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Novel Catalytic Strategies for the Synthesis of Furans and Their...
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Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: closed (10 December 2023) | Viewed by 11042

Special Issue Editor

Dr. Sara Fulignati

E-Mail Website
Guest Editor
Department of Chemistry and Industrial Chemistry, University of Pisa, Via Giuseppe Moruzzi 13, 56124 Pisa, Italy
Interests: biomass exploitation; polysaccharide and monosaccharide hydrolysis; 5-hydroxymethylfurfural and derivatives; levulinic acid and derivatives; MW-assisted chemistry; hydrogenation; etherification; flow chemistry; homogeneous and heterogeneous catalysis; biofuels and biochemical

Special Issue Information

Dear Colleagues,

The depletion of fossil resources and their environmental impact make the transition toward alternative carbon sources even more urgent. Under this perspective, renewable lignocellulosic biomass looks like a promising feedstock for the chemical industry, and in recent years, research has focused on the development of a feasible biorefinery, proposing several strategies for the conversion of biomass and its structural components to platform chemicals. Among them, furans such as furfural and 5-hydroxymethylfurfural (HMF) represent strategic compounds thanks to their great reactivity. In fact, they can be involved in several reactions (hydrogenation, hydrogenolysis, hydrogen transfer, oxidation, etherification, etc.), leading to the production of innovative biofuels and biochemicals, such as monomers, surfactants, solvents, and adhesives. However, the proper tuning of the properties of catalysts (homogeneous/heterogeneous) applied in furan synthesis and in their exploitations, as well as the adopted process conditions, still represent critical aspects for the development of a sustainable and feasible process; thus, continuous investigations are undoubtedly necessary.

This Special Issue will present the most recent and significant advances in both furan synthesis and exploitation, focusing on the proposed catalytic systems, the applied process conditions, and the kinetic aspects. Original papers on the above topics and reviews are welcome for submission.

Dr. Sara Fulignati
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • waste biomass conversion
  • polysaccharides and monosaccharides
  • 5-hydroxymethylfurfural and its derivatives
  • furfural and its derivatives
  • biofuels
  • biochemicals
  • homogeneous and heterogeneous catalysis
  • batch and flow chemistry
  • new functional materials for catalysis

Published Papers (7 papers)

