FDCA Yield Research Articles

Self-supported ultrathin Co3O4 nanoarray enabling efficient paired electrolysis of 5-hydroxymethylfurfural for simultaneous dihydroxymethylfuran (DHMF) and furandicarboxylic acid (FDCA) production

Production of value-added chemicals and fuels from biomass via electrochemical methods has been of emerging interest in light of the increasing environmental, economic, and political challenges. Paired electrolysis, with anodic oxidation and cathodic reduction reactions pairing in a single electrochemical cell, offers an effective way to produce desired products in both electrodes, thus achieving complete electron economy. In this work, an efficient 5-hydroxymethylfurfural (HMF) paired electrolysis system is developed over a self-supported ultrathin Co3O4 nanoarray electrocatalyst for simultaneous production of value-added 2,5-dihydroxymethylfuran (DHMF) and 2,5-furandicarboxylic acid (FDCA). The as-designed paired electrolysis cell achieves a high HMF conversion and DHMF/FDCA selectivity at both anode and cathode without external hydrogen and oxygen input. A near-quantitative yield (95.7%) of FDCA and 78.8% yield of DHMF can be achieved in the paired electrolysis system, with a total Faradaic efficiency of 127%. This work will open up new opportunities in designing efficient electrochemical devices to simultaneously produce building-block chemicals from biomass-derived molecules in both anode and cathode.

In-situ Electrochemical Transformed Cu Oxide from Cu Sulfide for Efficient Upgrading of Biomass Derived 5-Hydroxymethylfurfural in Anion Exchange Membrane Electrolyzer.

The electrochemical transformation of biomass to high value-added products is attractive. Herein, Cu sulfide-mediated in-situ synthesis of Cu oxide was achieved for efficient electro-oxidation of biomass derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). The copper foam-supported Cu sulfide (Cu-S/CF) was in-situ converted to Cu oxide during the electro-oxidation process. The in-situ formed Cu oxide presented high HMF conversion, FDCA yield, and faradaic efficiency in 1 m KOH with HMF concentration up to 100 mm. The oxidation of HMF on Cu oxide started with the formation of high-valence Cu species with the assistance of OH- , which then oxidized HMF spontaneously. An anion exchange membrane (AEM) electrolyzer with Cu-S/CF as the anode was assembled to continuously produce FDCA with H2 generation at the cathode. The AEM electrolyzer ran stably for 60 h with FDCA content higher than 85 % at a cell voltage between 1.50 and 1.60 V.

Synergistic effect of the fourth metal component on Co/Mn/Br catalyst in 2, 5-furanediformic acid preparation

2,5-furandicarboxylic acid(FDCA) has the potential to replace terephthalic acid in the synthesis of bio-based resins. The catalytic activity of Co/Mn/Br catalyst and the effect of the fourth metal component for FDCA preparation were investigated. The highest yield of FDCA achieved 76.3% with Co/Mn/Br catalyst. Cu(OAc)2·H2O could greatly reduce the dosage of catalyst without sacrificing the activity, and the highest yield of FDCA with Co/Mn/Br/Cu catalyst was 77.2%. And the reaction processes with Co/Mn/Br catalyst and Co/Mn/Br/Cu catalyst were explored.

Aerobic Oxidation of 5-Hydroxymethyl-furfural to 2,5-Furandicarboxylic Acid at 20 °C by Optimizing Adsorption on AgPd Alloy Nanoparticle Catalysts

Production of 2,5-furandicarboxylic acid (FDCA, a platform chemical for the chemical industry in the future) by the selective aerobic oxidation of 5-hydroxymethyl-furfural is a crucial component to enable the FDCA production from sugars. The challenge is to achieve a high FDCA yield at low temperatures. Here, we report a catalyst composed of alloyed nanoparticles (containing 1.5 wt % Ag and 1.5 wt % Pd) supported on CeO2 nanofibers, which achieved an excellent FDCA yield (93%) at 20 °C. Interesting observations include yield deterioration at higher reaction temperatures; water is the source of the oxygen atom(s) added to the oxidized intermediates and product, while O2 molecules adsorbed onto the catalyst scavenge electrons, yielding OH• radicals from OH– ions in the reaction system to drive the oxidation. At 20 °C, we avoid side reactions, but there is no external energy provided for overcoming the activation barriers. The barriers for activating the alcohol groups are significant. We find that the appropriate chemisorption on the catalyst is critical for a high FDCA yield. By tuning the Ag/Pd ratio, we attained the most catalytically active sites, bimetallic surface sites, at the boundaries between Ag and Pd clusters. The chemisorption at these sites is strong enough to cause the selective oxidation of both the aldehyde and alcohol groups in HMF at 20 °C, avoiding side reactions at high temperatures. The knowledge acquired from this study is expected to have implications for other catalytic systems where competitive reactions proceed.

