Multiscale Analysis of Electrocatalytic Particle Activities: Linking Nanoscale Measurements and Ensemble Behavior

Nanostructured electrocatalysts exhibit variations in electrochemical properties across different length scales, and the intrinsic catalytic characteristics measured at the nanoscale often differ from those at the macro-level due to complexity in electrode structure and/or composition. This aspect of electrocatalysis is addressed herein, where the oxygen evolution reaction (OER) activity of β-Co(OH)₂ platelet particles of well-defined structure is investigated in alkaline media using multiscale scanning electrochemical cell microscopy (SECCM). Microscale SECCM probes of ∼50 μm diameter provide voltammograms from small particle ensembles (ca. 40-250 particles) and reveal increasing dispersion in the OER rates for samples of the same size as the particle population within the sample decreases. This suggests the underlying significance of heterogeneous activity at the single-particle level that is confirmed through single-particle measurements with SECCM probes of ∼5 μm diameter. These measurements of multiple individual particles directly reveal significant variability in the OER activity at the single-particle level that do not simply correlate with the particle size, basal plane roughness, or exposed edge plane area. In combination, these measurements demarcate a transition from an "individual particle" to an "ensemble average" response at a population size of ca. 130 particles, above which the OER current density closely reflects that measured in bulk at conventional macroscopic particle-modified electrodes. Nanoscale SECCM probes (ca. 120 and 440 nm in diameter) enable measurements at the subparticle level, revealing that there is selective OER activity at the edges of particles and highlighting the importance of the three-phase boundary where the catalyst, electrolyte, and supporting carbon electrode meet, for efficient electrocatalysis. Furthermore, subparticle measurements unveil heterogeneity in the OER activity among particles that appear superficially similar, attributable to differences in defect density within the individual particles, as well as to variations in electrical and physical contact with the support material. Overall this study provides a roadmap for the multiscale analysis of nanostructured electrocatalysts, directly demonstrating the importance of multilength scale factors, including particle structure, particle-support interaction, presence of defects, etc., in governing the electrochemical activities of β-Co(OH)₂ platelet particles and ultimately guiding the rational design and optimization of these materials for alkaline water electrolysis.