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Square-Wave Electrogravimetry Combined with Voltammetry Reveals Reversible Submonolayer Adsorption of Redox-Active Ions.

Christian LeppinArne LanghoffDiethelm Johannsmann
Published in: Analytical chemistry (2022)
Square-wave voltammetry on electrolytes containing reversible redox pairs in solution was complemented by acoustic microgravimetry, where multifrequency lock-in amplification provides for a time resolution of 2.5 ms and a frequency resolution after accumulation of 12 mHz. The instrument operates similar to a quartz crystal microbalance with dissipation monitoring (QCM-D). The use of square-waves rather than linear ramps makes the analysis more transparent because it reduces the contribution of non-Faraday currents. Also, square-wave electrogravimetry determines the rates of mass transfer with much better sensitivity than its counterpart based on linear voltage ramps. The shifts of frequency and bandwidth are in agreement with the Sauerbrey prediction, meaning that the overtone-normalized frequency shifts, Δ f / n , are similar on the different overtones and that the shifts in half bandwidth, ΔΓ, are smaller than the shifts in frequency. Small deviations from the Sauerbrey prediction presumably result from the softness of the adsorbed layer. Because the response time of the QCM signals is much longer than the RC time of double layer recharging as determined with electrochemical impedance spectroscopy (EIS), interpretation in terms of adsorption and desorption is more plausible than interpretation in terms of changed viscosity in the diffuse double layer. Ions of methyl viologen (MV) were found to adsorb to the electrode surface more strongly in the state with a single charge than in the fully oxidized state carrying two charges. The difference in apparent thickness between the oxidized and the reduced state was up to 2 nm, depending on concentration. The gravimetric results obtained on flavin adenine dinucleotide (FAD) depended on pH. At neutral pH, adsorption was largest close to the redox potential. Presumably, the adsorbed molecules are semiquinones, that is, are the intermediates of the underlying two-electron process.
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