In situ IR difference spectra of 11-mercaptoundecanoic acid monolayers deposited on gold have been recorded as a function of both solution pH⁎ and substrate’s potential. IR spectra recorded under voltammetric conditions indicate that the potential-induced ionization of the monolayer is a slow process, involving a simultaneous rearrangement of the hydrocarbon chains, and that a significant population of carboxylic groups are not dissociated at positive potentials in a pH⁎ 9 solution. Steep potentiostatic IR titration curves, consistent with a monolayer pKa = 4.3, are obtained at negative potentials. As the potential is made more positive, titration curves become lower, broader and are shifted towards more basic pHs. Rather than acting directly on the electrostatic energy of the carboxylate groups, the electrode potential seems to control the ionization of the monolayer by attracting (or repelling) cations from the electrolyte and by reorienting the thiol head groups inside and outside the low permittivity layer of methylene chains.
This work was supported by the Spanish DGICYT under grant CTQ2008-00371 and by the Junta de Andalucía under grant P07-FQM-02492.
- acid monolayers
- surface IR titration
- potential-induced reorientation
- potential-induced proton transfer