Article,

A molecular-beam study of the cataytic-oxidation of CO on a Pt(111) surface

, and .
J. Chem. Phys., 73 (11): 5862--5873 (1980)
DOI: 10.1063/1.440029

Abstract

The oxidation of carbon monoxide catalyzed by Pt(111) was studied in ultrahigh vacuum using reactive molecular beam--surface scattering. Under all conditions studied, the reaction follows a Langmuir--Hinshelwood mechanism: the combination of a chemisorbed CO molecule and an oxygen adatom. When both reactants are at low coverage, the reaction proceeds with an activation energy E(/sub LH/ =24.1 kcal/mole and a pre-exponential upsilon/sub 4/ =0.11 cm/sup 2/ particles/sup -1/ sec/sup -1/. At very high oxygen coverage, E(/sub LH/ decreases to about 11.7 kcal/mole and upsilon/sub 4/ to about 2 x 10/sup -6/ cm/sup 2/ particles/sup -1/ sec/sup -1/. This is largely attributed to the corresponding increase in the energy of the adsorbed reactants. When a CO molecule incident from the gas phase strikes the surface presaturated with oxygen, it enters a weakly held precursor state to chemisorption. Desorption from this state causes a decrease in chemisorption probability with temperature. Once chemisorbed, the CO molecule then has almost unit probability of reacting to produce CO/sub 2/ below 540 K. The CO/sub 2/ product angular distribution varies from cos..gamma.. to cos/sup 4/..gamma.. depending sensitively upon the adsorbed reactant concentrations.

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