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Research

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16 pages, 2009 KiB  
Article
Kinetic and Mechanistic Study of Aldose Conversion to Functionalized Furans in Aqueous Solutions
by Stefan S. Warthegau, Magnus Karlsson, Robert Madsen, Pernille Rose Jensen and Sebastian Meier
Catalysts 2024, 14(3), 199; https://doi.org/10.3390/catal14030199 - 18 Mar 2024
Cited by 1 | Viewed by 798
Abstract
Reaction mixtures of naturally abundant aldoses and CH nucleophiles allow for the formation of functionalized furan precursors using low temperatures and metal-free catalysis in aqueous solutions of dilute base catalysts. We employ in situ NMR assays to clarify the mechanism and kinetics of [...] Read more.
Reaction mixtures of naturally abundant aldoses and CH nucleophiles allow for the formation of functionalized furan precursors using low temperatures and metal-free catalysis in aqueous solutions of dilute base catalysts. We employ in situ NMR assays to clarify the mechanism and kinetics of the conversion. Catalysis serves a double role in ring-opening of stable aldoses such as glucose and xylose and facilitating the subsequent reactions with CH acids such as malononitrile or cyanoacetamide. Resultant acyclic products are shown to convert quickly to a monocyclic product prior to the slower formation of a more stable bicyclic intermediate and dehydration to tri-functionalized furan. Especially the reversible 5-exo-dig ring closure entailing oxygen attack onto a nitrile carbon is surprisingly fast with an equilibrium vastly towards the cyclic state, sequestering reactive groups and allowing the selective conversion to tri-functionalized furan. The reaction hinges on the fast formation of intermediates without CH acidity and competes with the oligomerization of CH nucleophiles. Insight derived from in situ NMR analysis shows the prowess of high-resolution in situ spectroscopy in clarifying the interplay between catalysts and reactants. Such insight will be vital for the optimization of reactions that upgrade biorenewables under benign conditions. Full article
(This article belongs to the Special Issue Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives)
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14 pages, 1320 KiB  
Article
Iron(III) Sulfate-Mediated Synthesis of 2,5-Furandicarboxylic Acid Dimethyl Ester from Galactaric Acid
by Giacomo Trapasso, Beatriz Chícharo, Thomas Gherardi, Davide Redolfi-Bristol and Fabio Aricò
Catalysts 2023, 13(7), 1114; https://doi.org/10.3390/catal13071114 - 17 Jul 2023
Cited by 2 | Viewed by 1908
Abstract
2,5-furandicarboxylic acid (FDCA) is one of the most studied bio-based monomers, being considered the best substitute for fossil-derived terephthalic acid in plastic production. FDCA is employed in the preparation of polyethylene furanoate (PEF), demonstrating superior mechanical and thermal proprieties compared to the widely [...] Read more.
2,5-furandicarboxylic acid (FDCA) is one of the most studied bio-based monomers, being considered the best substitute for fossil-derived terephthalic acid in plastic production. FDCA is employed in the preparation of polyethylene furanoate (PEF), demonstrating superior mechanical and thermal proprieties compared to the widely used polyethylene terephthalate (PET). Nevertheless, FDCA synthesis mostly relies on the oxidation of the bio-based platform chemical hydroxymethyl furfural (HMF), whose notoriously instable nature renders FDCA yield and industrial scale-up production complicated. On the contrary, FDCA esters are less studied, even though they have greater solubility in organic media, which would favor their isolation and potential application as monomers for PEF. On these premises, we report herein an alternative green synthetic approach to FDCA methyl ester (FDME) using galactaric acid as the substrate, dimethyl carbonate (DMC) as the green media, and Fe2(SO4)3 as the heterogeneous Lewis acid. Optimization of the reaction conditions allowed the selective production of FDME in a 70% isolated yield; product purification was achieved via flash column chromatography over silica. Furthermore, it was possible to employ up to 5.0 g of galactaric acid in a single reaction, leading to a good isolated yield of FDME. Full article
(This article belongs to the Special Issue Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives)
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17 pages, 3728 KiB  
Article
Effect of Capping Ligands for the Synthesis of Gold Nanoparticles and on the Catalytic Performance for the Oxidation of 5-Hydroxymethyl-2-furfural
by Francesca Liuzzi, Alessia Ventimiglia, Alessandro Allegri, Elena Rodríguez-Aguado, Juan Antonio Cecilia, Ivan Rivalta, Nikolaos Dimitratos and Stefania Albonetti
Catalysts 2023, 13(6), 990; https://doi.org/10.3390/catal13060990 - 09 Jun 2023
Viewed by 1433
Abstract
Different series of Au on carbon catalysts were prepared via sol-immobilization to investigate the role of polymers (polyvinylpyrrolidone PVP, polyethylene glycol PEG and polyvinyl alcohol PVA), employed as gold nanoparticle (NP) stabilizers, on catalyst properties and on catalytic activity. The synthesized materials were [...] Read more.
