Research

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16 pages, 2837 KiB

Open AccessArticle

Gas Phase Hydrogenation of Furaldehydes via Coupling with Alcohol Dehydrogenation over Ceria Supported Au-Cu

by Chiara Pischetola, Laura Collado, Mark A. Keane and Fernando Cárdenas-Lizana

Molecules 2018, 23(11), 2905; https://doi.org/10.3390/molecules23112905 - 07 Nov 2018

Cited by 11 | Viewed by 3833

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 Au^δ⁻ 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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24 pages, 6874 KiB

Open AccessArticle

Selective Oxidation of HMF via Catalytic and Photocatalytic Processes Using Metal-Supported Catalysts

by Alice Lolli, Valeriia Maslova, Danilo Bonincontro, Francesco Basile, Simona Ortelli and Stefania Albonetti

Molecules 2018, 23(11), 2792; https://doi.org/10.3390/molecules23112792 - 27 Oct 2018

Cited by 41 | Viewed by 6957

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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13 pages, 3633 KiB

Open AccessFeature PaperArticle

Ruthenium on Carbonaceous Materials for the Selective Hydrogenation of HMF

by Stefano Cattaneo, Hadi Naslhajian, Ferenc Somodi, Claudio Evangelisti, Alberto Villa and Laura Prati

Molecules 2018, 23(8), 2007; https://doi.org/10.3390/molecules23082007 - 11 Aug 2018

Cited by 14 | Viewed by 3520

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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11 pages, 2085 KiB

Open AccessArticle

Catalytic Dehydration of Fructose to 5-Hydroxymethylfurfural (HMF) in Low-Boiling Solvent Hexafluoroisopropanol (HFIP)

by Sarah Tschirner, Eric Weingart, Linda Teevs and Ulf Prüße

Molecules 2018, 23(8), 1866; https://doi.org/10.3390/molecules23081866 - 26 Jul 2018

Cited by 14 | Viewed by 4402

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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8 pages, 1299 KiB

Open AccessArticle

Conversion of Fructose to HMF in a Continuous Fixed Bed Reactor with Outstanding Selectivity

by Eric Weingart, Sarah Tschirner, Linda Teevs and Ulf Prüße

Molecules 2018, 23(7), 1802; https://doi.org/10.3390/molecules23071802 - 20 Jul 2018

Cited by 13 | Viewed by 3993

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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13 pages, 32184 KiB

Open AccessArticle

Microwave-Assisted Oxalic Acid Pretreatment for the Enhancing of Enzyme Hydrolysis in the Production of Xylose and Arabinose from Bagasse

by Yuhuan Yan, Chunhui Zhang, Qixuan Lin, Xiaohui Wang, Banggui Cheng, Huiling Li and Junli Ren

Molecules 2018, 23(4), 862; https://doi.org/10.3390/molecules23040862 - 10 Apr 2018

Cited by 48 | Viewed by 5356

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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821 KiB

Open AccessArticle

Facile Chemical Access to Biologically Active Norcantharidin Derivatives from Biomass

by Konstantin I. Galkin, Fedor A. Kucherov, Oleg N. Markov, Ksenia S. Egorova, Alexandra V. Posvyatenko and Valentine P. Ananikov

Molecules 2017, 22(12), 2210; https://doi.org/10.3390/molecules22122210 - 12 Dec 2017

Cited by 20 | Viewed by 4956

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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18 pages, 3919 KiB

Open AccessFeature PaperReview

5-Hydroxymethylfurfural (HMF) Production from Real Biomasses

by Federica Menegazzo, Elena Ghedini and Michela Signoretto

Molecules 2018, 23(9), 2201; https://doi.org/10.3390/molecules23092201 - 31 Aug 2018

Cited by 171 | Viewed by 16712

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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16 pages, 3872 KiB

Open AccessReview

Recent Advances in the Microwave-Assisted Production of Hydroxymethylfurfural by Hydrolysis of Cellulose Derivatives—A Review

by Frederic Delbecq and Christophe Len

Molecules 2018, 23(8), 1973; https://doi.org/10.3390/molecules23081973 - 07 Aug 2018

Cited by 60 | Viewed by 5561

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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