Furandicarboxylic Acid Research Articles

Oxygen vacancy boosted oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid over CuCoOx

A bimetallic catalyst CuCoOx was developed for the efficient production of 2, 5-Furandicarboxylic acid (FDCA) by the catalytic oxidation 5-hydroxymethylfurfural (HMF) using NaClO as oxidant. CuCoOx exhibited remarkable catalytic activity and exceptional stability. Under optimized conditions, complete conversion of HMF, as well as the 96 % FDCA yield was obtained at ambient temperature within 15 min. The oxidation of HMF toward FDCA proceeds though 5-hydroxymethyl-2- furoic acid (HMFCA) and 5-Formyl-2-furoic acid (FFCA) as key intermediates in sequence. The synergistic interaction between Cu and Co species boosted oxygen vacancy, enhanced oxygen species mobility, and created an appropriate amount of strong acid/basic sites, improving catalytic activity of CuCoOx. The oxidation of -C-OH in HMF was a rate-determining step. The involvement of lattice oxygen was proved to be crucial in facilitating the whole oxidation process from HMF toward FDCA. Combining reaction kinetics and oxidation mechanism studies, the oxygen vacancy density on the surface CuCoOx was identified as the oxidation rate controlling factor during the whole HMF oxidation process toward FDCA.

Synergistic Interaction between Ruthenium Catalysts and Grafted Niobium on SBA-15 for 2,5-Furandicarboxylic Acid Production Using 5-Hydroxymethylfurfural.

This study entailed the synthesis of Ru nanocatalyst decorated on Nb-grafted SBA-15. A Nb-grafted SBA-15 support with varying Nb contents was utilized as a support for the Ru nanoparticles. The effect of Nb grafting on the immobilized Ru nanoparticle catalyst was systematically investigated, and its catalytic performance in the synthesis of furandicarboxylic acid using 5-hydroxymethylfurfural under base-free reaction conditions was evaluated. The results indicate the increased productivity of the Ru@Nb-grafted SBA-15 catalyst with a yield exceeding 95%, representing a significant advancement in catalysis. This study also affords insights into the complex relationship between the catalytic activity and selectivity and its unique surface attributes. Moreover, acidic sites were created, and the electron density within the active sites was modulated by monomeric Nb oxide species on the SBA-15. Additionally, the role of high-electron-density Ru atoms in facilitating the efficient adsorption and activation of the reactant, resulting in enhanced catalytic efficacy, was highlighted.

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

Orange peel and sugar beet pulp contain large quantities of pectin, which can be turned via galactaric acid into furan dicarboxylic acid (FDCA) and its esters. In this work, we show the polymerisation of these FDCA esters into high-molecular-weight, 70-100 kg/mol, poly(ethylene 2,5-furanoate) (PEF). PEF is an emerging bio-based alternative for poly(ethylene terephthalate) (PET), widely used in for example packaging applications. Closing the loop, we also demonstrated and confirmed that PEF can be hydrolysed by enzymes, which are known to hydrolyse PET, back into FDCA for convenient recycling and recovery of monomers.

Synthesis of vinyl esters of some furan carboxylic acids based on vinyl acetate

Investigation of synthesized vinyl esters of several furancarboxylic acids: 2-furancarboxylic, 3-furancarboxylic, 5-formyl-2- furancarboxylic, 5-nitro-2-furanoic and 2,5-furandicarboxylic from vinyl acetate using the reaction vinyl substitution in the presence of the system: 2- chloro-4,6-dimethoxy-1,3,5-triazine, as well as Zn(OTf)2, 3,3’-Ph2BINOL- 2Li, KOtrBu and BuLi has been carried out. At the same time increasing of the catalytic activity of these systems was identified as following: 3,3’- Ph2BINOL-2Li < BuLi < KOtrBu < Zn(OTf)2. The influence of various factors on products yield was studied. Optimal conditions for the formation of vinyl esters of carboxylic acids were: temperature -30°C, the Zn(OTf)2 system, the molar ratio of carboxylic acid and vinyl acetate is 1:1.2. The yields of vinyl esters of the studied furancarboxylic acids has increased in the following order: vinyl ester of 5-nitro-2-furancarboxylic acid < vinyl ester of 5-formyl-2-furancarboxylic acid < vinyl ester of 2-furancarboxylic acid < vinyl ester of 3-furancarboxylic acid < vinyl ester 2 ,5- furandicarboxylic acid. The structure of the synthesized compounds was confirmed by IR, 1H, 13C spectroscopy and gas chromatography-mass spectrometry.

