FDCA Production Research Articles

Surface reconstructed Ni0.95Pt0.05/Si photoelectrodes for bias-free hydrogen evolution coupled with 5-hydroxymethylfurfural oxidation.

Coupling hydrogen evolution reaction (HER) with biomass valorization using a photoelectrochemical (PEC) system presents a promising approach for effectively converting solar energy to chemical energy..A crucial biomass valorization reaction is the production of value-added 2,5-furandicarboxylic acid (FDCA) via 5-Hydroxymethylfurfural (HMF) oxidation reaction (HMFOR). To achieve efficient FDCA production, we demonstrate an efficient photoanode strategy that combines metal silicidation, dopant segregation, and surface reconstruction to create a bimetallic silicide Ni0.95Pt0.05Si/n-Si photoanode. The oxide-free Ni0.95Pt0.05Si/n-Si interface prepared by the metal-silicidation process ensures efficient interfacial charge transport, while dopant segregation enhances the Schottky barrier height and photovoltage, and surface reconstruction dramatically improves the catalytic activity of the photoanode surface. The as-prepared Ni0.95Pt0.05Si/n-Si photoanode exhibited excellent PEC performance for HMFOR with high conversion of HMF (97.2%) and yield of FDCA (80.3%) under illumination. Furthermore, by integrating a surface reconstructed Ni0.95Pt0.05Si/n-Si photoanode with a Ni0.95Pt0.05Si/p-Si photocathode, a dual-photoelectrode system was constructed capable of simultaneous production of FDCA and H2, which achieves high photocurrent density of 5 mA cm-2 at zero bias under illumination. This study offers an auspicious prospect for high cost-effectiveness conversion from solar energy to industrial monomers.

Plasmonic antenna enhancement on Pd cluster towards high selective FDCA production

2,5-Furandicarboxylic acid (FDCA), an excellent precursor for producing value-added green polymers, has recently garnered much attention. Traditional methods for oxidizing 5-Hydroxymethylfurfural (HMF) to FDCA typically require harsh conditions, such as high pressure, high temperature, and non-eco-friendly reactants, making them neither green nor economical. In this study, we present a novel photocatalytic system utilizing a plasmonic antenna effect to enhance Pd clusters supported on ceria (CeO2). This system drives the transformation from HMF to FDCA under ambient conditions, achieving an impressive yield of over 90% within 4 h under green light irradiation. Notably, the palladium content in this system is minimal. This discovery could pave the way for the development of new photocatalytic systems with varied nanostructures or elemental compositions for efficient chemical reactions.

Efficient synthesis of 2,5‐furandicarboxylic acid from corncob biomass using Ru/C and sulfonated carbon catalysts in a one‐pot system

AbstractThis study proposes a novel one‐pot method to produce 2,5‐furandicarboxylic acid (FDCA), which effectively simplifies the preparation process of FDCA by directly utilizing the biomass raw material corncob and its derived carbon‐based catalysts. In this work, we first prepared two different carbon‐based catalysts from corncobs: a ruthenium‐supported catalyst (Ru/C) and a sulfonated carbon catalyst. After detailed characterization and performance testing, these two catalysts were used to catalyze the pretreated corncob mixture to produce FDCA. Under optimized conditions, even using 0.12 g of Ru/C catalyst at a microwave power of 200 W, the yield of FDCA can reach 27 mol%. In comparison, the FDCA yield of the sulfonated carbon catalyst under the same conditions was 19 mol%. This work not only demonstrates the possibility of efficient production of FDCA by utilizing biomass resources and a simplified chemical conversion process, but also highlights the importance of selecting appropriate catalysts and controlling reaction conditions in improving yields. Through this method, we can promote the development of biomass conversion technology in a more efficient and environmentally friendly direction, providing technical support for the commercial production of bio‐based chemicals.

Catalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid using Co-N/C catalysts with stepwise base addition approach

The production of 2,5-furandicarboxylic acid (FDCA) through green reaction routes is of crucial scientific value for the production of sustainable polymers. This study explores the active centers in cobalt-nitrogen-doped carbon (Co-N/C) for FDCA production. It was established that Co-Nx synergistically along with the nitrogen-doped carbon acted as centers for 5-hydroxymethylfurfural (HMF) oxidation. This study demonstrates a sustainable method for FDCA production from HMF without using precious metals, organic solvents, and harsh basic environments. Co-N/C catalyst displayed a high FDCA yield of ∼90% in an aqueous medium under mildly basic conditions in 34 h with 100% HMF conversion. An innovative strategy of stepwise base addition has been proposed to effectively accelerate the generation reaction of FDCA. The detrimental effects of high heating rate and calcination temperature on the active centers were also thoroughly investigated. Through DFT simulations it was established that Co-Nx aided in the activation of oxygen for HMF oxidation.

