Understanding the Effect of Solvent Environment on the Interaction of Hydronium Ion with Biomass Derived Species: A Molecular Dynamics and Metadynamics Investigation.

The addition of aprotic solvents results in higher reactivities and selectivities in many key aqueous phase biomass reactions, including the acid-catalyzed conversion of fructose to 5-hydroxyl methyl furfural (HMF). The addition of certain co-solvents inhibits the formation of humins via preferential solvation of key functional groups and can alter reaction kinetics. An important factor in this context is the relative stability of the hydronium ion (the catalyst) in the vicinity of the biomass moiety as compared to that in bulk, as it could determine its efficacy in the protonation step. Hence, in the present work, molecular dynamics (MD) simulations of HMF (the model product) and fructose (the model reactant) in acidic water and water-DMSO mixtures are performed to analyze their interaction with the hydronium ions. We show that the presence of DMSO favors the interaction of the hydronium ion with fructose, whereas it has a detrimental effect on the interaction of hydronium ion with HMF. Well-tempered metadynamics (WT-MTD) simulations are performed to determine the relative stability of the hydronium ion in the immediate vicinity of fructose and HMF, as compared to that in the bulk solvent phase, as a function of solvent composition. We find that DMSO improves the stabilization of the hydronium ions in the first solvation shell of fructose compared to that in the bulk solvent. On the other hand, hydronium ions become less stable in the immediate vicinity of HMF, as the concentration of DMSO increases.

Probing electrosynthetic reactions with furfural on copper surfaces.

This work entails the integrated use of electrochemistry and operando Raman spectroscopy to probe the reduction of a biomass platform, furfural, to value-added chemicals on Cu electrodes. The results reveal key structural differences of the Cu that dictate selectivity for furfuryl alcohol or 2-methylfuran.

Biomass valorization: Sulfated lignin-catalyzed production of 5-hydroxymethylfurfural from fructose.

This study is aimed at the investigation of the preparation of sulfated lignin (SL) as a Bronsted acid catalyst for the preparation of 5-hydroxymethylfurfural (5-HMF). SL was characterized by different methods including FT-IR, FESEM, XRD, and EDS analyses. It shows promising results after 60 min of reaction at 140 °C, reaching 100% conversion of fructose precursor and 99% yield of 5-HMF, with a fructose: catalyst mass ratio of 10:6.

Synthesis of lignin-carbohydrate complex-based catalyst from Eragrostis tef straw and its catalytic performance in xylose dehydration to furfural.

A new catalyst was successfully prepared by functionalization of the lignin-carbohydrate complex structure in the Eragrostis tef straw via simultaneous carbonization and sulfonation. The physical and chemical properties of the surface of the synthesized catalyst were checked by FTIR and XRD. The FTIR results indicate the prepared catalyst exhibited functional groups such as -SO3H, -COOH, and -OH. The synthesis conditions like the temperature and time of carbonization and sulfonation showed significant effect the amount of the strong acid doped into the carbonized lignin-carbohydrate matrix. The newly prepared catalyst was checked for dehydration of xylose to furfural and revealed of course that it has the potential. The maximum yield of furfural 62.4% was achieved and the catalyst showed excellent reusability for 5 runs without significant loss of catalystic activity. The use of catalysts prepared from Eragrostis tef straw is a green strategy for converting xylose to furfural, as these catalysts are solving the problems associated with the use of mineral acid catalysts.

Two-Step One-Pot Reductive Amination of Furanic Aldehydes Using CuAlOx Catalyst in a Flow Reactor.

Aminomethylhydroxymethylfuran derivatives are well known compounds which are used in the pharmaceutical industry. Reductive amination of 5-hydroxymethylfurfural (HMF) derived from available non-edible lignocellulosic biomass is an attractive method for the synthesis of this class of compounds. In the present study, the synthesis of N-substituted 5-(hydroxymethyl)-2-furfuryl amines and 5-(acetoxymethyl)-2-furfuryl amines was performed by two-step process, which includes the condensation of furanic aldehydes (HMF and 5-acetoxymethylfurfural) with primary amines in methanol on the first step and the reduction of obtained imines with hydrogen in a flow reactor over CuAlOx catalyst derived from layered double hydroxide on the second step. This process does not require isolation and purification of intermediate imines and can be used to synthesize a number of aminomethylhydroxymethylfurans in good to excellent yield.

Toward Sustainable Hydroxymethylfurfural Production Using Seaweeds.

