Synthesis of Transition Metal Clusters and Their Catalytic and Optical Properties

ABSTRACTMetal Clusters may be synthesized in the interior of surfactant aggregates called inverse micelles. These nanosize chemical reactors permit the controlled growth of several types of metal clusters. We describe this process for the formation of Au, Ag, Pd, Pt and Ir clusters and cluster alloys. Two size-control strategies are described: 1)variation of micelle size by alteration of the surfacant and/or solvent combination used, and 2) judicious use of micelle interactions or phase behavior. Using these two methods size control in the range of 1-100 nm is possible. The optical properties of metal clusters of gold, silver, and gold/silver alloys are described and the surface plasmon resonances are shown to have dramatic blue shifts and extensive line broadening with decreasing size in the range of 10-1 nm. In the case of gold clusters, the distinct resonancein the visible disappears for sizes less than 2.0 nm and new features appear in the UV. The optical spectra of alloys of gold and silver are shown to differ dramatically from their homoatomic counterparts of the same average size. We use electron and X-ray diffraction to determine the phase structure of the metal clusters and small angle X-ray scattering, neutron scattering, light scattering and TEM to characterize the average size and size distributions of these clusters. Finally, we describe measurements of the catalytic activity of Pd clusters and demonstrate a dramatic increase in hydrogenation activity on the size range of 2-10 nm.