Electrochemical Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy: Bonding, Structure, and Ion-Pairing of the Positive Charge Bearing Pyridinium Ring Terminated Monolayer at Smooth Gold Electrode
| Autor: | Ieva Matulaitienė, Algirdas Matijoška, Algirdas Selskis, Martynas Skapas, Tatjana Charkova, Olegas Eicher-Lorka, Agnė Zdaniauskienė, Gediminas Niaura |
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| Rok vydání: | 2018 |
| Předmět: |
Materials science
02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry Electrochemistry 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Perchlorate chemistry.chemical_compound symbols.namesake General Energy chemistry Monolayer Electrode symbols Pyridinium Physical and Theoretical Chemistry 0210 nano-technology Raman spectroscopy Electrochemical potential Electrode potential |
| Zdroj: | The Journal of Physical Chemistry C. 122:1234-1242 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/acs.jpcc.7b09970 |
| Popis: | Electrode potential effect on the molecular structure of adsorbed species at an interface is one of the most important issues in physical electrochemistry. In this study, shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) was used to probe the electrochemical potential effect on bonding with surface, ion-pairing, and molecular structure of a positive charge bearing self-assembled monolayer formed from N-(6-mercapto)hexylpyridinium (MHP) at a smooth gold electrode in aqueous perchlorate solutions. In situ electrochemical SHINERS results show that the Au–S stretching frequency exhibits near linear blue-shift as the electrode potential was tuned to more positive values. The frequency tuning rate was found to be as high as 18.6 ± 0.9 cm–1/V. Analysis of ion-pairing at the interface revealed a decrease in intensity of the vibrational spectrum of electrostatically attracted perchlorate anions as the electrode potential shifts progressively to more negative values. Spectroscopic evidence for poten... |
| Databáze: | OpenAIRE |
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