Chemical manufacturing involves carbon sources releasing CO2 into the atmosphere. By contrast, seaweeds are carbon sinks that can absorb released CO2 and therefore have great potential for use as feedstocks in sustainable chemical manufacturing. In particular, seaweeds could contribute to mitigating vast amounts of global CO2 emissions. Accordingly, seaweeds could be an excellent candidate biomaterial for sustainable production of hydroxymethylfurfural (HMF), called a 'sleeping giant' platform chemical due to its wide versatility in chemical manufacturing. HMF is produced through sugar dehydration mechanisms, and seaweed storage glucans comprised of glucose can be appropriate feeding substrates for its production. This opinion article introduces a new opportunity for sustainable production of HMF using storage glucan-rich seaweeds.

Synthesis of sulfonated chitosan-derived carbon-based catalysts and their applications in the production of 5-hydroxymethylfurfural.

A novel sulfonated chitosan-derived carbon-based catalyst was successfully prepared via isoamyl nitrite-assisted sulfanilic acid sulfonation, and its catalytic activity was examined using dehydration of fructose. The structural and chemical properties of sulfonated chitosan-derived carbon were characterized by SEM, FTIR, XRD, XPS, element analysis, N2 adsorption-desorption experiment, and acid-base titration experiment. KOH was used as activating agent in the synthesizing of carbon supports, and it was found that properly increasing the dose of KOH during activation stage had a positive effect on the subsequent sulfonation of prepared activated carbon. 4KSCC, with the highest sulfonation degree (2.04 mmol/g), exhibited high performance for the conversion of fructose to HMF in various solvent, and an optimal HMF yield of 80.9% was obtained at 140 °C in 40 min. In addition, the reusability of 4KSCC for fructose dehydration was fairly good.

A comparative study on the chemo-enzymatic upgrading of renewable biomass to 5-Hydroxymethylfurfural.

5-hydroxymethylfurfural (HMF) obtained from renewable biomass-derived carbohydrates is a potential sustainable substitute to petroleum-based building blocks. In the present work, we constituted a comparative study on the production of HMF from two widely available real biomasses in India- Agave americana and Casuarina equisetifolia. In the initial hydrolysis studies for the production of reducing sugars, 649.5 mg/g of fructose was obtained from the hydrolysis of 5% (w/v) A. americana biomass by the enzyme inulinase in 3 h at 50°C. Similarly, upon hydrolysis of 15% (w/v) C. equisetifolia biomass by the lignocellulolytic enzymes (laccase, cellulase and xylanase) from Trichoderma atroviride, 456.65 mg/g of reducing sugars was released in 24 h at 30°C. Subsequently, the dehydration of the obtained reducing sugars to HMF was achieved with titanium dioxide as the catalyst. The dehydration of A. americana-derived fructose at 140°C led to a maximum HMF yield of 92.6% in 15 min with 10% catalyst load. Contrarily, upon optimizing the process parameters for dehydration of C. equisetifolia derived reducing sugars, the maximum HMF yield of 85.7% was obtained at 110°C in 25 min with a TiO2 concentration of 10%. This study reports for the first time the utilization of C. equisetifolia biomass for HMF production and thus, by utilizing these inexpensive, abundantly available and highly functionalized polysaccharides, a strategical approach can be developed for the production of fine chemicals, eliminating the need of fossil-based chemicals. Implications: The catalytic upgrading of lignocellulosic biomass into high-valued platform chemicals like 5-Hydroxymethylfurfural (HMF) implies an extremely significant challenge to the attempts of establishing a green economy. Casuarina equisetifolia and Agave americana represents a sustainable feedstock for the production of HMF through catalytic integration. The present work describes a two-step reaction process where the initial depolymerization step comprises of an enzymatic hydrolysis followed by a chemical-catalyst mediated dehydration process. The utilization of a biocatalytic approach followed by mild chemical catalyst eliminates the need of hazardous chemical conversion processes. Thus, the HMF produced via sustainable can bridge the gap between carbohydrate chemistry and petroleum-based industrial chemistry because of the wide range of chemical intermediates and end-products that can be derived from this compound.

Utilizing Furfural-Based Bifuran Diester as Monomer and Comonomer for High-Performance Bioplastics: Properties of Poly(butylene furanoate), Poly(butylene bifuranoate), and Their Copolyesters.

