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Special Issue "Platform Chemical: Hydroxymethylfurfural (HMF)"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (30 June 2018)

Special Issue Editors

Guest Editor
Prof. Michela Signoretto

Department of Molecular Sciences and Nano Systems, Università Ca’ Foscari Venezia, and INSTM Consortium, Via Torino 155, 30172 Mestre Venezia, Italy
Website 1 | Website 2 | E-Mail
Interests: development of catalysts and processes for the production of fine chemicals and fuels from biomass; photocatalysts design for fuel production; design of dermo-cosmetic and pharmaceutical formulates; formulation of multifunctional materials for bio-building applications; catalytic production of hydrogen from biomass; development of heterogeneous catalysts and their use in industrial chemistry
Guest Editor
Dr. Federica Menegazzo

Department of Molecular Sciences and Nano Systems, Università Ca’ Foscari Venezia, and INSTM Consortium, Via Torino 155, 30172 Mestre Venezia, Italy
Website 1 | Website 2 | E-Mail
Interests: development of heterogeneous catalysts and processes for biomass valorization; synthesis and characterization of metal nanoparticles; sustainable industrial processes; formulation of materials for green applications; hydrogen production; steam and dry reforming

Special Issue Information

Dear Colleagues,

Biomass conversion to value-added chemicals and fuels over heterogeneous, homogeneous, enzymatic catalysts is one of the goal for the future. 5-hydroxymethyl furfural (HMF) is one of the most important and renewable platform chemicals in the bio-based renaissance. HMF can be obtained from fructose, sucrose, glucose, as well as directly from cellulose, and it can be further transformed into a wide variety of high performance products.

The aim of this Special Issue is to present a current overview of recent developments in the field of the still-open challenges for both HMF production and HMF applications.

All researchers working in the field are cordially invited to contribute original research papers to this Special Issue of Molecules. Reviews are also welcome.

Prof. Dr. Michela Signoretto
Dr. Federica Menegazzo
Guest Editors

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 papers will be 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. Molecules 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 1800 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

  • HMF
  • Biomass valorization
  • biorefinery
  • catalysis
  • renewables
  • lignocellulosic biomasses
  • platform chemicals

Published Papers (9 papers)

