title: Generator-collector experiments at a single electrode: exploring the general applicability of this approach by comparing the performance of surface immobilized versus solution phase sensing molecules.
abstract: We demonstrate proof-of-concept that generator-collector experiments can be performed at a single macroelectrode and used to determine mechanistic information. The practical advantages of such a system over conventional generator-collector techniques are also outlined. The single-electrode generator-collector technique is applied to study the known mechanism of oxygen reduction in aqueous conditions as a model system. We seek to demonstrate that the single-electrode generator-collector approach is capable of detecting local pH changes, immediately adjacent to the electrode surface during a redox reaction. Experiments are performed using a molecular pH probe attached to the electrode surface. Comparison of experimental data with numerical simulations verifies that the reduction of oxygen at pH 6.8 proceeds via a two-electron, two-proton mechanism. Experiments were also performed with a molecular pH probe dissolved in the electrolyte solution in order to explore the feasibility of this approach, which is potentially applicable to a much wider range of electrochemical systems.
authors.affiliation: Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
authors.forename: Martin C
authors.initials: MC
authors.lastname: Henstridge
authors.forename: Gregory G
authors.initials: GG
authors.lastname: Wildgoose
authors.forename: Richard G
authors.initials: RG
authors.lastname: Compton