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In-Situ Surface EXAFS at Chemically Modified Electrodes.
Technical rept. no. 7, Oct 86-Jul 87,
CORNELL UNIV ITHACA NY BAKER LAB
Pagination or Media Count:
The surface EXAFS and near edge structure of electropolymerized films of Ruv-bpy32 on platinum electrodes have been studied as a function of surface coverage and applied potential by measuring the characteristic RuKa fluorescence intensity. Spectra for electrodes modified with 1, 5 and 50 monolayers were obtained. Analysis and comparison of EXAFS and XANES features for these films with those of bulk Rubpy32 showed similar morphological and electronic characteristics in agreement with previous electrochemical studies showing that solution redox properties of monomer complexes can be transferred to electrode surfaces by electrodeposition as polymer films of varying thickness. Electrochemical oxidation of the films resulted in a shift of 2 eV in the edge position towards higher energy, consistent with the higher charge on the ruthenium centers. Other spectral features, however, remained essentially unchanged. The applicability of these studies to the in-situ investigation of electrocatalytic systems is discussed. Keywords Modified electrodes, Synchrotron radiation.
APPROVED FOR PUBLIC RELEASE