Regensburg 2019 – scientific programme
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O: Fachverband Oberflächenphysik
O 55: Metal Oxide Surfaces III: Adsorption and Reactivity
O 55.9: Talk
Wednesday, April 3, 2019, 17:00–17:15, H5
CH-Bond Activation via electronically excited SO2 on TiO2-Anatase-(101) and -Rutile-(110).Ab Initio Electronic Structure Investigation — •Luca Gerhards and Thorsten Klüner — Carl von Ossietzky Universität, Oldenburg, Germany
The photocatalytic heterogeneous sulfoxidation on titanium dioxides, which requires visible light, seems to be a promising new and more energy efficient alternative to the industrially applied reaction via UV-light.[1,2] Experimental investigations on the mechanism revealed that the adsorption of SO2 and its electronic excitation lead to a formation of a charge-transfer complex on the surface which catalyzes the subsequent chain reaction.[1] These results stand in contrast to the industrial mechanism and need a deeper investigation. In this contribution, we examine the adsorption and electronic excitation of SO2 and the CH-bond activation of alkanes on ideal TiO2-anatase-(101) and -rutile-(110) surfaces from a quantum chemical perspective. Both mechansims (heterogeneous and industrial) will be analysed via high accuracy multireference methods like CASSCF and NEVPT2 to attain a clearer insight into the behavior of this complex radical reaction. An embedded cluster model is designed and compared to calculations with periodic boundary conditions.
[1] F. Parrino, A. Ramakrishnan, H. Kisch, Angew. Chem. Int. Ed., 47(37), p. 7107-7109, 2008.
[2] R. Graf, Textilhilfsmittel-Laboratorium der Farbwerke Hoechst, 50-82, 1952.