Direct and TEMPO‐Mediated Electro‐Oxidation of 5‐(Hydroxymethyl)furfural in Organic and Hydro‐Organic Media

AbstractBiomass‐derived 5‐hydroxymethyl furfural (5‐HMF) is a promising starting substrate for producing two high value‐added products 2,5‐diformylfuran (DFF) and 2,5‐furandicarboxylic acid (FDCA). DFF, which is produced by selectively oxidizing the hydroxymethyl group of 5‐HMF to an aldehyde group, has many applications in pharmaceuticals, macrocyclic ligands and fluorescent materials. Oxidizing both aldehyde and hydroxymethyl groups of 5‐HMF leads to FDCA, which is an important monomer in the production of a bioplastic polyethylene furanoate polymer. Electrochemical conversion of 5‐HMF is a potential route for sustainable chemical production of DFF and FDCA. In fact, using 2,2,6,6‐tetramethyl‐ piperidine‐1‐oxyl (TEMPO) as a redox mediator leads to a highly efficient and selective electro‐oxidation of 5‐HMF into FDCA in a basic buffer solution. In this report, the direct and TEMPO‐mediated electro‐oxidation of 5‐HMF was investigated in various organic and hydro‐organic media at room temperature. Direct electro‐oxidation leads to a low selective conversion of 5‐HMF to DFF (10 % of yield) and the formation of unwanted products such as formic acid and protoanemonin (90 % and 37 % of yield respectively) in acetonitrile. Electrocatalytic 5‐HMF conversion in the presence of TEMPO as a redox mediator achieved a near‐quantitative yield of DFF in acetonitrile and γ‐valerolactone. Importantly, we demonstrate the role of water in the conversion of aldehydes to carboxylic acids.

Engineering crystal plane of NiCo2O4 to regulate oxygen vacancies and acid sites for alkali-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products, making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process. To achieve the efficient selective oxidation of HMF to FDCA, a series of NiCo2O4 catalysts with different morphologies, such as flaky, echinoids, pompon and corolla, were prepared and characterized by XRD, SEM, TEM, BET, XPS, and FTIR. Among the four catalysts, flaky NiCo2O4 exhibited the most excellent catalytic activity and stability, with a FDCA yield of 60.1% within 12 h at 80 °C without alkali participation. The excellent performance of flaky NiCo2O4 catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed (400) facets. The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb –CHO and –CH2-OH of HMF, respectively, and this synergistic effect promotes the efficient production of FDCA. This work is of great significance for fundamentally study the effect of micro-topography or crystal–plane reaction properties on surfaces.

Oxygen-vacancy-rich MnOx supported RuOx for efficient base-free oxidation of 5-hydroxymethylfurfural and 5-methoxymethylfurfural to 2,5-furandicarboxylic acid

2,5-Furandicarboxylic acid (FDCA) is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources. However, the green and efficient production of FDCA through the oxidation of 5-hydroxymethylfurfural (HMF) and its derivatives is still rudimentary under base-free conditions. In this work, oxygen-vacancy-rich MnOx was prepared and displayed a strong adsorption and anchoring ability to Ru species that mainly exposed the (210) plane of RuO2, bringing about highly dispersed and active interfacial Ru-O-Mn structures. Experimental results and density functional theory calculations confirm that these above features greatly facilitate the adsorption/activation of oxygen and the dehydrogenation-oxidation of HMF/5-methoxymethylfurfural (MMF), which enables an efficient FDCA production under base-free and mild conditions. Notably, a desirable FDCA yield of 86.56% was still obtained from concentrated HMF (10 wt%) under base-free conditions over oxygen-vacancy-rich MnOx supported RuOx (1.0 MPa O2, 120 °C, 6 h). This work delineates a facile catalyst preparation strategy for HMF/MMF oxidation, and might open a new avenue for the green synthesis of FDCA under base-free conditions.

