Dynamic tuning of acidic oxygen evolution reaction pathways in Ru catalysts via Cu-induced surface restructuring

doi:10.1016/S1872-2067(26)64970-4

Abstract

Abstract:

Achieving both high activity and long-term stability for the oxygen evolution reaction (OER) in acidic media remains a critical challenge for proton exchange membrane water electrolyzers (PEMWEs). In this study, we proposed a Cu-incorporated ruthenium (Ru) catalyst (CuRu-250) that exhibited superior performance via dynamic surface modulation during operation. Rather than serving solely as a static dopant, Cu actively influenced the catalyst surface by undergoing partial dissolution and inducing surface restructuring. This dynamic behavior enabled pathway tuning from the adsorbate evolution mechanism to the oxide path mechanism, enhancing the intermediate turnover and suppressing the overoxidation of Ru. Consequently, CuRu-250 demonstrated markedly improved durability and competitive activity compared to undoped Ru and commercial RuO₂. Single-cell PEMWE tests validated its catalytic performance under realistic conditions. These findings highlight the role of active dopant behavior in tuning acidic OER pathways and improving electrochemical resilience, thus offering a practical strategy for advanced catalyst design.

Key words: Ruthenium, Dynamic surface restructuring, Oxygen evolution reaction, Proton exchange membrane water electrolyzer, Oxide path mechanism

Hyunseok Yoon, Hee Jo Song, Yumin Park, Andi Haryanto, Dohun Kim, Kyuri Cho, Chanyeon Kim, Wooyul Kim, Chan Woo Lee, Dong-Wan Kim. Dynamic tuning of acidic oxygen evolution reaction pathways in Ru catalysts via Cu-induced surface restructuring[J]. Chinese Journal of Catalysis, 2026, 83: 363-375.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64970-4

https://www.cjcatal.com/EN/Y2026/V83/I4/363

Figures/Tables 6

Scheme 1. Schematic illustration of the dynamic surface modulation of Ru catalysts induced by Cu incorporation.

Fig. 1. (a,b) SEM micrographs of a CuRu-250 synthesized on Ti mesh substrate. (c) The cross-sectional SEM image and corresponding EDS analysis of CuRu-250. HR-TEM image (d) and corresponding electron diffraction pattern (e) of CuRu-250. (f) TEM-EDS elemental mapping of CuRu-250. (g) XRD patterns of Ru-250 and CuRu-250. (h) Ru 3d and (i) Cu 2p XPS spectra of Ru-250 and CuRu-250, respectively.

Fig. 2. (a) The OER polarization curves of Ru-250, CuRu-250 and Comm-RuO2 in 0.5 mol L?1 H2SO4 electrolyte. (b) Chronopotentiometric stability tests of Ru-250 and CuRu-250. (c) Dissolved metal elements concentration in electrolyte for Ru-250 and CuRu-250 determined via ICP-MS. (d) Calculated S-number for Ru-250 and CuRu-250 in acidic OER. (e) The comparison of the required overpotential at 10 mA cm?2 and stability in acidic OER for previous reported electrocatalysts. (Table S2).

Fig. 3. Operando DEMS signals of O2 products for Ru-250 (a) and CuRu-250 (b). (c) Atomistic structure for key reaction steps in the AEM and OPM reaction pathways. The free energy diagrams for acidic OER based on each AEM and OPM reaction pathways of Ru-250 (d) and CuRu-250 (e) at 1.23 V vs. RHE.

Fig. 4. Operando ATR-SEIRAS measurements in the range of 900−1300 cm−1 at various applied potentials for Ru-250 (a) and CuRu-250 (b). Contour plots of in-situ electrochemical Raman spectroscopy of Ru-250 (c) and CuRu-250 (d) in 0.5 mol L−1 H2SO4.

Fig. 5. (a) Schematic illustration of the stack structure and operation principle of PEMWE. (b) The cross-sectional SEM image and corresponding EDS mapping of the MEA prepared using CuRu-250 as anode. (c) I-V curves of PEMWE with Ru-250, CuRu-250 and Comm-RuO2 as anode without iR compensation. (d) Chronoamperometry curves of the PEMWE at 1.35 V using Ru-250 and CuRu-250 as anode.

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