durable seawater splitting.