Electrochemical reductive desorption of alkyl self-assembled monolayers studied in situ by spectroscopic ellipsometry: evidence for formation of a low refractive index region after desorption.

Gold-sulphur bonds holding self-assembled monolayers (SAMs) on their gold substrate can be broken by electrochemical reduction, which typically occurs in an electrode potential range where the electrochemical hydrogen evolution reaction (HER) is thermodynamically possible. This work uses an in situ coupling between cyclic voltammetry and spectroscopic ellipsometry to compare the interfacial structure after desorption of the aliphatic thiols 1-Dodecanethiol (DDT) and 1-Octadecanethiol (ODT), and the ω-hydroxythiol 11-Mercapto-1-undecanol (MUD). For MUD and DDT, the data can only be explained by the presence of a substance with a significantly lower refractive index than the aqueous electrolyte in the interfacial region. This substance is likely to be H2. The hypothesis is put forward here that for MUD and DDT, desorbed molecules stabilise "nanobubbles" of H2. The resulting aggregates form as initial stages of the process of complete disintegration of the SAMs, i.e. the loss of the SAM-forming molecules into solution. On the other hand, desorption and readsorption of ODT are fully reversible - the presence of a layer with low refractive index can neither be excluded nor confirmed in this case. The results indicate that different SAM-stabilities are a consequence of solubility of the thiolates.