The regulation of interface structure improves the performance of the MoxOy/Co3O4 electrocatalytic oxygen evolution reaction in acidic media

doi:10.1016/S1872-2067(26)65083-8

Abstract

Abstract:

This paper proposes a multi-level structure design strategy, a dense cobalt oxide layer (d-Co₃O₄), a cobalt oxide catalytic layer (h-Co₃O₄), and an amorphous molybdenum oxide (a-Mo_xO_y) co-catalytic layer are constructed layer by layer on nickel foam (NF) through the combination of electro-deposition and oxidation. The a-Mo_xO_y/h-Co₃O₄/d-Co₃O₄/NF composite catalyst with both high catalytic activity and high stability was thus prepared. The main function of the d-Co₃O₄ layer is to prevent NF from coming into direct contact with acidic media to stop its electrochemical corrosion. The h-Co₃O₄ catalytic layer thus acquires a larger specific surface area, thereby exposing more active sites. The main function of the a-Mo_xO_y co-catalytic layer is to regulate the electronic structure on the surface of h-Co₃O₄, reduce the electron cloud density of the Co active sites, and thereby promote the adsorption and oxidation of the oxygen in a water molecule on it. The electrochemical test results show that the overpotential of a-Mo_xO_y/h-Co₃O₄/d-Co₃O₄/NF at a current density of 10 mA cm^-2 is 254 mV, the Tafel slope is 118 mV dec^-1, and the stability exceeds 12 h in 0.5 mol L^-1 H₂SO₄. Raman, X-ray photoelectron spectroscopy characterization and theoretical calculations indicate that the a-Mo_xO_y-Co₃O₄ interface promotes the transfer of electrons from Co to Mo, optimizes the electronic structure of the active site, and reduces the adsorption and desorption energy barriers of the reaction intermediates OOH*, OH* and O*, thereby enhancing the oxygen evolution reaction performance of the catalyst. This study provides a new structural design strategy for constructing stable transition metal-based oxide catalysts on NF for acidic oxygen evolution reaction.

Key words: Electrodeposition, Electrocatalysis, Cobalt-molybdenum oxides, Interfacial effect, Acidic oxygen evolution reaction

Qi Tang, Bomiao Wang, Chongtai Wang, DaoXiong Wu, Ziming Cheng, Huimin Han, Leiyun Han, Huaxia Chen, Yingjie Hua. The regulation of interface structure improves the performance of the Mo_xO_y/Co₃O₄ electrocatalytic oxygen evolution reaction in acidic media[J]. Chinese Journal of Catalysis, 2026, 88: 295-306.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65083-8

https://www.cjcatal.com/EN/Y2026/V88/I9/295

Figures/Tables 9

Scheme 1. Schematic illustration of the controlled growth of diverse Co3O4 morphologies and their subsequent integration with MoxOy to construct the MoxOy/Co3O4 catalyst.

Fig. 1. SEM images of NF (a,b), d-Co3O4/NF (c,d), h-Co3O4/NF (e,f), and cross-sections of h-Co3O4/NF (g) and d-Co3O4/NF (h).

Fig. 2. (a) Raman spectrum, (b) XRD patterns, XPS of (c) Co 2p and (d) O 1s.

Fig. 3. Electrochemical properties of h-Co3O4/NF and d-Co3O4/NF in 0.5 mol L?1 H2SO4: (a) LSV Curve (inset: stability tests), (b) EIS, (c) Tafel Slope, (d) Cdl. CV Curves of d-Co3O4/NF (e) and h-Co3O4/NF (f).

Fig. 4. SEM images of h-Co3O4/d-Co3O4/NF (a,b) and a-MoxOy/h-Co3O4/d-Co3O4/NF (c,d). Cross-sections of h-Co3O4/d-Co3O4/ NF (e) and a-MoxOy/h-Co3O4/d-Co3O4/NF (f). TEM images of h-Co3O4/ d-Co3O4/NF (g) and a-MoxOy/h-Co3O4/d-Co3O4/NF (h).

Fig. 5. Raman spectra (a), XRD patterns (b), and survey XPS spectra (c) of h-Co3O4/d-Co3O4/NF, a-MoxOy/d-Co3O4/NF and a-MoxOy/h-Co3O4/d-Co3O4/NF. XPS spectra of Co 2p (d), O 1s (e), and Mo 3d (f).

Fig. 6. Electrochemical performance of h-Co3O4/d-Co3O4/NF, a-MoxOy/h-Co3O4/d-Co3O4/NF and a-MoxOy/d-Co3O4/NF in 0.5 mol L-1 H2SO4. (a) LSV curve. (b) Chronopotentiometry curves at a current density of 10 mA cm-2. (c) Dissolution amounts of Co and Ni from the catalyst during the acidic OER stability test (0.5 mol L-1 H2SO4, 10 mA cm-2) as a function of time, determined by ICP-MS. (d) Tafel slope. (e) EIS. (f) Cdl. CV Curves of h-Co3O4/d-Co3O4/NF (g) and a-MoxOy/h-Co3O4/d-Co3O4/NF (h). In-situ Raman of h-Co3O4/d-Co3O4/NF (i,j) and a-MoxOy/h-Co3O4/d-Co3O4/NF (k-l), recorded at different applied potentials (vs. RHE).

Fig. 7. Characterization of a-MoxOy/h-Co3O4/d-Co3O4/NF after stability test. (a,b) SEM images. (c) XRD patterns. XPS spectra of Mo 3d (d), O 1s (e), and Co 2p (f).

Fig. 8. Optimized atomic structures for H2O adsorption on MoO3, Co3O4, and MoO3@Co3O4 surfaces (a), and the corresponding adsorption Gibbs free energies (b). (c) Proposed OER reaction pathway mediated by MoO3@Co3O4. (d) Calculated Gibbs free energy profiles for the OER on MoO3, Co3O4, and MoO3@Co3O4. (e) Comparison of the Gibbs free energies for OOH* intermediate adsorption on MoO3, Co3O4, and MoO3@Co3O4.

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The regulation of interface structure improves the performance of the Mo_xO_y/Co₃O₄ electrocatalytic oxygen evolution reaction in acidic media

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