Adsorption of acetone on rutile TiO2: a DFT and FTIRS study

Acetone adsorbed on rutile TiO 2 nanoparticles was investigated with respect to its energetic, vibrational, and chemical properties. Temperature-dependent ultrahigh-vacuum Fourier transform infrared spectroscopy measurements for different acetone dosages (4.5-900 L) give insights into the acetone adsorption behavior. Those experiments indicate thermal-induced reactions of acetone on rutile TiO 2 surfaces yielding new species. Density functional theory calculations were performed to investigate acetone adsorption on rutile TiO 2 (110). Particularly, the importance of sampling the adsorption configuration space is shown. Adsorption geometries that are energetically significantly more favorable than the commonly used high-symmetry configurations are presented. To facilitate the comparability to the experiment, theoretical infrared spectra were computed using density functional perturbation theory for various acetone adsorption geometries using different exchange-correlation functionals. Additionally, computational spectra were obtained for several species which are potential products from reactions of acetone on TiO 2 surfaces. The investigated species are η 2 -acetate, η 2 -diolate, η 1 -enolate, and mesityl oxide. For η 1 -acetone, experimental and calculated spectra fit well for low temperatures, whereas for elevated temperatures, emerging bands indicate the formation of diolate.

DDC Class

620: Ingenieurwissenschaften

Funding(s)

SFB 986, Teilproject A4 - Ab-initio basierende Modellierung und Beeinflussung der mechanischen Eigenschaften von Hybridgrenzflächen

Lizenz

https://creativecommons.org/licenses/by/4.0/

Name

acs.jpcc.8b04222.pdf

Size

3.95 MB

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Adobe PDF

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Adsorption of acetone on rutile TiO2: a DFT and FTIRS study