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Research

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Open AccessArticle Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu
Molecules 2018, 23(11), 2905; https://doi.org/10.3390/molecules23112905
Received: 7 October 2018 / Revised: 4 November 2018 / Accepted: 5 November 2018 / Published: 7 November 2018
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Abstract
We have investigated the synthesis and application of Au-Cu/CeO2 (Cu: Au = 2) in the continuous gas phase (P = 1 atm; T = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis revealed a close surface proximity
[...] Read more.
We have investigated the synthesis and application of Au-Cu/CeO2 (Cu: Au = 2) in the continuous gas phase (P = 1 atm; T = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis revealed a close surface proximity of both metals in Au-Cu/CeO2 post-TPR. XPS measurements suggest (support → metal) charge transfer to form Auδ and strong metal-support interactions to generate Cu0 and Cu+. Au-Cu/CeO2 promoted the sole formation of 2,5-dihydroxymethylfuran (DHMF) and 2-butanone in the HMF/2-butanol coupling with full hydrogen utilisation. Under the same reaction conditions, Au/CeO2 was fully selective to DHMF in standard HMF hydrogenation (using an external hydrogen supply), but delivered a lower production rate and utilised less than 0.2% of the hydrogen supplied. Exclusive -C=O hydrogenation and -OH dehydrogenation is also demonstrated for the coupling of a series of m-substituted (-CH3, -CH2CH3, -CH2OH, -CF3, -N(CH3)2, -H) furaldehydes with alcohol (1-propanol, 1-butanol, 2-propanol, 2-butanol, cyclohexanol) dehydrogenation over Au-Cu/CeO2, consistent with a nucleophilic mechanism. In each case, we observed a greater hydrogenation rate and hydrogen utilisation efficiency with a 3–15 times lower E-factor in the coupling process relative to standard hydrogenation. Our results demonstrate the feasibility of using hydrogen generated in situ through alcohol dehydrogenation for the selective hydrogenation of m-furaldehydes with important industrial applications. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Open AccessArticle Selective Oxidation of HMF via Catalytic and Photocatalytic Processes Using Metal-Supported Catalysts
Molecules 2018, 23(11), 2792; https://doi.org/10.3390/molecules23112792
Received: 5 October 2018 / Revised: 23 October 2018 / Accepted: 25 October 2018 / Published: 27 October 2018
PDF Full-text (6874 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In this study, 5-hydroxymethylfurfural (HMF) oxidation was carried out via both the catalytic and the photocatalytic approach. Special attention was devoted to the preparation of the TiO2-based catalysts, since this oxide has been widely used for catalytic and photocatalytic application in
[...] Read more.
In this study, 5-hydroxymethylfurfural (HMF) oxidation was carried out via both the catalytic and the photocatalytic approach. Special attention was devoted to the preparation of the TiO2-based catalysts, since this oxide has been widely used for catalytic and photocatalytic application in alcohol oxidation reactions. Thus, in the catalytic process, the colloidal heterocoagulation of very stable sols, followed by the spray-freeze-drying (SFD) approach, was successfully applied for the preparation of nanostructured porous TiO2-SiO2 mixed-oxides with high surface areas. The versatility of the process made it possible to encapsulate Pt particles and use this material in the liquid-phase oxidation of HMF. The photocatalytic activity of a commercial titania and a homemade oxide prepared with the microemulsion technique was then compared. The influence of gold, base addition, and oxygen content on product distribution in the photocatalytic process was evaluated. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Open AccessFeature PaperArticle Ruthenium on Carbonaceous Materials for the Selective Hydrogenation of HMF
Molecules 2018, 23(8), 2007; https://doi.org/10.3390/molecules23082007
Received: 15 July 2018 / Revised: 5 August 2018 / Accepted: 8 August 2018 / Published: 11 August 2018
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Abstract
We report the use of Ru catalysts supported in the activated carbon (AC) and carbon nanofibers (CNFs) for the selective production of liquid fuel dimethylfuran (DMF) and fuel additives alkoxymethyl furfurals (AMF). Parameters such as the reaction temperature and hydrogen pressure were firstly
[...] Read more.
We report the use of Ru catalysts supported in the activated carbon (AC) and carbon nanofibers (CNFs) for the selective production of liquid fuel dimethylfuran (DMF) and fuel additives alkoxymethyl furfurals (AMF). Parameters such as the reaction temperature and hydrogen pressure were firstly investigated in order to optimise the synthesis of the desired products. Simply by using a different support, the selectivity of the reaction drastically changed. DMF was produced with AC as support, while a high amount of AMF was produced when CNFs were employed. Moreover, the reusability of the catalysts was tested and deactivation phenomena were identified and properly addressed. Further studies need to be performed in order to optimise the stability of the catalysts. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Open AccessArticle Catalytic Dehydration of Fructose to 5-Hydroxymethylfurfural (HMF) in Low-Boiling Solvent Hexafluoroisopropanol (HFIP)
Molecules 2018, 23(8), 1866; https://doi.org/10.3390/molecules23081866
Received: 28 June 2018 / Revised: 17 July 2018 / Accepted: 23 July 2018 / Published: 26 July 2018
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Abstract
A mixture of hexafluoroisopropanol (HFIP) and water was used as a new and unknown monophasic reaction solvent for fructose dehydration in order to produce HMF. HFIP is a low-boiling fluorous alcohol (b.p. 58 °C). Hence, HFIP can be recovered cost efficiently by distillation.
[...] Read more.
