Surface anions-mediated dynamic interfacial free water enriched microenvironment on RuO2 for efficient acidic oxygen evolution

doi:10.1016/S1872-2067(26)64993-5

Abstract

Abstract:

Recent studies have revealed that the slow kinetics of active free water molecule replenishment on the surface of catalyst can be the potential cause responsible for the sluggish reaction kinetics of oxygen evolution reaction (OER) under acidic electrolyte. However, engineering the dynamic interfacial water structure to form the free water enriched microenvironment has rarely been implemented due to the relatively inherent inert catalyst surface. Herein, we demonstrate that surface modification of ruthenium dioxide (RuO₂) with PO₄^3- anions (RuP_0.4O_x) can effectively regulate the free water enriched microenvironment and significantly enhance the acidic OER performance. Experimental results including operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy reveal that the introduction of PO₄^3- species can manipulate the interfacial water structure, resulting in a free-H₂O-enriched interfacial environment, which is conducive to the continuous supply of reactants. Moreover, theoretical studies indicate that the surface modified PO₄^3- could facilitate proton transfer to the oxygen sites of the PO₄^3- group, enabling a PO₄^3--assisted adsorption evolution mechanism with enhanced reaction kinetics. Consequently, the obtained RuP_0.4O_x catalyst, featuring a Ru-O-P local environment and modified by surface PO₄^3- anions, displays a low overpotential of 200 mV at 10 mA cm^-2 and operates stably for 500 h during the acidic OER process.

Key words: Ruthenium dioxide, Acidic oxygen evolution reaction, Interfacial water structure, Surface anion modification

Liqing Wu, Wenxia Huang, Bingbing Zhao, Ping Cai, Wei Luo. Surface anions-mediated dynamic interfacial free water enriched microenvironment on RuO₂ for efficient acidic oxygen evolution[J]. Chinese Journal of Catalysis, 2026, 85: 237-246.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64993-5

https://www.cjcatal.com/EN/Y2026/V85/I6/237

Figures/Tables 4

Fig. 1. (a) XRD patterns of RuP0.4Ox and RuO2 catalysts. (b) The HAADF-STEM image of RuP0.4Ox. (c) The atomic resolution HAADF-STEM image of RuP0.4Ox. (d) HAADF image and corresponding elemental mappings of Ru, P, and O in RuP0.4Ox. (e) High resolution XPS spectra of Ru 3p for RuP0.4Ox and RuO2 catalysts. (f) High resolution XPS spectrum of P 2p for RuP0.4Ox catalyst. (g) FTIR spectra of RuP0.4Ox and RuO2 catalysts.

Fig. 2. (a) LSV curves of RuP0.4Ox, RuO2, and Com. RuO2 catalysts in acidic electrolyte. (b) Tafel slopes of RuP0.4Ox, RuO2, and Com. RuO2 catalysts. (c) The calculated Cdl values for RuP0.4Ox and RuO2. (d) The ECSA-normalized LSV curves of RuP0.4Ox and RuO2 catalysts. (e) EIS patterns of RuP0.4Ox and RuO2 at the potential of 1.5 V. (f) Phase peak angles obtained at different potentials of RuP0.4Ox and RuO2. (g) Stability tests of RuP0.4Ox and RuO2 at the current density of 10 mA cm-2 in 0.5 mol L-1 H2SO4. (h) Comparison of the activity and stability between RuP0.4Ox and other recently reported catalysts.

Fig. 3. (a) LSV curves of RuP0.4Ox and RuO2 in 0.5 mol L-1 H2SO4 electrolyte with or without the addition of TMA+. (b) The LSV curves of OER and MOR for RuP0.4Ox and RuO2. (c) Potential ratios (VOER/VMOR) for RuP0.4Ox and RuO2 at different current densities. The operando ATR-SEIRAS spectra of RuP0.4Ox (d) and RuO2 (e) in the range of 2800 to 3800 cm-1. (f) Comparison of the proportions of 4-HB-H2O, 2-HB-H2O, and free-H2O between RuP0.4Ox and RuO2 at 1.5 V vs. RHE. (g) The proportions of free-H2O at varied potentials of RuP0.4Ox and RuO2 catalysts.

Fig. 4. (a) The top view of RuP0.4Ox (110) surface. The oxygen atom marked within the black circle corresponds to the O in the PO43- group. The light grey balls, purple balls, and red balls represent Ru atoms, P atoms, and O atoms, respectively. (b) The PDOS analysis of Ru 4d and O 2p orbitals in the model of RuO2. (c) The PDOS analysis of Ru 4d, P 3p, and O 2p orbitals in the model of RuP0.4Ox. (d) Gibbs free energy diagrams for the adsorption of H atom on the surface of RuP0.4Ox and RuO2. The light grey balls, purple balls, white ball, and red balls represent Ru atoms, P atoms, H atom, and O atoms, respectively. (e) The free energy diagram of RuP0.4Ox. The light grey balls, purple balls, white balls, and red balls represent Ru atoms, P atoms, H atoms, and O atoms, respectively. (f) The scheme illustration of the reaction pathway for RuP0.4Ox and RuO2. The light grey balls, purple balls, red balls, and white balls represent Ru atoms, P atoms, O atoms, and H atoms, respectively.

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Surface anions-mediated dynamic interfacial free water enriched microenvironment on RuO₂ for efficient acidic oxygen evolution

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