Field electron microscopy (FEM) is employed to monitor local brightnes
s fluctuations that occur during catalytic CO oxidation on a Pt field
emitter tip and that are caused by local variations in the adsorbate c
overages. The reaction is studied in the bistability range at T = 310
K with fixed p(O2) = 4.0 x 10(-4) Torr and p(CO) = 3.0 x 10(-7) Torr.
The measurements are conducted on the apex plane of a [100]-oriented P
t tip. Local time series are obtained by digitization of the video-rec
orded FEM image (40 ms time resolution) and integration of the intensi
ty in windows of 100 x 100 Angstrom and 20 x 100 Angstrom size. From t
he measured time series, the autocorrelation and cross-correlation fun
ctions were determined. Fluctuations on the reactive (oxygen covered)
and on the inactive (CO covered) branch of the reaction exhibit quits
substantial differences. On the reactive branch, spatial correlations
extend over much longer distances (several hundred angstroms) than on
the unreactive branch, and time correlations decay much more slowly. T
hese differences are discussed on the basis of the Langmuir-Hinshelwoo
d mechanism for catalytic CO oxidation. The fluctuations on the unreac
tive branch apparently originate from CO diffusion alone. (C) 1998 Els
evier Science B.V. All rights reserved.