Surface enhanced Raman spectroscopy in the near-infrared
Surface enhanced Raman spectroscopy in the near-infrared
Surface Enhanced Raman Scattering (SERS) is a well established technique in the field of surface science because, together with infared spectroscopy, it provides unique vibrational information concerning adsorbed species. SERS using conventional Raman spectroscopy was a very difficult and expensive technique. The advent of Fourier transform Raman spectroscopy, in the near-infrared, has changed the situation, causing a `renaissance' of Raman spectroscopy. The work presented in this Thesis is restricted to the application of SERS to the electrode-electrolyte interface. This Thesis sets out to show that SERS spectra can be obtained using a near-infrared laser at silver, gold, platinum, copper and copper plated surfaces. SERS spectra of pyridine for a wide range of pH values, different potentials and concentrations are compared. At low pH values pyridinium ions are mainly adsorbed to the surface. At more basic pH, physisorbed pyridine with a small contribution of Lewis coordinated species are observed. The study of the ferro/ferricyanide redox couple at gold electrodes shows strong interaction of these species with the surface. There is a marked difference in the spectra when the effect of base electrolyte cation is studied. The technique has been found to be very effective in probing commercial corrosion inhibitors at copper surfaces. Competitive adsorption of mixtures of different inhibitors can be easily recorded and interpreted. All the results show that SERS is still strong in the near-infrared. The anticipated advantages of the new technique, i.e. reduction of fluorescence combined with a large throughput, high resolution and good wavenumber accuracy, indicate that FT-Raman spectroscopy - as well as having considerable advantages in its own right - is a perfect complement to the infrared technique.
University of Southampton
1992
Sockalingum, Dhuvananda
(1992)
Surface enhanced Raman spectroscopy in the near-infrared.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Surface Enhanced Raman Scattering (SERS) is a well established technique in the field of surface science because, together with infared spectroscopy, it provides unique vibrational information concerning adsorbed species. SERS using conventional Raman spectroscopy was a very difficult and expensive technique. The advent of Fourier transform Raman spectroscopy, in the near-infrared, has changed the situation, causing a `renaissance' of Raman spectroscopy. The work presented in this Thesis is restricted to the application of SERS to the electrode-electrolyte interface. This Thesis sets out to show that SERS spectra can be obtained using a near-infrared laser at silver, gold, platinum, copper and copper plated surfaces. SERS spectra of pyridine for a wide range of pH values, different potentials and concentrations are compared. At low pH values pyridinium ions are mainly adsorbed to the surface. At more basic pH, physisorbed pyridine with a small contribution of Lewis coordinated species are observed. The study of the ferro/ferricyanide redox couple at gold electrodes shows strong interaction of these species with the surface. There is a marked difference in the spectra when the effect of base electrolyte cation is studied. The technique has been found to be very effective in probing commercial corrosion inhibitors at copper surfaces. Competitive adsorption of mixtures of different inhibitors can be easily recorded and interpreted. All the results show that SERS is still strong in the near-infrared. The anticipated advantages of the new technique, i.e. reduction of fluorescence combined with a large throughput, high resolution and good wavenumber accuracy, indicate that FT-Raman spectroscopy - as well as having considerable advantages in its own right - is a perfect complement to the infrared technique.
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Published date: 1992
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Local EPrints ID: 461250
URI: http://eprints.soton.ac.uk/id/eprint/461250
PURE UUID: ff587ce2-2703-4b69-95f4-4e90271f4eda
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Date deposited: 04 Jul 2022 18:41
Last modified: 04 Jul 2022 18:41
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Author:
Dhuvananda Sockalingum
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