Characterizing Redoxmer – Electrode Kinetics Using a SECM-Based Spot Analysis Method

A spot analysis approach that captures asymmetries in ET kinetics as well as difference in interfacial kinetics at different electrode materials

Scientific Achievement

Identified asymmetries in electron transfer (ET) kinetics between the reduction and oxidation of ferrocene-based redoxmers by measuring the ET rate constants (kf/kb) as a function of electrode potential.

Significance and Impact

An SECM protocol was developed to electrochemically characterize the electrode-electrolyte interfaces. Our work revealed a unique interplay between the solvent, electrolyte, and carbon electrode that results in slower ET during the reduction of Fc+ but enhancement during the oxidation of Fc.

Research Details

  • Reliable quantification of Butler – Volmer (B-V) kinetic parameters such as kf and α. As well as discern deviations from idealities
  • Lower rate constants were measured for the reduction of Fc+ consistently over a wide range carbon electrodes in PC solvent. However, no such impeded kinetics observed during the oxidation of Fc
  • Investigated ET behavior of interfaces at high redoxmer concentrations, which is not possible via conventional electrochemical techniques

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DOI: 10.1002/asia.202201120

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