A mixture of hexafluoroisopropanol (HFIP) and water was used as a new and unknown monophasic reaction solvent for fructose dehydration in order to produce HMF. HFIP is a low-boiling fluorous alcohol (b.p. 58 °C). Hence, HFIP can be recovered cost efficiently by distillation. Different ion-exchange resins were screened for the HFIP/water system in batch experiments. The best results were obtained for acidic macroporous ion-exchange resins, and high HMF yields up to 70% were achieved. The effects of various reaction conditions like initial fructose concentration, catalyst concentration, water content in HFIP, temperature and influence of the catalyst particle size were evaluated. Up to 76% HMF yield was attained at optimized reaction conditions for high initial fructose concentration of 0.5 M (90 g/L). The ion-exchange resin can simply be recovered by filtration and reused several times. This reaction system with HFIP/water as solvent and the ion-exchange resin Lewatit K2420 as catalyst shows excellent performance for HMF synthesis. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Open AccessArticle Conversion of Fructose to HMF in a Continuous Fixed Bed Reactor with Outstanding Selectivity
Molecules 2018, 23(7), 1802; https://doi.org/10.3390/molecules23071802
Received: 28 June 2018 / Revised: 12 July 2018 / Accepted: 18 July 2018 / Published: 20 July 2018
Cited by 1 | PDF Full-text (1299 KB) | HTML Full-text | XML Full-text
Abstract
5-Hydroxymethylfurfural (HMF) is a very promising component for bio-based plastics. Efficient synthesis of HMF from biomass is still challenging because of fast degradation of HMF to by-products under formation conditions. Therefore, different studies, conducted mainly in monophasic and biphasic batch systems with and
[...] Read more.
5-Hydroxymethylfurfural (HMF) is a very promising component for bio-based plastics. Efficient synthesis of HMF from biomass is still challenging because of fast degradation of HMF to by-products under formation conditions. Therefore, different studies, conducted mainly in monophasic and biphasic batch systems with and without water addition have been published and are still under investigation. However, to produce HMF at a large scale, a continuous process is preferable. Until now, only a few studies have been published in this context. In this work, it is shown that fluorous alcohol hexafluoroisopropanol (HFIP) can act as superior reaction solvent for HMF synthesis from fructose in a fixed bed reactor. Very high yields of 76% HMF can be achieved in this system under optimized conditions, whilst the catalyst is very stable over several days. Such high yields are only described elsewhere with high boiling reaction solvents like dimethylsulfoxide (DMSO), whereas HFIP with a boiling point of 58 °C is very easy to separate from HMF. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Open AccessArticle Microwave-Assisted Oxalic Acid Pretreatment for the Enhancing of Enzyme Hydrolysis in the Production of Xylose and Arabinose from Bagasse
Molecules 2018, 23(4), 862; https://doi.org/10.3390/molecules23040862
Received: 22 March 2018 / Revised: 31 March 2018 / Accepted: 4 April 2018 / Published: 10 April 2018
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Abstract
In this study, highly-efficient hydrolysis of bagasse into xylose and arabinose sugars (C5 sugars) was developed by microwave-assisted oxalic acid pretreatment under mild reaction conditions. The effects of acid and hydrolysis conditions on the C5 sugar yields were discussed. The results showed that
[...] Read more.
In this study, highly-efficient hydrolysis of bagasse into xylose and arabinose sugars (C5 sugars) was developed by microwave-assisted oxalic acid pretreatment under mild reaction conditions. The effects of acid and hydrolysis conditions on the C5 sugar yields were discussed. The results showed that oxalic acid performed better than hydrochloric acid and maleic acid, and was a promising alternative to sulfuric acid for xylose production at the same acid concentration. The maximum yields of xylose (95.7%) and arabinose (91.5%) were achieved via the microwave-assisted oxalic acid pretreatment (120 °C, 10 min, 0.4 mol/L, solid–liquid ratio of 1:50 g/mL), indicating that almost all xylan-type hemicelluloses were released from the cell wall and hydrolyzed into C5 sugars. After pretreatment, more than 90% of the cellulose in the residual bagasse was converted to glucose (92.2%) by enzymatic hydrolysis. This approach could realize the highly-efficient hydrolysis of xylan from bagasse into C5 sugars, which would enhance the enzyme hydrolysis of treated bagasse into glucose. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Open AccessArticle Facile Chemical Access to Biologically Active Norcantharidin Derivatives from Biomass
Molecules 2017, 22(12), 2210; https://doi.org/10.3390/molecules22122210
Received: 9 November 2017 / Revised: 30 November 2017 / Accepted: 7 December 2017 / Published: 12 December 2017
Cited by 2 | PDF Full-text (821 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Reductive amination of 2,5-diformylfuran (DFF) was used to implement the transition from bio-derived 5-hydroxymethylfurfural (HMF) to pharmaceuticals. The synthesized bis(aminomethyl)furans were utilized as building blocks for the construction of new derivatives with structural cores of naturally occurring biologically active compounds. Using the one-pot
[...] Read more.
Reductive amination of 2,5-diformylfuran (DFF) was used to implement the transition from bio-derived 5-hydroxymethylfurfural (HMF) to pharmaceuticals. The synthesized bis(aminomethyl)furans were utilized as building blocks for the construction of new derivatives with structural cores of naturally occurring biologically active compounds. Using the one-pot procedure, which included the Diels–Alder reaction followed by hydrogenation of the double bond, bio-derived analogues of the anticancer drug norcantharidin were obtained. The cyclization process was diastereoselective, and resulted in the formation of tricyclic products with the endo configuration. Analysis of cytotoxycity for the resulting tricyclic amine-containing compounds showed an increase of anticancer activity as compared with the unsubstituted norcantharimide. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Review

