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TiO2 Nanoparticles Enabling Photocatalytic Desulfurization for C-C Coupling Reaction Using Visible Light
Shea Stewart1, Matas Simukaitis1, H Christopher Fry2
1Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.
None:
We uncover a surface-mediated mechanism for visible-light-driven photocatalytic desulfurization of thiols on titanium dioxide (TiO2) nanoparticles under LED illumination (>420 nm). Combined diffuse reflectance, infrared, and cryogenic electron paramagnetic resonance spectroscopy verify the formation of a surface thiol-Ti charge-transfer complex that introduces visible-light absorption into an otherwise UV-active reaction system. Selective photoexcitation of this surface complex drives interfacial charge transfer, directly activating the adsorbed thiol and inducing C-S bond scission without the band gap excitation of TiO2. The resulting carbon-centered radical intermediates are intercepted by styrene to form C-C coupling products. These results uncover a distinct surface-mediated photocatalytic mechanism in which charge-transfer complex formation governs both light absorption and chemical activation, providing a mechanistic framework for extending visible-light reactivity to wide-bandgap metal oxide photocatalysts.
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