Enhanced Basicity of MnOx-Supported Ru for the Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

The present study focused on developing a stable basic MnOx support for Ru (RuMn) for the efficient oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in water in the absence of an external base. A series of MnOx supports, synthesized via hydrothermal approach using urea as precipitant, was prepared by thermal treatment at various temperatures (300-800 °C) before doping with Ru. The RuMn-2 (1 wt % Ru, MnOx calcined at 400 °C) possessed a large number of basic sites (1.72 mmol g-1 ) based on CO2 temperature-programmed desorption analysis, affording an FDCA yield of 87 % with a turnover frequency of 22 h-1 . Transmission electron microscopy energy-dispersive X-ray spectroscopy elemental mapping of RuMn-2 showed a high dispersion of Ru over the surface of MnOx, contributing to the efficient HMF oxidation. Moreover, X-ray diffraction, X-ray photoelectron spectroscopy, and H2 temperature-programmed reduction indicated that the predominant MnO2 phase (ϵ-MnO2 ) played a vital role in HMF oxidation. RuMn-2 was recyclable for up to four runs without significant loss in the activity and retained its structural integrity.

Oxygen vacancy and support adsorption synergistic effect in aerobic oxidation of HMF to FDCA: A case study using nitrogen-doped porous carbon supported Bi-CeO2

BackgroundThe conversion of 5-Hydroxymethylfurfural into high value-added 2,5-furandicarboxylic acid is of great significance for industrial production and people's life. Rationally regulation of oxygen vacancy and reactant adsorption are keys to developing an efficient metal oxide catalyst for aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. MethodIn this research, nitrogen-doped porous carbon-supported Bi-doped CeO2 (x%Bi-CeO2/N-PCT) catalysts were successfully prepared by co-calcination method. Significant findingsOxygen vacancy concentration of CeO2 can be effectively enlarged by Bi-doping, which was strongly related to the catalytic performance. In-situ FTIR and adsorption experiment results showed that the introduction of N-PCT can enhance the HMF adsorption performance of catalyst. Density functional theory calculation and XPS results proved that the HMF adsorption performance depend on content of graphitic N in N-PCT, thus effecting the catalytic performance of HMF oxidation. Synergistic effect of oxygen vacancy and HMF adsorption ability can enhance the catalytic performance, the FDCA yield of 10%Bi-CeO2/N-PC800 was about 70 times higher than that of pure CeO2. 10%Bi-CeO2/N-PC800 as support for Au nanoparticles demonstrated an excellent yield of FDCA (92.8%). This study provides a novel idea for design of CeO2-based catalyst for oxidation of HMF to high value-added downstream chemicals.

Base‐free synthesis of bio‐derived 2,5‐furandicarboxylic acid using SBA‐15 supported heteropoly acids in ionic liquids

A novel SBA-15 supported Keggin phosphormolybdic acid (HPM/SBA-15) was employed for the synthesis of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) in [Bmim]Cl solvent. Multiple hydrogen bonds were formed between [Bmim]Cl and HMF, promoting the dissolving and oxidation. Under optimized conditions, HPM/SBA-15 provided 76 % yield of FDCA and 60 % after 5 runs, with complete conversions of HMF.

Boosting 2,5-Furandicarboxylic acid production via coating carbon over CeO2 in a Pt catalyst

Production of 2,5-furandicarboxylic acid (FDCA) via aerobic oxidation of 5-hydroxylmethylfurfural (HMF) is promising but still challenging due to the unsatisfied activity and stability of catalyst. Herein, we prepared a composite of CeO2 coated carbon supporting Pt catalyst and use it in the oxidation of HMF with assistance of Na2CO3. A high FDCA yield of 99.0 % was achieved on 5 %Pt/CeO2 @C catalyst under the optimized condition. To reveal the functions of the CeO2 and carbon coating, control experiments, catalyst characterizations and HMF adsorption experiment were conducted. Combining these results, a possible mechanism is proposed. The synergism between CeO2 and carbon is proposed and the role of CeO2 and carbon coating is discussed. CeO2 is in charge of storage/release electrons to activate oxygen due to its superior redox ability, while carbon coating is responsible for adsorbing HMF and conducting electrons between CeO2 core and carbon surface. In addition, the stability was also evaluated and after 5 recycles, the yield of FDCA did not change obviously.

