Furandicarboxylic Acid Research Articles

Bifunctional MoNi4/nickel foam electro-catalyst for ultra-efficient oxidation of high-concentration 5-hydroxymethylfurfural and HER.

The electro-catalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) provides an attractive route to produce 2, 5-furandicarboxylic acid (FDCA) as a substitute for terephthalic acid used in the plastics industry. Herein, we prepared MoNi4 alloy on nickel foam (NF) using a simple hydrothermal method followed by hydrogen reduction. Applied MoNi4/NF as the bifunctional electrodes for the electro-catalytic HMF oxidation reaction (HMFOR) and HER, 98.7% FDCA yield and 97.3% Faraday efficiency (FE) can be achieved even with HMF concentration as high as 200 mM. Notably, no obvious deactivation was observed after ten consecutive cycles. In-situ Raman, XANES and EXAFS results show that the nickel species of MoNi4/NF is first oxidized to Ni3+ species under the applied voltage, and after undergoing the electro-catalytic HMFOR, then reduced to Ni2-δ state (with a valence between 0 and +2) due to the electron-donating effect from Mo. MoNi4/NF with more than one electron transfer between Ni3+ and Ni2-δ during the HMFOR enables it to have excellent electro-catalytic oxidation ability toward HMFOR.

Intensification of fructose dehydration into 5‐HMF and subsequent oxidation to 2,5‐FDCA using ultrasound

AbstractUltrasound‐assisted dehydration of fructose into 5‐hydroxymethylfurfural (5‐HMF) and subsequent oxidation to furandicarboxylic acid (2, 5‐FDCA) is studied in the current work with the main objective being to elucidate the effectiveness of ultrasound for intensified synthesis. The effect of reaction parameters like ultrasound power, duty cycle, reaction time, reaction temperature, solid to solvent ratio, and fructose concentration on the dehydration of fructose into 5‐HMF has been studied. Optimized conditions established were ultrasonic power of 140 W, duty cycle of 60%, reaction time of 60 min, temperature of 100°C, and fructose:dimethylsulfoxide (DMSO) ratio of 3:100 (g/mL), which resulted in the highest 5‐HMF yield of 96% and fructose conversion of 100%. The conventional method carried out at optimized conditions resulted in only 13.5% as 5‐HMF yield. The obtained 5‐HMF was further oxidized to FDCA using Pd/C as the catalyst, H2O/DMSO as solvent, and K2CO3 as a base also using ultrasonic irradiation at 140 W power and 22 kHz frequency in the presence and absence of O2 as oxidant. 100% conversion of 5‐ HMF was obtained in 30 min and 4 h using ultrasound in the presence of O2 and in absence of O2, respectively. 75% conversion of 5‐HMF was observed using the conventional method in 5 h in the presence of O2. Overall, the intensification benefits of using ultrasound at both steps of synthesis has been successfully elucidated.

Enhanced electrocatalytic biomass oxidation at low voltage by Ni2+-O-Pd interfaces

Challenges in direct catalytic oxidation of biomass-derived aldehyde and alcohol into acid with high activity and selectivity hinder the widespread biomass application. Herein, we demonstrate that a Pd/Ni(OH)2 catalyst with abundant Ni2+-O-Pd interfaces allows electrooxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid with a selectivity near 100 % and 2, 5-furandicarboxylic acid yield of 97.3% at 0.6 volts (versus a reversible hydrogen electrode) in 1 M KOH electrolyte under ambient conditions. The rate-determining step of the intermediate oxidation of 5-hydroxymethyl-2-furancarboxylic acid is promoted by the increased OH species and low C–H activation energy barrier at Ni2+-O-Pd interfaces. Further, the Ni2+-O-Pd interfaces prevent the agglomeration of Pd nanoparticles during the reaction, greatly improving the stability of the catalyst. In this work, Pd/Ni(OH)2 catalyst can achieve 100% 5-hydroxymethylfurfural conversion and >90% 2, 5-furandicarboxylic acid selectivity in a flow-cell and work stably over 200 h under a fixed cell voltage of 0.85 V.

