On the protonation of oxo- and hydroxo-groups of the goethite (α-FeOOH) surface: A FTIR spectroscopic investigation of surface O–H stretching vibrations

The O–H stretching region of goethite particles evaporated at different levels of acidity was investigated by Attenuated Total Reflectance (ATR)-Fourier Transform InfraRed (FTIR) spectroscopy. Two-dimensional IR Correlation Spectroscopy was used to identify correlations between different sets of discrete surface OH stretches and a Multivariate Curve Resolution analysis was used to resolve the predominant spectral components. Two dominant groups of hydroxyls were identified on the basis of their differences in proton affinity. Group I hydroxyls appear as two 3698/3541 and 3660/3490 cm−1 band pairs. Group II hydroxyls are manifested through the 3648 and 3578 cm−1 bands at greater levels of surface proton loading. There is consequently no correlation between O–H stretching frequencies and proton affinity. Groups I and II were assigned to mostly singly- (–OH) and doubly- (μ-OH) coordinated hydroxyls, respectively. Stretches arising from triply-coordinated (μ3-OH) are proposed to be embedded within the dominant O–H band of bulk goethite. The possibility that these sites contribute to Group I and II hydroxyls should, however, not be entirely dismissed without further investigations.A reexamination of Temperature Programmed Desorption (TPD)-FTIR data of one goethite sample evaporated from alkaline conditions [Boily J.-F., Szanyi J., Felmy A. R. (2006) A combined FTIR and TPD study on the bulk and surface dehydroxylation and decarbonation of synthetic goethite. Geochim. Cosmochim. Acta70, 3613–3624] provided further constraints to this band assignment by providing clues to the network of surface hydrogen bonds. Important cooperative effects between hydrogen-bonded surface hydroxyls are suggested to play a crucial role on the variations of the position and intensity of discrete O–H stretching bands as a function of protonation level and temperature.