  We present a combined experimental/theoretical study of Pt$_n$/SiO$_2$ and
Pt$_n$Sn$_x$/SiO$_2$ (n = 4, 7) model catalysts for the endothermic
dehydrogenation of hydrocarbons, using the ethylene intermediate as a model
reactant. Supported pure Ptn clusters are found to be highly active toward
dehydrogenation of C2D4, quickly deactivating due to a combination of carbon
deposition and sintering, resulting in loss of accessible Pt sites. Addition of
Sn to Ptn clusters results in the complete suppression of C2D4 dehydrogenation
and carbon deposition, and also stabilizes the clusters against thermal
sintering. Theory shows that both systems have thermal access to a multitude of
cluster structures and adsorbate configurations that form a statistical
ensemble. While Pt4/SiO2 clusters bind ethylene in both di-sigma and pi-bonded
configurations, Pt$_4$Sn$_3$/SiO$_2$ binds C2H4 only in the pi-mode, with
di-sigma bonding suppressed by a combination of electronic and geometric
features of the PtSn clusters. Dehydrogenation reaction profiles on the
accessible cluster isomers were calculated using the climbing image nudged
elastic band (CI-NEB) method.