Roles of Metal‐Organic Framework Supports in Base‐Free Oxidation of 5‐Hydroxymethylfurfural to Furan‐2,5‐Dicarboxylic Acid over Pt‐Based Catalysts

AbstractThe catalytic oxidation of 5‐hydroxymethylfurfural (HMF) is an important process for producing a renewable furan‐2,5‐dicarboxylic acid (FDCA). Although several Pt‐based catalysts have been reported to efficiently catalyze the oxidation of HMF, the functional roles of catalyst supports, as corroborated by spectroscopic techniques, have not been fully described. Here, we report on Pt nanoparticles supported on metal‐organic frameworks (MOFs) that catalyze the oxidation of HMF to FDCA in the absence of base. Several catalysts are prepared by immobilizing pre‐synthesized Pt nanoparticles on supports, allowing for the investigation of the role of the supports without the influence of the size of Pt nanoparticles (Pt NPs). By analyzing the catalytic performances along with the electronic properties using X‐ray photoelectron spectroscopy and surface properties of the catalysts using in situ infrared spectroscopy of adsorbed CO2, we find that the presence of Pt NPs in the metallic phase and basic hydroxyl groups on the support promote the HMF oxidation.

Microfluidic Continuous Synthesis of Size- and Facet-Controlled Porous Bi2O3 Nanospheres for Efficient CO2 to Formate Catalysis.

Bismuth-based catalysts are effective in converting carbon dioxide into formate via electrocatalysis. Precise control of the morphology, size, and facets of bismuth-based catalysts is crucial for achieving high selectivity and activity. In this work, an efficient, large-scale continuous production strategy is developed for achieving a porous nanospheres Bi2O3-FDCA material. First-principles simulations conducted in advance indicate that the Bi2O3 (111)/(200) facets help reduce the overpotential for formate production in electrocatalytic carbon dioxide reduction reaction (ECO2RR). Subsequently, using microfluidic technology and molecular control to precisely adjust the amount of 2, 5-furandicarboxylic acid, nanomaterials rich in (111)/(200) facets are successfully synthesized. Additionally, the morphology of the porous nanospheres significantly increases the adsorption capacity and active sites for carbon dioxide. These synergistic effects allow the porous Bi2O3-FDCA nanospheres to stably operate for 90h in a flow cell at a current density of ≈250mA cm- 2, with an average Faradaic efficiency for formate exceeding 90%. The approach of theoretically guided microfluidic technology for the large-scale synthesis of finely structured, efficient bismuth-based materials for ECO2RR may provide valuable references for the chemical engineering of intelligent nanocatalysts.

Accelerating alcohol oxidation kinetics for electrochemical biomass upgrading via photoinduced active CuIII-O generation

Copper-based compounds exhibit broad prospects in the electrocatalytic oxidation of biomass for sustainable production of high-value-added chemicals due to their passivated oxygen evolution reaction (OER) competitiveness. However, the sluggish reaction kinetics remain the main challenge in constraining their scalable application. Herein, a highly selective electrooxidation of 5-hydroxymethylfurfural (HMF) to 2, 5-furandicarboxylic acid (FDCA) on CuO is achieved via photoinduced surface reconstruction. The experimental results confirmed that the photogenerated hole accumulation on the surface of CuO with matched valence band position can promote the CuOOH active phase generation. Density functional theory (DFT) calculations and the overall relationship between structure and selectivity indicate the CuOOH species can accelerate the spontaneous dehydrogenation process of hydroxyl group. Therefore, the activated CuO electrode under illumination can effectively regulate the conversion of 5-Hydroxymethyl-2-furancarboxylic acid (HMFCA) key intermediates and exhibits accelerated reaction kinetics, FDCA yield increased by 17.79 % compared to dark condition. Additionally, a general enhancement effect on the oxidation of benzyl alcohol and furfuryl alcohol was also revealed. This work introduces photoassistance effect for the first time in HMF oxidation, opening up prospects for the application of photoelectric synergy in biomass value-added conversion and providing insights into the activity mechanism of Cu-based catalysts in organic oxidation.

