Infrared spectra of adsorbed CO have been used as a probe to monitor change
s in Pt site character induced by the coking of Pt/Al2O3 and Pt-Sn/Al2O3 ca
talysts by heat treatment in heptane/hydrogen. Four distinguishable types o
f Pt site for the linear adsorption of CO on Pt/Al2O3 were poisoned to diff
erent extents showing the heterogeneity of the exposed Pt atoms. The lowest
coordination Pt atoms (nu(CO) < 2030 cm(-1)) were unpoisoned whereas the h
ighest coordination sites in large ensembles of Pt atoms (2080 cm(-1)) were
highly poisoned, as were sites of intermediate coordination (2030-2060 cm(
-1)). Sites in smaller two-dimensional ensembles of Pt atoms (2060-2065 cm(
-1)) were partially poisoned, as were sites for the adsorption of CO in a b
ridging configuration. The addition of Sn blocked the lowest coordination s
ites and destroyed large ensembles of Pt by a geometric dilution effect. Th
e poisoning of other sites by coke was impeded by Sn, this effect being mag
nified for Cl-containing catalyst. Oxidation or oxychlorination of coked ca
talyst at 823 K followed by reduction completely removed coke from the cata
lyst surfaces.