- Tunable mixed oxides based on CeO2 for the selective aerobic oxidation of 5-(hydroxymethyl)furfural to FDCA in water
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Chemicals derived from 5-HMF, via selective oxidation of its pending arms are becoming increasingly important due to their applications. This paper discusses the use of Earth crust abundant new mixed oxides based on CeO2 able to perform the selective oxidation of 5-HMF to 2,5-furandicarboxylic acid (99%), in water, using oxygen as the oxidant.
- Ventura, Maria,Nocito, Francesco,De Giglio, Elvira,Cometa, Stefania,Altomare, Angela,Dibenedetto, Angela
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- Salt-mediated synthesis of bimetallic networks with structural defects and their enhanced catalytic performances
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A method to synthesize bimetallic alloys with tunable morphologies and controlled structural defects was proposed using the characteristics of emulsions tailored by salts. AuPd and PtPd nanowire networks with abundant structural defects exhibited outstanding catalytic performances for oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid, because of the strong ability to generate radicals.
- Zhang, Pei,Zhang, Xiudong,Kang, Xinchen,Liu, Huizhen,Chen, Chunjun,Xie, Chao,Han, Buxing
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- Surface modification of ferrite nanoparticles with dicarboxylic acids for the synthesis of 5-hydroxymethylfurfural: A novel and green protocol
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Surface modification of nanomaterials is one of the rapidly growing research areas. Ferrite nanoparticles (inverse spinels) with an average diameter of about 14 nm were modified with various structurally divergent dicarboxylic acids. Successful surface modification allows them to prevent the nanoparticle aggregation. The modified materials showed good catalytic activity in the dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) under solvent free conditions for the first time. 5-HMF was synthesized in high yields under heterogeneous conditions. The flexible ligand-modified ferrites showed better catalytic activity than the rigid ligand-modified ferrites.
- Shaikh, Melad,Sahu, Mahendra,Atyam, Kiran Kumar,Ranganath, Kalluri V. S.
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- Aerobic oxidation of 5-hydroxymethylfurfural (HMF) effectively catalyzed by a Ce0.8Bi0.2O2-δ supported Pt catalyst at room temperature
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The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) was efficiently catalyzed when Pt nanoparticles (NPs) were supported onto a Ce0.8Bi0.2O2-δ solid solution. 98% yield of FDCA was achieved within 30 min at room temperature and the catalyst was reused five times without much loss of FDCA selectivity. It is the first report on the oxidation of HMF, an alcohol and an aldehyde, effectively catalyzed by a ceria-based material supported Pt catalyst. The individual properties of the Pt NPs and the ceria-based support were retained and not affected after their combination. The superior oxygen activation ability of the Bi-doped ceria thoroughly changed the performance of the ceria supported Pt catalyst. Pt NPs were responsible for the formation of the Pt-alkoxide intermediate, followed by β-H elimination with the help of hydroxide ions. Bi-containing ceria accelerated the oxygen reduction process because of the presence of a large amount of oxygen vacancies and the cleavage of the peroxide intermediate promoted by bismuth. These specific functions were well incorporated during the catalytic oxidation cycle, leading to the generation of the highly efficient Pt/Ce0.8Bi0.2O2-δ catalyst for HMF oxidation at room temperature. This journal is
- Miao, Zhenzhen,Wu, Tianxiao,Li, Jingwei,Yi, Ting,Zhang, Yibo,Yang, Xiangguang
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- Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2-Supported Gold Catalyst
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The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO2-supported Au catalyst and Na2CO3 in water gives a 90–95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10–20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH? and Lewis acid sites on CeO2, and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production.
- Kim, Minjune,Su, Yaqiong,Fukuoka, Atsushi,Hensen, Emiel J. M.,Nakajima, Kiyotaka
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- Poly-benzylic ammonium chloride resins as solid catalysts for fructose dehydration
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5-hydroxymethylfurfural (HMF) is one of the most promising platform molecules, and can be converted into a variety of interesting chemicals. The production of HMF is essentially targeted at bulk chemicals downstream, such as chemicals for the fuels and plastics industries. One critical challenge in HMF production processes is the link to further value-adding reactions in a simple and efficient way (e.g., fewer isolation and purification steps). Herein, a novel poly-benzyl ammonium chloride (PBnNH3Cl) resin is developed as a highly efficient and stable catalyst for dehydration of carbohydrates into HMF. In the isopropanol system, PBnNH3Cl produces high purity HMF that is suitable as feedstock for oxidation to 2,5-furandicarboxylic acid (FDCA). The excellent catalytic properties together with its easy synthesis, low cost, and nontoxic nature make this poly-ammonium resin a promising catalyst for the development of new and efficient processes for biomass-based chemicals.
- Teong, Siew Ping,Yi, Guangshun,Cao, Xueqin,Zhang, Yugen
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- Hydrophilic mesoporous poly(ionic liquid)-supported Au-Pd alloy nanoparticles towards aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild conditions
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Design of stable high-performance heterogeneous catalysts has become crucial for efficient catalytic conversion of renewable biomass into high value-added chemicals. Noble metal alloy nanoparticles (NPs) are of great interest due to their unique tunable structures and high activity. In this study, Au-Pd alloy NPs supported on hydrophilic mesoporous poly(ionic liquid) (MPIL) exhibited encouragingly high performance in the aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in water under mild conditions. Nearly complete conversion of HMF is attained at a low temperature of 90 °C under atmospheric O2, resulting in 99% FDCA yield and high turnover number (TON) of up to 350. After reaction, the catalyst can be facilely recovered and reused with stable activity. Surface wettability plays a dominant role in the oxidation of HMF to FDCA, and synergistic alloy effect accounts for high activity. The results also show that MPILs are a promising support platform to achieve stable and efficient metal NPs through task-specific design of functional monomers.
- Wang, Qian,Hou, Wei,Li, Shuai,Xie, Jingyan,Li, Jing,Zhou, Yu,Wang, Jun
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- One-pot FDCA diester synthesis from mucic acid and their solvent-free regioselective polytransesterification for production of glycerol-based furanic polyesters
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A one pot-two step procedure for the synthesis of diethyl furan-2,5-dicarboxylate (DEFDC) starting from mucic acid without isolation of the intermediate furan dicarboxylic acid (FDCA) was studied. Then, the production of three different kinds of furan-based polyesters—polyethylene-2,5-furan dicarboxylate (PEF), polyhydropropyl-2,5-furan dicarboxylate(PHPF) and polydiglycerol-2,5-furandicarboxylate (PDGF)—was realized through a Co(Ac)2·4H2O catalyzed polytransesterification performed at 160?C between DEFDC and a defined diol furan-based prepolymer or pure diglycerol. In parallel to polymerization process, an unattended regioselective 1-OH acylation of glycerol by direct microwave-heated FDCA diester transesterification led to the formation of a symmetric prepolymer ready for further polymerization and clearly identified by 2D NMR sequences. Furthermore, the synthesis of a more soluble and hydrophilic diglycerol-based furanic polyester was also achieved. The resulting biobased polymers were characterized by NMR, FT-IR spectroscopy, DSC, TGA and XRD. The morphologies of the resulted polymers were observed by FE-SEM and the purity of the material by EDX.