Different series of Au on carbon catalysts were prepared via sol-immobilization to investigate the role of polymers (polyvinylpyrrolidone PVP, polyethylene glycol PEG and polyvinyl alcohol PVA), employed as gold nanoparticle (NP) stabilizers, on catalyst properties and on catalytic activity. The synthesized materials were widely characterized with several techniques (DLS, XRD, TEM and XPS) and used as catalysts in the 5-hydroxymethylfurfural (HMF) oxidation to produce 2,5-furandicarboxylic acid (FDCA). The obtained results clearly demonstrated the PVA leading to the formation of smaller and more active NPs. On the contrary, polyethylene glycol was shown to affect gold exposure and, as a consequence, to reduce the catalyst activity due to steric effects while PVP-based catalysts presented bigger and more covered Au NPs. The investigation on the reusability of the catalysts demonstrated the presence of a significant deactivation on all prepared materials, but the presence of higher amounts of polymer seems to have a positive effect on catalyst stability even if associated with lower reactivity. Computational studies have provided interesting information on the NP-polymer interactions and consequently on the catalytic activities. Full article
(This article belongs to the Special Issue Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives)
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19 pages, 4638 KiB  
Article
The Effect of Support on Catalytic Performance of Ni-Doped Mo Carbide Catalysts in 2-Methylfuran Production
by Andrey Smirnov, Ivan N. Shilov, Maria V. Alekseeva, Olga A. Bulavchenko, Andrey A. Saraev and Vadim A. Yakovlev
Catalysts 2023, 13(5), 870; https://doi.org/10.3390/catal13050870 - 10 May 2023
Viewed by 1370
Abstract
Ni-doped Mo carbide with Ni/Mo atomic ratio of 0.1 was supported on SiO2, Al2O3, and a porous carbon material (C), using a combination of gel combustion and impregnation methods. XRD, XPS, XANES, and EXAFS analyses indicated that [...] Read more.
Ni-doped Mo carbide with Ni/Mo atomic ratio of 0.1 was supported on SiO2, Al2O3, and a porous carbon material (C), using a combination of gel combustion and impregnation methods. XRD, XPS, XANES, and EXAFS analyses indicated that the main active sites for the supported catalysts were metallic nickel and Mo carbides. The catalysts were evaluated in furfural hydrogenation to produce 2-methylfuran (2-MF) in a batch reactor at 150 °C under a hydrogen pressure of 6.0 MPa. The carbide materials supported on C showed the highest activity and selectivity towards 2-MF formation, with a yield of 61 mol.% after 3.5 h. Using furfuryl alcohol as the feedstock instead of furfural resulted in a high selectivity to 2-MF production. The carbon-supported sample was tested in a fixed-bed reactor at 160–260 °C with a pressure of 5.0 MPa in the hydrogenation of furfuryl alcohol, leading to the formation of up to 82 mol.% of 2-MF at 160–200 °C. The higher temperature (260 °C) resulted in the formation of C5 alcohols and hydrocarbons, while the hydrogenation of furfural at the same temperature led to 100 mol.% conversion, and up to an 86 mol.% yield of 2-MF. Full article
(This article belongs to the Special Issue Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives)
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12 pages, 1386 KiB  
Article
One-Pot Conversion of Furfural to γ-Valerolactone over Co- and Pt-Doped ZSM-5 Catalysts
by Weerachon Tolek, Warucha Auppahad, Patcharaporn Weerachawanasak, Okorn Mekasuwandumrong, Piyasan Praserthdam and Joongjai Panpranot
Catalysts 2023, 13(3), 498; https://doi.org/10.3390/catal13030498 - 28 Feb 2023
Cited by 1 | Viewed by 1228
Abstract
γ-Valerolactone (GVL) is one of the useful biomass compounds produced via different reaction pathways from hemicellulose. In this study, Co- and Pt-doped/ZSM-5 catalysts with different Co loadings (0–10 wt.%) and Pt loadings (0.5–2 wt.%) were prepared by impregnation method and employed in a [...] Read more.
γ-Valerolactone (GVL) is one of the useful biomass compounds produced via different reaction pathways from hemicellulose. In this study, Co- and Pt-doped/ZSM-5 catalysts with different Co loadings (0–10 wt.%) and Pt loadings (0.5–2 wt.%) were prepared by impregnation method and employed in a one-pot conversion of furfural to GVL. The yield of GVL increased with increasing reaction temperature from 100 to 140 °C. At the reaction temperature of 120 °C, higher amounts of secondary products such as AL and IPL can be converted to GVL, especially on the Co- and Pt-modified ZSM-5 catalysts. Compared to the non-modified H-ZSM-5 (GVL yield 35.4%), Co- and Pt-doped ZSM-5 catalysts exhibited much higher yield of GVL with the 1%Pt/ZSM-5 catalyst showing the highest yield of GVL at 85.4% at 120 °C and 1 bar N2 without the use of liquid acid or external H2 supply. The catalyst performances were correlated to the physicochemical properties of the catalysts such as the amount and type of acid sites. The NH3-TPD and in situ FTIR spectra of pyridine adsorption results revealed that Co- and Pt-loaded on ZSM-5 enhanced Lewis and weak acid sites, which are beneficial for the reaction. The results present a simple strategy to obtain high GVL yield under relatively mild conditions. Full article
(This article belongs to the Special Issue Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives)
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Review

