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Importance of the electrolyte cation on the non-covalent interactions in the electrooxidation of 1-heptanol on gold in 0.1 M alkali metal hydroxides
- Source :
- Digital.CSIC. Repositorio Institucional del CSIC, instname
- Publication Year :
- 2020
- Publisher :
- Elsevier BV, 2020.
-
Abstract
- 6 pags., 7 figs., 1 tab.<br />In order to determine the possible non-covalent influence of the alkali metal cation on the electrooxidation of 1-heptanol on gold in alkali metal hydroxides, 0.1 M MOH solutions, where M = Li, Na, K, Rb, and Cs, have been used. The charge-transfer resistance, determined by Electrochemical Impedance Spectroscopy, of heptanol oxidation at a fixed potential increased monotonically by a factor of 4 from LiOH to RbOH, that is, the heptanol oxidation current decreased. Since the degree of hydration of the OH group of the alcohol, as estimated by Molecular Dynamics Simulation, increased by a factor of 5 from LiOH to RbOH, it can be concluded that the decrease of the heptanol oxidation current from LiOH to RbOH is due to an increasing hydration of the heptanol OH group, which would hinder its access to the electrode surface. This result is in line with the previous finding [M.S. Ureta-Zañartu, C. Mascayano, C. Gutiérrez, doi:10.1016/j.electacta.2015.02.230] that the increase of the alcohol oxidation current at a fixed potential of linear saturated aliphatic alcohols from C1 to C7 on gold, both in a pH 11 buffer and in 0.1 M NaOH, increased with increasing chain length, that is, with decreasing hydration (because of the increasing hydrophobicity) of the alcoholic OH group.<br />This work was supported by Fondo Nacional de Ciencia y Tecnología (FONDECYT-CONICYT-Chile), under Grants 1140207 and 1120379 and by Universidad de Santiago de Chile (USACh), Vicerrectoría de Inves-tigacion, Desarrollo e Innovacion (VRIDEI)-Grant USA 1899, 021941UZ- PAP and Direccion de Investigacion en Ciencia y Tecnología (DICYT)- USACh 021841UZ.
- Subjects :
- chemistry.chemical_classification
Non-covalent interactions
Inorganic chemistry
Hydration
Alcohol
02 engineering and technology
010402 general chemistry
021001 nanoscience & nanotechnology
Condensed Matter Physics
Alkali metal
01 natural sciences
0104 chemical sciences
Dielectric spectroscopy
chemistry.chemical_compound
chemistry
Alcohol oxidation
Electrode
Alkali metal hydroxides
cardiovascular system
Alcohol electrooxidation
General Materials Science
1-Heptanol
0210 nano-technology
Heptanol
Subjects
Details
- Database :
- OpenAIRE
- Journal :
- Digital.CSIC. Repositorio Institucional del CSIC, instname
- Accession number :
- edsair.doi.dedup.....9bf50a7b2b89dabc4a9e00f56d733896