Three-Electrode TiO2 + rGO Cells: Classical Controls and Interpretation within a Quantum-Discord Framework

Abstract

In three-electrode electrochemical impedance spectroscopy (EIS), the impedance/capacitance response of the working electrode (WE) is measured relative to the reference electrode (RE), whereas the current required by potentiostatic control flows between the WE and the counter electrode (CE). Under classical three-electrode operation, the measured WE-RE response should therefore be independent of the properties of the electrode used as the CE, provided that conventional electrochemical and instrumental artifacts are negligible. Here, we test this expectation in cells containing nanostructured electrodes TiO2 + rGO and examine the results within a framework motivated by quantum discord to describe effective interelectrode correlations. We used dummy-cell measurements, a two-electrode bar-bar control, comparisons between Pt and bar CEs, a dummy circuit introduced into the CE branch, and CE ensemble comparisons to distinguish additive circuit behavior from CE-dependent behavior specific to the three-electrode configuration. In these experiments, the measured three-electrode capacitance response depends on CE, an effect that is not reproduced by the dummy-circuit controls examined. These findings identify a macroscopic CE-dependent capacitance response that departs from the tested classical expectation and is compatible with an effective interelectrode-correlation framework motivated by quantum discord, although the capacitance evidence alone does not constitute a direct measurement of quantum discord.

31 pages, 7 figures; Supplementary Material: 9 pages, 4 figures