The relationship between surface structure and reactivity is investiga
ted by means of n-butane hydrogenolysis, a known structure sensitive r
eaction, for planar and faceted Pt/W(111) surfaces. The W(111) surface
reconstructs to form pyramidal facets with [211] orientation upon vap
or deposition of Pt (> 1.3 ML) and annealing above 750 K. The hydrogen
olysis kinetics over the planar and the faceted surface are found to b
e quite different. The planar surface has a higher selectivity towards
ethane formation and a higher reaction rate. The apparent activation
energies are found to be 33 +/- 4 kJ/mol for the planar surface and 76
+/- 6 kJ/mol for a surface covered with approximately 20 nm facets. T
here appears to be a correlation between the concentration of fourfold
coordination (C4) sites on the surface and the amount of ethane produ
ced. The C4 concentration is altered by changing the facet size (annea
ling temperature). The results indicate the presence of a different in
termediate on the C4 sites as evidenced by the differences in the appa
rent activation energy, the reaction rate and the overall selectivity.