Base-free conversion of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over a Ru/C catalyst

Yi, Guangshun; Teong, Siew Ping; Zhang, Yugen

doi:10.1039/c5gc01584g

Cited by 222 publications

(157 citation statements)

References 55 publications

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“…The oxidation of HMF or other furans to FDCA has been achieved mainly by metal-based catalysis [4][5][6][7]. Yet, the search for an efficient chemical process for converting HMF into valuable building blocks such as FDCA is still ongoing.…”

Section: Introductionmentioning

confidence: 99%

Conversion of Furans by Baeyer-Villiger Monooxygenases

Kumar

Fraaije

2017

Catalysts

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Various furans are considered as valuable platform chemicals as they can be derived from plant biomass. Yet, for their exploitation, follow-up chemistry is required. Here we demonstrate that Baeyer-Villiger monooxygenases (BVMOs) can be used as biocatalysts for the selective oxidation of several furans, including 5-(hydroxymethyl) furfural (HMF) and furfural. A total of 15 different BVMOs were tested for their activity on furfural, which revealed that most of the biocatalysts were active on this aromatic aldehyde. Phenylacetone monooxygenase (PAMO) and a mutant thereof (PAMO M446G ) were selected for studying their biocatalytic potential in converting furfural and some other furans. While BVMOs are usually known to form an ester or lactone as a 'normal' product by inserting an oxygen atom adjacent to the carbonyl carbon of the substrate, our results reveal that both biocatalysts produce furanoid acids as the main product from the corresponding aldehydes. Altogether, our study shows that BVMOs can be employed for the selective oxidation of furans.

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Section: Introductionmentioning

confidence: 99%

Conversion of Furans by Baeyer-Villiger Monooxygenases

Kumar

Fraaije

2017

Catalysts

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“…By controlling the amount of surface Pd atoms to be identical, Pd nanocrystals with the same shape but different particle sizes exhibited very similar catalytic performances for HMF oxidation. Ruthenium catalysts supported on carbon materials were studied by Yi et al, 23 however very high metal : HMF ratios are required to achieve signicant catalytic yield to FDCA.…”

Section: Introductionmentioning

confidence: 99%

Direct catalytic effect of nitrogen functional groups exposed on graphenic materials when acting cooperatively with Ru nanoparticles

et al. 2017

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A number of inorganic carbonaceous materials (activated carbon, high surface area graphite and graphenic materials) have been used as supports of Ru nanoparticles in order to determine their catalytic properties in the base-free aqueous-phase oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). In particular, we have studied in detail reduced graphene oxide (rGO) and nitrogen doped reduced graphene oxide (NrGO), which are the support materials that produce more selective ruthenium catalysts. Also the effects of different metal precursors used in the preparation of the Ru nanocrystallites have been evaluated. Both support materials and Ru catalysts were characterized by elemental analysis, nitrogen physisorption (BET), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The point of zero charge (PZC) for the graphenic materials was also determined. Interestingly the different supports significantly modify the catalytic performances, the graphenic materials being those that under our experimental reaction conditions produce the highest selectivity to FDCA. On these supports (rGO and NrGO) the highest HMF conversion was achieved by using triruthenium dodecacarbonyl as the ruthenium precursor. For the improved catalyst, Ru supported on NrGO, the yield of FDCA becomes close to 80%. This catalyst has been reused several times with neither loss of activity nor modification in selectivity values. Characterization data indicate these catalytic results can be correlated to the basic properties of the NrGO support as well as to the surface properties of Ru nanoparticles. These findings indicated that the metal precursor and the surface functional groups exposed on the support can modulate the catalytic properties, in particular amending the selectivity towards FDCA production.

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“…[13][14][15][16][17][18] As a matter of fact, FDCA already results to be an excellent substitute of terephthalic acid in the production of polyesters. Polyethylene furanoate (PEF), obtained from polycondensation of FDCA and ethylene glycol, showed up to be a perfect substitute of PET thanks also to the improved barrier properties.…”

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confidence: 99%

Green approaches in the synthesis of furan-based diepoxy monomers

et al. 2018

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Two eco-respectful, one-step synthetic routes for the preparation of a bio-based epoxy monomer derived from furan precursors are developed. The diglycidyl ester products are throughly characterized in terms of structure and thermal properties. Gathered results indicate that the two selected approaches allow the preparation of pure, furanic diglycidyl ester, which represents a viable bio-based alternative to its petrochemical aromatic counterpart.Research on bio-based polymers has been rapidly increasing in past years, pushed by growing environmental and economic concerns, as well as by the uncertainty about future availability of nite petrochemical resources.1 Sustainability is a keyword in this process. In this frame, products that are respectful towards the environment, including eco-compatible building blocks and additives, are now researched to replace petroleum-based polymers with those derived from naturally occurring feedstocks.2-4 In the eld of epoxy resins, this trend is related also to the necessity to nd a good candidate to substitute the controversial building block bisphenol A (BPA), a molecule recognized as an endocrine disrupter and reprotoxic substance.5 Epoxy resins are very versatile thermosetting polymers, extremely resistant to corrosion, moisture and chemicals, with good adhesive strength toward most materials (wettability) and low shrinkage upon curing. Due to their high glass transition temperatures and excellent mechanical strength, epoxy resins are widely employed in a broad range of applications, such as electronics, structural adhesives, aerospace composites and protective coatings. In the latter application, the use of BPA results in hazard for customers of food and beverage products packed into containers treated with epoxy resins. The effects of human body contamination caused by BPA are diabetes, cardiovascular diseases, altered liver enzymes and reproductive apparatus damages.5 For these reasons, this molecule has been banned in many countries for the manufacturing of child products, and in France and Canada from all the materials in direct contact with food. Therefore, the necessity to nd non-toxic and sustainable building blocks to replace BPA in the production of epoxy resins results mandatory. If one considers also the decreasing availability of oilderived feedstock, the research of new molecules is logically focusing on bio-derived chemicals. Epoxidized vegetable oils have been widely studied for their use in epoxy resins preparation, thanks to their characteristics, availability and low cost.6-8 Mechanical properties of epoxy resins obtained using these long aliphatic molecules, alone or mixed to aromatic epoxy comonomers, are encouraging.9,10 In order to further improve chemical, thermal and mechanical properties of epoxy resins, the presence of signicant content of aromatic moieties is required. In this frame, lignin derivatives appear to be the natural substitutes of BPA. However, time-and energyconsuming extraction processes make lignin-based epoxies expensive and b...

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Base-free conversion of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over a Ru/C catalyst

Abstract: The catalytic conversion of 5-hydroxymethyl furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) over a commercial Ru/C catalyst in a base-free aqueous solution was studied with up to 88% FDCA yield.

Cited by 222 publications

References 55 publications

Conversion of Furans by Baeyer-Villiger Monooxygenases

Conversion of Furans by Baeyer-Villiger Monooxygenases

Direct catalytic effect of nitrogen functional groups exposed on graphenic materials when acting cooperatively with Ru nanoparticles

Green approaches in the synthesis of furan-based diepoxy monomers

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