- Zhao, Deyang,Delbecq, Frederic,Len, Christophe
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- The direct conversion of sugars into 2,5-furandicarboxylic acid in a triphasic system
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A one-pot conversion of sugars into 2,5-furandicarboxylic acid (FDCA) is demonstrated in a triphasic system: tetraethylammonium bromide (TEAB) or water - methyl isobutyl ketone (MIBK) - water. In this reaction, sugars are first converted into 5-hydroxymethylfurfural (HMF) in TEAB or water (Phase I). The HMF in Phase I is then extracted to MIBK (Phase II) and transferred to water (Phase III), where HMF is converted into FDCA. Phase II plays multiple roles: as a bridge for HMF extraction, transportation and purification. Overall FDCA yields of 78% and 50% are achieved from fructose and glucose respectively. You cant win if you dont tri: The one-pot conversion of sugars into 2,5-furandicarboxylic acid (FDCA) is demonstrated in a triphasic reactor. Sugars are first converted into 5-hydroxymethylfurfural (HMF) in Phase I, the HMF in Phase I is then extracted into Phase II and transferred to Phase III, where it is converted into FDCA. Overall FDCA yields of 78% and 50% are achieved from fructose and glucose, respectively.
- Yi, Guangshun,Teong, Siew Ping,Zhang, Yugen
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- Pt nanoparticles loaded on reduced graphene oxide as an effective catalyst for the direct oxidation of 5-hydroxymethylfurfural (HMF) to produce 2,5-furandicarboxylic acid (FDCA) under mild conditions
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Reduced graphene oxide (RGO) is one of the most promising catalyst supports because it has faintly acidic sites together with a large amount of functional groups on its surface. In this report, we prove that, for the first time, Pt-loaded RGO (Pt/RGO) is an efficient, robust, and durable catalyst for oxidizing 5-hydroxymethylfurfural (HMF) directly to 2,5-furandicarboxylic acid (FDCA) under mild conditions. The selectivity of FDCA reaches up to 84% along with 100% HMF conversion in the presence of excess base. We deduce that the total reaction on the Pt/RGO catalyst includes several consecutive steps, in which 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) acts as an intermediate. The finding in this report is a significant advancement not only for RGO-based catalyst development, but also for scalable FDCA production, because the total reaction is performed smoothly without using the previously reported harsh reaction conditions.
- Niu, Wenqi,Wang, Ding,Yang, Guohui,Sun, Jian,Wu, Mingbo,Yoneyama, Yoshiharu,Tsubaki, Noritatsu
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- Encapsulation of ultrafine metal-oxide nanoparticles within mesopores for biomass-derived catalytic applications
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The development of efficient encapsulation strategies has attracted intense interest for preparing highly active and stable heterogeneous metal catalysts. However, issues related to low loadings, costly precursors and complex synthesis processes restrict their potential applications. Herein, we report a novel and general strategy to encapsulate various ultrafine metal-oxides nanoparticles (NPs) into the mesoporous KIT-6. The synthesis is facile, which only involves self-assembly of a metal-organic framework (MOF) precursor in the silica mesopores and a subsequent calcination process to transform the MOF into metal-oxide NPs. After the controlled calcination, the metal-oxide NPs produced from MOF decomposition are exclusively confined and uniformly distributed in the mesopores of KIT-6 with high metal loadings. Benefitting from the encapsulation effects, as-synthesized Co@KIT-6 materials exhibit superior catalytic activity and recycling stability in biomass-derived HMF oxidation under mild reaction conditions.
- Fang, Ruiqi,Tian, Panliang,Yang, Xianfeng,Luque, Rafael,Li, Yingwei
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- Paired Electrocatalytic Oxygenation and Hydrogenation of Organic Substrates with Water as the Oxygen and Hydrogen Source
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The use of water as an oxygen and hydrogen source for the paired oxygenation and hydrogenation of organic substrates to produce valuable chemicals is of utmost importance as a means of establishing green chemical syntheses. Inspired by the active Ni3+ intermediates involved in electrocatalytic water oxidation by nickel-based materials, we prepared NiBx as a catalyst and used water as the oxygen source for the oxygenation of various organic compounds. NiBx was further employed as both an anode and a cathode in a paired electrosynthesis cell for the respective oxygenation and hydrogenation of organic compounds, with water as both the oxygen and hydrogen source. Conversion efficiency and selectivity of ≥99 % were observed during the oxygenation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the simultaneous hydrogenation of p-nitrophenol to p-aminophenol. This paired electrosynthesis cell has also been coupled to a solar cell as a stand-alone reactor in response to sunlight.
- Zhang, Peili,Sheng, Xia,Chen, Xiaoyu,Fang, Zhiyong,Jiang, Jian,Wang, Mei,Li, Fusheng,Fan, Lizhou,Ren, Yansong,Zhang, Biaobiao,Timmer, Brian J. J.,Ahlquist, M?rten S. G.,Sun, Licheng
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- Thermoset coatings from epoxidized sucrose soyate and blocked, bio-based dicarboxylic acids
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A new 100 % bio-based thermosetting coating system was developed from epoxidized sucrose soyate crosslinked with blocked bio-based dicarboxylic acids. A solvent-free, green method was used to block the carboxylic acid groups and render the acids miscible with the epoxy resin. The thermal reversibility of this blocking allowed for the formulation of epoxy-acid thermoset coatings that are 100 % bio-based. This was possible due to the volatility of the vinyl ethers under curing conditions. These systems have good adhesion to metal substrates and perform well under chemical and physical stress. Additionally, the hardness of the coating system is dependent on the chain length of the diacid used, making it tunable.
- Kovash Jr., Curtiss S.,Pavlacky, Erin,Selvakumar, Sermadurai,Sibi, Mukund P.,Webster, Dean C.
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- Stability of gold nanocatalysts supported on mesoporous silica for the oxidation of 5-hydroxymethyl furfural to furan-2,5-dicarboxylic acid
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The synthesis of furan-2,5-dicarboxylic acid via catalytic oxidation of 5-hydroxymethyl furfural is an important step for the production of bio-sourced polymers. We report on the activity of SiO2-supported Au catalysts for this reaction. These catalysts reached 74% furan-2,5-dicarboxylic acid yield at 90 °C in 5 h when 5-hydroxymethyl furfural to Au molar ratio was 72. We also investigated the influence of the morphologies of the silica supports on the growth of Au nanoparticles under reaction conditions. Pronounced growth of Au nanoparticles occurred on Aerosil, SiO2 with a disordered porosity and 50 nm average pore diameter: Au nanoparticles grew from 2.4 to 10.1 nm. However, by using ordered mesoporous supports, the growth of the gold nanoparticles was successfully minimized. Also the reaction conditions influenced the particle growth; for instance using HCO3? as a base led to more pronounced particle growth than using NaOH. Particle diffusion in solution, and subsequent coalescence and agglomeration was proposed to be the dominant particle growth mechanism. Our results show the importance of support morphology in mitigation of Au particle growth in liquid phase oxidation reactions.
- Masoud, Nazila,Donoeva, Baira,de Jongh, Petra E.
