Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

Journal Article · Sat Jul 25 00:00:00 EDT 2015 · Green Chemistry

DOI:https://doi.org/10.1039/c5gc01257k· OSTI ID:1370906

Swift, T. Dallas ^[1]; Nguyen, Hannah ^[1]; Anderko, Andrzej ^[2]; Nikolakis, Vladimiros ^[1]; Vlachos, Dionisios G. ^[1]

---

1. Univ. of Delaware, Newark, DE (United States)
2. OLI Systems Inc., Cedar Knolls, NJ (United States)

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl₃–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl₃ concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl₃ concentration. This is attributed to the interactions between HCl and CrCl₃ speciation in solution that leads to HMF yield being maximized at moderate HCl concentrations for each CrCl₃ concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: SC0001004
• OSTI ID: 1370906
• Journal Information: Green Chemistry, Vol. 17, Issue 10; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; ISSN 1463-9262
• Publisher: Royal Society of Chemistry
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
biofuels (including algae and biomass)
bio-inspired
hydrogen and fuel cells
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)
synthesis (scalable processing)