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Combining ToF-SIMS and Multivariate Analysis to Resolve Active Sites on Ni-Based HER Catalysts.

Matjaž Finšgar1, Katja Andrina Varda1, Dzevad K Kozlica1,2,3

  • 1Faculty of Chemistry and Chemical Engineering, University of Maribor, Maribor, 2000, Slovenia.

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|January 16, 2026
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Summary
This summary is machine-generated.

Identifying active sites in catalysis is challenging. This study combines ToF-SIMS with statistical analysis to map nanoscale catalytic sites, revealing a marker for hydrogen evolution reaction activity on nickel electrodes.

Keywords:
HER active sitesMultivariate statistical analysisNickel catalystsToF‐SIMS

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Area of Science:

  • Surface Science
  • Catalysis
  • Materials Science

Background:

  • Identifying active sites in heterogeneous catalysis is crucial but difficult, especially for complex materials.
  • Nanoscale characterization of ultrathin, chemically mixed surface layers presents unique challenges.

Purpose of the Study:

  • To develop a generalizable method for nanoscale active site identification in catalysis.
  • To correlate surface motifs with catalytic activity using advanced analytical techniques.

Main Methods:

  • Utilized time-of-flight secondary ion mass spectrometry (ToF-SIMS) for high-resolution surface analysis.
  • Applied multivariate statistical analysis, including principal component analysis (PCA) and multivariate curve resolution (MCR), to interpret ToF-SIMS data.
  • Employed density functional theory (DFT) calculations to understand the origin of catalytic activity.

Main Results:

  • PCA distinguished hydroxide-, oxide-, and metal-rich regions on nickel electrodes.
  • MCR resolved depth profiles and 3D images into distinct nanoscale layers (hydroxide, oxide, metallic).
  • A unique marker, NiO3H3-, was identified in hydroxide-rich areas and correlated with hydrogen evolution reaction (HER) activity.

Conclusions:

  • The combined ToF-SIMS and statistical analysis approach enables nanoscale resolution of catalytic active sites.
  • Ni(OH)2 clusters adjacent to metallic Ni were identified as key sites for water dissociation in HER.
  • This workflow transforms ToF-SIMS into a predictive tool for designing efficient catalysts.