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- Nanoscale center-hollowed hexagon MnCo2O4 spinel catalyzed aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid
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A series of bimetallic Mn-Co-O catalysts were synthesized by a simple hydrothermal method, and the catalytic performance was evaluated. Among these catalysts, center-hollowed hexagon MnCo2O4 exhibited excellent catalytic effect in aerobic oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-furandicarboxylic acid (FDCA). A 99.5% 5-HMF conversion and 70.9% FDCA yield can be obtained under molecular oxygen and weak base condition. The efficient catalytic performance was attributed to the Mn3+ ions on the surface of MnCo2O4 catalyst, and its high oxygen mobility and reducibility. Furthermore, this simple synthesis process of non-precious metal catalyst is beneficial to the production of FDCA.
- Zhang, Shuang,Sun, Xiaozhu,Zheng, Zaihang,Zhang, Long
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- Synthesis of 2,5-furandicarboxylic acid by catalytic carbonylation of renewable furfural derived 5-bromofuroic acid
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2,5-Furandicarboxylic acid (FDCA) is regarded as a biomass based alternative to p-phthalic acid in polymer industry. Although it can be produced through catalytic oxidation of hydroxylmethyl furfural (HMF), HMF itself is currently produced in limited volume from mono- and polysaccharides like glucose and fructose, thus blocking the utilization of FDCA to replace p-phthalic acid as monomer in industrial applications. This work presents an alternative route for FDCA synthesis originally from renewable furfural through carbonylation of 5-bromofuroic acid with common palladium catalysts, which achieves >99% yield of FDCA based on HPLC analysis, or above 90% isolated yield in gram scale. The influences of the palladium sources, phosphine ligands and bases were investigated in details, and a simplified mechanism was also presented.
- Shen, Guanfei,Zhang, Sicheng,Lei, Yu,Chen, Zhuqi,Yin, Guochuan
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- Efficient synthesis of diallyl esters of the furan series from fructose and preparation of copolymers on their basis
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New unsaturated derivatives of the furan series, diallyl esters of furan-2,5-dicarboxylic acid and 5,5′-[oxybis(methylene)]di(2-furoic acid), which can be used as monomers and cross linking agents, were synthesized by the aerobic oxidation of 5-hydroxymethylfurfural and 5,5′-oxybis(5-methylene-2-furaldehyde) obtained by catalytic dehydration of fructose. Optimum conditions for the synthesis of the above-mentioned compounds and their copolymerization with butyl methacrylate were determined. Varying the amount of the cross-linking agent, the thermal stability, adhesion, strength and optical properties of copolymers can be controlled. New cross-linking agents obtained from renewable resources can be considered as an alternative to the important cross-linking agent, diallyl phthalate, produced from petroleum.
- Klushin,Kashparova,Kashparov,Chus, Yu. A.,Chizhikova,Molodtsova,Smirnova
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- Newly developed electrochemical synthesis of Co-based layered double hydroxides: Toward noble metal-free electro-catalysis
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A novel and enhanced electrosynthesis protocol that allows the deposition of thin films of Co/Al and Co/Fe layered double hydroxides (LDHs) on different supports is hereby proposed. The approach is based on potentiodynamic cathodic reduction. All the films have been characterised by cyclic voltammetry, powder X-ray diffraction, scanning electron microscopy, and Raman and atomic emission spectroscopies. Moreover, LDHs electrosynthesised on carbonaceous materials have also been investigated by X-ray absorption spectroscopy to analyse their local metal structure. These substrates are particularly interesting for the plethora of LDH applications ranging from energy storage, sensing, and electrocatalysis, and are also of industrial importance, due to their low cost, ecocompatibility, and easy handling. In particular, the material was exploited for 5-(hydroxymethyl)furfural (HMF) electro-oxidation.
- Musella, Elisa,Gualandi, Isacco,Scavetta, Erika,Rivalta, Arianna,Venuti, Elisabetta,Christian, Meganne,Morandi, Vittorio,Mullaliu, Angelo,Giorgetti, Marco,Tonelli, Domenica
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- MnCo2O4 spinel supported ruthenium catalyst for air-oxidation of HMF to FDCA under aqueous phase and base-free conditions
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A new class of MnCo2O4 spinel supported Ru catalyst, Ru/MnCo2O4, was exploited to afford the highest yield of FDCA (99.1%) from base-free air-oxidation of HMF in water. The catalyst Ru/MnCo2O4 having both Lewis and Br?nsted acidic active sites greatly enhanced the FDCA yield. The catalyst was recyclable up to five successive runs without considerable loss of its original activity.
- Mishra, Dinesh Kumar,Lee, Hye Jin,Kim, Jinsung,Lee, Hong-Shik,Cho, Jin Ku,Suh, Young-Woong,Yi, Yongjin,Kim, Yong Jin
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- Gold nanoclusters confined in a supercage of Y zeolite for aerobic oxidation of HMF under mild conditions
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Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2, 5-furandicar-boxylic acid (FDCA). It achieved >99 % yield of 2, 5-furandicarboxylic acid in water under mild conditions (60°C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2, CeO2, and Mg(OH)2) and channel-type zeolites (ZSM-5 and H-MOR). Detailed characterizations, such as X-ray diffraction, transmission electron microscopy, N2-physisorption, and H2-temperature-programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA.
- Cai, Jiaying,Ma, Hong,Zhang, Junjie,Song, Qi,Du, Zhongtian,Huang, Yizheng,Xu, Jie
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- A novel magnetic palladium catalyst for the mild aerobic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid in water
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In this study, magnetically separable, graphene oxide-supported palladium nanoparticles (C-Fe3O4-Pd) were successfully prepared via a one-step solvothermal route. The C-Fe3O4-Pd catalyst showed excellent catalytic performance in the aerobic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). The base concentration and reaction temperature significantly affected both HMF conversion and FDCA selectivity. High HMF conversion (98.2%) and FDCA yield (91.8%) were obtained after 4 h at 80°C with a K2CO3/HMF molar ratio of 0.5. The C-Fe3O4-Pd catalyst was easily collected by an external magnet and reused without significant loss of its catalytic activity. The developed method is a green and sustainable process for the production of valuable FDCA from renewable, bio-based HMF in terms of the use of water as solvent, the use of stoichiometric amount of base, high catalytic activity under atmospheric oxygen pressure, and facile recyclability of the catalyst.
- Mei, Nan,Liu, Bing,Zheng, Judunn,Lv, Kangle,Tang, Dingguo,Zhang, Zehui
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- Selective oxidation of 5-hydroxymethyl-2-furfural over TiO 2-supported gold-copper catalysts prepared from preformed nanoparticles: Effect of Au/Cu ratio
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5-Hydroxymethyl-2-furfural (HMF) oxidation to furandicarboxylic acid (FDCA) was performed under mild reaction conditions using TiO2-supported Au and Au-Cu catalysts synthesized from pre-formed nanoparticles of different composition. Catalysts were characterized by BET, XRD and XPS. The Au 3Cu1/TiO2 catalyst exhibited the best catalytic performance for FDCA yield. Moreover, after reaction, bimetallic Au-Cu catalysts with high gold content can be recovered by filtration and reused without significant loss of activity and selectivity; whereas, the monometallic gold materials are not stable.
