Fe-S dually modulated adsorbate evolution and lattice oxygen compatible mechanism for water oxidation

Abstract

Simultaneously activating metal and lattice oxygen sites to construct a compatible multi-mechanism catalysis is expected for the oxygen evolution reaction (OER) by providing highly available active sites and mediate catalytic activity/stability, but significant challenges remain. Herein, Fe and S dually modulated NiFe oxyhydroxide (R-NiFeOOH@SO₄) is conceived by complete reconstruction of NiMoO₄·xH₂O@Fe,S during OER, and achieves compatible adsorbate evolution mechanism and lattice oxygen oxidation mechanism with simultaneously optimized metal/oxygen sites, as substantiated by in situ spectroscopy/mass spectrometry and chemical probe. Further theoretical analyses reveal that Fe promotes the OER kinetics under adsorbate evolution mechanism, while S excites the lattice oxygen activity under lattice oxygen oxidation mechanism, featuring upshifted O 2p band centers, enlarged d-d Coulomb interaction, weakened metal-oxygen bond and optimized intermediate adsorption free energy. Benefiting from the compatible multi-mechanism, R-NiFeOOH@SO₄ only requires overpotentials of 251 ± 5/291 ± 1 mV to drive current densities of 100/500 mA cm⁻² in alkaline media, with robust stability for over 300 h. This work provides insights in understanding the OER mechanism to better design high-performance OER catalysts.

The oxygen evolution reaction is crucial for energy conversion but faces challenges in catalyst optimization. Here, the authors present a dual-modulated NiFe oxyhydroxide (R-NiFeOOH@SO4) that enhances OER performance through optimized metal and lattice oxygen sites, achieving a compatible multi-mechanism.