Ordered bimetallic Sn/Pt(111) surface alloys have been prepared in an
ultrahigh vacuum system and used in model moderate pressure (1-200 Tor
r) batch catalytic reactions. Hydrogenolysis of n-butane (H-2/n-C-4 =
100) was conducted on these surfaces to characterize the effects of or
dered bimetallic ensembles relative to those available at the Pt(111)
surface over the temperature range 525-625 K. For these conditions, sp
ecific n-butane hydrogenolysis reaction rates were determined for the
p(2 x 2) Sn/Pt(111) surface alloy, the (root 3 x root 3)R30 degrees Sn
/Pt(111) surface alloy, and Pt(111) as a function of temperature. The
order of relative activities is p(2 x 2) Sn/Pt(111) surface alloy > Pt
(111) > (root 3 x root 3)R30 degrees Sn/Pt(111) surface alloy with spe
cific activation energies of 29 +/- 2 kcal mol(-1) for all three surfa
ces below 575 K. A leveling in activity is seen for all three surfaces
at temperatures above 575 K. The hydrogenolysis activity of the p(2 x
2) Sn/Pt(111) surface alloy is approximately 5-6 times greater than t
hat seen over Pt(111) and the (root 3 x root 3)R30 degrees Sn/Pt(111)
surface alloy is approximately an order of magnitude less active. Prod
uct distributions and catalytic deactivation were found to be substant
ially different for these three surfaces. These results are discussed
in terms of the ensemble requirement differences inherent to the hydro
genolysis pathways available at each of the base metals under these co
nditions of temperature, pressure, and hydrogen/hydrocarbon ratio. (C)
1994 Academic Press, Inc.