Potential dependence of the stretching frequency of carbon monoxide bound to the surface of platinum dispersed in an electrode-confined redox polymer
Variation in the electrochemical potential of the electrode results in a change in the stretching frequency of CO bound to elemental Pt dispersed in an electrode-confined redox polymer, (PQ/sup 2+/+/)/sub n/, derived from an N,N'-dialkyl-4,4'-bipyridinium monomer. The stretching frequency of the CO, about 2000 cm/sup -1/, can be monitored by transmission infrared spectroscopy using a Fourier transform infrared (FTIR) spectrometer and moves to lower values with movement of the potential to more negative values. Spectroelectrochemical studies were conducted by using an IR-transparent n-Si/((PQ/sup 2+/+/Pt(CO)/sub x/)/sub n/) electrode assembly in an electrochemical cell with the derivatized surface exposed to the electrolyte solution. Experiments have been carried out with both natural-abundance and 99% /sup 13/C-enriched CO, and the potential dependence is the same, about 20 cm/sup -1/ V/sup -1/, over the potential range studied, approximately 0.0 to -1.4 V vs. Ag/sup +//Ag in CH/sub 3/CN/2 M LiClO/sub 4/. The stretching frequency of natural-abundance CO in the same assembly has been studied in H/sub 2/O/3 M LiCl and shows a slightly larger potential dependence, about 35 cm/sup -1/ V/sup -1/, in the range -0.2 to -1.0 V vs. AgCl/Ag. The data for the CO bound to the Pt dispersed in the polymer is in accord with similar data obtained for CO bound to smooth Pt electrode surfaces.
- Research Organization:
- Massachusetts Institute of Technology, Cambridge
- OSTI ID:
- 5896597
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:4; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ABSORPTION SPECTROSCOPY
ALKANES
AZINES
BIPYRIDINES
CARBON 13
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
DATA
DISPERSIONS
ELECTRIC POTENTIAL
ELECTRODES
ELEMENTS
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
ISOTOPE APPLICATIONS
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
METALS
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PLATINUM
PLATINUM METALS
POLYMERS
PYRIDINES
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
TRACER TECHNIQUES
TRANSITION ELEMENTS