Selective oxidation of aliphatic alcohols using molecular oxygen at ambient temperature : Mixed-valence vanadium oxide photocatalysts

Zavahir, Sifani, Xiao, Qi, Sarina, Sarina, Zhao, Jian, Bottle, Steven, Wellard, Robert Mark, Jia, Jianfeng, Jing, Liqiang, Huang, Yiming, Blinco, James P., Wu, Haishun, & Zhu, Huai-Yong (2016) Selective oxidation of aliphatic alcohols using molecular oxygen at ambient temperature : Mixed-valence vanadium oxide photocatalysts. ACS Catalysis, 6, pp. 3580-3588.

View at publisher


Here we report a class of photocatalysts: mixed-valence vanadium oxide particles grafted onto a variety of oxide supports. In these catalysts V6O13 species with mixed oxidation states (V4+ or V5+) are believed to be catalytically active sites. These catalysts successfully enable alcohol oxidation to selectively produce aldehydes and ketones using O2 as the oxidant. The catalytic process is driven by visible light irradiation at room temperature and, most importantly, progresses with negligible overoxidation. The catalysts can even selectively oxidize aliphatic alcohols, which are much more challenging to control in comparison to aromatic analogues. They can also be applied to the activation and oxidation of the otherwise stable C–H bonds of saturated aromatic hydrocarbons, such as toluene and xylene, under irradiation. Both experimental results and density functional theory (DFT) simulations suggest the formation of V6O13-alkoxide species as the initial step in the catalytic cycle. The V6O13-alkoxide then acts as the light harvester, being excited by light of wavelength shorter than 550 nm. Facile room-temperature C–H bond cleavage in the excited state V6O13-alkoxide in the presence of O2 leads to the carbonyl-containing products. These findings demonstrate an example of light-driven selective oxidation of diverse alcohols via in situ formation of photoresponsive V6O13-alkoxide species. This catalytic process is especially valuable for the synthesis of temperature-sensitive products and represents an alternative pathway to many conventional thermal oxidation reactions.

Impact and interest:

0 citations in Scopus
Search Google Scholar™
1 citations in Web of Science®

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 95700
Item Type: Journal Article
Refereed: Yes
Keywords: selective oxidation; photocatalysis; aliphatic alcohols; V6O13; visible light
DOI: 10.1021/acscatal.6b00753
ISSN: 2155-5435
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Copyright Owner: Copyright 2016 American Chemical Society
Deposited On: 24 May 2016 02:18
Last Modified: 20 Dec 2016 02:44

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page