Transforming liquid flow fuel cells to controllable reactors for highly-efficient oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid at low temperature

Highly-efficient oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) at low temperature with air as the oxidant is still challenging. Herein, inspired by the respiratory electron transport chain (ETC) of living cells mediated by electron carriers, we constructed artificial ETCs and transformed liquid flow fuel cells (LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions. This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and (VO2)2SO4 as a cathode electron carrier to facilitate the electron transfer to air. The reaction rate could be easily controlled by selecting the anode catalyst, adjusting the external loading and changing the cathodic electron carrier or oxidants. A maximal power density of 44.9 mW cm−2 at room temperature was achieved, while for FDCA production, short-circuit condition was preferred to achieve quick transfer of electrons. For a single batch operation with 0.1 M initial HMF, FDCA yield reached 97.1%. By fed-batch operation, FDCA concentration reached 144.5 g L–1 with a total yield of 96%. Ni2+/Ni3+ redox couple was the active species mediating the electron transfer, while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.

A novel route to synthesize 2,5-furandicarboxylic: Direct carboxylation of 2-furoic acid with formate

Furan-2,5-dicarboxylic acid (FDCA) is an important biomass-derived diacid, and it is the most promising substitute for terephthalic acid. The common method of FDCA usually involves 5-hydroxymethylfurfural oxidation. Edible fructose is often used as the feedstock of 5-hydroxymethylfurfural, and the oxidation step would generate undesirable impurities. Herein, FDCA was novelty synthesized by carboxylation of formate and 2-furoic acid (FA) derived from unedible-biomass. This route is potentially advantageous because it is simple to operate and does not require any additional additives. The reaction mechanism has been elucidated by density functional theory (DFT) calculations. In the carboxylation process, the C(sp2)-H bond of formate (HCOOM) undergoes cleavage, generating the carbon dioxide radical anion (CO2•−). Subsequently, CO2•− attacks the C5 of FA, forming the CC bond and ultimately yielding FDCA. The conversion of HCOOM to CO2•− is an effective way to achieve carboxylation reaction. The rate-determining step of the carboxylation reaction is the cleavage of the C(sp2)-H bond of HCOO− with activation barrier of 159.11 kJ⋅mol−1. The investigation would provide a new strategy for the mechanism of carboxylation reactions, and hold the potential to establish pathways for FDCA production.

Bio-based high gas barrier polyesters based on furandicarboxylic acid: Trade-off between ethylene and propylene diols

A series of bio-based poly(ethylene-co-propylene furandicarboxylate) (PEPF) copolyesters with different compositions were synthesized from dimethyl-2,5-furandicarboxylate, ethylene glycol and 1,3-propanediol by transesterification and melting polycondensation. Their chemical structure, composition and sequence distribution were confirmed by 1H NMR and 13C NMR. The results of GPC showed that the obtained copolyesters had a high number average molecular weight between 25000 g/mol and 30900 g/mol. The thermal properties characterized by DSC showed that the Tg increased with the mole fraction of EF from 64.4℃ for PEPF-23 to 83.2℃ for PEPF-84 as well as the samples displayed a high Young's modulus between 2800 and 3360 MPa and tensile strength between 56 and 89 MPa. Furthermore, the PEPF copolyesters exhibited excellent CO2, O2 and H2O barrier properties compared with poly(ethylene terephthalate) with the BIFp of 8.7–10 times, 3.7–4.4 times and 1.5–1.6 times, respectively. The transparency of PEPFs was up to 89% by cutoff at 700 nm and had better solvent resistance. This work builds a bridge between poly(ethylene 2,5-furandicarboxylate) and poly(propylene 2,5-furandicarboxylate) and PEPFs owned excellent thermo-mechanical and gas barrier properties could be used in food packaging fields.

Amorphous Ni-Mo-B-O Bifunctional Electrocatalyst for Simultaneous Production of Hydrogen and Value-added Chemicals.

Hydrogen evolution reaction (HER) coupled with biomass conversion is a sustainable route to produce clean energy H2 and value-added chemicals simultaneously. Herein, an amorphous Ni-Mo-B-O bifunctional electrocatalyst was synthesized through a facile electrodeposition method and employed as a cathode for HER to produce H2 and as an anode for the conversion of hydroxymethylfurfural (HMF) to furandicarboxylic acid (FDCA). Besides leading to the formation of amorphous structures, the introduction of Mo and B can increase the electron density and optimize the electronic structure of the electrocatalyst, thus substantially increasing the catalytic activity of the catalyst. After continuous reaction at a constant potential of 0.58 V vs. Hg/HgO for 8 hours, the conversion of HMF reached 98.86 %, and the selectivity of the target product FDCA was as high as 92.97 %. Finally, a two-electrolyzer system was constructed using the amorphous Ni-Mo-B-O as both cathode and anode to achieve simultaneous H2 production in the cathode chamber and FDCA production in the anode chamber at a low voltage. This work presents a promising strategy for the design and synthesis of high-performance non-noble metal electrocatalysts for efficient and cost-effective H2 production.