- Albonetti, Stefania,Pasini, Thomas,Lolli, Alice,Blosi, Magda,Piccinini, Marco,Dimitratos, Nikolaos,Lopez-Sanchez, Jose A.,Morgan, David J.,Carley, Albert F.,Hutchings, Graham J.,Cavani, Fabrizio
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- N-doped carbon supported Pt catalyst for base-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid
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A new kind of N-doped carbon supported Pt catalyst (Pt/C) has been prepared for the selective oxidation of 5-Hydroxymethylfurfural (HMF) to 2,5-Furandicarboxylic Acid (FDCA) in base-free conditions. The catalyst (Pt/C-EDA-x) prepared by using ethylenediamine (EDA) as nitrogen source showed higher activity than those prepared by N,N-dimethylaniline (DMA), ammonia (NH3) or acetonitrile (ACN) as nitrogen sources. The Pt/C-EDA-4.1 catalyst showed the highest activity in the oxidation of HMF to FDCA and as high as 96.0% FDCA was obtained under optimal reaction conditions (110?°C, 1.0?MPa O2, 12?h). The samples were characterized by XRD, XPS, CO2-TPD, TEM, SEM, and elemental analysis. XPS results showed that the pyridine-type nitrogen (N-6) played a key role in the selective oxidation of HMF, which can be attributed to the basicity of N-6 site. CO2-TPD measurements also showed that the involving of N elements in catalyst preparation introduced a new kind of medium basic site on the support surface. The influence of reaction time, catalyst dosage, and temperature on the HMF oxidation to FDCA catalyzed by Pt/C-EDA-4.1 was studied.
- Han, Xuewang,Li, Chaoqun,Guo, Yong,Liu, Xiaohui,Zhang, Yongguang,Wang, Yanqin
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- An active, selective, and stable manganese oxide-supported atomic Pd catalyst for aerobic oxidation of 5-hydroxymethylfurfural
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Here we report for the first time a Pd-MnO2 catalyst with a single-atom feature that can convert 5-hydroxylmethyfurfural (HMF) into the important bioplastic building block 2,5-furandicarboxylic acid (FDCA) with a high yield of 88% in aqueous solution using O2 as an oxidant at ambient pressure. Pd-MnO2 shows higher activity in the productivity of FDCA (100.91 mmol h-1 gPd-1) than its Pd nanoparticle counterpart (45.57 mmol h-1 gPd-1) and state-of-the-art Pd-based catalysts. Pd-MnO2 displays promising recyclability with no degradation after five catalytic runs. Experimental and theoretical results suggest that the single-atom Pd sites that have enhanced binding affinity to HMF and their surrounding sites on the MnO2 support work synergistically toward HMF oxidation.
- Liao, Xuemei,Hou, Jindou,Wang, Ya,Zhang, Hao,Sun, Yu,Li, Xiaopeng,Tang, Siyang,Kato, Kenichi,Yamauchi, Miho,Jiang, Zheng
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- Hydrogen-Binding-Initiated Activation of O?H Bonds on a Nitrogen-Doped Surface for the Catalytic Oxidation of Biomass Hydroxyl Compounds
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Hydrogen binding of molecules on solid surfaces is an attractive interaction that can be used as the driving force for bond activation, material-directed assembly, protein protection, etc. However, the lack of a quantitative characterization method for hydrogen bonds (HBs) on surfaces seriously limits its application. We measured the standard Gibbs free energy change (ΔG0) of on-surface HBs using NMR. The HB-accepting ability of the surface was investigated by comparing ΔG0 values employing the model biomass platform 5-hydroxymethylfurfural on a series of Co-N-C-n catalysts with adjustable electron-rich nitrogen-doped contents. Decreasing ΔG0 improves the HB-accepting ability of the nitrogen-doped surface and promotes the selectively initiated activation of O?H bonds in the oxidation of 5-hydroxymethylfurfural. As a result, the reaction kinetics is accelerated. In addition to the excellent catalytic performance, the turnover frequency (TOF) for this oxidation is much higher than for reported non-noble-metal catalysts.
- Liu, Xin,Luo, Yang,Ma, Hong,Zhang, Shujing,Che, Penghua,Zhang, Meiyun,Gao, Jin,Xu, Jie
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- A scalable carboxylation route to furan-2,5-dicarboxylic acid
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Furan-2,5-dicarboxylic acid (FDCA) is a biomass-derived diacid that can be used to make polymers including polyethylene furandicarboxylate (PEF), a highly attractive substitute for petroleum-derived polyethylene terephthalate (PET). Current FDCA syntheses require edible fructose as the feedstock, entail a difficult oxidation step that generates undesirable aldehyde impurities, and have moderate yields. As an alternative, carbonate-promoted C-H carboxylation enables the synthesis of FDCA from 2-furoic acid and CO2. This route is potentially advantageous because 2-furoic acid is made from furfural, a feedstock produced commercially from inedible lignocellulosic biomass, and it obviates late-stage oxidation. In the carboxylation reaction, salt mixtures composed of alkali furan-2-carboxylate (furoate) and alkali carbonate (M2CO3) are heated under CO2 in the absence of solvent or catalysts to form furan-2,5-dicarboxylate (FDCA2-), which is subsequently protonated to produce FDCA. Previously, high yields were achieved on small-scale reactions using caesium furoate and Cs2CO3. In this work, we investigate the carboxylation reaction using alkali furoate/M2CO3 salts containing cation blends and describe reaction conditions that provide high yields on a preparative scale. We show that the carboxylation proceeds efficiently with K+/Cs+ blends that have a high K+ content (up to 4:1 K+:Cs+). Removing H2O, which is a by-product of the reaction, is important for suppressing decomposition pathways. The accumulation of the FDCA2- product inhibits the reaction. Integrating these lessons, we demonstrate the carboxylation of furoate on a 1 mol scale using a fixed-bed flow reactor with 89% isolated yield of pure FDCA upon protonation.
- Dick, Graham R.,Frankhouser, Amy D.,Banerjee, Aanindeeta,Kanan, Matthew W.
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- The one-pot synthesis of 2,5-diformylfuran, a promising synthon for organic materials in the conversion of biomass
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The organic ionic oxidant 4-acetamido-2,2,6,6-tetramethyl-1-oxopiperidinium tetrafluoroborate, [Pip?(O)][BF4], was found to be compatible with both classical organic solvents and the ionic liquids [BMIm][Cl]/[BMIm][BF4] (BMIm is 1-butyl-3-methylimidazolium), which are essential in the conversion of cellulose biomass. A unique NMR monitoring procedure developed in our group was used to study the conversion of fructose to 2,5-diformylfuran in ionic liquids. This process can successfully be carried out in a "one-pot" fashion; [Pip?(O)][BF4] efficiently oxidizes intermediate 5-hydroxymethylfurfural. The reaction is highly selective, giving 2,5-diformylfuran in 95% yield.
- Kashparova,Khokhlova,Galkin,Chernyshev,Ananikov
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- Platinum deposited on cerium coordination polymer for catalytic oxidation of hydroxymethylfurfural producing 2,5-furandicarboxylic acid
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2,5-Furandicarboxylic acid (FDCA) is a value added chemical that can be used as a polymer building block for the synthesis of biobased polymers. Developing efficient catalysts is fundamentally important for the selective oxidation of 5-hydroxymethylfurfural (HMF) into FDCA. In this work, a novel catalyst was prepared at mild conditions by forming platinum nanoparticles on a cerium coordination polymer (CeCP), which was synthesized using 1,3,5-benzenetricarboxylic acid as the ligand. The CeCP@Pt catalyst was utilized for the selective oxidation of highly concentrated HMF into FDCA. The yield of FDCA could reach 96.2% after 12 h of reaction at 70 °C in water at atmospheric conditions. Furthermore, this catalyst can be reused at least five times without significant activity loss. After five recycling cycles, the leaching of Pt from CeCP@Pt was negligible. This work demonstrated the advantages of the CeCP@Pt catalyst, including its easy preparation in mild conditions, application at relatively low temperatures and in atmospheric conditions, catalyzing the oxidation of HMF with a high concentration, and its reuse with a high stability.
