Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites:fact or fiction?

Ardemani, Leandro, Cibin, Giannantonio, Dent, Andrew J., Isaacs, Mark A., Kyriakou, Georgios, Lee, Adam F., Parlett, Christopher M.A., Parry, Stephen A. and Wilson, Karen (2015). Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites:fact or fiction? Chemical Science, 6 (8), pp. 4940-4945.

Abstract

Nanoparticulate gold has emerged as a promising catalyst for diverse mild and efficient selective aerobic oxidations. However, the mechanism of such atom-economical transformations, and synergy with functional supports, remains poorly understood. Alkali-free Mg-Al hydrotalcites are excellent solid base catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA), but only in concert with high concentrations of metallic gold nanoparticles. In the absence of soluble base, competitive adsorption between strongly-bound HMF and reactively-formed oxidation intermediates site-blocks gold. Aqueous NaOH dramatically promotes solution phase HMF activation, liberating free gold sites able to activate the alcohol function within the metastable 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) reactive intermediate. Synergistic effects between moderate strength base sites within alkali-free hydrotalcites and high gold surface concentrations can afford highly selective and entirely heterogeneous catalysts for aqueous phase aldehyde and alcohol cascade oxidations pertinent to biomass transformation.

Publication DOI: https://doi.org/10.1039/c5sc00854a
Divisions: Engineering & Applied Sciences > European Bioenergy Research Institute (EBRI)
Engineering & Applied Sciences > Chemical engineering & applied chemistry
Engineering & Applied Sciences
Additional Information: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Funding: EPSRC (EP/G0075944); Leadership Fellowship; Studentship support; Royal Society for an Industry Fellowship; Diamond Light Source for a beam time award (SP8688).
Uncontrolled Keywords: Chemistry(all)
Full Text Link: http://www.scopus.com/inward/record.url?scp=84937208674&partnerID=8YFLogxK Full Text Link: http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC00854A#!divAbstract
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Published Date: 2015-08
Authors: Ardemani, Leandro
Cibin, Giannantonio
Dent, Andrew J.
Isaacs, Mark A.
Kyriakou, Georgios
Lee, Adam F. ( 0000-0002-2153-1391)
Parlett, Christopher M.A. ( 0000-0002-3651-7314)
Parry, Stephen A.
Wilson, Karen ( 0000-0003-4873-708X)

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