Correction to “Kinetic Modeling of Homogenous Catalytic Oxidation of 5-Hydroxymethylfurfural to 2, 5-Furandicarboxylic Acid”

Correction to “Kinetic Modeling of Homogenous Catalytic Oxidation of 5-Hydroxymethylfurfural to 2, 5-Furandicarboxylic Acid”

Syntheses and High Proton Conductivities of Two 3D Zr(IV)/Hf(IV)-MOFs from Furandicarboxylic Acid.

With the gradual progress of research on proton-conducting metal-organic framework (MOFs), it has become a challenging task to find MOF materials that are easy to prepare and have low toxicity, high stability, and splendid proton conductivity. With the abovementioned objectives in mind, we selected the non-toxic organic ligand 2,5-furandicarboxylic acid and the low toxic quadrivalent metals zirconium(IV) or hafnium(IV) as starting materials and successfully obtained 2 three-dimensional porous MOFs, [M6O4(OH)4(FDC)4(OH)4(H2O)4] [M = ZrIV (1) and HfIV (2)], with ultrahigh water stability using a rapid and green synthesis approach. Their proton conductive ability is remarkable, thanks to the large number of Lewis acidic sites contained in their porous frameworks and the abundant H-bonding network, hydroxyl groups, as well as coordination and crystalline water molecules. The positive correlation of their proton conductivity with relative humidity (RH) and the temperature was observed. Notably, their optimized proton conductivities are 2.80 × 10-3 S·cm-1 of 1 and 3.38 × 10-3 S·cm-1 of 2 under 100 °C/98% RH, which are at the forefront of Zr(IV)/Hf(IV) MOFs with prominent proton conductivity. Logically, their framework features, nitrogen/water adsorption/desorption data, and activation energy values are integrated to deduce their proton conductivity and conducting mechanism differences.

Biobased furan-functionalized high-performance poly (aryl ether ketone) with low dielectric constant and low dielectric loss

Furandicarboxylic acid is considered one of the most representative biomass matrix platforms and has been widely used to synthesize various novel biomaterials. In this study, a series of copolymerized poly (aryl ether ketone) resins with excellent properties have been prepared by combining the nonlinear structure of furan ketone with the weakly polarized cyclohexane structure. And the relationship between the structure and properties of the resins has been systematically studied. The results showed that the synthesized resins had excellent thermal properties, and the 5% thermal decomposition temperature could reach up to 478 °C. In addition, the resin exhibits good solubility and can be dissolved in the most common solvents. Its water absorption is deficient, at only 0.71%. At 10 GHz, the lowest dielectric constant of the resin is 3.05. Most importantly, using bio-based monomers in this study provides an environmentally friendly strategy for material design and synthesis, providing a green way to develop high-performance low-dielectric materials.

Boosting hydrogen evolution via anodic oxidation of 5-hydroxymethylfurfural in anion exchange membrane electrolyzer over a metallic heterostructure

Coupling electrocatalytic 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) with hydrogen evolution reaction (HER) is capable of potentially enhancing energy efficiency for hydrogen production and converting biomass into high-valued products. Herein, a novel metallic heterostructure based on Ni3S2 and Co9S8 (Co9S8@Ni3S2/NF) was designed for H2 production and selective oxidation of HMF into 2, 5-furandicarboxylic acid (FDCA). Benefiting from the merit of metal heterojunction, Co9S8@Ni3S2/NF not only possesses appropriate H∗ adsorption energy, but also promotes the adsorption and desorption process of organic, thus making reaction dynamics for both HER and HMFOR more exceptional. Furthermore, the anion exchange membrane (AEM) electrolyzer with Co9S8@Ni3S2/NF as anode and cathode electrodes toward HMFOR and HER only required a low potential of 1.61 V for continuous hydrogen and FDCA production at the initial current density of 50 mA/cm2. The generation rate of H2 and FDCA are as high as 45.6 L/h/m2 and 7.25 mg/h/cm2, corresponding to the Faraday efficiency of ∼100% and 93.0%, respectively. The in-situ Raman and theoretical calculations demonstrated that the electron transfer from Ni3S2 to Co9S8 at heterogeneous interface contributes to the formation of Ni/Co–OOH, which is the active species of HMFOR.