Two homopolyesters and a series of novel random copolyesters were synthesized from two bio-based diacid esters, dimethyl 2,5-furandicarboxylate, a well-known renewable monomer, and dimethyl 2,2'-bifuran-5,5'-dicarboxylate, a more uncommon diacid based on biochemical furfural. Compared to homopolyesters poly(butylene furanoate) (PBF) and poly(butylene bifuranoate) (PBBf), their random copolyesters differed dramatically in that their melting temperatures were either lowered significantly or they showed no crystallinity at all. However, the thermal stabilities of the homopolyesters and the copolyesters were comparable. Based on tensile tests from amorphous film specimens, it was concluded that the elastic moduli, tensile strengths, and elongation at break values for all copolyesters were similar as well, irrespective of the furan:bifuran molar ratio. Tensile moduli of approximately 2 GPa and tensile strengths up to 66 MPa were observed for amorphous film specimens prepared from the copolyesters. However, copolymerizing bifuran units into PBF allowed the glass transition temperature to be increased by increasing the amount of bifuran units. Besides enhancing the glass transition temperatures, the bifuran units also conferred the copolyesters with significant UV absorbance. This combined with the highly amorphous nature of the copolyesters allowed them to be melt-pressed into highly transparent films with very low ultraviolet light transmission. It was also found that furan-bifuran copolyesters could be as effective, or better, oxygen barrier materials as neat PBF or PBBf, which themselves were found superior to common barrier polyesters such as PET.

Synthesis of 5-hydroxymethylfurfural from highly concentrated aqueous fructose solutions using activated carbon.

An efficient and environmentally friendly system for producing 5-hydroxymethylfurfural (5-HMF) from fructose has been proposed. Substrate concentration is an important factor for practical application of the process; however, use of a high concentration of fructose has rarely been tested in the reaction because the conditions accelerate intermolecular side reactions to form adhesive humins. Humin byproducts stuck on reactor surfaces can make the production of 5-HMF on an industrial scale difficult. Therefore, developing a catalytic reaction system that can promote the synthesis of 5-HMF from highly concentrated fructose without causing adhesion of humins to reactors is needed. The present study demonstrated that activated carbons are promising materials for this system. Activated carbon catalyzed the conversion of fructose to 5-HMF without adhesion of humins to reactor vessels under practical conditions of high substrate concentration up to 73.2%. The catalytic activity was determined not only by the amount of surface weakly acidic oxygenated groups but also by the adsorption of fructose. In addition, strong adsorption of 5-HMF led to low selectivity of 5-HMF and the formation of adhesive humins. This is the first report to describe the synthesis of 5-HMF from solutions containing a fructose concentration greater than 70%.

Aluminum alkoxy-catalyzed biomass conversion of glucose to 5-hydroxymethylfurfural: Mechanistic study of the cooperative bifunctional catalysis.

Density functional theory calculations were performed to understand the detailed reaction mechanism of aluminum alkoxy-catalyzed conversion of glucose to 5-hydroxymethylfurfural (HMF) using Al(OMe)3 as catalyst. Potential energy surfaces were studied for aggregates formed between the organic compounds and Al(OMe)3 and effects of the medium were considered via continuum solvent models. The reaction takes place via two stages: isomerization from glucose to fructose (stage I) and transformation of fructose to HMF (stage II). Stage II includes three successive dehydrations, which begins with a 1,2-elimination to form an enolate (i.e., B), continues with the formation of the acrolein moiety (i.e., D), and ends with the formation of the furan ring (i.e., HMF). All of these steps are facilitated by aluminum alkoxy catalysis. The highest barriers for stage I and stage II are 23.9 and 31.2 kcal/mol, respectively, and the overall catalytic reaction is highly exothermic. The energetic and geometric results indicate that the catalyzed reaction path has feasible kinetics and thermodynamics and is consistent with the experimental process under high temperature (i.e., 120 °C). Remarkably, the released water molecules in stage II act as the product, reactant, proton shuttle, as well as stabilizer in the conversion of fructose to HMF. The metal-ligand functionality of the Al(OMe)3 catalyst, which combines cooperative Lewis acid and Lewis base properties and thereby enables proton shuttling, plays a crucial role in the overall catalysis and is responsible for the high reactivity. © 2019 Wiley Periodicals, Inc.

Influences of stir-frying and baking on flavonoid profile, antioxidant property, and hydroxymethylfurfural formation during preparation of blueberry-filled pastries.