- Gong, Wei,Zheng, Kunkun,Ji, Peijun
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- Dehydrogenase-Catalyzed Oxidation of Furanics: Exploitation of Hemoglobin Catalytic Promiscuity
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The catalytic promiscuity of hemoglobin (Hb) was explored for regenerating oxidized nicotinamide cofactors [NAD(P)+]. With H2O2 as oxidant, Hb efficiently oxidized NAD(P)H into NAD(P)+ within 30 min. The new NAD(P)+ regeneration system was coupled with horse liver alcohol dehydrogenase (HLADH) for the oxidation of bio-based furanics such as furfural and 5-hydroxymethylfurfural (HMF). The target acids (e.g., 2,5-furandicarboxylic acid, FDCA) were prepared with moderate-to-good yields. The enzymatic regeneration method was applied in l-glutamic dehydrogenase (DH)-mediated oxidative deamination of lglutamate and for l-lactic-DH-mediated oxidation of l-lactate, which furnished α-ketoglutarate and pyruvate in yields of 97 % and 81 %, respectively. A total turnover number (TTON) of up to approximately 5000 for cofactor and an E factor of less than 110 were obtained in the bi-enzymatic cascade synthesis of α-ketoglutarate. Overall, a proof-of-concept based on catalytic promiscuity of Hb was provided for in situ regeneration of NAD(P)+ in DH-catalyzed oxidation reactions.
- Jia, Hao-Yu,Zong, Min-Hua,Yu, Hui-Lei,Li, Ning
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- Pd-modified Au on carbon as an effective and durable catalyst for the direct oxidation of HMF to 2,5-furandicarboxylic acid
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Mixed noblility: We show that the modification of a gold/carbon catalyst with platinum or palladium produces stable and recyclable catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA): the support and nanoparticle chemistry directly mediate the selective oxidation of terminal hydroxyl groups in bio-derived HMF. This finding is a significant advance over current conversion technology because of the technological importance of FDCA.
- Villa, Alberto,Schiavoni, Marco,Campisi, Sebastiano,Veith, Gabriel M.,Prati, Laura
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- Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural over Heterogeneous Silver-Gold Nanoparticle Catalysts
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Bimetallic silver-gold alloy nanoparticles on zirconia with varying Ag/Au ratios were designed by a rational approach and tested as catalysts for the selective oxidation of the promising biomass platform molecule 5-(hydroxymethyl)furfural (HMF). For this purpose, colloidal AgxAu10-x particles with molar compositions x=1/3/5/7/9 were prepared by laser ablation in liquids, a surfactant-free method for the preparation of highly pure nanoparticles, before adsorption on zirconia. In-depth characterization of the supported catalysts evidenced alloyed nanoparticles with distinct trends of the surface and bulk composition depending on the overall Ag/Au molar ratio as determined by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS), respectively. To uncover the synergistic effect of the Ag/Au ratio, the catalysts were further studied in terms of the catalytic activity and selectivity in HMF oxidation. Either the aldehyde moiety or both functional groups of HMF were selectively oxidized depending on the Ag/Au composition resulting in 5-hydroxymethyl-2-furan-carboxylic acid (HFCA) or 2,5-furandicarboxylic acid (FDCA), respectively. Optimization of the reaction conditions allowed the quantitative production of HFCA over most catalysts, also after re-use. Only gold rich catalysts Ag1Au9/ZrO2 and particularly Ag3Au7/ZrO2 were highly active in FDCA synthesis. While Ag3Au7/ZrO2 deactivated upon re-use due to sintering, no structural changes were observed for the other catalysts and all catalysts were stable against metal leaching. The present work thus provides fundamental insights into the synergistic effect of Ag and Au in alloyed nanoparticles as active and stable catalysts for the oxidation of HMF. (Figure presented.).
- Schade, Oliver R.,Stein, Frederic,Reichenberger, Sven,Gaur, Abhijeet,Sara?i, Erisa,Barcikowski, Stephan,Grunwaldt, Jan-Dierk
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- Supported gold- and silver-based catalysts for the selective aerobic oxidation of 5-(hydroxymethyl)furfural to 2,5-furandicarboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid
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The sustainable synthesis of two important intermediates relevant for the production of bio-based polymers, 2,5-furandicarboxylic acid (FDCA) and 5-hydroxymethyl-2-furancarboxylic acid (HFCA), via oxidation of 5-(hydroxymethyl)furfural (HMF) was investigated using supported gold- and silver-based catalysts in water with air as the oxidant. High yields and selectivities for the production of FDCA (89%) and HFCA (≥98%) were achieved under the optimized reaction conditions with Au/ZrO2 and Ag/ZrO2 catalysts, respectively. While FDCA was mainly formed in the presence of gold catalysts at a maximum productivity of 67 molFDCA h-1 molAu-1, silver catalysts showed a remarkably high activity in aldehyde oxidation producing HFCA in almost quantitative yields with a maximum productivity of 400 molHFCA h-1 molAg-1. By variation of the reaction parameters, the Au/ZrO2 catalyst could be tuned to produce also HFCA, whereas the Ag/ZrO2 catalyst exclusively produced HFCA in a wide range of reaction parameters. The observed differences in catalyst selectivities can be taken as a starting point for further mechanistic investigation on the oxidation of HMF, contributing to a fundamental understanding of this reaction which is particularly important for establishing the production of bio-based polymers.
- Schade, Oliver R.,Kalz, Kai F.,Neukum, Dominik,Kleist, Wolfgang,Grunwaldt, Jan-Dierk
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- Efficient synthesis of 2,5-furandicarboxylic acid from biomass-derived 5-hydroxymethylfurfural in 1,4-dioxane/H2O mixture
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The catalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a renewably sourced substitution for petroleum-derived terephthalic acid, at a high concentration is highly demanding but challenging. Herein, the efficient conversion of HMF (10–25 wt%) in 1,4-dioxane/H2O was achieved, and a desirable FDCA yield of 98% was obtained from HMF (10 wt%) over commercial Ru/C (2 Equiv. NaHCO3, 4 MPa O2, 3 h, and 140 ℃). In addition, a two-step cascade reaction was developed for FDCA production, in which FDCA was employed as the acid catalyst to promote the dehydration of fructose (10 wt%) to HMF, followed by oxidation in 1,4-dioxane/H2O to FDCA over Ru/C. As compared to pure water or 1,4-dioxane, the better stability of HMF in 1,4-dioxane/H2O with a weak alkaline environment and the enhancement of superoxide radicals (·O2-) in 1,4-dioxane/H2O could ensure high FDCA yield at high HMF concentration.
