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Ambient base-free glycerol oxidation over bimetallic PdFe/SiO2 by in situ generated active oxygen species

Underhill, Ricci, Douthwaite, Mark, Lewis, Richard J., Miedziak, Peter J., Armstrong, Robert D., Morgan, David J., Freakley, Simon J., Davies, Thomas, Folli, Andrea, Murphy, Damien M., He, Qian, Akdim, Ouardia, Edwards, Jennifer K. and Hutchings, Graham J. 2021. Ambient base-free glycerol oxidation over bimetallic PdFe/SiO2 by in situ generated active oxygen species. Research on Chemical Intermediates 10.1007/s11164-020-04333-2

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Abstract

Low temperature oxidation of alcohols over heterogeneous catalysts is exceptionally challenging, particularly under neutral conditions. Herein, we report on an efficient, base-free method to oxidise glycerol over a 0.5%Pd-0.5þ/SiO2 catalyst at ambient temperature in the presence of gaseous H2 and O2. The exceptional catalytic performance was attributed to the in situ formation of highly reactive surface-bound oxygenated species, which promote the dehydrogenation on the alcohol. The PdFe bimetallic catalyst was determined to be significantly more active than corresponding monometallic analogues, highlighting the important role both metals have in this oxidative transformation. Fe leaching was confirmed to occur over the course of the reaction but sequestering experiments, involving the addition of bare carbon to the reactions, confirmed that the reaction was predominantly heterogeneous in nature. Investigations with electron paramagnetic resonance spectroscopy suggested that the reactivity in the early stages was mediated by surface-bound reactive oxygen species; no homogeneous radical species were observed in solution. This theory was further evidenced by a direct H2O2 synthesis study, which confirmed that the presence of Fe in the bimetallic catalyst neither improved the synthesis of H2O2 nor promoted its decomposition over the PdFe/SiO2 catalyst.

Item Type: Article
Date Type: Published Online
Status: In Press
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Additional Information: This article is licensed under a Creative Commons Attribution 4.0 International License
Publisher: Springer Verlag (Germany)
ISSN: 0922-6168
Date of First Compliant Deposit: 11 January 2021
Date of Acceptance: 26 October 2020
Last Modified: 12 Jan 2021 10:00
URI: http://orca.cf.ac.uk/id/eprint/137536

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