Aerobic oxidation of toluene and benzyl alcohol to benzaldehyde using a visible light-responsive titanium-oxide cluster

Wenli Wu, Guanyun Zhang, Jian Zhang, Guo Wang, Chen Ho Tung, Yifeng Wang

Research output: Contribution to journalArticlepeer-review

18 Scopus citations

Abstract

Photocatalytic selective oxidation using sunlight and O2 can serve as a green and cost-effective method for the transformation of organic raw materials to value-added products. Here, we report a [Ti6O8(OH2)20]8+ cluster modified with Br (denoted as Ti6B) triggers the selective conversion of toluene and benzyl alcohol to benzaldehyde under visible light irradiation with high efficiency. The absorption edge of Ti6B in MeCN solution is ca. 500 nm. The conversion of toluene, operated under non-solvent conditions, reached 4.7% with ca. 80% selectivity. The yield of benzaldehyde from benzyl alcohol reached 96%. Common substituents could be tolerated. ESR analyses indicate superoxide is directly involved in the reactions. The results of 17O NMR, IR and small angle scattering indicate Ti6B is the true photocatalyst. Mechanistic studies suggest Br binds to Ti4+ at the Ti-oxo core of Ti6B and the photo-driven electronic transition is from HOMO comprised of Br2p to LUMO + 1 comprised of Ti3d orbitals.

Original languageEnglish
Article number126433
JournalChemical Engineering Journal
Volume404
DOIs
StatePublished - 15 Jan 2021
Externally publishedYes

Keywords

  • Br–association
  • Photocatalysis
  • Selective oxidation
  • Titanium-oxide cluster
  • Visible light

ASJC Scopus subject areas

  • Chemistry (all)
  • Environmental Chemistry
  • Chemical Engineering (all)
  • Industrial and Manufacturing Engineering

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