An electrochemical quartz crystal microbalance (EQCM) based on microelectrode arrays allows to distinguish between adsorption and electrodeposition†

Abstract

Using a precise electrochemical quartz crystal microbalance (EQCM), it was shown that electrogravimetry can be carried out with microelectrode arrays (MEAs). MEAs were prepared on the resonator surface by coating it with a thin polymer layer containing holes, where the holes constitute the microelectrodes. The preparation procedures, their benefits, and their limitations are discussed. Microelectrode-based electrogravimetry is challenging because the reduced active area reduces the QCM signal. It is still feasible. This work is limited to linear voltage ramps (as opposed to steps). The processes chosen for demonstration were the electrodeposition/stripping of copper and the redox cycling of methyl viologen dichloride (MVC). The current trace often showed microelectrodic behavior, depending on the sweep rate. For the case of copper deposition, the mass transfer rate was proportional to the electric current. For the case of MVC, the electric current showed a plateau at the ends of the current–voltage diagram, but the mass transfer rate did not change. The difference can be explained by adsorption and desorption going into saturation at the two ends of the voltage range. Based on whether or not a microelectrodic gravimetric signal is seen, it can be stated whether the mass transfer is closely linked to the current. Further advantages of the microelectrode-based EQCM are an improved access to fast processes, reduced effects of double layer recharging, and the possibility to work at a low electrolyte support.