Theoretical investigation of CH-bond activation by photocatalytic excited SO 2 and the effects of C-, N-, S-, and Se-doped TiO 2 .

The photocatalytic sulfoxidation on TiO 2 discovered by Parrino et al. represents a new, interesting and lower energy route for the synthesis of sulfonic acids. Sulfonic acids are important precursors for dyes, detergents and drugs. In the commonly known industrial process, SO 2 and a specific hydrocarbon are converted into sulfonic acids using high-energy UV light. In this reaction, SO 2 is excited into a metastable triplet state ( 3 SO 2 ), which has the potential to activate a CH-bond of hydrocarbons and start a radical reaction cycle. By introducing TiO 2 as a photocatalyst, it has been shown that visible light can be used for the synthesis. This offers the potential to be a cost-effective reaction approach for industrial use. However, experimental studies indicate that the initial excitation mechanism of SO 2 on TiO 2 is significantly different from the catalyst-free mechanism. Parrino et al. were able to reveal first evidence for the existence of a charge-transfer process from SO 2 to the TiO 2 surface by means of electrochemical experiments. First theoretical investigations from first principles were able to further substantiate the existence of a charge-transfer. However, to fully understand this mechanism, more accurate methods such as Time Dependent Density Functional Theory (TD-DFT) or ab initio multireference methods such as the Complete Active Space Self Consistent Field (CASSCF) method are required. Furthermore, after understanding the charge-transfer mechanism, the introduction of dopants into TiO 2 can be investigated in order to possibly redshift the excitation energy. This might open the route to using lower energy light for the sulfoxidation of hydrocarbons on TiO 2 as a new potential industrial reaction for the synthesis of sulfonic acids. In this work, we will study the initial step of the photocatalytic sulfoxidation of hydrocarbons using the TD-DFT and CASSCF methods by using a combined approach consisting of calculations with periodic boundary conditions and a newly constructed embedded cluster model. Furthermore, we will explore the effects of doping by introducing four heteroatoms (C, N, S, and Se) into the TiO 2 surfaces anatase[101] and rutile[110] to find a possible enhancement of the photocatalytic reactivity by lowering the electronic excitation energy.