Abstract Unambiguous identification of active sites in heterogeneous catalysis remains a major challenge, particularly for materials with ultrathin, chemically mixed surface layers. Here, we demonstrate a generalizable approach that combines time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) with multivariate statistical analysis (principal component analysis PCA and multivariate curve resolution MCR) to resolve catalytically relevant motifs at the nanoscale. Using Ni electrodes as a model system, PCA distinguished hydroxide‐enriched domains from oxide‐ and metal‐rich regions, while MCR decomposed depth profiles and 3D images into hydroxide, oxide, and metallic layers with nanometer resolution. A unique secondary‐ion fragment, NiO 3 H 3 − ( m / z 108.94), emerged as a marker of hydroxide‐rich environments and correlated with hydrogen evolution reaction (HER) activity across a series of Ni electrodes. Complementary density functional theory (DFT) calculations revealed that Ni(OH) 2 clusters adjacent to metallic Ni offer the most favorable water dissociation energetics, establishing the structural origin of the marker. While illustrated here for Ni‐based HER, this workflow provides a broadly applicable framework to isolate and rank near‐surface patterns that govern catalytic activity, thereby extending ToF‐SIMS from a qualitative probe to a predictive tool for active site identification.
Finšgar et al. (Thu,) studied this question.