The properties of supported Ag nanoparticles are investigated, with the focus on specific structural and electronic qualities. Using a statistical analysis it is shown that large Ag particles move over the surface after being deposited on Si(111)7x7. Surface photovoltage measurements reveal the band topology of nanoscale metal-semiconductor systems. The findings are discussed with a band topology model and in terms of current transport mechanisms. Grazing-incidence small angle X-ray scattering is used to monitor in situ the size and shape change of Ag nanoparticles during a catalytic reaction.