Browse
Submit Data
Databases
API
Help

Dataset Information

21 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Catalytic Furfural/5-Hydroxymethyl Furfural Oxidation to Furoic Acid/Furan-2,5-dicarboxylic Acid with H₂ Production Using Alkaline Water as the Formal Oxidant.

ABSTRACT: Furfural and 5-hydroxymethyl furfural (HMF) are abundantly available biomass-derived renewable chemical feedstocks, and their oxidation to furoic acid and furan-2,5-dicarboxylic acid (FDCA), respectively, is a research area with huge prospective applications in food, cosmetics, optics, and renewable polymer industries. Water-based oxidation of furfural/HMF is a lucrative approach for simultaneous generation of H₂ and furoic acid/FDCA. However, this process is currently limited to (photo)electrochemical methods that can be challenging to control, improve, and scale up. Herein, we report well-defined ruthenium pincer catalysts for direct homogeneous oxidation of furfural/HMF to furoic acid/FDCA, using alkaline water as the formal oxidant while producing pure H₂ as the reaction byproduct. Mechanistic studies indicate that the ruthenium complex not only catalyzes the aqueous oxidation but also actively suppresses background decomposition by facilitating initial Tishchenko coupling of substrates, which is crucial for reaction selectivity. With further improvement, this process can be used in scaled-up facilities for a simultaneous renewable building block and fuel production.

SUBMITTER: Kar S

PROVIDER: S-EPMC8796234 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Enzymatic Carboxylation of 2-Furoic Acid Yields 2,5-Furandicarboxylic Acid (FDCA).

Project description:The biological production of FDCA is of considerable value as a potential replacement for petrochemical-derived monomers such as terephthalate, used in polyethylene terephthalate (PET) plastics. HmfF belongs to an uncharacterized branch of the prenylated flavin (prFMN) dependent UbiD family of reversible (de)carboxylases and is proposed to convert 2,5-furandicarboxylic acid (FDCA) to furoic acid in vivo. We present a detailed characterization of HmfF and demonstrate that HmfF can catalyze furoic acid carboxylation at elevated CO2 levels in vitro. We report the crystal structure of a thermophilic HmfF from Pelotomaculum thermopropionicum, revealing that the active site located above the prFMN cofactor contains a furoic acid/FDCA binding site composed of residues H296-R304-R331 specific to the HmfF branch of UbiD enzymes. Variants of the latter are compromised in activity, while H296N alters the substrate preference to pyrrole compounds. Solution studies and crystal structure determination of an engineered dimeric form of the enzyme revealed an unexpected key role for a UbiD family wide conserved Leu residue in activity. The structural insights into substrate and cofactor binding provide a template for further exploitation of HmfF in the production of FDCA plastic precursors and improve our understanding of catalysis by members of the UbiD enzyme family.

| S-EPMC6497424 | biostudies-literature

Effective Biobased Phosphorus Flame Retardants from Starch-Derived bis-2,5-(Hydroxymethyl)Furan.

Project description:A series of biobased phosphorus flame retardants has been prepared by converting starch-derived bis-2,5-(hydroxymethyl)furan to the corresponding diacrylate followed by Michael addition of phosphite to generate derivatives with phosphorus moieties attached via P-C bonds. All compounds behave as effective flame retardants in DGEBA epoxy resin. The most effective is the DOPO derivative, 2,5-di[(3-dopyl-propanoyl)methyl]furan. When incorporated into a DGEBA blend at a level to provide 2% phosphorus, a material displaying a LOI of 30, an UL 94 rating of V0 and a 40% reduction in combustion peak heat release rate compared to that for resin containing no additive is obtained. The analogous compounds generated from bisphenol A and tetrabromobisphenol A exhibit similar flame-retarding properties.

| S-EPMC7037623 | biostudies-literature

Operando generated copper-based catalyst enabling efficient electrosynthesis of 2,5-bis(hydroxymethyl)furan.

Project description:Electrocatalytic upgrading of biomass-derived platform molecules has emerged as a sustainable and environmentally benign route to produce high-value chemicals. The main challenge lies in developing efficient catalysts for the selective activation of designated chemical bonds in the presence of various reducible groups. This work demonstrated a high-efficiency electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF), an important industrial synthetic reagent. A highly porous Cu-based catalyst was developed that achieved nearly 100% BHMF selectivity and long-term stability. Through comprehensive operando and ex-situ structural characterizations, an electrochemically generated catalyst with abundant Cu/Cu2O interfaces was identified as a catalytically active phase for HMF conversion. Deuterated BHMF, with the potential to produce deuterated drugs, was also synthesized using D2O as the deuterium source. Density functional theory calculations show that the Cu/Cu2O interface structure exhibits relatively low energy barriers for the hydrogenation of HMF to BHMF. This work provides insights into the origin of electrocatalytic hydrogenation activity and highlights the promising potential of the electrocatalytic synthesis of high-value chemicals.

| S-EPMC11197742 | biostudies-literature

Microporous Humins Synthesized in Concentrated Sulfuric Acid Using 5-Hydroxymethyl Furfural.

