Nature Communications (Sep 2024)

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

  • Xu Luo,
  • Hongyu Zhao,
  • Xin Tan,
  • Sheng Lin,
  • Kesong Yu,
  • Xueqin Mu,
  • Zhenhua Tao,
  • Pengxia Ji,
  • Shichun Mu

DOI
https://doi.org/10.1038/s41467-024-52682-y
Journal volume & issue
Vol. 15, no. 1
pp. 1 – 11

Abstract

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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.