Efficient targeted acquisition 2,5-furandicarboxylic acid derived from 5-hydroxymethylfurfural over novel copper and vanadium oxide-functionalized catalysts

2,5-Furandicarboxylic acid (FDCA), which is recognized as a valuable alternative to petroleum-derived terephthalic acid and produce more bio-based polymers, has attracted considerable attention in recent years. Herein, a series of nitrogen-containing polymer nanosheets bearing Cu2+ and VO2+ (Cu2+-VO2+/PDVTA) were designed and displayed superior catalytic performance in the selective oxidation of 5-hydroxymethylfurfural (HMF) to FDCA. The catalyst was characterized by FT-IR, SEM, XPS, TG, UV–Vis DRS, PL, and ICP-AES analysis techniques. The effects of various reaction parameters, including the tert-butyl hydroperoxide dosage, temperature, and solvents on the HMF oxidation were systematically investigated, and the results were discussed in details. The Cu2+-VO2+/PDVTA catalyst achieved 100% conversion of HMF with 98.6% selectivity toward FDCA without the requirement for any basic additives under mild conditions (90 °C, 10 h), as well as has a good reusability. Coupling of the active sites of Cu2+ and VO2+ provide a synergistic effect for FDCA production. This study may provide a novel method for the development of efficient non-precious metal catalyst without addition of alkali additives, benefiting the valorization of furan-based compounds into high-valued chemicals in industrial processes.

Unraveling the Electrocatalytic Activity in HMF Oxidation to FDCA by Fine-Tuning the Degree of NiOOH Phase Over Ni Nanoparticles Supported on Graphene Oxide.

The development of an efficient electrocatalyst for HMF oxidation to FDCA has been in the early stages. Herein, the NiNPs/GO-Ni-foam is fabricated as an electrocatalyst for FDCA production. However, the electrocatalytic performance of the untreated NiNPs/GO-Ni-foam is observed with moderate Faradaic efficiency (FE) (73.0%) and FDCA yield (80.2%). By electrochemically treating the NiNPs/GO-Ni-foam in an alkaline solution with positive potential at different treatment durations, the degree of NiOOH on metal surfaces is changed. The distinctive electrocatalytic activity obtained when using the different NiOOH degrees allows to understand the crucial impact of NiOOH species in HMF electrooxidation. Enhancing the portion of the NiOOH phase on the electrocatalyst surface improves electrocatalytic activity in terms of FE and FDCA yield up to 94.8±4.8% and 86.9±4.1%, respectively. Interestingly, as long as the NiOOH portion on the electrocatalyst surface is preserved or regenerated, the electrocatalyst performance can be intact even after several catalytic cycles. The theoretical study via density functional theory (DFT) also agrees with the experimental observations and confirms that the NiOOH phase facilitates the electrochemical transformation of HMF to FDCA through the HMFCA pathway, and the potential limiting step of the overall reaction is the oxidation of FFCA to FDCA.

Electron-rich ruthenium nanoparticles on nitrogen-doped carbon for the efficient catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid

Modulating the electronic structure of metal nanoparticles (NPs) demonstrates to be useful for the optimization of the catalytic performance. Herein, electron-sufficient ruthenium NPs were successfully constructed on a nitrogen-doped carbon support (Rux-NC), which displayed excellent catalytic activity for the oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). Especially, a high FDCA yield of 97% was implemented over Ru2.0/NC catalyst in water. The FDCA productivity in this case is also as high as 4.8 molFDCA‧molRu−1‧h−1, which value exceeds most of the previous reported Ru-based catalysts for the production of FDCA. It has been disclosed that the Ru2.0/NC was endowed with high N content and abundant electron-rich Ru0 NPs evoked by the electronic interactions between the NC support the Ru NPs. These facts greatly contribute to the activation of O2, and accelerate the oxidation both of the hydroxymethyl and aldehyde groups of HMF to the carboxyl one. This work provides new understanding for the development of effective Ru-based catalysts for the catalytic oxidation reactions by the electronic structure regulation strategy.

Bifunctional nickel phosphide nanoparticle/nickel cobalt sulfide nanosheet framework for electrocatalytic simultaneous hydrogen evolution and 2,5-Furandicaroxylic acid production

Replacing the O2 evolution reaction of water splitting with a thermodynamically more favorable reaction has attracted considerable attention for simultaneous value-added feedstock formation coupled with H2 production. Herein, bifunctional nickel phosphide nanoparticle/nickel cobalt sulfide nanosheet framework (NCSP150) is constructed on Ni foam for electrocatalytic hydrogen evolution reaction (HER) and 5-hydroxymethyl furfural (HMF) oxidation reaction (HMFOR) to 2,5-furandicaroxylic acid (FDCA) in 0.1 M KOH where HMF degradation is negligible. NCSP150 respectively demonstrates a Faradaic efficiency of 98.5 % for H2 generation at 10 mA cm−2 in 0.1 M KOH aqueous solution and exhibits a Faradaic efficiency of 95.2 % for FDCA formation at 1.52 V vs. RHE in a 10 mM HMF/0.1 M KOH aqueous solution. Moreover, NCSP150 sustains superior electrocatalytic performances for at least 12 h in the 0.1 M KOH electrolyte. In a two-electrode H cell using NCSP150 as both cathode and anode, the cell voltage required to afford the current density of 10 mA cm−2 is less 153 mV than water electrolysis when adding 5 mM HMF in 0.1 M KOH. This work emphasizes bifunctional NCSP150 as a promising non-precious-metal electrocatalyst for simultaneous hydrogen evolution and FDCA production in 0.1 M KOH, suitable for scaling up industrial production.

