Constructing high-entropy spinel oxide thin films via magnetron sputtering for efficiently electrocatalyzing alkaline oxygen evolution reaction

doi:10.1016/S1872-2067(25)64771-1

Abstract

Abstract:

Ensuring high electrocatalytic performance simultaneously with low or even no precious-metal usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction (OER) in anion exchange membrane water electrolysis. Here, homogeneous high entropy oxide (HEO) film is in-situ fabricated on nickel foam (NF) substrate via magnetron sputtering technology without annealing process in air, which is composed of many spinel-structured (FeCoNiCrMo)₃O₄grains with an average particle size of 2.5 nm. The resulting HEO film (abbreviated as (FeCoNiCrMo)₃O₄) exhibits a superior OER performance with a low OER overpotential of 216 mV at 10 mA cm^-2 and steadily operates at 100 mA cm^-2 for 200 h with a decay of only 272 μV h^-1, which is far better than that of commercial IrO₂ catalyst (290 mV, 1090 μV h^-1). Tetramethylammonium cation (TMA⁺) probe experiment, activation energy analysis and theoretical calculations unveil that the OER on (FeCoNiCrMo)₃O₄ follows an adsorbate evolution mechanism pathway, where the energy barrier of rate-determining step for OER on (FeCoNiCrMo)₃O₄ is substantially lowered. Also, methanol molecular probe experiment suggests that a weakened *OH bonding on the (FeCoNiCrMo)₃O₄ surface and a rapid deprotonation of *OH, further enhancing its OER performance. This work provides a feasible solution for designing efficient high entropy oxides electrocatalysts for OER, accelerating the practical process of water electrolysis for H₂ production.

Key words: High entropy spinel oxide, Magnetron sputtering, Alkaline water electrolysis, Oxygen evolution reaction

Yuhui Chen, Congbao Guo, Yi Wang, Kun Wang, Shuqin Song. Constructing high-entropy spinel oxide thin films via magnetron sputtering for efficiently electrocatalyzing alkaline oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2025, 77: 210-219.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64771-1

https://www.cjcatal.com/EN/Y2025/V77/I10/210

Figures/Tables 5

Fig. 1. (a) Schematic illustrations of the synthesis of (FeCoNiCrMo)3O4. (b) XRD patterns of (FeCoNiCrMo)3O4, (FeCoNiCr)3O4 and blank. TEM (c), HRTEM (d) and HAADF-STEM images and corresponding elemental mappings (e) of the (FeCoNiCrMo)3O4.

Fig. 2. High-resolution XPS spectra of (FeCoNiCrMo)3O4. (a) Fe 2p; (b) Co 2p; (c) Ni 2p; (d) Cr 2p; (e) Mo 3d; (f) O 1s.

Fig. 3. (a) LSV curves in 1.0 mol L-1 KOH solution at room temperature. (b) OER overpotentials of (FeCoNiCrMo)3O4, (FeCoNiCr)3O4, IrO2, and NF at 10 mA cm-2. (c) Comparison of OER overpotentials and Tafel slope of this work and other already reported works. EIS Nyquist plots (d), and stability test (e) of (FeCoNiCrMo)3O4 and IrO2 at 100?mA?cm-2 for 200?h.

Fig. 4. (a) The pH dependence of the (FeCoNiCr)3O4 and (FeCoNiCrMo)3O4 on the OER potential at the SHE scales. (b) LSV curves of the (FeCoNiCr)3O4 and comparative samples in the presence or absence of TMAOH in KOH electrolytes. (c) Arrhenius plots for calculating activation energies of OER kinetics at 1.55 V vs. RHE. (d) LSV curves of the (FeCoNiCr)3O4 and (FeCoNiCrMo)3O4 in 1.0 mol L-1 KOH with and without methanol (0.602 mol L-1).

Fig. 5. TDOS (a) and PDOS (b) of Ni site in (FeCoNiCrMo)3O4 and (FeCoNiCr)3O4. (c) Reaction free energy step diagram of the (FeCoNiCrMo)3O4 and (FeCoNiCr)3O4 under the AEM pathway. The insets present the schematic diagram of each step evolving the *OH, *O, and *OOH intermediates on (FeCoNiCrMo)3O4 models

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