Modified Halloysite as Catalyst for the Conversion of Hydroxymethylfurfural to Furandicarboxylic Acid: A DFT Investigation

AbstractThe reaction steps involved in the 5‐hydroxymethylfurfural to 2,5‐furandicarboxylic acid conversion by means of H2O2 were investigated employing a dedicated computational protocol based on density functional theory. The catalytic environment of choice was a molecular model representing a portion of the halloysite nanotube outer surface, functionalized by an organosilane, the 3‐aminopropyltriethoxysilane, whose amino group bonds one gold atom. At this stage of the investigation, the process was fully detailed in terms of the interactions between the reaction intermediates and the catalyst, and the reaction standard free energies. In addition, the energy barriers of the elementary steps involving the hydrogen migration from the adsorbed organic species to the gold atom were analyzed. On the basis of the interaction geometries, a certain distinction among the preferred reaction path can be inferred as a function of the net negative charge characterizing the catalyst outer surface. Since the inner surface of halloysite can represent the acid environment needed to obtain 5‐hydroxymethylfurfural through dehydration of fructose, the present study is framed in a wider research field where the possibility to consider functionalized halloysite as one‐pot reactor for the valorization of biomass is explored.

Synthesis of N‐Substituted Pyrrole‐2,5‐dicarboxylic Acids from Pyrroles

AbstractPyrrole‐2,5‐dicarboxylic acid (PDCA) is a heterocyclic aromatic dicarboxylic acid that may emerge as a new monomer for polyester production. Compared to its structurally related and bio‐based furan‐2,5‐dicarboxylic acid (FDCA) that is already used for the production of polyethylene furanoate (PEF), PDCA shows excellent potential as its nitrogen can be targeted for further derivatization, thus enabling tuning of the properties of a PDCA containing polymer. In light of this, we recognized the need to explore efficient synthetic approaches for producing PDCAs in high yields. Here, we report a five‐step synthesis route for N‐substituted PDCAs starting from pyrrole, with total yields up to 42 %. The synthetic approach allowed the introduction of several different functional moieties to the pyrrole nitrogen, such as aliphatic saturated and unsaturated side‐chains, as well as benzylic groups.

One-pot two-step biocatalytic upgrading of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid (FDCA) through a sequential oxidation process

2, 5-furandicarboxylic acid (FDCA) is a versatile bio-based building block that can be used for the synthesis of degradable polymers. Recently, developing green and sustainable catalytic processes for producing FDCA from renewable platform chemical molecules has attracted continuing attention. In this study, we proposed a green and sustainable one-pot, two-step biocatalytic process for the sequential oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to form FDCA with good yield and excellent selectivity. The initial step involves the oxidation of HMF to 2, 5-diformylfuran (DFF) and 5-formyl-2-furancarboxylic acid (FFCA) catalyzed by recombinant E. coli cells expressing a 5-hydroxymethylfurfural oxidase. The second step is to convert DFF and FFCA into FDCA final product via aldehyde oxidation reaction catalyzed by Deinococcus wulumuqiensis R12 whole cells. Combining the two different whole-cell biocatalysts, 180 mM of HMF could be easily converted into FDCA with a yield of 99% under optimized reaction conditions. This study offers an efficient and sustainable approach for the valorization of biomass-based HMF to form value-added FDCA.

Upcycling of Agricultural Waste Stream to High-Molecular-Weight Bio-based Poly(ethylene 2,5-furanoate).

Invited for this issue's cover is the group of Dr. Adina Anghelescu-Hakala at the VTT Technical Research Centre of Finland. The image shows that high-molecular-weight poly(ethylene 2,5-furanoate) (PEF) polymer can be produced from furan dicarboxylic acid (FDCA) or its esters as bio-based alternative to replace fossil-based poly(ethylene terephthalate) (PET). The Research Article itself is available at 10.1002/cssc.202301551.