Base-free oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid over palygorskite-supported bimetallic Pt–Pd catalyst

Aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2, 5-furandicarboxylic acid (FDCA) is an important reaction for producing green and sustainable chemicals. Herein, natural clay mineral palygorskite (Pal)-supported bimetallic Pt–Pd catalyst for the oxidation of HMF to FDCA in water without the addition of any bases was developed. The 1Pt9Pd1/Pal catalyst with Pt/Pd molar ratio of 9/1 exhibited excellent catalytic performance, and 100% HMF conversion and 99% FDCA yield were obtained under optimum reaction conditions after 12 h, which was mainly attributed to the synergy between palygorskite and bimetallic Pt–Pd nanoparticles. Palygorskite used as support realized the immobilization and dispersion of bimetallic nanoparticles, increasing the catalytic activity. The basicity of palygorskite and alloying effects between Pt and Pd facilitated the formation of FDCA by synergistically catalyzing the oxidation of alcohol and aldehyde groups in the reactants and intermediates. Furthermore, this catalyst showed good stability and reusability. The present work provides a highly efficient, cost-effective, and environmentally benign catalyst for the base-free oxidation of HMF to FDCA in practical industrial applications.

In-situ growth of MnO2 on hierarchical porous carbon foam with enhanced oxygen vacancy concentration and charge transfer for efficient catalytic oxidation of 5-hydroxymethylfurfural

The catalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to prepare 2,5-furandicarboxylic acid (FDCA) is a promising route to produce biomass-based functional materials. It is significant to develop non-noble metal-based catalysts for efficient conversion of HMF to FDCA. In this study, a facile and green technology was developed to prepare hierarchical porous carbon foam (CF)-supported MnO2 (MnO2/CF) catalyst by in-situ growth of MnO2 nanoparticles on blocky CF, and the catalytic activity of MnO2/CF for the oxidation of HMF to FDCA was evaluated. Under mild reaction conditions, the MnO2/CF catalyst achieved 99.8% conversion of HMF and 97.0% yield of FDCA, which was well beyond the catalytic performance of single MnO2. The results indicated that the CF with hierarchical porous structure and oxygen-containing groups could facilitate the diffusion of reactant molecules and regulate the crystal structure and morphology of MnO2. The synergistic interaction of CF and MnO2 effectively enhanced specific surface area, surface acid-base sites, oxygen vacancy concentration, and charge transfer efficiency of MnO2/CF composite, contributing to favorable catalytic performance. Additionally, the MnO2/CF catalyst showed promising stability and reusability. This work provides new insights into the development of efficient, stable, and economical non-noble metal-based catalysts for catalytic conversion of biomass-based chemicals.

Manipulating interfacial atomic structure of Pt/Ce1−xYxO2−δ to improve charge transfer capacity and catalytic activity in aerobic oxidation of HMF

The electronic interaction between metal and support plays a significant role in varying catalytic activity of oxide-supported metal catalysts for the aerobic oxidation of biomass-based alcohols and aldehydes. Employing Y3+-doped ceria supported Pt catalysts, Pt/Ce1-xYxO2-δ, different interfacial atomic structures, including Pt/Ce-Vo(-Ce)2, Pt/Y-Vo(-Ce)2, Pt/Ce-Vo(-Y)2, and Pt/Y-Vo(-Y)2 (Vo represents an oxygen vacancy), were created in this work to modulate the interfacial electron transfer capacity. The results of experimental and theoretical investigations showed that the Pt/Y-Vo(-Ce)2 interfacial structure owned the highest electron transfer capacity from Pt to the support, resulting in more Ptδ+/Y-Vo(-Ce)2 sites. Accordingly, the catalyst Pt/Ce0.75Y0.25O2-δ owning the largest amount of Ptδ+/Y-Vo(-Ce)2 sites exhibited notably promoted catalytic activity for the oxidation of 5-hydroxymethylfurfural (HMF) toward 2,5-furandicarboxylic acid (FDCA), affording a complete conversion of HMF and 96.6% yield of FDCA in 6 h. This work provided a facile and versatile strategy to modulate the electron transfer capacity of oxide supported metal catalysts by manipulating the interfacial atomic structure for promoting their activities in various catalytic oxidation reactions.

