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Journal ArticleDOI

Infrared Spectroelectrochemical Analysis of Adsorbed Hexacyanoferrate Species Formed during Potential Cycling in the Ferrocyanide/Ferricyanide Redox Couple

Christine M. Pharr† and, +1 more
- 15 Nov 1997 - 
- Vol. 69, Iss: 22, pp 4673-4679
TLDR
In this article, the formation of an adsorbed hexacyanoferrate (HCF) species on a platinum electrode during potential cycling in the ferri/ferrocyanide redox couple was investigated.
Abstract
External reflection FT-IR techniques allowed for in situ examination of interfacial electrochemical events occurring in a thin-layer spectroelectrochemical cell. The formation of an adsorbed hexacyanoferrate (HCF) species on a platinum electrode during potential cycling in the ferri-/ferrocyanide redox couple was investigated. At neutral pH with KCl as electrolyte, a hexacyanoferrate complex forms during potential cycling in the ferri-/ferrocyanide redox couple, but only if the potential limits are quite large. Characterization of the adsorbed complex indicates that it initially adsorbs as soluble Prussian Blue (KFeII[FeIII(CN)6]) with no evidence of the presence of insoluble Prussian Blue [Fe4III(Fe2II(CN)6]. This HCF complex can reversibly adsorb and grow on the electrode surface and desorb and decompose to reform solution-phase ferricyanide and ferrocyanide. Adsorption of the HCF complex decreases, but does not completely inhibit, electron transfer.

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PatentDOI

Scanning electrochemical microscopy

TL;DR: A method for locating a chemical substance on the surface of a material and for determining the contour of a surface of the material using a scanning electrochemical microscope is provided in this article.
Journal ArticleDOI

Single-crystal FeFe(CN)6 nanoparticles: a high capacity and high rate cathode for Na-ion batteries

TL;DR: In this paper, the purity and crystallinity of the Prussian blue lattices were controlled to achieve high capacity and high cyclability for Na ion battery applications, and a single-crystal FeIIIFeIII(CN)6 nanoparticles were synthesized and found to have a sufficiently high capacity of 120 mA h g−1, an exceptional rate capability at 20 C and superior cyclability with 87% capacity retention over 500 cycles.
Journal ArticleDOI

A new view of electrochemistry at highly oriented pyrolytic graphite.

TL;DR: High spatial resolution electrochemical imaging with scanning electrochemical cell microscopy, on the highest quality mechanically cleaved HOPG, demonstrates definitively that the pristine basal surface supports fast electron transfer (ET) kinetics, and that ET is not confined to step edges.
Journal ArticleDOI

Charging-free electrochemical system for harvesting low-grade thermal energy

TL;DR: A charging-free TREC consisting of an inexpensive soluble Fe(CN)63−/4− redox pair and solid Prussian blue particles as active materials for the two electrodes is demonstrated, which may have potential application for harvesting low-grade heat from the environment, especially in remote areas.
Journal ArticleDOI

Definitive Evidence for Fast Electron Transfer at Pristine Basal Plane Graphite from High‐Resolution Electrochemical Imaging

TL;DR: High-resolution scanning electrochemical cell microscopy demonstrates that electron transfer at the basal plane of highly oriented pyrolytic graphite (HOPG) is fast, and this finding requires radical revision of the current textbook model for HOPG electrochemistry.
References
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Journal ArticleDOI

The influence of alkali metal cations on the rate of the Fe(CN)64−/Fe(CN)63− electrode process

TL;DR: In this article, the rate of the hexacyanoferrate redox system shows a first order dependence on the concentration of the cationic component of the supporting electrolyte.
Journal ArticleDOI

Electrochemically modulated infrared spectroscopy (EMIRS): Experimental details

TL;DR: In this paper, the experimental details regarding the methods and equipment necessary for the EMIRS technique are described and a description of the experimental results of the EM IRS technique is given.
Journal ArticleDOI

Electrode/electrolyte interphase study using polarization modulated ftir reflection-absorption spectroscopy

TL;DR: In this paper, a polarization modulated Fourier transform infrared reflection-absorption spectroscopy (FT-IRRAS) was applied to the studies of adsorption and oxidation of CO on a platinum electrode in 0.5 M sulfuric acid and of cyanide on gold and silver electrodes in 0.5 M potassium sulfate.
Journal ArticleDOI

Stark effect of adsorbate vibrations

TL;DR: The theory of the vibrational Stark effect of adsorbates is discussed in this paper, where the reported linear variation of CO vibrational frequency with potential difference across the Pt-electrolyte interface is shown to be consistent with a recent measurement of the Stark tuning rate of CO on Ni in UHV and the differential capacitance of the Pt electrode interface.
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