LASER-INDUCED THERMAL DECAY OF PYRIDINE AND CHLORIDE SURFACE-ENHANCED RAMAN SCATTERING AS A PROBE OF SILVER SURFACE-ACTIVE SITES
The activation parameters for the temperature dependent irreversible loss of surface-enhanced Raman scattered (SERS) intensity from pyridine and chloride adsorbed at silver surfaces in an electrochemical environment have been determined. Laser-induced heating is introduced as a probe of the chemical...
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| Language: | en_US |
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The University of Arizona.
1987
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| Online Access: | http://hdl.handle.net/10150/276553 |
| Summary: | The activation parameters for the temperature dependent irreversible loss of surface-enhanced Raman scattered (SERS) intensity from pyridine and chloride adsorbed at silver surfaces in an electrochemical environment have been determined. Laser-induced heating is introduced as a probe of the chemical nature of SERS-active sites. Surface temperatures are calculated from spectroscopic data. The activation energies associated with the destruction of SERS-active sites at a surface roughened by an illuminated oxidation-reduction cycle (ORC) are 12.8 ± 3.2 kcal/mole and 27.7 ± 3.1 kcal/mole for pyridine at two different types of sites on the Ag surface. Similarly, values for coadsorbed chloride are found to be 11.1 ± 2.4 kcal/mole and 24.5 ± 3.8 kcal/mole. An activation energy of 27.4 ± 1.9 kcal/mole is obtained for pyridine on a silver surface roughened by a nonilluminated ORC. Evidence for the desorption of pyridine and chloride is presented. |
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