Biobased high barrier copolyesters derived from furandicarboxylic acid and citric acid

Biobased feedstocks developed from renewable resources play a crucial role in polymers. Dimethyl octahydro-2,5-pentalenediol (MeOPD) with excellent thermal stability and rigidity is a biobased bicyclic diol derived from citric acid. In this work, MeOPD was first reacted with dimethyl carbonate (DMC) to form oligo (dimethyl octahydro-2,5-pentalenediol carbonate) (OMC). Subsequently, a series of poly(butylene-co-dimethyl octahydro-2,5-pentalenediol furanoate-co-carbonate) (PBMFC) polyesters with MeOPD units ranging from 5 to 31 mol% were synthesized via melt polycondensation from OMC, dimethyl furan-2,5-dicarboxylate (DMFD) and 1,4-butanediol (BDO). Due to the low reactivity of MeOPD, its actual content in copolymer is much lower than that in the feed, and as the MeOPD content rises, the number-average molecular weight of PBMFCs drops from 25,200 g/mol of PBMFC5 to 12,800 g/mol of PBMFC31. Despite the presence of MC units weakens thermal stability, PBMFCs still maintain good thermal stability, evidenced by Td,5% ranging from 294-325 °C in N2 and from 295-339 °C in air. The mechanical properties are also satisfactory, exhibiting tensile modulus ≥ 500 MPa, tensile strength ≥ 23 MPa, and elongation at break ≥ 150 %. Compared to PET, PBMFCs demonstrate commendable gas barrier properties, with CO2 and O2 barrier capability being 4.7–11.0 times and 2.0–3.6 times that of PET, respectively. All results indicate that PBMFCs can serve as a renewable potential material for packaging application.

A novel strategy for the synthesis of samarium/europium-metal organic frameworks, and their utilization for detection of Cr3+, Pb2+, and acetone as a luminescent sensor with superior selectivity and sensitivity properties

With outstanding detection selectivity and sensitivity characteristics, samarium/europium-metal organic frameworks (Sm/Eu-MOF) is capable of functioning as a versatile light-emitting sensor particularly for detecting acetone, Cr3+, and Pb2+ in aqueous environment. While considering maximum detectable concentrations of 0.85 μM, 0.46 μM, and 1.04 μM, respectively, competitive energy interactions for acetone, absorption of energy for Cr3+, and substitution of ions for Pb2+ are the elucidated mechanisms of detecting these substances by Sm/Eu-MOF. Successful formulation and synthesis of a core–shell structured Sm/Eu-MOF, which has endurance to acid/alkali conditions and hydration/heat-stability, can be accomplished by utilizing Samarium and Europium nitrate ions, terephthalic acid, and 2, 5-furandicarboxylic acid. The recovery rate of acetone, Cr3+, and Pb2+ detection from real samples were 95.0–101.0 %, 99.8–101.0 %, and 99.9–104.0 %, respectively.

Polyesters Using Bioderived Furandicarboxylic Acid: Recent Advancement and Challenges toward Green PET

Polyesters Using Bioderived Furandicarboxylic Acid: Recent Advancement and Challenges toward Green PET

Enhanced electrochemical oxidation of 5-hydroxymethylfurfural over tailored nickel nanoparticle assembly

Nickel-based materials are promising electrocatalysts for anodic oxidation of 5-hydroxymethylfurfural (HMF) to value-added 2, 5-furandicarboxylic acid (FDCA). However, their catalytic efficiency is impeded by the sluggish phase transformation of Ni(II) hydroxide to the active Ni(III) oxyhydroxide. Herein, we demonstrate for the first time that the phase transformation kinetics and the HMF oxidation activity of nickel nanoparticles can be modulated by creating self-assemblies with different particle aggregation structures: ordered nanoarrays, disordered nanoarrays, and random aggregates. Notably, the nanoparticle assembly featuring an ordered nanoarray structure exhibits the highest activity, achieving 99.8 % HMF conversion and 99.2 % FDCA yield at 1.36 V. In situ Raman spectroscopy and electrochemical analysis reveal that the ordered nanoarray effectively accelerates the transformation kinetics, attributed to the reduced dehydrogenation barrier of Ni(II) hydroxide as confirmed by density functional theory calculations. This work contributes new insights into the structure-performance relationship of Ni-based catalysts, offering valuable guidance for designing high-performing electrocatalysts.