Bakery products with fruit fillings are growing fast. Blueberry-filled pastries are widely consumed in China. This study aimed to investigate the effects of two thermal processing procedures (stir-frying and baking) on flavonoid profile, antioxidant property, and hydroxymethylfurfural (HMF) formation during preparation of blueberry-filled pastries. Stir-frying contributed the most to the variations in these values in blueberry filling. Anthocyanins (48%-53% reduction in total) were more susceptible to thermal processing than flavonols (11%-16%). Among anthocyanins, delphinidin glycosides (61%-67% reduction) were the most unstable, followed by malvidin (52%-58%), petunidin (40%-45%), and cyanidin (38%-41%). A high level of HMF (300 mg/kg) was formed during stir-frying. Except for anthocyanins, baking did not significantly influence HMF formation, flavonol degradation, and antioxidant property in the fillings. Stir-frying processing conditions rather than baking must be further investigated for nutrient retention and HMF inhibition.

One Step Conversion of Glucose into 5-Hydroxymethylfurfural (HMF) via a Basic Catalyst in Mixed Solvent Systems of Ionic Liquid-Dimethyl Sulfoxide.

A simple solid base catalyst, ammonium aluminum carbonate hydroxide (AACH), was prepared and its structure was characterized by many technologies, including XRD, FT-IR, SEM, BET and Elemental Analysis. The prepared catalyst was used to catalyze the conversion of glucose into 5-hydroxymethylfurfural (HMF) in ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]+Cl-) and dimethyl sulfoxide (DMSO) mixtures. Various reaction conditions, including catalyst loading, reaction temperature, reaction duration and solvent, were investigated. A moderated HMF yield of 52.17 % was obtained at the mild reaction conditions (120°C for 4 h). More importantly, the catalyst could be reused for several times without the loss of its significant catalytic activities. After five reaction runs, a HMF yield about 49.34 % was also obtained.

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

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.

Hybrid Organic-Inorganic Anatase as a Bifunctional Catalyst for Enhanced Production of 5-Hydroxymethylfurfural from Glucose in Water.

Hybrid organic-inorganic anatase (hybrid-TiO2 ) is prepared by a facile hydrothermal synthesis method employing citric acid. The synthetic approach results in a high surface-area nanocrystalline anatase polymorph of TiO2 . The uncalcined hybrid-TiO2 is directly studied as a catalyst for the conversion of glucose into 5-hydroxymethylfurfural (HMF). In the presence of the hybrid-TiO2 , HMF yields up to 45 % at glucose conversions up to 75 % were achieved in water at 130 °C in a monophasic batch reactor. As identified by Ti K-edge XANES, hybrid-TiO2 contains a large fraction of fivefold coordinatively unsaturated TiIV sites, which act as the Lewis acid catalyst for the conversion of glucose into fructose. As citric acid is anchored in the structure of hybrid-TiO2 , carboxylate groups seem to catalyze the sequential conversion of fructose into HMF. The fate of citric acid bound to anatase and the TiIV Lewis acid sites throughout recycling experiments is also investigated. In a broader context, this contribution outlines the importance of hydrothermal synthesis for the creation of water-resistant Lewis acid sites for the conversion of sugars. Importantly, the use of the hybrid-TiO2 with no calcination step contributes to dramatically decreasing the energy consumption in the catalyst preparation.

Starbon/High-Amylose Corn Starch-Supported N-Heterocyclic Carbene-Iron(III) Catalyst for Conversion of Fructose into 5-Hydroxymethylfurfural.

Iron-N-heterocyclic carbene complexes (Fe-NHCs) have come to prominence because of their applicability in diverse catalytic reactions, ranging from C-C cross-coupling and C-X bond formation to substitution, reduction, polymerization, and dehydration reactions. The detailed synthesis, characterization, and application of novel heterogeneous Fe-NHC catalysts immobilized on mesoporous expanded high-amylose corn starch (HACS) and Starbon 350 (S350) for facile fructose conversion into 5-hydroxymethylfurfural (HMF) is reported. Both catalyst types showed good performance for the dehydration of fructose to HMF when the reaction was tested at 100 °C with varying time (10 min, 20 min, 0.5 h, 1 h, 3 h and 6 h). For Fe-NHC/S350, the highest HMF yield was 81.7 % (t=0.5 h), with a TOF of 169 h-1 , fructose conversion of 95 %, and HMF selectivity of 85.7 %, whereas for Fe-NHC/expanded HACS, the highest yield was 86 % (t=0.5 h), with a TOF of 206 h-1 , fructose conversion of 87 %, and HMF selectivity of 99 %. Iron loadings of 0.26 and 0.30 mmol g-1 were achieved for Fe-NHC/expanded starch and Fe-NHC/S350, respectively.