- Fang, Huayu,Ke, Xixian,Li, Tianyuan,Lin, Lu,Liu, Huai,Sun, Yong,Tang, Xing,Xie, Weizhen,Zeng, Xianhai
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- Efficient Electrocatalytic Oxidation of 5-Hydroxymethylfurfural Coupled with 4-Nitrophenol Hydrogenation in a Water System
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Electrocatalytic conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to value-added 2,5-furandicarboxylic acid (FDCA) is of great significance for sustainable chemical production. The key challenge is to establish an electrocatalytic system with a wide potential window, which can selectively oxidize HMF to FDCA without causing water oxidation. In this study, Cu foam decorated with Cu(OH)2 (CF-Cu(OH)2) was successfully fabricated as an efficient catalyst, and CuOOH active species generated by electrochemistry were demonstrated as the main catalytic sites for HMF oxidation. As a result, the current density of CF-Cu(OH)2 reached up to 198.2 mA/cm2 (100 mM HMF, 1.0 M KOH, 0.8 V vs Ag/AgCl), and a high faradic efficiency close to 100% for FDCA production (yield: 98.7%) was realized. Moreover, we reveal the mechanism for the electro-oxidation of HMF to FDCA and further provide an insight into the oxidation pathway for HMF. A paired electrochemical system exhibits superior catalytic performance of synergetic reactions (HMF oxidation and 4-NP reduction). Therefore, this work proposes a strategy to simultaneously produce two types of value-added chemicals at both electrodes, which can be applied in other electrocatalytic systems for the green synthesis of organic compounds.
- Pang, Xuliang,Bai, Hongye,Zhao, Huaiquan,Fan, Weiqiang,Shi, Weidong
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p. 1545 - 1557
(2022/01/28)
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- Enabling Efficient Aerobic 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid in Water by Interfacial Engineering Reinforced Cu?Mn Oxides Hollow Nanofiber
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Herein, a one-dimensional hollow nanofiber catalyst composed of tightly packed multiphase metal oxides of Mn2O3 and Cu1.4Mn1.6O4 was constructed by electrospinning and tailored thermal treatment procedure. The characterization results comprehensively confirmed the special morphology and composition of various comparative catalysts. This strategy endowed the catalyst with abundant interfacial characteristics of components Mn2O3 and Cu1.4Mn1.6O4 nanocrystal. Impressively, the tuning thermal treatment resulted in tailored CuI sites and surface oxygen species of the catalyst, thus affording optimized oxygen vacancies for reinforced oxygen adsorption, while the concomitant enhanced lattice oxygen activity in the constructed composite catalyst ensured the higher catalytic oxidation ability. More importantly, the regulated proportion of oxygen vacancy and lattice oxygen in the composite catalyst was obtained in the best catalyst, beneficial to accelerate the reaction cycle. Compared to other counterparts obtained by different temperatures, the CMO-500 sample exhibited superior selective aerobic 5-hydroxymethylfurfural (HMF) oxidation to 2,5-furandicarboxylic acid (FDCA, 96 % yield) in alkali-bearing aqueous solution using O2 at 120 °C, which resulted from the above-mentioned composition optimization and interfacial engineering reinforced surface oxygen consumption and regeneration cycle. The reaction mechanism was further proposed to uncover the lattice oxygen and oxygen vacancy participating HMF conversion process.
- Dong, Xuexue,Guo, Zengjing,Song, Hua,Wang, Qian,Wang, Xuyu,Yang, Fu,Yuan, Aihua,Zhang, Yue
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- Oxidation of 2,5-bis(hydroxymethyl)furan to 2,5-furandicarboxylic acid catalyzed by carbon nanotube-supported Pd catalysts
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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.
- Chen, Chunlin,Hao, Panpan,Huai, Liyuan,Li, Zhenyu,Wang, Yongzhao,Zhang, Bingsen,Zhang, Jian,Zhao, Xi
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p. 793 - 801
(2022/02/05)
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- Aerobic oxidation of 5-[(formyloxy)methyl]furfural to 2,5-furandicarboxylic acid over MoCuOx catalyst
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Generally, 5-hydroxymethylfurfural (HMF) is used as feedstock to produce 2,5-furandicarboxylic acid (FDCA). Whereas, its poor stability in alkaline environment results in low yield of FDCA. By contrast, 5-[(formyloxy)methyl]furfural (FMF), a novel platform compound derived from HMF, with higher thermal and alkaline stability than HMF, is more promising to replace HMF as substrate for the production of FDCA. In this study, FMF was successfully converted into FDCA over MoCuOx by using NaClO as oxidant, undergoing 2,5-diformylfuran (DFF) and 5-hydroxymethylfuran-2-carboxylic acid (HMFCA) as intermediates. Under optimization condition (30 min, 40 °C), 100% yield of FDCA was obtained. Furthermore, it was also demonstrated that the yield of FDCA up to 90% was gained in 5 wt % FMF concentration. Higher oxygen species mobility and lattice oxygen ratio endowed MoCuOx excellent catalytic activity. The synergy of Mo and Cu species in MoCuOx ensured an efficient conversion of HMF to FDCA through synergistic redox couple of Mo6+/Mo5+ and Cu2+/Cu+.
- Wang, Qian,Zhang, Jie,Jia, Wenlong,Yu, Xin,Chen, Jiahong,Sun, Yong,Wei, Zuojun,Yang, Shuliang,Tang, Xing,Zeng, Xianhai,Lin, Lu
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- PROCESS FOR PRODUCING 2,5-FURANDICARBOXYLIC ACID FROM ETHERS OF 5-HYDROXYMETHYLFURFURAL
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Process for producing a carboxylic acid composition comprising 2,5-furandicarboxylic acid, comprising the steps: a) oxidizing an oxidizable compound comprising 5-alkoxymethylfurfural in an oxidation reactor in the presence of a saturated organic acid solvent having from 2 to 6 carbon atoms and a catalyst system comprising cobalt, manganese and bromine using an oxidizing gas at a temperature in the range of 160 to 210 °C to obtain a crude carboxylic acid composition comprising mono alkyl ester of 2,5-furandicarboxylic acid and solid 2,5- furandicarboxylic acid, b) isolating at least a portion of the solid 2,5-furandicarboxylic acid from the crude carboxylic acid composition in a solid-liquid separation zone to generate a solid cake and a mother liquor, c) determining the amount of manganese and/or cobalt in the cake, and d) increasing the amount of one or more controlling acids in the oxidation reactor, if the determined amount of manganese and/or cobalt in the cake exceeds a predefined threshold value, wherein the one or more controlling acids are selected from the group consisting of hydrobromic acid and mono- or dicarboxylic acids having from 2 to 5 carbon atoms and a pKa of less than 3.2, wherein the mother liquor comprises mono alkyl ester of 2,5-furandicarboxylic acid in the range of 0.5 to 7 % by weight with respect to the weight of the mother liquor.
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Page/Page column 19; 20; 24
(2021/06/26)
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- Method for synthesizing 2, 5-furandicarboxylic acid through visible light catalysis
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The invention relates to the technical field of compound synthesis, in particular to a method for synthesizing 2, 5-furandicarboxylic acid through visible light catalysis. The method comprises the following steps: adding a substrate as shown in a formula (1) and a reaction aid into a solvent for mixing, then carrying out carboxylation reaction with CO2 under the condition of visible light, and then acidifying to obtain 2, 5-furandicarboxylic acid, wherein the reaction aid contains a visible light photosensitizer, a carboxylation catalyst, a ligand, an electron donor and alkali metal carbonate; R1 is H or halogen; and R2 is H or alkyl. The method uses visible light as a light source, and has the characteristics of mild reaction conditions, simple operation and high yield.