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Open AccessFeature PaperReview 5-Hydroxymethylfurfural (HMF) Production from Real Biomasses
Molecules 2018, 23(9), 2201; https://doi.org/10.3390/molecules23092201
Received: 30 July 2018 / Revised: 24 August 2018 / Accepted: 27 August 2018 / Published: 31 August 2018
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Abstract
The present paper reviews recent advances on the direct synthesis of 5-hydroxymethylfurfural (HMF) from different kinds of raw biomasses. In particular, in the paper HMF production from: (i) edible biomasses; (ii) non-edible lignocellulosic biomasses; (iii) food wastes (FW) have been reviewed. The different
[...] Read more.
The present paper reviews recent advances on the direct synthesis of 5-hydroxymethylfurfural (HMF) from different kinds of raw biomasses. In particular, in the paper HMF production from: (i) edible biomasses; (ii) non-edible lignocellulosic biomasses; (iii) food wastes (FW) have been reviewed. The different processes and catalytic systems have been reviewed and their merits, demerits and requirements for commercialisation outlined. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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Open AccessReview Recent Advances in the Microwave-Assisted Production of Hydroxymethylfurfural by Hydrolysis of Cellulose Derivatives—A Review
Molecules 2018, 23(8), 1973; https://doi.org/10.3390/molecules23081973
Received: 6 July 2018 / Revised: 3 August 2018 / Accepted: 3 August 2018 / Published: 7 August 2018
Cited by 1 | PDF Full-text (3872 KB) | HTML Full-text | XML Full-text
Abstract
The concepts of sustainable development, bioeconomy, and circular economy are being increasingly applied for the synthesis of molecules of industrial interest. Among these molecules, hydroxymethylfurfural as a platform molecule is the subject of various research approaches to improve its synthesis and productivity, and
[...] Read more.
The concepts of sustainable development, bioeconomy, and circular economy are being increasingly applied for the synthesis of molecules of industrial interest. Among these molecules, hydroxymethylfurfural as a platform molecule is the subject of various research approaches to improve its synthesis and productivity, and extend its potential uses. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of hydroxymethylfurfural production from sugars and polysaccharide feedstocks under microwave-assisted technology. The review discusses advances obtained via microwave activation in major production pathways recently explored, split into the following categories: (i) use of various homogeneous catalysts like mineral or organic acids, metal salts, or ionic liquids; (ii) feedstock dehydration making use of various solid acid catalysts; and (iii) non-catalytic routes. Full article
(This article belongs to the Special Issue Platform Chemical: Hydroxymethylfurfural (HMF))
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