Photoelectrochemical Valorization of Biomass Derivatives with Hematite Photoanodes Modified by Cocatalysts

The solar‐driven oxidation of biomass to valuable chemicals is rising as a promising anodic reaction in photoelectrochemical cells, replacing the sluggish oxygen evolution reaction and improving the added value of the energy conversion process. Herein, the photooxidation of 5‐hydroxymethylfurfural into furan dicarboxylic acid (FDCA) is performed in basic aqueous environment (borate buffer, pH 9.2), with the addition of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) as redox mediator. Because of its good stability, cost‐effectiveness, and nontoxicity, titanium‐modified hematite (Ti:Fe2O3) photoanodes are investigated to this aim, and their performance is tuned by engineering the semiconductor surface with a thin layer of Co‐based cocatalysts, i.e., cobalt iron oxide (CoFeO x ) and cobalt phosphate (CoPi). Interestingly, the electrode modified with CoPi shows improved efficiency and selectivity toward the final product FDCA The source of this enhancement is correlated to the effect of the cocatalyst on the charge carrier dynamics, which is investigated by electrochemical impedance spectroscopy and intensity‐modulated photocurrent spectroscopy analysis. In addition, the results of the latter are interpreted through a novel approach called Lasso distribution of relaxation time, revealing that CoPi cocatalyst is effective in the suppression of the recombination processes and in the enhancement of direct hole transfer to TEMPO.

Production of biohydrogen and green platform compound 2, 5-furandicarboxylic acid using rice straw hydrolysate

Lignocellulosic hydrolysate contains several inhibitors that hinder downstream biological processes. The immobilized strain Burkholderia sp. H-2 was used in this study to biodetoxify real rice straw hydrolysate and biotransform 5-hydroxymethylfurfural (5-HMF), an inhibitor, into 2, 5-furandicarboxylic acid (FDCA), a valuable platform compound. An electrodialysis with bipolar membranes (EDBM) system was applied to recover FDCA and perform secondary detoxification of the biodetoxified real rice straw hydrolysate. The rice straw hydrolysate after biodetoxification and EDBM treatment was used for anaerobic dark fermentative hydrogen production. The immobilized Burkholderia sp. H-2 could completely biotransform 1843 mg/L 5-HMF into 1532 mg/L FDCA within 24 h when the 2-fold diluted rice straw hydrolysate was used as the feedstock. The optimal EDBM system parameters to recover FDCA were a hydrolysate pH of 6, operated at a current density of 17.86 mA/cm2. The FDCA recovery efficiency was 44.6 %, when using the biodetoxified real rice straw hydrolysate as the EDBM feedstock. The rice straw hydrolysate after biodetoxification and EDBM treatment had better biohydrogen production performance than the undetoxified and biodetoxified rice straw hydrolysates.

Liquid flow fuel cell with an electrodeposition-modified nickel foam anode for efficient oxidation of 5-hydroxymethylfurfural to produce 2, 5-furandicarboxylic acid with co-generation of electricity

Liquid flow fuel cells were developed as reactors for efficient conversion of 5-hydroxymethylfurfural (HMF) to 2, 5-furandicarboxylic acid (FDCA) at room temperature with co-generation of electricity. Electrodeposition modification of nickel foam (NF) with CoSO4 and NaH2PO2 (Co-P@NF anode) was found to significantly increase HMF oxidation efficiency, due to the reduction of polarization resistance of NF and increased electrochemical active area. However, the active species of Co-P@NF anode for HMF oxidation actually was NiOOH rather than cobalt. By using (VO2)2SO4 as a cathodic electron carrier, peak power density of 38.9 mW/cm2 at room temperature was obtained with 100% HMF conversion and 89.0–93.4% FDCA yield. FDCA concentration reached 81.8 g/L with 90% total yield after feeding HMF for six batches. Therefore, efficient production of FDCA was achieved under mild conditions with oxygen (air) as the final oxidant via the electron transport chains constructed by active nickel species and cathode electron carriers.

