Awakening catalytically active surface of BaRuO3 thin film for alkaline hydrogen evolution

doi:10.1016/S1872-2067(26)64972-8

Abstract

Abstract:

The dynamic reconstruction of surfaces during electrochemical reactions plays a crucial role in determining the performance of electrocatalysts. However, because reconstructions occur at the atomic level, direct observation and elucidation of the underlying mechanism are challenging for conventional powder-type catalysts with ill-defined lattices. In this study, the catalytically active surface of 3C BaRuO₃ (BRO) epitaxial thin films emerges upon the dynamic introduction of surface Ru clusters, for the alkaline hydrogen evolution reaction (HER). Based on the mass activity at overpotential 100 mV, the intrinsic HER performance increases dramatically from 0.11 to 7.72 A mg_Ru⁻¹ immediately after the initial HER cycle and eventually saturates at 1.05 A mg_Ru⁻¹ after continuous operation. The formation of Ru clusters on the catalyst surface, driven by selective Ba leaching under alkaline HER conditions, is observed experimentally. Density functional theory calculations demonstrate that HER activity increased with enhanced H* adsorption owing to the dynamic Ru₆ cluster formation. A strategy for stabilizing the ‘awakened’ active surface of BRO is further proposed by validating that the atomic-scale control of the film thickness can effectively maintain the highly active state. This study offers fundamental insights into the design and stabilization of the highly active Ru-based electrocatalysts for the alkaline HER.

Key words: Hydrogen evolution reaction, Perovskite oxide, Epitaxial thin film, Surface reconstruction

Jegon Lee, Do-Hyun Kim, Seulgi Ji, Sangmoon Yoon, Seung Hyun Nam, Jucheol Park, Jin Young Oh, Seung Gyo Jeong, Jong-Seong Bae, Sang A. Lee, Heechae Choi, Woo Seok Choi. Awakening catalytically active surface of BaRuO₃ thin film for alkaline hydrogen evolution[J]. Chinese Journal of Catalysis, 2026, 83: 341-350.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64972-8

https://www.cjcatal.com/EN/Y2026/V83/I4/341

Figures/Tables 5

Fig. 1. Evolution of electrocatalytic activity with HER cycling. (a) Schematic of surface self-reconstruction. (b) CV measurement for 100 HER cycles. The 100 cycles are represented by rainbow-colored lines from violet (1st) to red (100th). The black, blue, and red squares indicate the experimental points for the 1st, 2nd, and 100th HER cycles, respectively. (c) HER overpotential at −1 mA cm−2. (d) Comparison of mass activity for the Ru loading at an overpotential of 0.1 V for various Ru-based catalysts; experimental conditions for each catalyst are provided in Table S2.

Fig. 2. Modification of lattice structures with HER cycling. XRD θ-2θ scans near (002) Bragg peak of 3C BRO for pristine (a), activated (b), saturated (c) thin films. STEM images in low- (d-f) and high- (g-i) magnification of pristine- (d,g), activated- (e,h), and saturated- (f,i) BROs. (g-i) Fast Fourier-transforms (FFTs) of four white box regions in the STEM images are displayed on the right panels of each image.

Fig. 3. Alteration of surface chemistry with HER cycling. XPS profiles of Ba 3d (a) and Ru 3d (b) core-level for BRO thin films with HER cycling, before Ar etching. (c) The Ba/Ru ratio was determined from spectral areas of each region for Ba 3d and Ru 3d, excluding carbon-related peaks. The depth-profiling results of Ba 3d (d) and Ru 3d (e) XPS spectra of BRO thin films with increasing time of Ar+ ion etching. (f) Atomic concentrations of dissolved ions in electrolytes after HER cycles, in which zero-cycle means pristine electrolyte. Note that the black and red dashed lines represent the experimental quantification limits for the Ba and Ru atoms, respectively, in the ICP-MS measurement. XPS profiles and deconvolution of peaks in Ru 3d spectra for pristine- (g), activated- (h), and saturated- (i) BRO. The navy, magenta, and grey lines indicate Ru4+ 3d peaks with satellite peaks, Ru3+ 3d peaks, and surface carbon-related peaks, respectively.

Fig. 4. DFT calculation results of the built-in electric field and the modeled supercells of BRO(7) (a), BRO(11) (b), and BRO(25) (c) models. (d) The magnitude of the dipole moment at the Ru6/BRO surface with different Ru coverages. (e) Gibbs free energy diagram for the H* intermediate with the reaction coordinate. (f) Gibbs free energy profiles for the H2O* intermediate in Ru6/BRO surfaces.

Fig. 5. Stabilization of the active phase of the BRO catalyst through film thickness engineering. (a) A color map representing the onset overpotential as a function of the number of HER cycles and film thickness. (b) Variation of onset overpotential trends for BRO thin films with thickness of 10 (top panel) and 200 nm (bottom panel).

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Awakening catalytically active surface of BaRuO₃ thin film for alkaline hydrogen evolution

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