Base-free synthesis of renewable furan-2,5-dicarboxylic acid (FDCA) over an earth-abundant magnetic catalyst

Being a biobased alternative to petroleum-based terephthalic acid (TPA), furan-2,5-dicarboxylic acid (FDCA) requires a low-cost and efficient catalytic system for its commercialization. This study describes FDCA production using whey permeate powder (WPP)-derived 5-(hydroxymethyl)furfural (HMF) in a base-free system over a magnetically recyclable catalyst composed of earth-abundant metals (Mn and Fe). The impact of MnCl2·4 H2O loading on the iron core was studied at different levels and found optimal at the ratio of 1:1. The in-situ oxidation of HMF was carried out using ozone and t-BuOOH as the oxidants in a γ-valerolactone (GVL) -water solvent system. It was observed that the ozone pre-treatment (3 h at room temperature) of HMF increased the FDCA yield from 39.7 % (without ozonation) to 60 % at a reaction condition of 130 °C for 2 h. The concentration profiles for the intermediates formed during HMF to FDCA oxidation i.e., 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), furan-2,5-dicarbaldehyde (DFF), and 5-formyl-2-furancarboxylic acid (FFCA) were analyzed at different reaction temperatures to evaluate the reaction kinetics. The kinetic study revealed that the present solvent-catalytic system favored HMFCA formation over DFF due to the requirement of higher activation energy for the latter. The HMF to FDCA catalytic solvent was tested for WPP, which afforded an overall FDCA yield of 14.6 % at 130 °C in 120 min. In addition, the Mn1Fe1 consisted of mixed phases of Mn3O4, Mn2O3, MnO2, Fe2O3, and Fe3O4 and demonstrated variation in oxidation states for Mn (Mn3+↔Mn2+) and Fe (Fe2+↔Fe3+) species.

Enzymatic Synthesis of Copolyesters with the Heteroaromatic Diol 3,4-Bis(hydroxymethyl)furan and Isomeric Dimethyl Furandicarboxylate Substitutions.

Polyesters from furandicarboxylic acid derivatives, i.e., dimethyl 2,5-furandicarboxylate (2,5-DMFDCA) and 2,4-DMFDCA, show interesting properties among bio-based polymers. Another potential heteroaromatic monomer, 3,4-bis(hydroxymethyl)furan (3,4-BHMF), is often overlooked but holds promise for biopolymer synthesis. Cleaning and greening synthetic procedures, i.e., enzymatic polymerization, offer sustainable pathways. This study explores the Candida antarctica lipase B (CALB)-catalyzed copolymerization of 3,4-BHMF with furan dicarboxylate isomers and aliphatic diols. The furanic copolyesters (co-FPEs) with higher polymerization degrees are obtained using 2,4-isomer, indicating CALB's preference. Material analysis revealed semicrystalline properties in all synthesized 2,5-FDCA-based co-FPEs, with multiple melting temperatures (Tm) from 53 to 124 °C and a glass-transition temperature (Tg) of 9-10 °C. 2,4-FDCA-based co-FPEs showed multiple Tm from 43 to 61 °C and Tg of -14 to 12 °C; one of them was amorphous. In addition, all co-FPEs showed a two-step decomposition profile, indicating aliphatic and semiaromatic segments in the polymer chains.

V-doped MoO3 nanorods for highly selective oxidation of 5-hydroxymethylfurfural to bio-monomer 2, 5-furandicarboxylic acid

2,5-Furanodicarboxylic acid (FDCA) is a significant chemical derived from biomass and holds the potential to replace traditional petrochemicals in the production of biodegradable polyester materials. In this study, a series of new-type V-doped MoO3 catalysts with different crystalline phases were prepared through the hydrothermal method. The V-doped α-MoO3 with growth along the [010] crystal plane demonstrated the most efficient catalytic activity in the selective oxidation of 5-hydroxymethylfurfural (HMF) to produce FDCA, potentially attributable to the [010] crystal plane's superior affinity for substrate interactions. The catalysts were analyzed using TEM, XPS, XRD, FT-IR, N2 adsorption isotherms and other characterization techniques. The Box-Behnken response surface method was utilized to investigate and successfully determine the optimal reaction conditions. A remarkable HMF conversion of 99.5% and a 97.4% selectivity toward FDCA were achieved at 80 °C after 10 h using tert-butanol as the solvent and tert-butyl hydroperoxide as the oxidant. Furthermore, the catalyst could be readily recovered conveniently and reused without any significant loss in catalytic activity.

