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Sustainable One-Pot Synthesis of 5-(Hydroxymethyl)furfural from C6-Sugars by Enhanced H+ Exchange Heterogeneous Catalysis

Thuy Vu, Thi Tuyet ; Liu, Shentan ; Jonušis, Mantas ; Jonušienė, Simona ; Choi, Jinsik ; Kawano, Riko ; Rehnberg, Nicola LU orcid ; Hatti-Kaul, Rajni LU and Pyo, Sang Hyun LU (2023) In ACS Sustainable Chemistry and Engineering 11(48). p.17130-17141
Abstract

This study focuses on the characterization of NaCl-induced enhancement of H+ exchange catalysis and preparation of the renewable C6 platform chemical, 5-(hydroxymethyl)furfural (5-HMF), through dehydration of fructose and glucose, C6-sugars, utilizing a heterogeneous catalyst. The effect of a catalytic amount of NaCl was explored to enhance the H+ exchange of cation exchangers, characterized on the distortion of tetrahedral sulfonates due to the formation of direct ionic bonds with Na+, as observed by FT-IR. Dehydration of high concentrations of C6-sugars (24%, w/v) was carried out as a one-pot multistep reaction to synthesize 5-HMF in DMSO/MIBK (0.35/0.65) at temperatures ranging from 110 to 120 °C... (More)

This study focuses on the characterization of NaCl-induced enhancement of H+ exchange catalysis and preparation of the renewable C6 platform chemical, 5-(hydroxymethyl)furfural (5-HMF), through dehydration of fructose and glucose, C6-sugars, utilizing a heterogeneous catalyst. The effect of a catalytic amount of NaCl was explored to enhance the H+ exchange of cation exchangers, characterized on the distortion of tetrahedral sulfonates due to the formation of direct ionic bonds with Na+, as observed by FT-IR. Dehydration of high concentrations of C6-sugars (24%, w/v) was carried out as a one-pot multistep reaction to synthesize 5-HMF in DMSO/MIBK (0.35/0.65) at temperatures ranging from 110 to 120 °C under ambient pressure. Cation exchangers (hydrogen form) were employed as catalysts in amounts ranging from 2.5% to 10% (w/w). The addition of NaCl resulted in a decrease in the pH of both water and organic solvents, leading to improved H+ exchange on cation exchangers. Consequently, this facilitated a reduction in catalyst quantity and significantly enhanced the dehydration of fructose and glucose to 5-HMF. At 110 °C, fructose achieved a 99% conversion rate with an 81% 5-HMF yield within 1 h, while at 120 °C, glucose conversion reached 92.2% with a 36.1% 5-HMF yield over 11 h. Furthermore, the catalyst exhibited consistent activity across at least five consecutive fructose dehydration batches. The NaCl-induced enhancement of H+ exchange catalysis was first proposed and successfully demonstrated for the dehydration of C6-sugars in the organic phase. This concept can be extended to various organic synthesis reactions using cation exchangers in both aqueous and organic systems, with the aim of reducing the catalyst amount and facilitating the reaction rate.

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; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
5-(hydroxymethyl)furfural, cation exchange catalysis, characterization of H exchange catalysis, dehydration of glucose and fructose, NaCl-induced enhancement of H exchange catalysis, one-pot multistep heterogeneous catalysis
in
ACS Sustainable Chemistry and Engineering
volume
11
issue
48
pages
12 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85179154965
ISSN
2168-0485
DOI
10.1021/acssuschemeng.3c05595
language
English
LU publication?
yes
id
0a2a3295-1be8-4ac7-a8ca-1dbdd66112a9
date added to LUP
2023-12-16 20:44:33
date last changed
2023-12-18 09:09:49
@article{0a2a3295-1be8-4ac7-a8ca-1dbdd66112a9,
  abstract     = {{<p>This study focuses on the characterization of NaCl-induced enhancement of H<sup>+</sup> exchange catalysis and preparation of the renewable C6 platform chemical, 5-(hydroxymethyl)furfural (5-HMF), through dehydration of fructose and glucose, C6-sugars, utilizing a heterogeneous catalyst. The effect of a catalytic amount of NaCl was explored to enhance the H<sup>+</sup> exchange of cation exchangers, characterized on the distortion of tetrahedral sulfonates due to the formation of direct ionic bonds with Na<sup>+</sup>, as observed by FT-IR. Dehydration of high concentrations of C6-sugars (24%, w/v) was carried out as a one-pot multistep reaction to synthesize 5-HMF in DMSO/MIBK (0.35/0.65) at temperatures ranging from 110 to 120 °C under ambient pressure. Cation exchangers (hydrogen form) were employed as catalysts in amounts ranging from 2.5% to 10% (w/w). The addition of NaCl resulted in a decrease in the pH of both water and organic solvents, leading to improved H<sup>+</sup> exchange on cation exchangers. Consequently, this facilitated a reduction in catalyst quantity and significantly enhanced the dehydration of fructose and glucose to 5-HMF. At 110 °C, fructose achieved a 99% conversion rate with an 81% 5-HMF yield within 1 h, while at 120 °C, glucose conversion reached 92.2% with a 36.1% 5-HMF yield over 11 h. Furthermore, the catalyst exhibited consistent activity across at least five consecutive fructose dehydration batches. The NaCl-induced enhancement of H<sup>+</sup> exchange catalysis was first proposed and successfully demonstrated for the dehydration of C6-sugars in the organic phase. This concept can be extended to various organic synthesis reactions using cation exchangers in both aqueous and organic systems, with the aim of reducing the catalyst amount and facilitating the reaction rate.</p>}},
  author       = {{Thuy Vu, Thi Tuyet and Liu, Shentan and Jonušis, Mantas and Jonušienė, Simona and Choi, Jinsik and Kawano, Riko and Rehnberg, Nicola and Hatti-Kaul, Rajni and Pyo, Sang Hyun}},
  issn         = {{2168-0485}},
  keywords     = {{5-(hydroxymethyl)furfural; cation exchange catalysis; characterization of H exchange catalysis; dehydration of glucose and fructose; NaCl-induced enhancement of H exchange catalysis; one-pot multistep heterogeneous catalysis}},
  language     = {{eng}},
  number       = {{48}},
  pages        = {{17130--17141}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{ACS Sustainable Chemistry and Engineering}},
  title        = {{Sustainable One-Pot Synthesis of 5-(Hydroxymethyl)furfural from C6-Sugars by Enhanced H<sup>+</sup> Exchange Heterogeneous Catalysis}},
  url          = {{http://dx.doi.org/10.1021/acssuschemeng.3c05595}},
  doi          = {{10.1021/acssuschemeng.3c05595}},
  volume       = {{11}},
  year         = {{2023}},
}