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Paragraph 0052-0053; 0056-0059; 0062-0067; 0070-0071
(2021/06/09)
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- Base-free atmospheric O2-mediated oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic acid triggered by Mg-bearing MTW zeolite supported Au nanoparticles
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Mg-bearing MTW silicalite zeolite, MgSi-ZSM-12, was straightforwardly synthesized by involving an unusual acidic pre-gelation system and engaged as the task-specific support for loading the Au nanoparticles (NPs). The resulting Au/MgSi-ZSM-12 catalyst showed stably excellent activity for the oxidation of HMF into FDCA in the presence of atmospheric dioxygen (O2) without externally adding any liquid base, affording a yield of 87 % and turnover number (TON) of 331 based on the surface Au sites. Superior basicity was evidenced by embedding Mg species into the all-silica zeolitic skeleton, which enables strong, weak, and near-zero affinity towards aldehyde, alcohol, and carboxyl groups, respectively, thus, allows rapid and high-uptake adsorption of HMF, but negligible adsorption of FDCA. This unique feature of the Mg-bearing all-silica zeolite support together with its synergy with the active sites of Au NPs is revealed to accelerate the production of FDCA under the base-free mild condition.
- Chen, Lei,Zhuang, Wenxia,Lan, Jingmin,Liu, Xiaoling,Jiang, Shi,Wang, Lei,Zhou, Yu,Wang, Jun
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- A PROCESS FOR THE SYNTHESIS OF FURANDICARBOXYLIC ACID
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The present invention provides a process for the synthesis of FDC A comprising heating a mixture of fructose, aqueous NaCl or KC1, solvent, methyl isobutyl ketone (MIBK) and a catalyst at a temperature in the range of 150 to 200°C in a sealed vessel for a time period in the range of 2 to 5 hours to yield crude 5-HMF. The crude HMF further reacts with a biocatalyst at a temperature in a range of 20 to 50°C for a period at a range of 24 to 96 hours to yield Furandicarboxylic acid (FDCA) ), wherein the conversion of 5- HMF to FDCA is in the range of 90 to 100%.
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Paragraph 00049; 00053-00055
(2021/06/26)
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- Efficient and selective oxidation of 5-hydroxymethylfurfural catalyzed by metal porphyrin supported by alkaline lignin: Solvent optimization and catalyst loading
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Cobalt (II)-meso-tetra(4-carboxyphenyl) porphyrin supported by deprotected lignin was synthesized through the covalent linkage between carboxy groups in the porphyrin and hydroxyl groups in the lignin. The resulting supporting catalysts were applied in the selective oxidation of 5-hydroxymethylfurfural. Through solvent optimization, 5-hydroxymethyl-2-furancarboxylic acid and 2,5-furandicarboxylic acid could be selectively obtained. Steric effect of lignin prevented unwanted aggregation-caused quenching, avoiding catalyst deactivation. Thus, supported catalysts displayed better catalytic efficiency compared free metal porphyrin catalyst. Unlike the excessive use of sodium hydroxide in the oxidation of HMF catalyzed by metal catalysts, an equivalent amount of sodium hydroxide was used in this oxidation process. Meanwhile, lower activation energy was detected when metal porphyrin supported by deprotected lignin was used. By adjusting the pH in the reaction, supported catalysts could be reused. The catalytic activity remained stable during the recycling experiments.
- Fang, Zheng,Guo, Kai,He, Wei,Wu, Hao,Yang, Xiaobing,Zhu, Yuchen
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- Defect-Rich High-Entropy Oxide Nanosheets for Efficient 5-Hydroxymethylfurfural Electrooxidation
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High-entropy oxides (HEOs), a new concept of entropy stabilization, exhibit unique structures and fascinating properties, and are thus important class of materials with significant technological potential. However, the conventional high-temperature synthesis techniques tend to afford micron-scale HEOs with low surface area, and the catalytic activity of available HEOs is still far from satisfactory because of their limited exposed active sites and poor intrinsic activity. Here we report a low-temperature plasma strategy for preparing defect-rich HEOs nanosheets with high surface area, and for the first time employ them for 5-hydroxymethylfurfural (HMF) electrooxidation. Owing to the nanosheets structure, abundant oxygen vacancies, and high surface area, the quinary (FeCrCoNiCu)3O4 nanosheets deliver improved activity for HMF oxidation with lower onset potential and faster kinetics, outperforming that of HEOs prepared by high-temperature method. Our method opens new opportunities for synthesizing nanostructured HEOs with great potential applications.
- Gu, Kaizhi,Huang, Gen,Liu, Yanbo,Tao, Li,Wang, Dongdong,Wang, Shuangyin,Wang, Tehua,Xie, Chao,Zou, Yuqin
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p. 20253 - 20258
(2021/08/03)
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- Method For Manufacturing 2,5-Furan dicarboxylic acid using 5-Acetoxymethyl-2-furaldehyde
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The present invention relates to a method for producing fructose acetoxymethyl 5 - furfuraldehyde (5-2 -2-acetoxymethyl, furaldehyde) using an intermediate produced through a dehydration reaction of fructosins (AMF). And/or) of 5 - acetoxymethyl -2 - furfuraldehyde (AMF) to prepare 2, 5 - furandicarboxylic acid (2, 5-Furan dicarboxylic acid, FDCA). A method for preparing 5 -furandicarboxylic acid (-2 -) using AMF acetoxymethyl 2, 5 - furfuraldehyde (FDCA) is provided.
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Paragraph 0120-0123; 0132; 0136
(2021/07/01)
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- Method for preparing 2, 5-furandicarboxylic acid by synergistically catalyzing dehydration cyclization of hexose diacid (salt) through haloid acid and metal halide
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The invention discloses a method for preparing 2, 5-furandicarboxylic acid by synergistically catalyzing dehydration cyclization of hexose diacid (salt) through haloid acid and metal halide. The method comprises the following steps: 1) adding sulfolane, halogen acid and metal halide into a high-temperature and high-pressure reaction kettle with a stirring function and a polytetrafluoroethylene lining, starting stirring, and then adding hexose diacid (salt); 2) heating to 100-130 DEG C, and carrying out dehydration cyclization reaction for 1-24 hours; and 3) after the reaction is finished, cooling to room temperature, filtering to obtain a solid phase which is a 2, 5-furandicarboxylic acid crude product, recrystallizing to obtain a 2, 5-furandicarboxylic acid product, and carrying out dehydration and impurity removal treatment on the filtrate for reuse. According to the method, a high-selectivity catalytic system for preparing the 2, 5-furandicarboxylic acid through dehydration and cyclization of hexose diacid (salt) is constructed, the molar yield of the 2, 5-furandicarboxylic acid is as high as 84.2%, the process is simple, the catalyst and the solvent can be repeatedly used, and the method has a good industrial prospect.
