Identifying Photocatalytic Active Sites of C₂H₆ C-H Bond Activation on TiO₂ via Combining First-Principles...

The activation of C-H bonds at low temperatures has attracted widespread interest in heterogeneous catalysis, which involves complex thermocatalytic and photocatalytic reaction processes. Herein, we systematically investigate the photothermal catalytic process of C-H bond activation in C₂H₆ dehydrogenation on rutile TiO₂(110). We demonstrate that the photochemical activity of the C₂H₆ molecule adsorbed on TiO₂(110) is site-sensitive and that C₂H₆ is more easily adsorbed at the Ti_5c site with a lower dehydrogenation energy barrier. The first C-H bond activation of the C₂H₆ adsorbed at the Ti_5c site tends to occur in the ground state, whereas O_br-adsorbed C₂H₆ is more photoactive during the initial adsorption. During the dehydrogenation of C₂H₆, the photogenerated electrons are always located at the Ti⁴⁺ sites of the TiO₂ substrate while the photogenerated holes can be captured by C₂H₆ to activate the C-H bond.