Alleviating hydroxyl poisoning on Ru through competitive adsorption regulation using anatase-rutile TiO2 heterostructures in alkaline hydrogen oxidation reaction

doi:10.1016/S1872-2067(25)64853-4

Abstract

Abstract:

Ruthenium (Ru) is a promising electrocatalyst for the alkaline hydrogen oxidation reaction (HOR), yet it suffers from deactivation at higher potentials due to excessive oxophilicity, which leads to hydroxyl adsorption poisoning. Here, we report a tri-phase heterostructured catalyst (Ru-P25-TiO₂) comprising Ru with anatase (A-) and rutile (R-)TiO₂. This catalyst exhibits remarkable HOR activity, delivering 0.82 mA μg_Ru^-1 along with superior electrochemical stability up to 0.9 V vs. RHE, positioning it as the state-of-the-art electrocatalyst for HOR. This enhanced performance is attributed to the optimized electron distribution and a tailored d band structure at the Ru surface, enabled by strong metal and support interaction, which weakens both hydrogen binding energy and hydroxyl binding energy. The highly oxyphilic P25-TiO₂ facilitates hydroxyl adsorption and establishes a continuous hydrogen-bond network at the catalyst/electrolyte interface, thereby promoting OH⁻ transport and alleviating competitive OH adsorption on the Ru surface. The synergistic interplay between anatase and rutile TiO₂ ideally endows Ru with both superior activity and excellent electrochemical stability. This work not only unravels the intrinsic role of biphasic TiO₂ in tailoring Ru electrocatalysis but also provides a generalizable synergistic heterostructure design strategy for developing efficient and durable electrocatalysts.

Key words: Anatase TiO₂, Rutile TiO₂Ruthenium, Synergistic interplay, Hydrogen oxidation reaction

Jie Gao, Jing Liu, Mengdi Wang, Nuo Sun, Hao Hu, Xuejing Cui, Xin Zhou, Luhua Jiang. Alleviating hydroxyl poisoning on Ru through competitive adsorption regulation using anatase-rutile TiO₂ heterostructures in alkaline hydrogen oxidation reaction[J]. Chinese Journal of Catalysis, 2026, 82: 74-83.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64853-4

https://www.cjcatal.com/EN/Y2026/V82/I3/74

Figures/Tables 6

Fig. 1. (a) Schematic diagram of the design strategy of Ru-TiO2. (b) AC HAADF-STEM image of Ru-P25-TiO2. (c) Elemental mapping images of Ru-P25-TiO2. TEM images of Ru-P25-TiO2 (d), Ru-R-TiO2 (e), and Ru-A-TiO2 (f). The insert is the histogram for Ru particle size distribution. (g) AC HRTEM image of Ru-P25-TiO2. g1 and g2 are the enlarged images of the smaller box region. (h) HRTEM image of Ru-R-TiO2. h1 and h2 are the enlarged images of the smaller box region. (i) HRTEM image of Ru-A-TiO2. i1 and i2 are the enlarged images of the smaller box region.

Fig. 2. Chemical state and atomic coordination environment of Ru-P25-TiO2, Ru-A-TiO2, and Ru-R-TiO2. C 1s, Ru 3d (a) and Ti 2p, Ru 3p (b) XPS spectra of Ru-P25-TiO2, Ru-A-TiO2, and Ru-R-TiO2. (c) Valance band XPS spectra of Ru-P25-TiO2, Ru-A-TiO2, and Ru-R-TiO2. Normalized Ru K-edge XANES spectra (d) and Ru K-edge FT-EXAFS spectra (e) of Ru-P25-TiO2, Ru-R-TiO2, Ru foil, and RuO2. (f) The wavelet transform EXAFS contour plots of Ru-P25-TiO2, Ru-R-TiO2, Ru foil, and RuO2. Normalized Ti K-edge XANES spectra (g) and Ti K-edge FT-EXAFS spectra (h) of Ru-P25-TiO2, Ru-R-TiO2, Ti foil, TiO2-A, and TiO2-R.

Fig. 3. Electrocatalytic HOR performances. (a) HOR polarization curves in H2-saturated 0.1 mol L-1 KOH at a scan rate of 10 mV s-1 of Ru-P25-TiO2, Ru-R-TiO2, Ru-A-TiO2, and Ru/C. Tafel plots (b) and comparison of j0,s and jk,m (c) of Ru-P25-TiO2, Ru-R-TiO2, Ru-A-TiO2, and Ru/C. (d) HOR polarization curves of Ru-P25-TiO2 before and after 5k, 10k cycles of ADT. (e) Chronoamperometry curves of Ru-P25-TiO2 and Ru-R-TiO2 at 0.9 V vs. RHE in H2-saturated 0.1 mol L-1 KOH at 400 rpm. (f) Deactivation potentials and mass activities of Ru-based nonprecious metal electrocatalysts for the alkaline HOR.

Fig. 4. In-situ SEIRAS spectra recorded at potentials from 0.35 to -0.05 V of Ru-P25-TiO2 (a,c) and Ru-R-TiO2 (b,d) electrocatalyst in 0.1 mol L-1 NaOH. Deconvolution of the O-H stretching vibration features of in-situ SEIRAS spectra recorded at 0.15 V (e) and 0.35 V (f) for Ru-P25-TiO2 and Ru-R-TiO2.

Fig. 5. DFT results of the model catalysts. The projected d-band states in Ru-A-TiO2 (a) and Ru-R-TiO2 (b). (c) The hydroxide binding energy of Ru-A-TiO2 and Ru-R-TiO2 on Ru and Ti sites. (d) The hydrogen binding energy of Ru-A-TiO2 and Ru-R-TiO2. (e) Free energy profiles of HOR over Ru-A-TiO2 and Ru-R-TiO2.

Fig. 6. Schematic illustration of the mechanism for the enhanced HOR activities of Ru-P25-TiO2.

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Alleviating hydroxyl poisoning on Ru through competitive adsorption regulation using anatase-rutile TiO₂ heterostructures in alkaline hydrogen oxidation reaction

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