Fourier transform reflection-absorption IR spectroscopy study of formate adsorption on TiO2(110)

The adsorption of the formate species produced by dissociative adsorption o f formic acid on TiO2(110) has been investigated using a combination of X-r ay photoelectron spectroscopy (XPS) and Fourier transform reflection-absorp tion IR spectroscopy (FT-RAIRS). Adsorption at 300 K produces a formate cov erage of 0.59 ML, in agreement with previous estimates and higher than that expected for a perfect(2 x 1) overlayer observed in low-energy electron di ffraction (LEED). p-Polarized FT-RAIRS measurements carried out as a functi on of azimuthal angle (Phi) reveal the presence of two formate species thro ugh the coupling of both the tangential (I,) and normal (I,) components of the radiation to the symmetric (v(sym)(OCO)) and antisymmetric (v(asym)(OCO )) vibrational modes of the molecule. Species A has the OCO plane aligned i n the [001] direction with C-2v symmetry; v(asym)(OCO) = 1566 cm(-1) is obs erved as an absorption band (coupled to I-t) at Phi= 90 degrees, and v(sym) (OCO) = 1363 cm(-1), observed as a transmission band (coupled to I-n). Spec ies B has the OCO plane aligned in the [110] direction with C-s symmetry; v (asym)(OCO) = 1535 cm(-1), observed as an absorption band (coupled to I-t) at Phi = 90 degrees, and v(sym)(OCO) = 1393 cm(-1), observed as a transmiss ion band (coupled to I-n). Changes in the region of the v(sym)(OCO) at 1363 cm(-1) for species A as a function of azimuthal angle (this band should be insensitive to Phi) are associated with an absorption band resulting from a coupling of v(sym)(OCO) of species B to I-t. This is a result of the redu ction in symmetry from C-2v to C-s and, as expected from the adsorption geo metry, is observed at Phi = 0 degrees and not at Phi = 90 degrees. We estim ate that the coverages of species A and species B at 300 K are 0.4 and 0.2 ML, respectively. Species A is the adsorbate responsible for the formation of the (2. x 1) ordered structure and adsorbed between the TiO2(110) oxygen rows. Species B we suggest is an adsorbed formate molecule with one of the oxygens incorporated in the TiO2(110) oxygen rows and is the species assoc iated with the so-called disordered phase. It is clear from FT-RAIRS that t he coverage of species B is increased by adsorbing formic acid at higher su rface temperatures. We suggest that species B adsorbs at defects (oxygen va cancies) created through dissociative adsorption of formic acid to produce species A and the subsequent reaction of two hydroxyl groups to produce wat er. The existence and interdependence of the two adsorbed formate species p rovide an explanation for the complex activity observed for various catalyt ic reactions of formic acid over titania.