The surface chemistry and catalytic conversion of cis- and trans-2-butenes on platinum (1 0 0) facets were characterized via surface-science and catalytic experiments. Temperature-programed desorption studies on Pt(1 0 0) single crystals pointed to the higher hydrogenation probability of the trans isomer at the expense of a lower extent of C=C double-bond isomerization. To test these trends under catalytic conditions, shape selective catalysts were prepared by dispersing cubic platinum colloidal nanoparticles (which expose only (1 0 0) facets) onto a high-surface-area silica xerogel support. Infrared absorption spectroscopy and transmission electron microscopy were used to determine the conditions needed to remove the organic surfactants without loosing the original narrow size distribution and cubic shape of the original metal nanoparticles. Catalytic kinetic measurements with these materials corroborated the surface-science predictions, and pointed to a switch in isomerization selectivity from preferential cis-to-trans conversion with Pt(1 0 0) surfaces to the reverse trans-to-cis reaction with Pt(1 1 1) facets. (C) 2009 Elsevier Inc. All rights reserved.