Photocatalytic selectivity switch to C–C scission: α-methyl ejection of tert-butanol on TiO2(110)
文献信息
Sebastian L. Kollmannsberger, Carla Courtois, Martin Tschurl
The thermal and photochemical mechanistic pathways for tertiary alcohols on the rutile TiO2(110)-surface are studied with the example of tert-butanol. While the thermal reaction is known to yield isobutene, the photochemical ejection of a methyl radical is observed at 100 K. The C–C scission, which is accompanied by the formation of acetone, is the only photochemical reaction pathway at this temperature and can be attributed to the reaction of photoholes that are created upon UV-light illumination at the surface of the n-type semiconductor. At 293 K the selectivity of the reaction changes, as isobutene is additionally formed photochemically. A comparison of the kinetics of the different reactions reveals further insights. Together with the quantitative evaluation of the reaction products at low temperatures and the comparison of the reaction pathways at different temperatures it is demonstrated how thermal effects can influence the selectivity of the reactions in photocatalysis.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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