Anaerobic Alcohol Conversion to Carbonyl Compounds over Nanoscaled Rh-Doped SrTiO 3 under Visible Light

Zhao, G. and Busser, G.W. and Froese, C. and Hu, B. and Bonke, S.A. and Schnegg, A. and Ai, Y. and Wei, D. and Wang, X. and Peng, B. and Muhler, M.

Volume: 10 Pages: 2075-2080
DOI: 10.1021/acs.jpclett.9b00621
Published: 2019

Photocatalytic oxidation of organic compounds on semiconductors provides a mild approach for organic synthesis and solar energy utilization. Herein, we identify the key points for the photocatalytic oxidation over Pt-loaded Rh-doped strontium titanate allowing the conversion of alcohols efficiently and selectively to aldehydes and ketones under anaerobic conditions and visible light with an apparent quantum efficiency of pure benzyl alcohol oxidation at 420 nm of ≤49.5%. Mechanistic investigations suggest that thermodynamically the controlled valence band edge position via Rh doping provides a suitable oxidation ability of photogenerated holes, avoiding the powerful hydroxyl radical intermediates prone to overoxidation resulting in high selectivity. Kinetically, oxygen vacancies induced by Rh 3+ substitution in the SrTiO 3 lattice not only favor the dissociative adsorption of alcohols yielding alkoxy species but also induce the weakening of the α-C-H bond facilitating its cleavage by the photogenerated holes. Pt nanoparticles deposited as a cocatalyst contribute to the final hydrogen evolution. © 2019 American Chemical Society.

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