One-step Preparation of Carbon-based Solid Acid Catalyst from Water Hyacinth Leaves for Esterification of Oleic Acid and Dehydration of Xylose.

Carbon-based solid acid catalysts were successfully obtained via one-step hydrothermal carbonization (HTC) of water hyacinth (WH) in the presence of p-toluenesulfonic acid (PTSA). Increasing the HTC temperature from 180 to 240 °C resulted in carbonaceous materials with increased sulfur content and less adsorbed water. The material obtained at 220 °C (WH-PTSA-220) contains the highest amount of acid sites and promotes the highest initial rate of two transformations, that is, methanolysis of oleic acid and dehydration of xylose to furfural. While all PSTA-treated WH catalysts gave comparable fatty acid conversions (≈97 %) and furfural yields (≈60 %) after prolonged reaction times, the WH-PTSA-240 system bearing a relatively low acid density maintains the most favorable reusability profile. Higher HTC temperatures (220-240 °C) improved the catalyst reusability profiles due to graphitization and hydrophobicity of the carbon surface. The catalyst systems derived herein from biomass may have potential applications in biorefining platforms, utilizing the conversion of waste biomass to chemicals.

Hydrothermal conversion of N-acetyl-d-glucosamine to 5-hydroxymethylfurfural using ionic liquid as a recycled catalyst in a water-dimethyl sulfoxide mixture.

Here, N-acetyl-d-glucosamine (GlcNAc), the monomer composing the second most abundant biopolymer, chitin, was efficiently converted into 5-hydroxymethylfurfural (5-HMF) using ionic liquid (IL) catalysts in a water/dimethyl sulfoxide (DMSO) mixture solvent. Various reaction parameters, including reaction temperature and time, DMSO/water mass ratios and catalyst dosage were optimized. A series of ILs with different structures were analyzed to explore their impact on GlcNAc conversion. The substrate scope was expanded from GlcNAc to d-glucosamine, chitin, chitosan and monosaccharides, although 5-HMF yields obtained from polymers and other monosaccharides were generally lower than those from GlcNAc. Moreover, the IL N-methylimidazolium hydrogen sulfate ([Hmim][HSO4]) exhibited the best catalyst performance (64.6% yield) when GlcNAc was dehydrated in a DMSO/water mixture at 180 °C for 6 h without the addition of extra catalysts. To summarize, these results could provide knowledge essential to the production of valuable chemicals that are derived from renewable marine resources and benefit biofuel-related applications.

Heterogeneously Catalyzed Hydrothermal Processing of C5-C6 Sugars.

Biomass has been long exploited as an anthropogenic energy source; however, the 21st century challenges of energy security and climate change are driving resurgence in its utilization both as a renewable alternative to fossil fuels and as a sustainable carbon feedstock for chemicals production. Deconstruction of cellulose and hemicellulose carbohydrate polymers into their constituent C5 and C6 sugars, and subsequent heterogeneously catalyzed transformations, offer the promise of unlocking diverse oxygenates such as furfural, 5-hydroxymethylfurfural, xylitol, sorbitol, mannitol, and gluconic acid as biorefinery platform chemicals. Here, we review recent advances in the design and development of catalysts and processes for C5-C6 sugar reforming into chemical intermediates and products, and highlight the challenges of aqueous phase operation and catalyst evaluation, in addition to process considerations such as solvent and reactor selection.

Furfural Production from d-Xylose and Xylan by Using Stable Nafion NR50 and NaCl in a Microwave-Assisted Biphasic Reaction.

Pentose dehydration and direct transformation of xylan into furfural were performed in a water-cyclopentyl methyl ether (CPME) biphasic system under microwave irradiation. Heated up between 170 and 190 °C in the presence of Nafion NR50 and NaCl, d-xylose, l-arabinose and xylan gave furfural with maximum yields of 80%, 42% and 55%, respectively. The influence of temperature and reaction time on the reaction kinetics was discussed. This study was also completed by the survey of different reactant ratios, such as organic layer-water or catalyst-inorganic salt ratios. The exchange between proton and cation induced by an excess of NaCl was monitored, and a synergetic effect between the remaining protons and the released HCl was also discovered.