Acetaldehyde adsorption and condensation on anatase TiO2: Influence of acetaldehyde dimerization

• Published in: Journal of molecular catalysis. A, Chemical Chemical, 2014-01, Vol.381, p.77-88
• Main Authors: Stefanov, B.I., Topalian, Z., Granqvist, C.G., Österlund, L.
• Format: Article
• Language: English
• Subjects: Acetaldehyde; Adsorption; Catalysis; Chemistry; DFT; Dimer; Exact sciences and technology; FTIR; General and physical chemistry; Surface physical chemistry; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; TiO2
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2013.10.005

•The condensation of acetaldehyde on the TiO2 surface was studied by in situ FTIR spectroscopy and DFT calculations.•Kinetic modelling and DFT were applied to identify key elementary surface reaction steps.•An unknown surface specie associated with an adsorbed dimer acetaldehyde was identified.•An improved general reaction scheme for acetaldehyde condensation on TiO2 is presented. Conversion of acetaldehyde to crotonaldehyde on anatase TiO2 films was studied by in situ Fourier transform infrared (FTIR) spectroscopy and by density functional theory (DFT) calculations. In situ FTIR showed that acetaldehyde adsorption is accompanied by the appearance of a hitherto non-assigned absorption band at 1643cm−1, which is shown to be due to acetaldehyde dimers. The results were supported by DFT calculations. Vibrational frequencies calculated within a partially relaxed cluster model for molecular acetaldehyde and its dimer, and for the corresponding adsorbed species on the anatase (101) surface, were in good agreement with experimental results. A kinetic model was constructed based on the combined FTIR and DFT results, and was shown to explain the essential features of the acetaldehyde condensation reaction.