Organometallic Control of Ru Decoration on CoNi: From Isolated Atoms to Nanoparticles

Engineering surface architectures in multimetallic nanoparticles is crucial for controlling their properties. This work investigates Ru-decorated CoNi nanoparticles prepared by an organometallic approach, yielding Ru as nanoparticles, subnanometric clusters, or isolated atoms. High-resolution electron microscopy (EM) and X-ray absorption spectroscopy (XAS) unambiguously establish these distinct Ru configurations, while X-ray photoelectron spectroscopy (XPS) reveals that Ru binding energies are influenced by coordination environment. Hydrogen-deuterium isotopic exchange further shows that subnanometric Ru maximizes activity, providing superior per-site reactivity. Together, these results demonstrate how the organometallic approach enables the controlled decoration of a platinum-group metal (i.e., Ru) on base metal (i.e., CoNi) nanoparticles, establishing direct correlations between surface architecture, electronic signatures, and potential catalytic functions.