Dithiocarbamate-protected ruthenium nanoparticles: Synthesis, spectroscopy, electrochemistry and STM studies

Stable ruthenium nanoparticles were synthesized in a biphasic system with a protecting monolayer of dithiocarbamate derivatives. The core size of the resulting Ru particles was found to vary with the initial ligand–metal feed ratio. UV–vis spectroscopic measurements showed a Mie scattering profile, with no obvious surface-plasmon resonance. The size and crystal structures of the particles were characterized by transmission electron microscopic (TEM) measurements. A significant fraction of the nanoparticles was found within the size range of 2–4 nm in diameter and of spherical shape from the TEM measurements. Clear lattice fringes could be observed in high-resolution TEM images with the fringe spacing consistent with the Ru(1 0 1) lattice planes. Electrochemical studies of Ru particles with different core size exhibited the solution-phase quantized charging of the particle double layers, analogous to those reported for gold and other transition-metal particles. The potential spacing between adjacent quantized charging peaks was found to vary with the particle core size, corresponding to the variation of the particle molecular capacitance. These charge-transfer properties were very consistent with the STM measurements of isolated nanoparticles which exhibit clear Coulomb blockade and staircase features.