Abstract
Formation and properties of thiol (HS(CH2)10COOH or HS(CH2)10CH3) monolayers were investigated at stationary electrodes based on silver, copper, bismuth and cadmium solid amalgams covered by a mercury meniscus or by a mercury film (m-AgSAE, MF-AgSAE, m-CuSAE, m-BiAgSAE and m-CdSAE). For comparison, parallel experiments were performed at a classical hanging mercury drop electrode (HMDE). Thiol monolayers were prepared at an optimal deposition potential (e.g., for HS(CH2)10COOH Eac=−350mV for HMDE and silver amalgam electrodes, Eac=−750 to −800mV for m-CuSAE and m-BiAgSAE, and Eac=−1050mV for m-CdSAE) at which the formed layers exhibit high density and stability. It was found that the potential of a reductive desorption peak of a thiol monolayer strongly depends on the metal which forms the amalgam (for HS(CH2)10COOH: Ep=−864 to −859mV for HMDE and silver amalgam electrodes, Em-BiAgSAE=−1079mV, Em-CuSAE=−1136mV and Em-CdSAE=−1248mV). This allows to create a stable thiol layer in different potential regions according to its application. The influence of a thiol layer charge on the reduction potential was determined.
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