Competition between Acetaldehyde and Crotonaldehyde during Adsorption and Reaction on Anatase and Rutile Titanium Dioxide

The adsorption of acetaldehyde and crotonaldehyde on the anatase and rutile polymorphs of TiO2 has been investigated with Fourier transform infrared spectroscopy (FTIR). Chemisorption of acetaldehyde on TiO2 involves a strong interaction between the surface and the carbonyl oxygen, causing a significant shift in the location of the ν(CO) vibrational mode to lower frequencies; no interaction with surface hydroxyl groups was observed. Capacities for acetaldehyde and crotonaldehyde adsorption under conditions relevant to aldolization reactions were determined in a novel reactor system providing simultaneous mass measurements and mass spectral analysis of gas-phase products. The coverage of acetaldehyde irreversibly adsorbed on TiO2 was similar to values previously reported for the adsorption of alcohols; coverages of crotonaldehyde were approximately 60% of those for acetaldehyde. Both gas-phase and surface analyses indicate that formation of crotonaldehyde by aldol condensation of acetaldehyde occurs on rutile TiO2 at temperatures as low as 313 K. This reaction was not observed on anatase at these conditions; higher temperatures were required. The production of crotonaldehyde on rutile at 313 K diminished with increasing exposure of acetaldehyde. Acetaldehyde and crotonaldehyde adsorbed in a similar fashion on both anatase and rutile, and either aldehyde could displace the other from the surface layer. Accordingly, the surface concentrations of adsorbed acetaldehyde and crotonaldehyde mirror those in the gas phase. Upon heating an adsorbed layer of acetaldehyde, small amounts of ethoxide and acetate species were formed, possibly from a Cannizzaro-type disproportionation reaction. The similarity of these results to those of studies on TiO2 single crystals illustrates the applicability of properly chosen metal oxide single-crystal surfaces as models for polycrystalline powders. Both demonstrate that the chemistry of aldehydes on TiO2 can be successfully explained in terms of the reactions of a few key surface species.