Publication

Article Metrics

Citations


Online attention

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

DOI: 10.1039/C5SC00854A DOI Help

Authors: Leandro Ardemani (Cardiff University) , Giannantonio Cibin (Diamond Light Source) , Andrew Dent (Diamond Light Source Ltd) , Mark A. Isaacs (European Bioenergy Research Institute, Aston University) , Georgios Kyriakou (University of Hull) , Adam F. Lee (European Bioenergy Research Institute, Aston University) , Christopher Parlett (Aston University) , Stephen A. Parry , Karen Wilson (Aston University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science , VOL 6 (8) , PAGES 4940 - 4945

State: Published (Approved)
Published: June 2015
Diamond Proposal Number(s): 8688

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.

Subject Areas: Chemistry


Instruments: B18-Core EXAFS