Aerobic oxidation of benzyl alcohols to benzaldehydes using monoclinic bismuth vanadate nanoparticles under visible light irradiation: Photocatalysis selectivity and inhibition

Christopher A. Unsworth, Ben Coulson, Victor Chechik, Richard E. Douthwaite*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Monoclinic bismuth vanadate nanoparticles (nan-BiVO4) have been used for the selective photo-oxidation of benzyl alcohols (13 examples) to benzaldehydes under visible light irradiation using dioxygen as oxidant. Illumination with a blue LED (λmax = 470 nm) gave yields more than 30 times greater than bulk BiVO4 with >99% selectivity for several cases. Photo-oxidation of PhCH2OH/PhCD2OH isotopomers gave a kinetic isotope effect of 1.3 indicating that C–H bond activation is not the rate determining step in contrast to other reported photocatalysts including TiO2 and carbon nitride. Collectively, structural characterisation, spectroscopic, and reactivity data are correlated with the greater surface area of nan-BiVO4 compared to bulk BiVO4. Furthermore, conversion is shown to be limited as reaction progresses. Control experiments indicate that photo-oxidation is retarded by product aldehyde and that trace amounts (<1%) of the corresponding benzoic acid, from over-oxidation, result in significant reduction in conversion.

Original languageEnglish
Pages (from-to)152-159
Number of pages8
JournalJournal of Catalysis
Early online date9 Sept 2017
Publication statusPublished - 1 Oct 2017

Bibliographical note

© 2017 Elsevier Inc. All rights reserved.This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy.


  • Catalyst poisoning
  • Mechanism
  • Metal oxide
  • Oxidation
  • Photocatalyst
  • Product inhibition

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