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Electrochemical behaviour of hexacyanoferrate(II)/(III) and ferrocene/ferricinium in lyotropic liquid crystals of polyoxyethylene (10) cetylether (Brij 56)

Electrochemical behaviour of hexacyanoferrate(II)/(III) and ferrocene/ferricinium in lyotropic liquid crystals of polyoxyethylene (10) cetylether (Brij 56)
Electrochemical behaviour of hexacyanoferrate(II)/(III) and ferrocene/ferricinium in lyotropic liquid crystals of polyoxyethylene (10) cetylether (Brij 56)
The conductivity of a lyotropic liquid crystal medium (LLC) consisting of 50:50 wt% Brij 56® and 0.5 M aqueous KCl was found to be five times lower than the purely aqueous solution. Electrochemical properties of potassium hexacyanoferrate(II/III) and ferrocene/ferricinium in the LLC were examined by cyclic voltammetry and chronoamperometry on platinum foil and microdisk electrodes. The hexacyanoferrate showed reversible redox behaviour under diffusion control with a diffusion coefficient of 0.5 – 1.0 × 10–6 cm2s–1, up to 14 times lower than in water. Ferricinium reduction, while complicated in water by precipitation of ferrocene, showed solution behaviour and normal diffusion control in the liquid crystal. Effective diffusion coefficients of ferrocene and ferrocinium in the lyotropic liquid crystal were found to be further reduced to 4 – 5 × 10–8 cm2s–1. The lower diffusion coefficients compared with those in liquid solvents were attributed to restricted mobility and channel size effects in the LLC. The results are relevant to the design of electrochemical syntheses using LLC as nanostructured templates or as amphiphilic solvents.
1572-6657
18-23
Reiter, Jakub
30c5abbb-2e17-4e6b-9eb0-6c17e87b47ce
Uhlířová, Tereza
21e62e4f-c6a1-4b37-8068-2503e0489ca9
Owen, John R.
067986ea-f3f3-4a83-bc87-7387cc5ac85d
Reiter, Jakub
30c5abbb-2e17-4e6b-9eb0-6c17e87b47ce
Uhlířová, Tereza
21e62e4f-c6a1-4b37-8068-2503e0489ca9
Owen, John R.
067986ea-f3f3-4a83-bc87-7387cc5ac85d

Reiter, Jakub, Uhlířová, Tereza and Owen, John R. (2010) Electrochemical behaviour of hexacyanoferrate(II)/(III) and ferrocene/ferricinium in lyotropic liquid crystals of polyoxyethylene (10) cetylether (Brij 56). Journal of Electroanalytical Chemistry, 646 (1-2), 18-23. (doi:10.1016/j.jelechem.2010.04.014).

Record type: Article

Abstract

The conductivity of a lyotropic liquid crystal medium (LLC) consisting of 50:50 wt% Brij 56® and 0.5 M aqueous KCl was found to be five times lower than the purely aqueous solution. Electrochemical properties of potassium hexacyanoferrate(II/III) and ferrocene/ferricinium in the LLC were examined by cyclic voltammetry and chronoamperometry on platinum foil and microdisk electrodes. The hexacyanoferrate showed reversible redox behaviour under diffusion control with a diffusion coefficient of 0.5 – 1.0 × 10–6 cm2s–1, up to 14 times lower than in water. Ferricinium reduction, while complicated in water by precipitation of ferrocene, showed solution behaviour and normal diffusion control in the liquid crystal. Effective diffusion coefficients of ferrocene and ferrocinium in the lyotropic liquid crystal were found to be further reduced to 4 – 5 × 10–8 cm2s–1. The lower diffusion coefficients compared with those in liquid solvents were attributed to restricted mobility and channel size effects in the LLC. The results are relevant to the design of electrochemical syntheses using LLC as nanostructured templates or as amphiphilic solvents.

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Published date: 2010

Identifiers

Local EPrints ID: 150633
URI: http://eprints.soton.ac.uk/id/eprint/150633
ISSN: 1572-6657
PURE UUID: 0b066912-53d0-4afa-a233-5d0c63931d57
ORCID for John R. Owen: ORCID iD orcid.org/0000-0002-4938-3693

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Date deposited: 06 May 2010 14:06
Last modified: 20 Jul 2019 01:22

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