Capacitive Impedance for Following In-Situ Grafting Kinetics of Diazonium Salts

A new method to follow in-situ grafting kinetics of diazonium compounds based on imposing small amplitude high frequency AC oscillations at grafting potential, is outlined. This enables the time-resolved measurements of capacitive impedance concomitantly with the growth of the organic layer at the working electrode. The impedance values were quantitatively correlated with the ex-situ (from voltammograms) and in-situ (from quartz crystal microbalance) measured surface coverages, providing a validation of the new methodology. The versatility of the developed approach was demonstrated on the grafting via reduction of 4-nitrobenzenediazonium on Au and glassy carbon (GC) substrates and via deposition of in-situ generated diazonium salts from 1-aminoanthraquinone and 4-ferrocenylaniline on GC. The capacitive impedance measurements are simple, fast, and non-destructive, making it an appealing methodology for an exploration of grafting kinetics of a wide range of diazonium salts.