Ce‐Modified MgFe−LDH Supported Au Particles: An Efficient Catalyst for Base‐Free Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid

Abstract5‐hydroxymethylfurfural (HMF) was selectively oxidized to 2,5‐furandicarboxylic acid (FDCA) using an effective catalytic system made of Au particles supported on Ce‐modified MgFe layered double hydroxide. The structural features and performance of the as‐prepared catalysts were examined using a range of characterizations, and the impact of altering reaction parameters was explored. It was demonstrated that the presence and quantity of Ce and Mg species in the catalyst formulation were the primary determinants of the activity of the Au@Mg−N−M−LDH catalysts (M=Ce, Cu, Mn, Zr, and N=Fe, Al). The catalyst Au@MgFeCe−LDH, loaded with 1 wt % Au, exhibited outstanding catalytic activity in the production of FDCA, achieving complete HMF conversion and 90 % FDCA selectivity. This was accomplished through a two‐step heating procedure, involving initial heating of the reaction medium at 40 °C for 2 hours followed by a subsequent heating at 100 °C for 6 hours, conducted under an oxygen pressure of 5 bar.

Base free HMF oxidation over Ru-MnO2 catalysts revisited: Evidence of Mn leaching to Mn-FDCA complexation and its implications on catalyst performance

2,5-furandicarboxylic acid (FDCA) is a high value bio-based chemical useful for the production of next generation renewable polymers, epoxy-resins and surfactants. Herein, we show that the performance and stability of MnO2 based oxidation catalysts used in FDCA production are considerably influence by process conditions (especially initial HMF conc. and presence of base additives). Although, base free aerobic oxidation of HMF to FDCA is known to be highly effective over Ru modified MnO2 catalysts, our experiments showed considerable leaching of MnO2 phase under reaction conditions with the formation of insoluble Mn-FDCA complexes. The formation of Mn-FDCA complex and Mn leaching was also supported by control experiments between FDCA and various Mn oxides under hydrothermal conditions and its structure confirmed by single crystal XRD. Formation of Mn-FDCA and Mn leaching was also identified as the underlying reason for carbon balance deficit, catalyst mass loss and deactivation observed upon reuse.

Interaction between copper and nickel species for electrooxidation of 2,5-bis(hydroxymethyl)furan

Schematic illustration of the concurrent realization of H2 evolution and FDCA production using a NixCu10−x–CF catalyst as the bifunctional electrocatalyst.

Modulating Ni-S coordination in Ni3S2 to promote electrocatalytic oxidation of 5-hydroxymethylfurfural at ampere-level current density.

Electricity-driven oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a highly attractive strategy for biomass transformation. However, achieving industrial-grade current densities remains a great challenge. Herein, by modulating the water content in a solvothermal system, Ni3S2/NF with stabilized and shorter Ni-S bonds as well as a tunable coordination environment of Ni sites was fabricated. The prepared Ni3S2/NF was highly efficient for electrocatalytic oxidation of HMF to produce FDCA, and the FDCA yield and Faraday efficiency could reach 98.8% and 97.6% at the HMF complete conversion. More importantly, an industrial-grade current density of 1000 mA cm-2 could be achieved at a potential of only 1.45 V vs. RHE for HMFOR and the current density could exceed 500 mA cm-2 with other bio-based compounds as the reactants. The excellent performance of Ni3S2/NF originated from the shorter Ni-S bonds and its better electrochemical properties, which significantly promoted the dehydrogenation step of oxidizing HMF. Besides, the gram-scale FDCA production could be realized on Ni3S2/NF in a MEA reactor. This work provides a robust electrocatalyst with high potential for practical applications for the electrocatalytic oxidation of biomass-derived compounds.

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.

