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

Abstract

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3–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/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leads to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 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.

Authors:
 [1];  [1];  [2];  [1];  [1]
  1. Univ. of Delaware, Newark, DE (United States)
  2. OLI Systems Inc., Cedar Knolls, NJ (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1370906
Grant/Contract Number:  
SC0001004
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 17; Journal 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; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
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)

Citation Formats

Swift, T. Dallas, Nguyen, Hannah, Anderko, Andrzej, Nikolakis, Vladimiros, and Vlachos, Dionisios G. Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution. United States: N. p., 2015. Web. doi:10.1039/c5gc01257k.
Swift, T. Dallas, Nguyen, Hannah, Anderko, Andrzej, Nikolakis, Vladimiros, & Vlachos, Dionisios G. Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution. United States. https://doi.org/10.1039/c5gc01257k
Swift, T. Dallas, Nguyen, Hannah, Anderko, Andrzej, Nikolakis, Vladimiros, and Vlachos, Dionisios G. Sat . "Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution". United States. https://doi.org/10.1039/c5gc01257k. https://www.osti.gov/servlets/purl/1370906.
@article{osti_1370906,
title = {Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution},
author = {Swift, T. Dallas and Nguyen, Hannah and Anderko, Andrzej and Nikolakis, Vladimiros and Vlachos, Dionisios G.},
abstractNote = {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.},
doi = {10.1039/c5gc01257k},
url = {https://www.osti.gov/biblio/1370906}, journal = {Green Chemistry},
issn = {1463-9262},
number = 10,
volume = 17,
place = {United States},
year = {2015},
month = {7}
}

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Cited by: 57 works
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Works referenced in this record:

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    Works referencing / citing this record:

    Conversion of carbohydrates into 5-hydroxymethylfurfural in a green reaction system of CO 2 -water-isopropanol
    journal, November 2016


    Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts
    journal, September 2018


    Pt catalysts for efficient aerobic oxidation of glucose to glucaric acid in water
    journal, January 2016


    Sulfonated polyaniline as a solid organocatalyst for dehydration of fructose into 5-hydroxymethylfurfural
    journal, January 2017


    Structural analysis of humins formed in the Brønsted acid catalyzed dehydration of fructose
    journal, January 2018


    Direct speciation methods to quantify catalytically active species of AlCl 3 in glucose isomerization
    journal, January 2018


    Ultrafast flow chemistry for the acid-catalyzed conversion of fructose
    journal, January 2019


    Replacement of Chromium by Non-Toxic Metals in Lewis-Acid MOFs: Assessment of Stability as Glucose Conversion Catalysts
    journal, May 2019