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Title: Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites

Effective carbon-carbon coupling of acetic acid to form larger products while minimizing CO 2 emissions is critical to achieving a step change in efficiency for the production of transportation fuels from sustainable biomass. Here, we report the direct acylation of methylfuran with acetic acid in the presence ofwater, all ofwhich can be readily produced from biomass. This direct coupling limits unwanted polymerization of furanics while producing acetyl methylfuran. Reaction kinetics and density functional theory calculations illustrate that the calculated apparent barrier for the dehydration of the acid to form surface acyl species is similar to the experimentally measured barrier, implying that this step plays a significant role in determining the net reaction rate. Water inhibits the overall rate, but selectivity to acylated products is not affected.We show that furanic species effectively stabilize the charge of the transition state, therefore lowering the overall activation barrier. These results demonstrate a promising new route to C–C bond–forming reactions for the production of higher-value products from biomass.
Authors:
 [1] ;  [1] ;  [1]
  1. Univ. of Oklahoma, Norman, OK (United States). School of Chemical, Biological and Materials Engineering
Publication Date:
Grant/Contract Number:
EE0006287; SC0004600
Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 2; Journal Issue: 9; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Research Org:
Univ. of Oklahoma, Norman, OK (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Acylation; carboxylic acids; biomass; zeolites; renewable energy
OSTI Identifier:
1437643

Gumidyala, Abhishek, Wang, Bin, and Crossley, Steven. Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites. United States: N. p., Web. doi:10.1126/sciadv.1601072.
Gumidyala, Abhishek, Wang, Bin, & Crossley, Steven. Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites. United States. doi:10.1126/sciadv.1601072.
Gumidyala, Abhishek, Wang, Bin, and Crossley, Steven. 2016. "Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites". United States. doi:10.1126/sciadv.1601072. https://www.osti.gov/servlets/purl/1437643.
@article{osti_1437643,
title = {Direct carbon-carbon coupling of furanics with acetic acid over Bronsted zeolites},
author = {Gumidyala, Abhishek and Wang, Bin and Crossley, Steven},
abstractNote = {Effective carbon-carbon coupling of acetic acid to form larger products while minimizing CO2 emissions is critical to achieving a step change in efficiency for the production of transportation fuels from sustainable biomass. Here, we report the direct acylation of methylfuran with acetic acid in the presence ofwater, all ofwhich can be readily produced from biomass. This direct coupling limits unwanted polymerization of furanics while producing acetyl methylfuran. Reaction kinetics and density functional theory calculations illustrate that the calculated apparent barrier for the dehydration of the acid to form surface acyl species is similar to the experimentally measured barrier, implying that this step plays a significant role in determining the net reaction rate. Water inhibits the overall rate, but selectivity to acylated products is not affected.We show that furanic species effectively stabilize the charge of the transition state, therefore lowering the overall activation barrier. These results demonstrate a promising new route to C–C bond–forming reactions for the production of higher-value products from biomass.},
doi = {10.1126/sciadv.1601072},
journal = {Science Advances},
number = 9,
volume = 2,
place = {United States},
year = {2016},
month = {9}
}