Scholarly Communications Project


Characterization of Electrochemical Interfaces by Infrared Spectroscopy

by

Jimin Huang

Dissertation submitted to the Faculty of the Virginia Polytechnic Institute and State University in partial fulfillment of the requirements for the degree of

Ph.D.

Approved

Dr. Mark R. Anderson, Chair
Dr. Karen J. Brewer
Dr. Gary L. Long
Dr. James M. Tanko
Dr. Brian M. Tissue

August 30, 1996
Blacksburg, Virginia


Abstract

The properties of electrochemical interfaces are studied using Fourier transform infrared spectroscopy. Potential difference infrared spectroscopy (PDIRS) was used in the investigation of carbon monoxide adsorbed on polycrystalline platinum electrodes. It is found that the infrared peak position of adsorbed carbon monoxide is linearly dependent on the applied electrode potential, and that the Stark tuning rate is a function of system temperature. The change in Stark tuning rate is the result of the variation of the interfacial dielectric constant with temperature. Self-assembled alkoxyalkanethiol monolayers were formed on gold substrates as surface modifiers of low dielectric constant designed to influence the interfacial capacitance. Polarization modulation infrared spectroscopy (PMIRS), ellipsometry, interfacial wetting, and cyclic voltammetry were conducted to characterize the modified interfaces. The interfacial capacitance is greatly reduced due to the adsorption of w-mercapto ethers on substrates. It was found that the solvation of the monolayer by solution is capable of improving the mass transport to maintain the Faradaic current while lowering the interfacial capacitance. The oxygen group in w-mercapto ethers at the monolayer-water interface interacts with water molecules to improve the monolayer solubility in water. The w-mercapto ether monolayers were found to be fluid-like in structure, giving better freedom to undergo structural change. The repulsion from the oxygen atoms in adjacent w-mercapto ether molecules adsorbed on the substrate introduces structural disorder to the alkyl chains in the monolayer, allowing better solvent permeation. This relieves some of the current blocking character of long chain alkanethiol monolayers. The interfacial contact angle to water for the w-mercapto ether monolayers is dependent on the oxygen position in the monolayer. 12-Methoxydodecanethiol has the lowest contact angle among all the w-mercapto ethers studied while 12-butoxydodecanethiol through 12-hexoxydodecanethiol have similar contact angles due to the ether oxygen being buried beneath several layers of methylene groups. The film thickness is roughly proportional to the total number of methylene groups in the two alkyl chains on w- mercapto ethers. w-Mercapto ethers that have a longer alkyl chain between the oxygen and thiol tend to form thicker monolayers on the substrates. In situ PMIRS measurements show that w-mercapto ether monolayers do not undergo structural change in the alkyl chains when in contact with either water or acetonitrile. The terminal methyl group, however, suffers from a shift in infrared peak position to lower frequency, and a decrease in peak height as the result of solvent load.

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