Chromium-doped CoFe2O4 for enhanced oxygen evolution via hydroxyl spillover

doi:10.1016/S1872-2067(26)65231-X

Abstract

Abstract:

Developing efficient, low-cost oxygen evolution reaction (OER) electrocatalysts capable of achieving high current densities is critical for advancing practical water electrolysis. Herein, we report a chromium-doped cobalt ferrite (i.e., Cr-CoFe₂O₄/IF) as an efficient OER electrocatalyst in alkaline media. The Cr-CoFe₂O₄/IF electrode exhibits overpotentials of 260 and 300 mV at current densities of 100 and 500 mA cm^-2, respectively, in a three-electrode system and maintains stable operation for more than 400 h, demonstrating its potential for practical application. Structural characterization demonstrates that Cr doping modulates the electronic structure of the Co/Fe active centers. Density functional theory calculations reveal that Cr incorporation introduces preferential hydroxyl adsorption sites, thereby decreasing the Gibbs free energy of the OER process. In particular, ^*OH species adsorbed on Cr sites can migrate to adjacent Co/Fe active sites through a dopant-mediated hydroxyl spillover pathway, which facilitates the formation of O-O coupling to lower the reaction energy barrier. This work establishes dopant-mediated hydroxyl spillover as an effective strategy for designing earth-abundant spinel oxides toward high-rate OER electrocatalysis.

Key words: Water splitting, Electrocatalyst, Non-noble-metal, Cr-doping, Hydroxyl spillover

Muhammad Umair Ul Hassan, Jizhang Wang, Rashid Mehmood, Fazal Shah, Kun Qi, Fuxiang Zhang. Chromium-doped CoFe₂O₄ for enhanced oxygen evolution via hydroxyl spillover[J]. Chinese Journal of Catalysis, 2026, 91: 232-240.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65231-X

https://www.cjcatal.com/EN/Y2026/V91/I12/232

Figures/Tables 4

Fig. 1. Synthesis and structural characterization of Cr-CoFe2O4/IF. (a) Schematic illustration of the synthesis of Cr-CoFe2O4/IF. (b) XRD patterns of Cr-CoFe2O4/IF and control sample CoFe2O4/IF. (c) Raman spectra for Cr-CoFe2O4/IF and control sample. (d,e) HRTEM images of Cr-CoFe2O4/IF. (f) Elemental mapping images of Cr-CoFe2O4/IF.

Fig. 2. Electronic structure characterizations. (a) Co 2p XPS spectra of Cr-CoFe2O4/IF and control sample. (b) Co K-edge XANES spectra of Cr-CoFe2O4/IF and control sample. (c) Corresponding Co EXAFS spectra of both samples. (d) Fe 2p XPS spectra of Cr-CoFe2O4/IF and control sample. Fe K-edge XANES spectra of Cr-CoFe2O4/IF and control sample (e), and corresponding Fe EXAFS spectra (f). (g) Cr 2p XPS spectra of Cr-CoFe2O4/IF. Cr K-edge XANES spectra of Cr-CoFe2O4/IF and Cr2O3 reference sample (h), and corresponding Cr EXAFS spectra (i).

Fig. 3. Electrocatalytic OER performance of Cr-CoFe2O4/IF and control samples. (a) LSV curves of Cr-CoFe2O4/IF and control samples. (b) Overpotential comparison of Cr-CoFe2O4/IF at different current densities. (c) Comparison of overpotential of our catalyst with some state-of-the-art OER catalysts. (d) Tafel plots for Cr-CoFe2O4/IF and control samples. (e) EIS of Cr-CoFe2O4/IF and control samples. (f) ECSA normalized current density of Cr-CoFe2O4/IF and control samples. (g) Long term stability test of Cr-CoFe2O4/IF at a current density of 100 mA cm-2.

Fig. 4. DFT calculations. (a) Dopant-assisted OH spillover mechanism on Cr-CoFe2O4 during OER. (b) OER pathway without OH spillover on CoFe2O4. (c) Calculated free energy profiles of Cr-CoFe2O4 and CoFe2O4.

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Chromium-doped CoFe₂O₄ for enhanced oxygen evolution via hydroxyl spillover

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