CO2‐Enhanced Production and Synthesis of 2,5‐ Furandicarboxylic Acid under CO2 Flow through Henkel Reaction

AbstractThe present study investigated the preparation of 2,5‐furandicarboxylic acid (FDCA) via the Henkel reaction between furoic acid alkali metal salts and zinc chloride under a continuous CO2 flow at atmospheric pressure. The results obtained were compared with those of previous studies that used high‐pressure conditions or toxic cadmium catalysts. The pathways and rate‐determining steps of the reaction are revealed for the first time. Furthermore, the enhanced formation of FDCA through the promotion of carboxyl exchange and rearrangement during the reaction under a CO2 flow was examined. The CO2‐rich environment afforded a high FDCA yield of 86.30 %, which is the highest yield obtained to date using the Henkel reaction. The findings of this study offer economically improved conditions for large‐scale FDCA production.

Nickel-phytic acid hybrid for highly efficient electrocatalytic upgrading of HMF.

Electrocatalytic upgrading of 5-hydroxymethylfurfural (HMF) provides a promising way to obtain both high-value-added biomass-derived chemicals and clean energy. However, development of efficient electrocatalysts for oxidizing HMF with depressed side reactions remains a challenge. Herein, we report a nickel-phytic acid hybrid (Ni-PA) using natural phytic acid as building block for highly efficient electrocatalytic oxidation of HMF to 2, 5-furandicarboxylic acid (FDCA). Due to the coordination of nickel ion and phosphate groups of phytic acid molecule, high selectivity and yield of FDCA were achieved at 1.6V vs. RHE. Besides, Ni-PA has a higher electrochemical surface area and lower charge-transfer resistance than Cu/Fe-PA, which significantly promotes the oxidation of HMF to FDCA. This work demonstrates the potential of metal-phytic acid hybrids as effective electrocatalysts for biomass valorization.

Theoretical study on the degradation mechanism, kinetics and toxicity for aqueous ozonation reaction of furan derivatives

The compounds including furan-2,5-dicarboxylic acid (FDCA), 2-methyl-3-furoic acid (MFA), and 2-furoic acid (FA), containing Furan ring are considered to be possessing high ozone reactivity, although in depth studies of their ozonation processes have not been carried out yet. Hence, mechanism, kinetics and toxicity by quantum chemical, and their structure activity relationship are being investigated in this study. Studies of reaction mechanisms revealed that during the ozonolysis of three furan derivatives containing C=C double bond, furan ring opening occurs. At temperature (298 K) and pressure of 1 atm, the degradations rates of 2.22 × 103 M−1 s−1 (FDCA), 5.81 × 106 M−1 s−1 (MFA) and 1.22 × 105 M−1 s−1 (FA) suggested that the reactivity order is: MFA > FA > FDCA. In the presence of water, oxygen and ozone, the Criegee intermediates (CIs) as the primary products of ozonation would produce lower molecule weight of aldehydes and carboxylic acids by undergoing degradation pathways. The aquatic toxicity reveals that three furan derivatives play green chemicals roles. Significantly, most of the degradation products are least harmful to organisms residing in the hydrosphere. The mutagenicity and developmental toxicity of FDCA is minimum as compared to FA and MFA, which shows the applicability of FDCA in a wider and broader field. Results of this study reveal its importance in the industrial sector and degradation experiments.

Microbispofurans A-C, plant growth-promoting furancarboxylic acids from plant root-derived Microbispora sp.

Microbispofurans A-C (1-3), new alkyl/alkenyl furancarboxylic acids, were isolated from the culture extract of the plant root-derived Microbispora sp. RD004716. The planar structures of 1-3 were determined by extensive analysis of 1D and 2D NMR spectroscopic data. Although 1-3 showed no appreciable antimicrobial activity or cytotoxicity, strong plant growth-promotion activity of the germinated red leaf lettuce seeds was observed at 10 μM. Furancarboxylic acids and their methyl esters were found in actinomycetes and fungi; however, the isolation of furandicarboxylic acid was unprecedented.

Chemical Chelation-Assisted Highly Oriented Perovskite Solar Cells with Reduced Non-radiative Loss

Shallow- and/or deep-level defects on perovskite surfaces and at grain boundaries serving as recombination centers can negatively affect photovoltaic device performance and stability, thus they need to be minimized. In this study, we modified perovskite films with furan-2,5-dicarboxylic acid (FDCA) to modulate perovskite crystallization and passivate multiple intrinsic shallow- and deep-level defects using an antisolvent method. Characterizations and density functional theory simulation were performed to investigate the coordination and hydrogen bonding interactions between FDCA and perovskite that led to oriented grains and reduced defects. The interactions between FDCA and perovskite reduced non-radiative recombination and improved charge transport. The FDCA-based solar cells exhibited a superior power conversion efficiency of over 24% with improved operation and storage stabilities. This passivation strategy reveals the mechanism behind the improvement of device performance.