Challenges of Green Production of 2,5-Furandicarboxylic Acid from Bio-Derived 5-Hydroxymethylfurfural: Overcoming Deactivation by Concomitant Amino Acids.

The oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) is highly attractive as FDCA is considered as substitute for the petrochemically derived terephthalic acid. There are only few reports on the direct use of unrefined HMF solutions from biomass resources and the influence of remaining constituents on the catalytic processes. In this work, the oxidation of HMF in a solution as obtained from hydrolysis and dehydration of saccharides in chicory roots was investigated without intermediate purification steps. The amount of base added to the solution was critical to increase the FDCA yield. Catalyst deactivation occurred and was attributed to poisoning by amino acids from the bio‐source. A strong influence of amino acids on the catalytic activity was found for all supported Au, Pt, Pd, and Ru catalysts. A supported AuPd(2 : 1)/C alloy catalyst exhibited both superior catalytic activity and higher stability against deactivation by the critical amino acids.

A Highly Efficient Nickel Phosphate Electrocatalyst for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF), one of biomass-derived platform compounds, is an attractive route to produce 2,5-furandicarboxylic acid (FDCA), an important monomer of bio-based polyesters. Here, we successfully synthesized a highly efficient and stable nickel phosphate (Ni3 (PO4)2) electrocatalyst by a simple hydrothermal method for the electrocatalytic oxidation of HMF to FDCA, in which the yield of FDCA reached 94.2% and the Faraday efficiency was 93.5% in 0.1 M KOH. Compared with nickel hydroxide (Ni (OH)2), the introduction of phosphorus enhanced the charge transfer ability of Ni-based catalysts by EIS and Tafel slope analysis. At the same time, the Ni2+ species in Ni3(PO4)2 was more likely to be oxidized to active nickel species than that in Ni (OH)2 from XPS and in situ Raman results. Moreover, in situ attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) over Ni3(PO4)2 were carried out to study the changes of nickel phosphate during the electrocatalytic oxidation of HMF. According to ATR-SEIRAS, XPS, and Raman results, it can be concluded that Ni2+ species under applied potential in KOH solution was transformed to the high-valence nickel species/Ni3+ species with P–OH and the ring-shaped P–O group. In addition, the phosphorus group was also involved in the electrocatalytic oxidation of HMF. Based on these evidences, a complete electrocatalytic oxidation process of HMF to FDCA on Ni3(PO4)2 was proposed.

Solvent-promoted and acid- controlled selectivity oxidation of 5-hydroxymethylfurfural over metal-free TEMPO catalyst

Achieving efficient metal-free synthesis of 2,5-diformylfuran and 2,5-furandicarboxylic acid is always a challenge. In this manuscript, the selective oxidation of 5-hydroxymethylfurfural was achieved by using TEMPO system in t-BuOH solvent with the suitable acid promoters. And t-BuOH was considered to be a suitable solvent due to its excellent stability, oxidation promotion and solubility for intermediates. Remarkably, 90% and 83% yield of DFF and FDCA can be obtained with acetic acid and phosphoric acid, respectively. Additionally, the role of acid additives was discussed in detail and the hydration degree of aldehyde intermediates was considered to be key to controlling the selectivity of this reaction. The isolated yield of 2,5-diformylfuran and 2,5-furandicarboxylic acid were 82% and 78% through the scale-up oxidation, respectively. This approach may be a promising alternative to traditional oxidations for the synthesis of carboxylic acids.

Oxidation of 5‐Hydroxymethyl Furfural to 2,5‐Furan Dicarboxylic Acid Under Mild Aqueous Conditions Catalysed by MIL‐100(Fe) Metal‐Organic Framework

AbstractWe present the use of the redox active MIL‐100(Fe) metal‐organic framework (MOF) as a catalyst for the oxidation of 5‐hydroxymethyl furfural (HMF) into 2,5‐furan dicarboxylic acid (FDCA) in water. The MOF is synthesised in water alone under mild hydrothermal conditions and 1H NMR is used to analyse the products of HMF oxidation. The MOF in combination with the co‐catalyst TEMPO provides a total selectivity of desired products of 74 % with a maximum FDCA yield of 57 % seen after 24 hours at only 70 °C. The catalyst is recycled ten times with no loss in activity and no evidence of a reduction in the crystallinity of the MOF.

