Surface Enhanced Infrared Studies of 4‑Methoxypyridine Adsorption on Gold Film Electrodes

This work uses electrochemical surface sensitive vibrational spectroscopy to characterize the adsorption of a known metal nanoparticle stabilizer and growth director, 4-methoxypyridine (MOP). Surface enhanced infrared absorption spectroscopy (SEIRAS) is employed to study the adsorption of 4-methoxypyridine on gold films. Experiments are performed under electrochemical control and in different electrolyte acidities to identify both the extent of protonation of the adsorbed species as well as its orientation with respect to the electrode surface. No evidence of adsorbed conjugated acid is found even when the electrolyte pH is considerably lower than the pK a. Through an analysis of the transition dipole moments, determined from DFT calculations, the SEIRA spectra support an adsorption configuration through the ring nitrogen which is particularly dominant in neutral pH conditions. Adsorption is dependent on both the electrical state of the Au film electrode as well as the presence of ions in the electrolyte that compete for adsorption sites at positive potentials. Combined differential capacitance measurements and spectroscopic data demonstrate that both a horizontal adsorption geometry and a vertical adsorption phase can be induced, with the former being found on negatively charged surfaces in acidic media and the latter over a wide range of polarizations in neutral solutions.