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Title: Efficient dual acidic carbo-catalyst for one-pot conversion of carbohydrates to levulinic acid

Abstract

Levulinic acid (LA) is an important platform intermediate for several high value renewable bioproducts. One-pot synthesis of LA from carbohydrates is disadvantaged by the lack of proximity of the active sites required for sequential isomerization, dehydration and rehydration reactions. Herein, we report an efficient one-pot conversion of C6 sugars to LA using a carbo-catalyst (ZrHyC), containing Lewis acidic zirconium and Brønsted acidic carboxyl and hydroxyl sites. The proximity of the two acid sites on a hydrothermally prepared carbon support makes the catalyst highly effective enabling a maximum 73% LA yield from glucose conversion. Fructose conversion achieved a higher LA yield (89%) because of a facile reaction without involving an isomerization step. The effects of solvents, the glucose to catalyst ratio, and the reaction time on glucose conversion and LA yield are systemically examined. Detailed characterization of the catalyst using FTIR, Raman spectroscopy, XPS, XRD, FESEM and NH3-TPD techniques are presented to elucidate the presence of the two acid sites and zirconium in the +4 oxidation state.

Authors:
 [1];  [2];  [3]
  1. Univ. of Delhi, New Delhi (India). Lab. of Catalysis, Dept. of Chemistry; Indian Inst. of Technology Kanpur, Kanpur (India). Dept. of Chemistry
  2. Indian Inst. of Technology Kanpur, Kanpur (India). Dept. of Chemistry
  3. Univ. of Delhi, New Delhi (India). Lab. of Catalysis, Dept. of Chemistry; Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1388587
Grant/Contract Number:  
SC0001004
Resource Type:
Accepted Manuscript
Journal Name:
RSC Advances
Additional Journal Information:
Journal Volume: 6; Journal Issue: 102; 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 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 09 BIOMASS FUELS; 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

Gupta, Dinesh, Kundu, Sabuj, and Saha, Basudeb. Efficient dual acidic carbo-catalyst for one-pot conversion of carbohydrates to levulinic acid. United States: N. p., 2016. Web. doi:10.1039/c6ra18513d.
Gupta, Dinesh, Kundu, Sabuj, & Saha, Basudeb. Efficient dual acidic carbo-catalyst for one-pot conversion of carbohydrates to levulinic acid. United States. doi:10.1039/c6ra18513d.
Gupta, Dinesh, Kundu, Sabuj, and Saha, Basudeb. Fri . "Efficient dual acidic carbo-catalyst for one-pot conversion of carbohydrates to levulinic acid". United States. doi:10.1039/c6ra18513d. https://www.osti.gov/servlets/purl/1388587.
@article{osti_1388587,
title = {Efficient dual acidic carbo-catalyst for one-pot conversion of carbohydrates to levulinic acid},
author = {Gupta, Dinesh and Kundu, Sabuj and Saha, Basudeb},
abstractNote = {Levulinic acid (LA) is an important platform intermediate for several high value renewable bioproducts. One-pot synthesis of LA from carbohydrates is disadvantaged by the lack of proximity of the active sites required for sequential isomerization, dehydration and rehydration reactions. Herein, we report an efficient one-pot conversion of C6 sugars to LA using a carbo-catalyst (ZrHyC), containing Lewis acidic zirconium and Brønsted acidic carboxyl and hydroxyl sites. The proximity of the two acid sites on a hydrothermally prepared carbon support makes the catalyst highly effective enabling a maximum 73% LA yield from glucose conversion. Fructose conversion achieved a higher LA yield (89%) because of a facile reaction without involving an isomerization step. The effects of solvents, the glucose to catalyst ratio, and the reaction time on glucose conversion and LA yield are systemically examined. Detailed characterization of the catalyst using FTIR, Raman spectroscopy, XPS, XRD, FESEM and NH3-TPD techniques are presented to elucidate the presence of the two acid sites and zirconium in the +4 oxidation state.},
doi = {10.1039/c6ra18513d},
journal = {RSC Advances},
number = 102,
volume = 6,
place = {United States},
year = {2016},
month = {10}
}

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Cited by: 2 works
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Figures / Tables:

Scheme 1 Scheme 1: Applications of LA for other bio-renewable chemicals.

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    Works referencing / citing this record: