Highly Efficient and Selective Aerobic Oxidation of Cinnamyl Alcohol under Visible Light over Pt-Loaded NaNbO3Enriched with Oxygen Vacancies by Ni Doping

Zhao, G. and Bonke, S.A. and Schmidt, S. and Wang, Z. and Hu, B. and Falk, T. and Hu, Y. and Rath, T. and Xia, W. and Peng, B. and Schnegg, A. and Weng, Y. and Muhler, M.

Volume: 9 Pages: 5422-5429
DOI: 10.1021/acssuschemeng.1c00460
Published: 2021

NaNbO3 enriched with oxygen vacancies by Ni doping was successfully synthesized via a polymerized complex method and applied as a photocatalyst in the oxidation of cinnamyl alcohol (CA) to cinnamaldehyde in air. Reaction rates as high as 45 μmol h-1 were achieved under visible light with a high apparent quantum efficiency of 67.2% and excellent chemoselectivity larger than 99%. UV-vis, electron paramagnetic resonance, and attenuated total reflectance infrared spectroscopy results indicate that the CA molecules preferentially adsorb at the oxygen vacancies, thus enabling electron transfer between coordinatively bound CA and NaNbO3 under visible light, inducing CA oxidation. The photocatalytic aerobic oxidation of CA is assumed to proceed via the one-photon pathway with H2O2 as the coupled product. The photodeposited Pt nanoparticles on the surface not only enhanced the oxidation rate but also improved the selectivity to cinnamaldehyde substantially because of the fast decomposition of formed H2O2, in this way avoiding its consecutive oxidation by H2O2. The oxygen vacancies on the surface generated by Ni doping are identified to play a decisive role in the chemisorption of cinnamyl alcohol and the interface charge transfer. © 2021 American Chemical Society. All rights reserved.

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