Ru single atoms-induced interfacial water structure regulation for efficient alkaline hydrogen oxidation reaction

doi:10.1016/S1872-2067(24)60283-4

Abstract

Abstract:

The employment of single atom catalysts (SACs) remarkably increases atomic utilization and catalytic efficiency in various electrochemical processes, especially when coupled with metal clusters/nanoparticles. However, the synergistic effects mainly focus on the energetics of key intermediates during the electrocatalysis, while the properties of electrode surface and electric-double-layer (EDL) structure are largely overlooked. Herein, we report the synthesis of Ru nanoparticles integrated with neighboring Ru single atoms on nitrogen doped carbon (Ru_1,_n/NC) as efficient catalysts toward hydrogen oxidation reaction (HOR) under alkaline electrolytes. Electrochemical data, in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy, and density functional theory calculations reveal that the positively charged Ru single atoms could lead to the dynamically regulated proportion of strongly hydrogen-bonded interfacial water structure with O-down conformation and optimized connectivity of the hydrogen-bond network in the EDL region, which contribute to the accelerated diffusion of hydroxide ions to the electrified interfaces. Consequently, the obtained Ru_1,_n/NC catalyst displays remarkable HOR performance with the mass activity of 1.15 mA μg_PGM^-1under alkaline electrolyte. This work demonstrates the promise of single atoms for interfacial water environment adjustment and mass transfer process modulation, providing new insights into rational design of highly-effective SAC-based electrocatalysts.

Key words: Electric double layer, Hydrogen oxidation reaction, Interfacial water structure, Mass transfer process, Single atoms

Yiming Jin, Wenjing Cheng, Wei Luo. Ru single atoms-induced interfacial water structure regulation for efficient alkaline hydrogen oxidation reaction[J]. Chinese Journal of Catalysis, 2025, 74: 240-249.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60283-4

https://www.cjcatal.com/EN/Y2025/V74/I7/240

Figures/Tables 5

Fig. 1. (a) XRD patterns of Ru1,n/NC, Ru/C and Ru1/NC. (b-d) TEM and HAADF-STEM images of Ru1,n/NC (Ru single atoms are highlighted by red circles). (e) EDS-elemental mappings of Ru1,n/NC.

Fig. 2. High-resolution XPS spectra of N 1s in Ru1,n/NC (a) and Ru 3p in Ru1,n/NC and Ru/C (b). Ru K-edge XANES (c), oxidation states analysis (d) and EXAFS spectra (e) of Ru foil, Ru1,n/NC and RuO2. (f) Ru K-edge EXAFS (point) and curvefit (line) shown in R-space of Ru1,n/NC. Wavelet transformation of Ru K-edge EXAFS data for Ru foil (g), Ru1,n/NC (h) and RuO2 (i).

Fig. 3. (a) HOR polarization curves in H2-saturated 0.1 mol L-1 KOH with a scan rate of 10 mV s-1 at a rotation rate of 1600 rpm. (b) Linear fitting curves in the micro-polarization region. (c) Tafel plots with the Butler-Volmer fitting lines. (d) Comparison of the mass-normalized kinetic current density (jk,m) and the ECSA-normalized exchange current density (j0,s). (e) Accelerated durability test for HOR of Ru1,n/NC in Ar-saturated 0.1 mol L-1 KOH solution. The inset histogram exhibits the j0 decline after 1000 cycle CVs test. (f) Comparison of jk,m with several previously reported noble metal-based electrocatalysts.

Fig. 4. (a,b) In situ SEIRAS spectra recorded at potentials from 0 to 0.2 VRHE for Ru1,n/NC, and Ru/C catalysts in H2-saturated 0.1 mol L-1 KOH solution. (c,d) Deconvolution of the OH stretching vibration peaks (around 3000 to 3600 cm-1) from 0 to 0.2 VRHE. (e) Changes in the proportion of strongly hydrogen-bonded water with applied potential (from 0 to 0.2 VRHE) for Ru1,n/NC and Ru/C. (f) Schematic illustration of interfacial water structures of Ru1,n/NC and the promoted OH- transfer assisted by strongly hydrogen-bonded water with O-down conformation.

Fig. 5. (a) Differential charge density of Ru1/NC, Ru1,n/NC and Ru/C (The yellow region represents for charge accumulation and the blue region for charge depletion). Free energy diagram of adsorbed hydrogen (b) and water binding energy (c) of Ru1/NC, Ru1,n/NC and Ru/C. (d) Local density of states of Ru d-orbitals in hydrogen adsorption sites for Ru1,n/NC and Ru/C. (e) COHP analysis of Ru ds-O 2p valence-electron-orbital interaction for Ru1,n/NC and Ru/C. (f) The adsorption energy of OH- with and without the assistance of adsorbed water of Ru1,n/NC (the left panel) and Ru/C (the right panel).

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