Adsorbate-substrate interaction between chlorodifluoromethane and titanium dioxide: Infrared spectroscopy and density functional theory studies

Infrared spectra of chlorodifluoromethane (CHClF2) adsorbed on titanium dioxide (TiO2) at room temperature have been investigated for the first time. From the comparison between the adsorption characteristics and the gas-phase spectra it can be deduced that the molecule interacts with the surface Lewis acid site (Ti4+) mainly through the Cl atom even if also the adsorption with one F atom is also observed. Moreover, the spectra show the presence of H-bonds between the CH group and the surface Lewis basic site (OH- or O2-). In order to obtain more information on the molecule orientation and the variation of the structural parameters, a DFT-B3LYP study has been carried out considering the anatase (1 0 1) surface and evaluating the adsorption energetics in terms of interaction, distortion and binding energies. The obtained geometries confirm that both the acid-base interactions through Cl or F atoms are possible and suggest the formation of one H-bond between the CH group of the molecule and the Lewis basic site of the surface. The calculated vibrational frequencies of the adsorbed molecule have been found to be in reasonable agreement with the experimental data. © 2011 Elsevier B.V. All Rights Reserved