Amorphous nickel hydroxide confined noble metal single atoms for enhanced alkaline hydrogen evolution reaction

doi:10.1016/S1872-2067(26)65166-2

Abstract

Abstract:

The dynamic regulation of the local atomic environment under operational conditions represents a frontier in the development of single-atom catalysts (SACs) for the alkaline hydrogen evolution reaction (HER). Here, we report a strategy that harnesses in-situ electrochemical reconstruction to construct a functional confinement structure for single atoms. Using Ru-doped NiP_x as a precursor, we guide its surface under HER conditions to form an reconstructed amorphous Ni(OH)₂ layer which acts as a robust host to confine and stabilize Ru single atoms. The reconstructed Ru-NiP_x(OH)_y catalyst delivers an extremely low overpotential of 9 mV at 10 mA/cm² and maintains stable operation for over 1000 h. Comprehensive characterization—combining vacuum-interconnected X-ray photoelectron spectroscopy and in-situ Raman spectroscopy—reveals that this confining amorphous layer not only modulates the electronic structure of Ru but also accelerates water dissociation and proton transport, thereby generating a local acid-like environment around the active sites. This synergy between atomic confinement and microenvironment engineering profoundly optimizes the overall HER kinetics. Furthermore, similar improvements are observed when Pt or Ir single atoms are introduced, demonstrating the universality of this reconstruction-driven activation strategy. This work establishes a paradigm for activating SACs by programming reconstruction to build integrated architectures where confinement and tailored microenvironments cooperate to boost catalytic performance.

Key words: Alkaline hydrogen evolution reaction, Single-atom confinement, Proton regulation, Reconstruction

Guang Yang, Xiliang Gong, Zeshuo Meng, Shuang Hou, Minghao Yang, Zhongmiao Gong, Rong Huang, Yi Cui. Amorphous nickel hydroxide confined noble metal single atoms for enhanced alkaline hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2026, 90: 264-275.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65166-2

https://www.cjcatal.com/EN/Y2026/V90/I11/264

Figures/Tables 5

Fig. 1. XRD patterns (a) and Raman spectra (b) of Ru-NiPx and NiPx. SEM image (c) and AFM image (d) of Ru-NiPx. (e) High-resolution STEM image of Ru-NiPx, where the bright spots circled in red represent Ru single atoms. (f) Three-dimensional Gaussian function-fitted atomic image of the region marked by the red box in (e). (g) STEM elemental mapping of P, O, Ni, and Ru.

Fig. 2. LSV curves of Ru-NiPx (a) and NiPx (b) after 1st and 10th HER cycles. Inset: Corresponding Tafel plots. (c) Chronopotentiometry curve of Ru-NiPx at 10 mA/cm2 for 100 h. Inset: Initial activation within 10 h. (d) Chronopotentiometry curve of NiPx at 10 mA/cm2 for 400 h.

Fig. 3. (a) Ru K-edge XANES spectra of Ru-NiPx, Ru-NiPx(OH)y, and references. Inset: Magnified pre-edge region. (b) Ru K-edge Fourier transform EXAFS spectra in R-space. (c) WT plots of Ru-NiPx and Ru-NiPx(OH)y. (d) TOF-SIMs 3D and 2D distribution maps of Ru-O fragments. (e) O 1s XPS spectra. (f) Ru 3p XPS spectra. (g) Ni 2p XPS spectra.

Fig. 4. (a) Schematic illustration of the in-situ Raman electrolytic cell. (b) Schematic illustration of a glovebox-electrochemical workstation and UHV-XPS chamber, connected via a vacuum transfer system. (c) In-situ Raman spectra under different applied potentials. (d) Quasi in-situ XPS spectra (recorded after emersion and transfer from the electrochemical cell under Ar protection) of the Ni 2p and Ru 3p regions for the electrode held at varying potentials. TOF-SIMs 3D (e) and 2D (f) distribution maps of H3O+ fragments.

Fig. 5. Polarization curves (a), Tafel slopes (b), Nyquist plots (c), and double-layer capacitance (d) comparisons of Ru-NiPx(OH)y and reference catalysts. (e,f) LSV curves and corresponding Tafel slopes normalized by ECSA. (g) Long-term durability test of Ru-NiPx(OH)y at 10 mA/cm2 in 1 mol/L KOH.

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