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Photoelectrochemical reduction of p-bromonitrobenzene: Mechanistic discrimination via channel microband array voltammetry

Abstract:
Two dimensional voltammetry using an array of channel microband electrodes varying in size from ca. 2 mm to under 1 micron in length, has been used to study the photoreduction of p-bromonitrobenzene. In the dark p-bromonitrobenzene is reduced al - 1.09 V (vs. SCE). On irradiation with strong white light significant photocurrents flowed which were recorded at flow rates from 2 x 10-3 cm3 s-1 to ca. 0.3 cm3 s-1 at various electrode sizes. Mechanistic analysis of these steady-state measurements is shown to unambiguously rule out an ECEE mechanism but suggests instead that an ECE description is the correct one. The analysis is carried out using a WWW based data analysis centre which uses stored working curves to provide best-tit values for the rate constant of the chemical step and for the mean diffusion coefficient of the species involved.
Publication status:
Published

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Physical & Theoretical Chem
Role:
Author


Journal:
ELECTROANALYSIS More from this journal
Volume:
10
Issue:
17
Pages:
1182-1187
Publication date:
1998-12-01
DOI:
ISSN:
1040-0397


Language:
English
Keywords:
UUID:
uuid:71e8c86f-6c45-4b9f-97bc-d032c8a95b48
Local pid:
pubs:36867
Source identifiers:
36867
Deposit date:
2012-12-19

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