Vibrational frequencies of CO adsorbed on silica supported Mo atoms from density functional calculations

The interaction of CO with silica supported molybdenum atoms has been studi ed by means of density functional calculations and cluster models. Experime ntally two bands in the IR spectra of adsorbed CO have been observed at 217 0 and 1990 cm(-1) with vibrational shifts of +27 and -153 cm(-1), respectiv ely, with respect to the gas-phase molecule, the peak at +27cm(-1) has been related to the presence of neutral Mo atoms anchored to two oxygen atoms o f the SiO2 substrate. Possible reactive sites at the Mo/SiO2 interface have been explored as candidates for CO adsorption. Mo atoms in various formal oxidation states, from +II to +VI, have been considered. Both molecular and cluster models of the Mo/SiO2 interface have been employed. The analysis s hows that a neutral Mo(II) atom, proposed to be responsible for the blue-sh ift of v(CO), is not likely to be the origin of the IR band at 2170 cm(-1). Only Mo atoms in high oxidation states or Mo cations carrying a real posit ive charge can account for the positive shifts in the CO frequency. (C) 200 1 Elsevier Science B.V. All rights reserved.