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Title: Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins

Abstract

We apply ATR-FTIR spectroscopy, Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS) experiments to investigate the molecular structure, morphology and growth mechanism of 5-hydroxymethyl furfural (HMF) derived humins as a function of HMF conversion. Our FTIR data support a reaction pathway in which humins form either through a ring opening mechanism and/or through substitution at the α or β position via nucleophilic attack. The addition of DMSO as a co-solvent leads to significant changes in the FTIR spectra of humins. We find that the nucleophilic attack pathway is suppressed in the presence of DMSO co-solvent and rationalizes the very small humin particles (~100 nm) observed in SEM images contrary to the large particles (with multimodal size distribution and largest particles of up to 3–4 μm) observed in neat water. DLS experiments under several reaction conditions further confirm the particle size distribution observed via SEM. A plausible reaction network for humin formation, which rationalizes qualitatively our experimental results as well as those reported in the literature, is also postulated.

Authors:
 [1]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [1]
  1. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1386780
Grant/Contract Number:  
SC0001004
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 18; Journal Issue: 7; 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

Citation Formats

Tsilomelekis, George, Orella, Michael J., Lin, Zhexi, Cheng, Ziwei, Zheng, Weiqing, Nikolakis, Vladimiros, and Vlachos, Dionisios G. Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins. United States: N. p., 2015. Web. doi:10.1039/C5GC01938A.
Tsilomelekis, George, Orella, Michael J., Lin, Zhexi, Cheng, Ziwei, Zheng, Weiqing, Nikolakis, Vladimiros, & Vlachos, Dionisios G. Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins. United States. doi:10.1039/C5GC01938A.
Tsilomelekis, George, Orella, Michael J., Lin, Zhexi, Cheng, Ziwei, Zheng, Weiqing, Nikolakis, Vladimiros, and Vlachos, Dionisios G. Tue . "Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins". United States. doi:10.1039/C5GC01938A. https://www.osti.gov/servlets/purl/1386780.
@article{osti_1386780,
title = {Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins},
author = {Tsilomelekis, George and Orella, Michael J. and Lin, Zhexi and Cheng, Ziwei and Zheng, Weiqing and Nikolakis, Vladimiros and Vlachos, Dionisios G.},
abstractNote = {We apply ATR-FTIR spectroscopy, Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS) experiments to investigate the molecular structure, morphology and growth mechanism of 5-hydroxymethyl furfural (HMF) derived humins as a function of HMF conversion. Our FTIR data support a reaction pathway in which humins form either through a ring opening mechanism and/or through substitution at the α or β position via nucleophilic attack. The addition of DMSO as a co-solvent leads to significant changes in the FTIR spectra of humins. We find that the nucleophilic attack pathway is suppressed in the presence of DMSO co-solvent and rationalizes the very small humin particles (~100 nm) observed in SEM images contrary to the large particles (with multimodal size distribution and largest particles of up to 3–4 μm) observed in neat water. DLS experiments under several reaction conditions further confirm the particle size distribution observed via SEM. A plausible reaction network for humin formation, which rationalizes qualitatively our experimental results as well as those reported in the literature, is also postulated.},
doi = {10.1039/C5GC01938A},
journal = {Green Chemistry},
number = 7,
volume = 18,
place = {United States},
year = {2015},
month = {11}
}

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Cited by: 135 works
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Figures / Tables:

Scheme 1 Scheme 1: Thermocatalytic reaction network of the solution phase acid catalyzed cellulosic biomass-derivatives conversion to fuels, chemicals and humins. Carbons are numbered for convenience.

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