Investigation of current oscillatory phenomena based on Fe3+/Fe2+ at the liquid/liquid interface

A new oscillatory phenomenon based on Fe3+/Fe2+ was investigated systematically at the water/1,2-dichloroethane (W/DCE) interface by cyclic voltammetric technique. We focus our attention on study the concentrations of Fe3+/Fe2+ influence on oscillatory phenomena appearance in this paper. It was found that the current oscillation only occurred in the site of oxidation peak of Fe2+, and was related to the concentration of Fe3+ in the aqueous phase, indicating that the oscillation is caused by the specific adsorption of ion pairs at the liquid–liquid interface between Fe3+ in the aqueous phase and TPB− in the organic phase. Furthermore, DFT theory was used to calculate the mechanism of ion pair formation for the first time. The result suggested that TPB−Fe3+TPB− ion pair has the lowest-energy state, which provided qualitative support for ion pair embodied state. Combining experiment results and theoretical calculation, a specific adsorption of ion pair model on liquid/liquid interface was proposed and a mechanism for the observed current oscillation is also discussed in this paper. In addition, a spectrophotometric experiment was performed to evidence a strong attractive interaction between Fe3+ and TPB−.

► We report a novel oscillatory phenomenon for Fe3+/Fe2+ at W/DCE interface.
► The irregular current spikes observed mainly related to Fe3+ and TPB− concentrations.
► A specific adsorption of ion pair model was proposed for explain the oscillation.
► DFT calculation and the UV spectra provided support for the ion pair model.