Sustainable biomass upgrading coupled with H2 generation over in-situ oxidized Co3O4 electrocatalysts

Substituting overall water splitting with simultaneous biomass upgrading and H2 evolution has drawn tremendous attention due to the lower energy barrier and higher safety. Developing a cheap, efficient, and durable electrocatalyst with dual function is crucial to this novel coupling system. Herein, we propose the in-situ electrochemical tuning nonporous CoSx to hydrangea-like Co3O4 as a highly effective versatile electrocatalyst for the first time. Due to the defective structures and abundant electroactive sites, the Co3O4 catalyst achieved a complete conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) with 93.2% yield and 92.9% faradaic efficiency (FE), as well as a pure hydrogen evolution with 99.8% FE. Interestingly, it harvested a better performance with 95.8% FDCA yield for electro-oxidation of the more stable 2,5-bis(hydroxymethyl)furan (BHMF). Finally, a solar-driven integration reaction was constructed for the first time using the photovoltaic electrocatalysis (PVEC) of BHMF for the efficient and sustainable production of FDCA and H2.

Oxidation of 2,5-bis(hydroxymethyl)furan to 2,5-furandicarboxylic acid catalyzed by carbon nanotube-supported Pd catalysts

The selective oxidation of 2,5-bis(hydroxymethyl)furan (BHMF) in this work was proven as a promising route to produce 2,5-furandicarboxylic acid (FDCA), an emerging bio-based building-block with wide application. Under ambient pressure, the modified carbon nanotube-supported Pd-based catalysts demonstrate the maximum FDCA yield of 93.0% with a full conversion of BHMF after 60 min at 60 °C, much superior to that of the traditional route using 5-hydroxymethylfurfural (HMF) as substrates (only a yield of 35.7%). The participation of PdHx active species with metallic Pd can be responsible for the encouraging performance. Meanwhile, a possible reaction pathway proceeding through 2,5-diformylfuran (DFF) and 5-formyl-2-furancarboxylic acid (FFCA) as process intermediates is suggested for BHMF route. The present work may provide new opportunities to synthesize other high value-added oxygenates by using BHMF as an alternative feedstock.

Pickering High Internal Phase Emulsions Templated CoOx−HPC Loading Bimetallic AuPd Nanoparticles for Catalytic Oxidation of 5‐Hydroxymethylfurfural to 2, 5‐Furan Dicarboxylic

AbstractThe supported bimetallic AuPd nanoparticles hold great promise for the selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2, 5‐furan dicarboxylic acid (FDCA), a substitute for petroleum derivative terephthalic acid (TPA). Herein, by combining a versatile Pickering high internal phase emulsions (HIPEs) template with subsequent carbonization process, cobalt‐based hierarchical porous carbon (CoOx−HPC) support was obtained. After loading bimetallic AuPd nanoparticles through the sol‐gel method, AuPd/CoOx−HPC catalyst was successfully synthesized. By changing the Pickering HIPEs parameters, carbonization temperature, the porous structure and cobalt valence of as‐synthesized catalyst can be adjusted. The obtained catalysts were systematically characterized by SEM, TEM, N2 adsorption‐desorption, XRD, XPS, and TGA. Benefiting from the synergistic effects of the high porosity of CoOx−HPC support and efficient AuPd nanoparticles, tandem oxidation of HMF to FDCA can be carried out in the water. We have clarified that the catalysts with various cobalt valence states showed superior performance, and the highest FDCA yield of 97.2 % will be obtained under the optimal reaction conditions. Meanwhile, the kinetics study indicated that the oxidation of FFCA to FDCA was the rate‐determining step. Moreover, the AuPd/CoOx−HPC catalyst revealed excellent stability in HMF oxidation during four cycles. The experimental results demonstrated that as‐prepared AuPd/CoOx−HPC catalysts are efficient towards FDCA production from the selective oxidation of HMF.

The highly efficient electrocatalytic oxidation of 5-hydroxymethylfurfural on copper nanocrystalline/carbon hybrid catalysts: structure–function relations

The Cu species in Cu(NSD)/CP exhibit a high electrochemical specific surface area, which allows efficient transformation from Cu0and Cu1+species to Cu2+with high catalytic capacity, resulting in excellent catalytic performance (96% yield of FDCA).

Ag substituted Au clusters supported on Mg-Al-hydrotalcite for highly efficient base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

A highly active and selective Au20Ag/MgAl-300 catalyst was developed for HMF oxidation to FDCA under base-free reaction conditions using molecular oxygen as the oxidant, with high conversion of HMF (100%) and high yield of FDCA (>95%).