Poly(ether‐ester)s synthesized from furandicarboxylic acid and ethylene glycol using an acidic binary catalyst

AbstractPoly(ethylene 2,5‐furandicarboxylate) (PEF) is an important biobased polyester with better thermal, mechanical, and gas barrier properties than poly(ethylene terephthalate). In PEF synthesis, diethylene glycol furandicarboxylate (DF) is inevitably formed via etherification side reaction. Taking advantage of the side reaction, poly(ethylene‐co‐diethylene furandicarboxylate) (PEDF) poly(ether‐ester)s were synthesized only from 2,5‐furandicarboxylic acid (FDCA) and ethylene glycol (EG), using a cheap binary propanedisulfonic acid/dibutyltin oxide (PSA/DBTO) catalyst. The polymers were characterized by 1H NMR, intrinsic viscosity, solubility, differential scanning calorimetry, thermogravimetric analysis, tensile, and gas barrier test. Due to strong acidity of PSA, not only major DF but also minor oligoethylene glycol furandicarboxylate ether‐containing units were formed. Their total content can be adjusted up to 78 mol% by simply increasing the dosage of PSA from 0 to 0.4 wt%. The effect of ether‐containing units on the solubility, thermal transition, mechanical, and oxygen barrier properties of the poly(ether‐ester)s were examined and compared with the poly(ether‐ester)s synthesized via copolycondensation.

Unraveling The Impact of Isomerism on Enzymatic Polymerization of Furanic Polyesters

AbstractAs awareness of the environmental impact of fossil‐based polymers grows, the demand for biobased alternatives rises. In this context, combining eco‐friendly synthesis techniques with renewable resources is important to produce polymers efficiently and sustainably. Furandicarboxylic acid (FDCA) is one of the key building blocks for producing biobased polymers. However, most studies predominantly focus on 2,5‐FDCA, while FDCA encompasses other noteworthy isomers, namely, 2,4‐ and 3,4‐FDCA. The polymers derived from these two isomers have recently gained attention due to their promising properties. In this study, an environmentally friendly approach for producing biobased polyesters from 2,5‐, 2,4‐, and 3,4‐FDCA dimethyl ester isomers is proposed. The synthesis is conducted under greener conditions, utilizing Candida antarctica lipase B (CALB) enzyme as a biocatalyst. The performance of the enzyme is assessed, revealing CALB preference for polymerizing 2,5‐FDCA over 2,4‐ and 3,4‐FDCA dimethyl ester, which is elucidated by docking analysis. Moreover, CALB shows varying rates of cyclic oligomer formation for each isomer, favoring 2,5‐FDCA cyclization. The structure‐property relationship, encompassing the variation in isomeric structure, is evaluated through structural characterization, thermal analysis, and surface properties. This study primarily emphasized enzymatic polymerization and highlighted its versatility in accommodating different monomer isomeric substitutions.

Synthesis of Biobased Poly(butylene Furandicarboxylate) Containing Polysulfone with Excellent Thermal Resistance Properties.

A synthetic biopolymer derived from furandicarboxylic acid monomer and hydroxyethyl-terminated poly(ether sulfone) is presented. The synthesis involves 4,4'-dichlorodiphenyl sulfone and 4,4-dihydroxydiphenyl sulfone, resulting in poly(butylene furandicarboxylate)-poly(ether sulfone) copolyesters (PBFES) through melt polycondensation with titanium-catalyzed polymerization. This facile method yields segmented polyesters incorporating polysulfone, creating a versatile group of high-temperature thermoplastics with adjustable thermomechanical properties. The PBFES copolyesters demonstrate an impressive tensile modulus of 2830 MPa and a tensile strength of 84 MPa for PBFES55. Additionally, the poly(ether sulfone) unit imparts a relatively high glass transition temperature (Tg), ranging from 36.6 °C for poly(butylene 2,5-furandicarboxylate) to 112.3 °C for PBFES62. Moreover, the complete amorphous film of PBFES exhibits excellent transparency and solvent resistance, making it suitable for applications, such as food packaging materials.