A Bi-doped RuO2 catalyst for efficient and durable acidic water oxidation

doi:10.1016/S1872-2067(23)64554-1

Abstract

Abstract:

Ruthenium oxide-based electrocatalysts have been regarded as promising alternatives to the state-of-the-art Iridium oxide (IrO₂) towards acidic oxygen evolution reaction (OER). However, their practical applications of proton exchange membrane water electrolyzer (PEMWE) are severely limited by the lack of efficient strategy to balance the seesaw relation between stability and activity of ruthenium oxide (RuO₂)-based catalysts. Herein, we report that both the activity and stability of RuO₂ can be significantly boosted though bismuth (Bi) doping. We find that the introduction of Bi can increase the initial valance state of Ru in Bi_0.15Ru_0.85O₂, which can promote the activation of Ru active sites, and facilitate the reaction kinetics of acidic OER. Besides, the presence of Bi can strengthen the electron interaction to maintain the structure stability and improve the electrocatalytic performance by reducing the energy barriers and avoiding the overoxidation of active species. The obtained Bi_0.15Ru_0.85O₂ catalyst shows a low overpotential of 200.0 mV to reach a current density of 10 mA cm^-2 under acidic media, and a long-term stability for over 100 hours. Our work provides an important inspiration to rational design RuO₂-based electrocatalysts with high activity and durability toward acidic OER.

Key words: Oxygen evolution reaction, RuO₂-based catalyst, Bismuth doping, Activity, Stability

Liqing Wu, Qing Liang, Jiayi Zhao, Juan Zhu, Hongnan Jia, Wei Zhang, Ping Cai, Wei Luo. A Bi-doped RuO₂ catalyst for efficient and durable acidic water oxidation[J]. Chinese Journal of Catalysis, 2023, 55: 182-190.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64554-1

https://www.cjcatal.com/EN/Y2023/V55/I12/182

Figures/Tables 4

Fig. 1. Morphology and structure analysis. (a) XRD patterns of Bi0.15Ru0.85O2 and RuO2. (b) and (c) HAADF-STEM image of Bi0.15Ru0.85O2. (d) HAADF-STEM image and corresponding EDS elemental mapping of Bi0.15Ru0.85O2. (e) The high-resolution XPS spectrum of Ru 3p in Bi0.15Ru0.85O2 and RuO2. (f) Experimental Ru L2,3-edges XANES spectra of Bi0.15Ru0.85O2 and RuO2.

Fig. 2. Electrochemical performance of Bi0.15Ru0.85O2 in acidic medium. (a) LSV curves of Bi0.15Ru0.85O2, RuO2, and C-RuO2, recorded with a scan rate of 5 mV s?1. (b) Tafel plots of Bi0.15Ru0.85O2, RuO2, and C-RuO2, derived from the LSV curves. The operando Bode phase plots of (c) Bi0.15Ru0.85O2 and (d) RuO2. (e) Phase peak angles varies with the changes of potentials for Bi0.15Ru0.85O2 and RuO2. (f) Chronopotentiometric stability test of Bi0.15Ru0.85O2.

Fig. 3. Kinetic analysis. (a) LSV curves of Bi0.15Ru0.85O2 and RuO2 recorded at 25 and 65 °C, respectively. (b) The corresponding Eapp data at different potentials of Bi0.15Ru0.85O2, derived from the LSV curves at different temperatures. (c) The corresponding Eapp data at different potentials of RuO2, derived from the LSV curves at different temperatures. (d) UPS spectra of Bi0.15Ru0.85O2 and RuO2. (e) UV spectra of Bi0.15Ru0.85O2 and RuO2. (f) Summary of some major OER performance metrics of Bi0.15Ru0.85O2 and RuO2. The Eapp was calculated at 1.45 V vs. RHE.

Fig. 4. Theoretical analysis. In situ Raman spectra of Bi0.15Ru0.85O2 (a) and RuO2 (b), in which the red square indicating the formation of the OOH*. (c) Charge density distribution image for Bi0.15Ru0.85O2 based on DFT analysis. (d) Reaction pathways of Bi0.15Ru0.85O2 and RuO2 for OER.

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A Bi-doped RuO₂ catalyst for efficient and durable acidic water oxidation

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