Single Particle Nanoelectrochemistry Reveals the Catalytic Oxygen Evolution Reaction Activity of Co3O4 Nanocubes

Co₃O₄ nanocubes are evaluated concerning their intrinsic electrocatalytic activity towards the oxygen evolution reaction (OER) by means of single-entity electrochemistry. Scanning electrochemical cell microscopy (SECCM) provides data on the electrocatalytic OER activity from several individual measurement areas covering one Co3O4 nanocube of a comparatively high number of individual particles with sufficient statistical reproducibility. Single-particle-on-nano-electrode measurements of Co₃O₄ nanocubes provide an accelerated stress test at highly alkaline conditions with current densities of up to 5.5 Acm^-2, and allows to derive TOF values of up to 2.8 X104 s^-1 at 1.92 V vs. RHE for surface Co atoms of a single cubic nanoparticle. Obtaining such high current densities combined with identical-location transmission electron microscopy allows monitoring the formation of an oxy(hydroxide) surface layer during electrocatalysis. Combining two independent single-entity electrochemistry techniques provides the basis for elucidating structure–activity relations of single electrocatalyst nanoparticles with well-defined surface structure.