Surface-enhanced infrared absorption studies of p-nitrothiophenol on silver

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Organic Compounds, Polymers, Organic Compounds And Polymers, Chromatography

Scientific paper

SEIRA spectra measured in the microtransmission mode have been used to investigate the chemistry of p-nitrothiophenol (PNTP) on silver films. By monitoring the S-H stretching band at ~2550 cm-1, we demonstrated that PNTP dimerizes oxidatively when applied to bare ZnSe substrate or Ag surfaces from acetone or methanol solution under ambient conditions. SEIRA spectra of the PNTP dimer were measured on both silver underlayer and overlayer surfaces by casting films of the dimer from solution. The SEIRA spectrum of PNTP dimer on the Ag overlayer is very different from, and more enhanced than, the corresponding underlayer spectrum. We conclude that the S-S bond of the dimer is broken and Ag-S bonds are formed when energetic silver atoms are vapor deposited on a film of the PNTP dimer already on ZnSe plate. PNTP monomer was passed through a GC column and deposited on a 5-nm Ag layer on a ZnSe plate mounted in a direct deposition GC/FT-IR interface. At temperatures above -30 °C, the SEIRA spectrum of PNTP monomer measured in this way is similar to that of PNTP dimer measured with an Ag overlayer, indicating that the active proton of the S-H group of the PNTP monomer dissociates and the PNTP chemisorbs on the Ag surface via an S-Ag bond. It was also found that the chemical reaction between PNTP monomer and the Ag surface can occur at temperatures as low as -30 °C, but not as low as -40 °C.

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