High-yield synthesis of 2,5-Furandicarboxylic acid from fructose via a two-step strategy without 5-Hydroxymethylfurfural isolation using dioxane as a bridging solvent

2,5-Furandicarboxylic acid (FDCA) is a crucial bio-platform molecule for renewable polymers and fine chemicals. Here, a two-step method including fructose dehydration and 5-hydroxymethylfurfural (HMF) oxidation has been reported as an effective strategy to produce FDCA with high yield from fructose directly. In this method, for fructose dehydration over CH3SO3H, tetramethylammonium chloride (TmaCl) was first used as phase modifier and co-solvent in a H2O-dioxane biphasic-solvent system, affording HMF yield up to 90.6 % under mild condition (383 K) with relatively high fructose concentration (e.g. 5–10 wt %). Detailed 13C NMR studies verified the interaction between TmaCl and fructose, which significantly promoted the proportion of fructofuranoses and helped to improve the fructose dehydration activity and HMF yield. After dehydration step, more than 97.8 % of CH3SO3H were recovered in reaction phase for catalyst reuse, while the dioxane solution of extracted HMF was separated via simple phase separation. Followed by water commixing, this HMF dioxane solution (with the HMF concentration of 6.3 wt %) was directly oxidized over Ru/C (393 K, 1 MPa O2) to produce FDCA without HMF isolation and alkali addition, affording FDCA yield near 90 %. This study integrates the fructose dehydration and HMF oxidation rationally via dioxane as the bridging solvent to achieve high FDCA yield without complex HMF purification steps, and thus proposes an applicable model for high-efficient production of FDCA in practice.

Integrated process towards sustainable renewable plastics: Production of 2,5-furandicarboxylic acid from fructose in a base-free environment

We report an integrated approach to produce 2,5-furandicarboxylic acid (FDCA) using fructose as a feedstock in a base-free environment, thus providing a promising alternative to the current protocol. FDCA, an alternative molecule to terephthalic acid (obtained from the petroleum route), is used to synthesize poly(ethylene-2,5-furanoate) (PEF), a renewable plastic. In our approach, we produced 5-hydroxymethylfurfural (HMF; 84% yield) by fructose dehydration in an acetone (Ace)/H2O solvent system. The obtained HMF feed was subsequently oxidized over Ru/MnO2, producing FDCA in 92% yield under base-free conditions. The Ru/MnO2 catalyst outperformed conventional Pt/C and Ru/C catalysts under identical reaction conditions. Our novel approach for FDCA production via an integrated process using an Ace/H2O solvent mixture under base-free conditions is economically feasible and environmentally friendly. To the best of our knowledge, this work is the first to report the production of FDCA via this route. We postulate that the high catalytic efficiency of the sulfonated porous organic polymer and Ru/MnO2 in an Ace/H2O system renders them superior to existing homogeneous catalytic routes for HMF production and conversion into FDCA via a scalable process.

Continuous conversion of fructose to 2,5-furandicarboxylic acid by tandem fixed bed system

The direct synthesis of 2,5-furandicarboxylic acid (FDCA) from readily renewable fructose, would provide a cost approach without separation of 5-hydroxymethylfurfural (HMF). The method would realize efficient and continuous production, reduced by-products, without cumbersome HMF separation process, and reduced production costs. In this work, we succeeded in converting fructose directly into FDCA over combined Amberlyst-15 and Pd/Al2O3 in fixed bed reactor. We firstly time, compared One-bed two-catalysts (OBTC), and two-bed two-catalysts (TBTC) system. For the individual merits of the Amberlyst-15 and Pd/Al2O3, the catalytic performance of the combined beds is significantly improved compared with individual one. The high yields of FDCA (48 %) and fructose conversion (100 %) were obtained, respectively. Our one-step continuously method makes the FDCA production much more economical, energy-saved.

A sustainable and low-cost route to 2,5-furandicarboxylic acid by carboxylation of biomass-based furoic acid and CO2

CO2 carboxylation is an important and attractive way of CO2 resourceful utilization, which could synthesize carboxylic acids. As the most promising alternative to terephthalic acid, 2,5-furandicarboxylic acid (FDCA) could be produced by direct carboxylation of the biomass-derived 2-furoic acid (FA) and CO2 promoted by Cs2CO3, but the high cost of cesium limits the development of the route. Herein, low-cost K2CO3 was only used to promote the carboxylation of FA and CO2 for the synthesis of FDCA, whose feasibility was demonstrated by theoretical calculations and experiments. However, the reaction system was strongly influenced by temperature only using K2CO3. The addition of low-cost HCOOK could effectively decrease the reaction temperature, and thus enhance the practicality of the reaction system. Based on experimental and theoretical simulations, it was revealed that the addition of HCOOK not only significantly lowered the melting temperature of the reaction system, but also effectively reduced the activation energy barrier of the hydrogen capture step. The investigation would provide potentiality for a large production of FDCA.