Project description:A new class of highly porous organic sorbents called microporous humins is presented. These microporous humins are derived from sustainable and industrially abundant resources, have high heat of CO2 sorption, and could potentially be useful for the separation of carbon dioxide from gas mixtures. Their synthesis involves the polymerization of 5-hydroxymethyl furfural (HMF) in concentrated sulfuric acid and treatment with diethyl ether and heat. In particular, the porosities were tuned by the heat treatment. HMF is a potential platform chemical from biorefineries and a common intermediate in carbohydrate chemistry. A high uptake of CO2 (up to 5.27 mmol/g at 0 °C and 1 bar) and high CO2-over-N2 and CO2-over-CH4 selectivities were observed. The microporous humins were aromatic and structurally amorphous, which was shown in a multipronged approach using 13C nuclear magnetic resonance and Fourier transform infrared spectroscopies, elemental analysis, and wide-angle X-ray scattering.

| S-EPMC6644757 | biostudies-literature

Selective Biosynthesis of Furoic Acid From Furfural by Pseudomonas Putida and Identification of Molybdate Transporter Involvement in Furfural Oxidation.

Project description:Upgrading of furanic aldehydes to their corresponding furancarboxylic acids has received considerable interest recently. Herein we reported selective oxidation of furfural (FAL) to furoic acid (FA) with quantitative yield using whole-cells of Pseudomonas putida KT2440. The biocatalytic capacity could be substantially promoted through adding 5-hydroxymethylfurfural into media at the middle exponential growth phase. The reaction pH and cell dosage had notable impacts on both FA titer and selectivity. Based on the validation of key factors for FAL conversion, the capacity of P. putida KT2440 to produce FAL was substantially improved. In batch bioconversion, 170 mM FA was produced with selectivity nearly 100% in 2 h, whereas 204 mM FA was produced with selectivity above 97% in 3 h in fed-batch bioconversion. Particularly, the role of molybdate transporter in oxidation of FAL and 5-hydroxymethylfurfural was demonstrated for the first time. The furancarboxylic acids synthesis was repressed markedly by destroying molybdate transporter, which implied Mo-dependent enzyme/molybdoenzyme played pivotal role in such oxidation reactions. This research further highlights the potential of P. putida KT2440 as next generation industrial workhorse and provides a novel understanding of molybdoenzyme in oxidation of furanic aldehydes.

| S-EPMC7545826 | biostudies-literature

Green conversion of 5-hydroxymethylfurfural to furan-2,5-dicarboxylic acid by heterogeneous expression of 5-hydroxymethylfurfural oxidase in Pseudomonas putida S12.

Project description:Transforming petrochemical processes into bioprocesses has become an important goal of sustainable development. The chemical synthesis of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) is expensive and environmentally unfavourable. The study aims to investigate a whole-cell biocatalyst for efficient biotransformation of HMF to FDCA. For the first time, a genetically engineered Pseudomonas putida S12 strain expressing 5-hydroxymethylfurfural oxidase (HMFO) was developed for the biocatalytic conversion of HMF to FDCA. This whole-cell biocatalyst produced 35.7 mM FDCA from 50 mM HMF in 24 h without notable inhibition. However, when the initial HMF concentration was elevated to 100 mM, remarkable inhibition on FDCA production was observed, resulting in a reduction of FDCA yield to 42%. We solve this substrate inhibition difficulty by increasing the inoculum density. Subsequently, we used a fed-batch strategy by maintaining low HMF concentration in the culture to maximize the final FDCA titre. Using this approach, 545 mM of FDCA was accumulatively produced after 72 hs, which is the highest production rate per unit mass of cells to the best of our knowledge.

| S-EPMC7264871 | biostudies-literature

Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts.

