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High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis Acid HScCl(4) Catalyst
[Image: see text] Lignocellulosic biorefineries have received considerable attention for the purpose of producing high-value chemicals and materials. Levulinic acid (LA) is an important biomass-derived platform chemical that is produced from sugar-based biomass. Unfortunately, the catalysts reported...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8223403/ https://www.ncbi.nlm.nih.gov/pubmed/34179638 http://dx.doi.org/10.1021/acsomega.1c01607 |
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author | Liu, Shiwei Cheng, Xueli Sun, Shiqin Chen, Yige Bian, Bing Liu, Yue Tong, Li Yu, Hailong Ni, Yonghao Yu, Shitao |
author_facet | Liu, Shiwei Cheng, Xueli Sun, Shiqin Chen, Yige Bian, Bing Liu, Yue Tong, Li Yu, Hailong Ni, Yonghao Yu, Shitao |
author_sort | Liu, Shiwei |
collection | PubMed |
description | [Image: see text] Lignocellulosic biorefineries have received considerable attention for the purpose of producing high-value chemicals and materials. Levulinic acid (LA) is an important biomass-derived platform chemical that is produced from sugar-based biomass. Unfortunately, the catalysts reported thus far have shortcomings, such as expensive starting materials, complicated synthesis or purification operations, and a low LA yield under harsh reaction conditions. Herein, we develop a novel dual-functional catalyst, HScCl(4), by combining Brønsted acid (HCl) and Lewis acid (ScCl(3)) sites. The as-prepared HScCl(4) catalyst shows high efficiency and high selectivity for converting 5-hydroxymethylfurfural (HMF) to LA in a biphasic system consisting of methyl isobutyl ketone (MIBK) and water. The density functional theory (DFT) results show that the synergistic catalytic effect, originating from the Brønsted and Lewis acidic sites of HScCl(4), significantly decreases the energy barriers of reactants and intermediates, thus facilitating the conversion of HMF to LA. Moreover, the efficient separation of LA in the water-MIBK biphasic system by extracting LA to the MIBK phase minimizes the side reactions of LA and thus the formation of humins while significantly improving the LA yield. The conversion of HMF and the selectivity for LA are 100 and 95.6% at 120 °C for 35 min, respectively. The free energy (ΔG) and activation energy (E(a)) of the reaction are −30 kcal mol(–1) and 13.7 kJ mol(–1), respectively. The developed process provides a green, sustainable, and efficient pathway to produce LA from biomass-derived HMF under mild conditions. |
format | Online Article Text |
id | pubmed-8223403 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-82234032021-06-25 High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis Acid HScCl(4) Catalyst Liu, Shiwei Cheng, Xueli Sun, Shiqin Chen, Yige Bian, Bing Liu, Yue Tong, Li Yu, Hailong Ni, Yonghao Yu, Shitao ACS Omega [Image: see text] Lignocellulosic biorefineries have received considerable attention for the purpose of producing high-value chemicals and materials. Levulinic acid (LA) is an important biomass-derived platform chemical that is produced from sugar-based biomass. Unfortunately, the catalysts reported thus far have shortcomings, such as expensive starting materials, complicated synthesis or purification operations, and a low LA yield under harsh reaction conditions. Herein, we develop a novel dual-functional catalyst, HScCl(4), by combining Brønsted acid (HCl) and Lewis acid (ScCl(3)) sites. The as-prepared HScCl(4) catalyst shows high efficiency and high selectivity for converting 5-hydroxymethylfurfural (HMF) to LA in a biphasic system consisting of methyl isobutyl ketone (MIBK) and water. The density functional theory (DFT) results show that the synergistic catalytic effect, originating from the Brønsted and Lewis acidic sites of HScCl(4), significantly decreases the energy barriers of reactants and intermediates, thus facilitating the conversion of HMF to LA. Moreover, the efficient separation of LA in the water-MIBK biphasic system by extracting LA to the MIBK phase minimizes the side reactions of LA and thus the formation of humins while significantly improving the LA yield. The conversion of HMF and the selectivity for LA are 100 and 95.6% at 120 °C for 35 min, respectively. The free energy (ΔG) and activation energy (E(a)) of the reaction are −30 kcal mol(–1) and 13.7 kJ mol(–1), respectively. The developed process provides a green, sustainable, and efficient pathway to produce LA from biomass-derived HMF under mild conditions. American Chemical Society 2021-06-09 /pmc/articles/PMC8223403/ /pubmed/34179638 http://dx.doi.org/10.1021/acsomega.1c01607 Text en © 2021 The Authors. Published by American Chemical Society Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Liu, Shiwei Cheng, Xueli Sun, Shiqin Chen, Yige Bian, Bing Liu, Yue Tong, Li Yu, Hailong Ni, Yonghao Yu, Shitao High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis Acid HScCl(4) Catalyst |
title | High-Yield and High-Efficiency
Conversion of HMF to Levulinic Acid
in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis
Acid HScCl(4) Catalyst |
title_full | High-Yield and High-Efficiency
Conversion of HMF to Levulinic Acid
in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis
Acid HScCl(4) Catalyst |
title_fullStr | High-Yield and High-Efficiency
Conversion of HMF to Levulinic Acid
in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis
Acid HScCl(4) Catalyst |
title_full_unstemmed | High-Yield and High-Efficiency
Conversion of HMF to Levulinic Acid
in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis
Acid HScCl(4) Catalyst |
title_short | High-Yield and High-Efficiency
Conversion of HMF to Levulinic Acid
in a Green and Facile Catalytic Process by a Dual-Function Brønsted-Lewis
Acid HScCl(4) Catalyst |
title_sort | high-yield and high-efficiency
conversion of hmf to levulinic acid
in a green and facile catalytic process by a dual-function brønsted-lewis
acid hsccl(4) catalyst |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8223403/ https://www.ncbi.nlm.nih.gov/pubmed/34179638 http://dx.doi.org/10.1021/acsomega.1c01607 |
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