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29 pages, 6681 KiB  
Review
Production and Synthetic Possibilities of 5-Chloromethylfurfural as Alternative Biobased Furan
by Dominik Soukup-Carne, Felipe Sanchez Bragagnolo, Cristiano Soleo Funari and Jesús Esteban
Catalysts 2024, 14(2), 117; https://doi.org/10.3390/catal14020117 - 01 Feb 2024
Viewed by 1063
Abstract
As fossil-based resource depletion intensifies and the use of lignocellulosic biomass gains more and more momentum for the development of biorefineries, the production of furans has received a great deal of attention considering their outstanding synthetic possibilities. The production of 5-hydroxymethylfurfural (HMF) is [...] Read more.
As fossil-based resource depletion intensifies and the use of lignocellulosic biomass gains more and more momentum for the development of biorefineries, the production of furans has received a great deal of attention considering their outstanding synthetic possibilities. The production of 5-hydroxymethylfurfural (HMF) is quite established in the recent scientific literature, with a large number of studies having been published in the last few years. Lately, there has been a growing interest in the synthesis of 5-chloromethylfurfural (CMF) as a novel building block of similar molecular structure to that of HMF. CMF has some advantages, such as its production taking place at milder reaction conditions, a lower polarity that enables easier separation with the aid of organic media, and the presence of chlorine as a better leaving group in synthesis. Precisely the latter aspect has given rise to several interesting products to be obtained therefrom, including 2,5-dimethylfuran, 2,5-furandicarboxylic acid, and 5-methylfurfural, to name a few. This work covers the most relevant aspects related to the production of CMF and an array of synthetic possibilities. Through varied catalysts and reaction conditions, value-added products can be obtained from this chemical, thus highlighting the advances in the production and use of this chemical in recent years. Full article
(This article belongs to the Special Issue Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives)
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46 pages, 2427 KiB  
Review
Novel Challenges on the Catalytic Synthesis of 5-Hydroxymethylfurfural (HMF) from Real Feedstocks
by Sara Fulignati, Domenico Licursi, Nicola Di Fidio, Claudia Antonetti and Anna Maria Raspolli Galletti
Catalysts 2022, 12(12), 1664; https://doi.org/10.3390/catal12121664 - 18 Dec 2022
Cited by 6 | Viewed by 2362
Abstract
The depletion of fossil resources makes the transition towards renewable ones more urgent. For this purpose, the synthesis of strategic platform-chemicals, such as 5-hydroxymethylfurfural (HMF), represents a fundamental challenge for the development of a feasible bio-refinery. HMF perfectly deals with this necessity, because [...] Read more.
The depletion of fossil resources makes the transition towards renewable ones more urgent. For this purpose, the synthesis of strategic platform-chemicals, such as 5-hydroxymethylfurfural (HMF), represents a fundamental challenge for the development of a feasible bio-refinery. HMF perfectly deals with this necessity, because it can be obtained from the hexose fraction of biomass. Thanks to its high reactivity, it can be exploited for the synthesis of renewable monomers, solvents, and bio-fuels. Sustainable HMF synthesis requires the use of waste biomasses, rather than model compounds such as monosaccharides or polysaccharides, making its production more economically advantageous from an industrial perspective. However, the production of HMF from real feedstocks generally suffers from scarce selectivity, due to their complex chemical composition and HMF instability. On this basis, different strategies have been adopted to maximize the HMF yield. Under this perspective, the properties of the catalytic system, as well as the choice of a suitable solvent and the addition of an eventual pretreatment of the biomass, represent key aspects of the optimization of HMF synthesis. On this basis, the present review summarizes and critically discusses the most recent and attractive strategies for HMF production from real feedstocks, focusing on the smartest catalytic systems and the overall sustainability of the adopted reaction conditions. Full article
(This article belongs to the Special Issue Novel Catalytic Strategies for the Synthesis of Furans and Their Derivatives)
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