Project description:Heterogeneous catalysis, which has served well the petrochemical industry, may valuably contribute towards a bio-based economy by sustainably enabling selective reactions to renewable chemicals. Carbohydrate-containing matter may be obtained from various widespread sources and selectively converted to furanic platform chemicals: furfural (Fur) and 5-(hydroxymethyl)furfural (Hmf). Valuable bioproducts may be obtained from these aldehydes via catalytic transfer hydrogenation (CTH) using alcohols as H-donors under relatively moderate reaction conditions. Hafnium-containing TUD-1 type catalysts were the first of ordered mesoporous silicates explored for the conversion of Fur and Hmf via CTH/alcohol strategies. The materials promoted CTH and acid reactions leading to the furanic ethers. The bioproducts spectrum was broader for the reaction of Fur than of Hmf. A Fur reaction mechanism based on literature data was discussed and supported by kinetic modelling. The influence of the Hf loading and reaction conditions (catalyst load, type of alcohol H-donor, temperature, initial substrate concentration) on the reaction kinetics was studied. The reaction conditions were optimized to maximize the yields of 2-(alkoxymethyl)furan ethers formed from Fur; up to 63% yield was reached at 88% Fur conversion, 4 h/150 °C, using Hf-TUD-1(75), which was a stable catalyst. The Hf-TUD-1(x) catalysts promoted the selective conversion of Hmf to bis(2-alkoxymethyl)furan; e.g., 96% selectivity at 98% Hmf conversion, 3 h/170 °C for Hf-TUD-1(50).

| S-EPMC8658772 | biostudies-literature

5-Hydroxymethyl-2-Furfural Oxidation Over Au/CexZr1-xO2 Catalysts.

Project description:A series of gold catalysts supported on pure CeO2, ZrO2, and two different Ce-Zr mixed oxides have been prepared and tested in the 5-hydroxymethyl-2-furfural oxidation reaction. All catalysts show high catalytic activity (100% conversion) and important selectivity (27-41%) to the desired product i.e., 2,5-furandicarboxylic acid at low base concentration. Products selectivity changes with the support nature as expected, however, the observed trend cannot be related neither to gold particle size, nor to catalyst reducibility and oxygen mobility. An important relation between the FDCA selectivity and the support textural properties is observed, conducing to the general requirement for optimal pore size for this reaction.

| S-EPMC7287476 | biostudies-literature

Improved Bio-Synthesis of 2,5-bis(hydroxymethyl)furan by Burkholderia contaminans NJPI-15 With Co-substrate.

Project description:Upgrading of biomass derived 5-hydroxymethylfurfural (HMF) has attracted considerable interest recently. A new highly HMF-tolerant strain of Burkholderia contaminans NJPI-15 was isolated in this study, and the biocatalytic reduction of HMF into 2,5-bis(hydroxymethyl)furan (BHMF) using whole cells was reported. Co-substrate was applied to improve the BHMF yield and selectivity of this strain as well as HMF-tolerant level. The catalytic capacity of the cells can be substantially improved by Mn2+ ion. The strain exhibited good catalytic performance at a pH range of 6.0-9.0 and a temperature range of 25°C-35°C. In addition, 100 mM HMF could be reduced to BHMF by the B. contaminans NJPI-15 resting cells in presence of 70 mM glutamine and 30 mM sucrose, with a yield of 95%. In the fed-batch strategy, 656 mM BHMF was obtained within 48 h, giving a yield of 93.7%. The reported utilization of HMF to produce BHMF is a promising industrially sound biocatalytic process.

| S-EPMC7901908 | biostudies-literature

Conversion and assimilation of furfural and 5-(hydroxymethyl)furfural by Pseudomonas putida KT2440.

Project description:The sugar dehydration products, furfural and 5-(hydroxymethyl)furfural (HMF), are commonly formed during high-temperature processing of lignocellulose, most often in thermochemical pretreatment, liquefaction, or pyrolysis. Typically, these two aldehydes are considered major inhibitors in microbial conversion processes. Many microbes can convert these compounds to their less toxic, dead-end alcohol counterparts, furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol. Recently, the genes responsible for aerobic catabolism of furfural and HMF were discovered in Cupriavidus basilensis HMF14 to enable complete conversion of these compounds to the TCA cycle intermediate, 2-oxo-glutarate. In this work, we engineer the robust soil microbe, Pseudomonas putida KT2440, to utilize furfural and HMF as sole carbon and energy sources via complete genomic integration of the 12 kB hmf gene cluster previously reported from Burkholderia phytofirmans. The common intermediate, 2-furoic acid, is shown to be a bottleneck for both furfural and HMF metabolism. When cultured on biomass hydrolysate containing representative amounts of furfural and HMF from dilute-acid pretreatment, the engineered strain outperforms the wild type microbe in terms of reduced lag time and enhanced growth rates due to catabolism of furfural and HMF. Overall, this study demonstrates that an approach for biological conversion of furfural and HMF, relative to the typical production of dead-end alcohols, enables both enhanced carbon conversion and substantially improves tolerance to hydrolysate inhibitors. This approach should find general utility both in emerging aerobic processes for the production of fuels and chemicals from biomass-derived sugars and in the biological conversion of high-temperature biomass streams from liquefaction or pyrolysis where furfural and HMF are much more abundant than in biomass hydrolysates from pretreatment.

| S-EPMC5779731 | biostudies-literature