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Paragraph 0045; 0050
(2021/07/01)
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- Hydroxyapatite-Supported Polyoxometalates for the Highly Selective Aerobic Oxidation of 5-Hydroxymethylfurfural or Glucose to 2,5-Diformylfuran under Atmospheric Pressure
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(NH4)5H6PV8Mo4O40 supported on hydroxyapatite (HAP) (PMo4V8/HAP (n)) was prepared through the ion exchange of hydroxy groups. This ion exchange favored the oxidative conversion of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF) in a one-pot cascade reaction with 96.0 % conversion and 83.8 % yield under 10 mL/min of O2 flow. PMo4V8/HAP (31) was used to explore the production of DFF directly from glucose with the highest yield of 47.9 % so far under atmospheric oxygen, whereas the yield of DFF increased to 54.7 % in a one-pot and two-step reaction. These results indicated that the active sites in PMo4V8/HAP (31) retained their activities without any interference toward one another, which enabled the production of DFF in a more cost-saving way by only using oxygen and one catalyst in a one-step reaction. Meanwhile, the rigid structure of HAP and strong interaction in PMo4V8/HAP (31) allowed this catalyst to be reused for at least six times with high stability and duration.
- Guan, Hongyu,Li, Ying,Wang, Qiwen,Wang, Xiaohong,Yu, Hang
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p. 997 - 1005
(2021/08/06)
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- Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid
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Encapsulating noble metal nanoparticles (NPs) within the zeolite framework enhances the stability and accessibility of active sites; however, direct synthesis remains a challenge because of the easy precipitation of noble metal species under strong alkali crystallization conditions. Herein, beta zeolite-encapsulated Pt NPs (Pt?Beta) were synthesized via a hydrothermal approach involving an unusual acid hydrolysis preaging step. The ligand—(3-mercaptopropyl)trimethoxysilane—and Pt precursor were cohydrolyzed and cocondensed with a silica source in an initially weak acidic environment to prevent colloidal precipitation by enhancing the interaction between the Pt and silica species. Thus, the resultant 0.2%Pt?Beta was highly active in the transformation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid (FDCA) under atmospheric O2 conditions by using water as the solvent while stably evincing a high yield (90%) associated with a large turnover number of 176. The excellent catalysis behavior is attributable to the enhanced stability that inhibits Pt leaching and strengthens the intermediates that accelerate the rate-determining step for the oxidation of 5-formyl-2-furan carboxylic acid into FDCA.
- Chen, Lei,Jiang, Shi,Liu, Xiaoling,Wang, Jun,Xu, Hongzhong,Zhou, Yu
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p. 994 - 1003
(2020/12/14)
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- A CuMn2O4spinel oxide as a superior catalyst for the aerobic oxidation of 5-hydroxymethylfurfural toward 2,5-furandicarboxylic acid in aqueous solvent
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A CuMn2O4spinel oxide was preparedviaa freezing-assisted sol-gel method and used in the aerobic oxidation of 5-hydroxylmethylfurfural (HMF) toward 2,5-furandicarboxylic acid (FDCA) in aqueous solvent. A highest FDCA yield of 92.1% over the CuMn2O4spinel oxide was achieved and the catalyst could be regenerated by calcination in air after the sixth consecutive run, outperforming several other Mn-based spinel and single oxide catalysts. Kinetic studies reveal that HMF → 2,5-diformylfuran → 5-formylfuran-2-carboxylic acid (FFCA) → FDCA is the primary reaction route of the reaction and that the oxidation of FFCA is the rate-determining step over the CuMn2O4spinel. Characterization measurements show that Mn species enrichment and proper Mn4+/Mn3+, Cu2+/Cu+and Cu/Mn ratios on the surface of the catalyst led to an appropriate Olatt./Oads.ratio, which facilitated oxygen mobility between the Olatt.consumption and the Olatt.generationviathe refilling of oxygen vacancies. Synergistic effects between Mn and Cu in the CuMn2O4spinel inhibit the secondary reaction and accelerate the rate-determining step rate to enhance FDCA formation.
- Wan, Xiaoyue,Tang, Nannan,Xie, Qi,Zhao, Shuangyan,Zhou, Chunmei,Dai, Yihu,Yang, Yanhui
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p. 1497 - 1509
(2021/03/14)
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- Electro-catalytic oxidation of HMF to FDCA over RuO2/MnO2/CNT catalysts in base-free solution
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The oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one of the most attractive reactions to establish a sustainable chemical process based on biomass resources. In this work, a CNT-supported ruthenium-manganese oxide nano-catalyst (RuO2/MnO2/CNT) was employed for the electro-catalytic oxidation of HMF in base-free aqueous solution. The activity test showed that α-MnO2 can effectively promote the activity of RuO2 in the oxidation of HMF. In comparison with RuO2/CNT, RuO2/MnO2/CNT possessed a lower activation energy and more than twice the FDCA formation rate. Under the optimized reaction conditions, the RuO2/MnO2/CNT catalyst afforded a FDCA yield of 72.1% in a 0.1 M K2SO4 aqueous solution at a 0.9 V (vs. Ag/AgCl) applied potential. To our knowledge, this is the first demonstration of FDCA formation as the primary product with high yield in an initially neutral electrolyte. The product FDCA can be easily separated after cooling the reaction solution to room temperature. This journal is
- Dai, Yihu,Jin, Yuguang,Song, Yu,Wan, Xiaoyue,Wang, Tianci,Yang, Yanhui,Zhao, Wanna,Zhou, Chunmei
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p. 21285 - 21292
(2021/12/09)
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- Synthesis of amides and esters containing furan rings under microwave-assisted conditions
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In this work, we present a novel method for the synthesis of ester and amide derivatives containing furan rings (furfural derivatives) under mild synthetic conditions supported by microwave radiation. N-(Furan-2-ylmethyl)furan-2-carboxamide and furan-2-ylmethyl furan-2-carboxylate were produced using 2-furoic acid, furfurylamine, and furfuryl alcohol. The reactions were carried out in a microwave reactor in the presence of effective coupling reagents: DMT/NMM/TsO? or EDC. The reaction time, the solvent, and the amounts of the substrates were optimized. After crystallization or flash chromatography, the final compounds were isolated with good or very good yields. Our method allows for the synthesis of N-blocked amides using N-blocked amino acids (Boc, Cbz, Fmoc) and amine. As well as compounds with a monoamide and ester moiety, products with diamides and diester bonds (N,N-bis(furan-2-ylmethyl) furan-2,5-dicarboxamide, bis(furan-2-ylmethyl) furan-2,5dicarboxylate, and furan-3,4-diylbis(methylene) bis(furan-2-carboxylate)) were synthesized with moderate yields in the presence of DMT/NMM/TsO– or EDC, using 2,5-furan-dicarboxylic acid and 3,4-bis(hydroxymethyl)furan as substrates.
- Janczewski, ?ukasz,Zieliński, Dariusz,Kolesińska, Beata
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p. 265 - 280
(2021/03/17)
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- Method for one-step synthesis of 2, 5-furandicarbonyl chloride
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The invention discloses a method for one-step synthesis of 2, 5-furandicarbonyl chloride, and relates to the technical field of organic synthesis, and the 2, 5-furandicarbonyl chloride is prepared from a raw material 5-formyl furoic acid through a one-pot method under the action of a catalyst and an organic solvent. Because the 5-formyl furoic acid used in the method can be prepared by selective oxidation of biomass platform molecule 5-hydroxymethylfurfural, the invention provides a sustainable development way for preparing 2, 5-furan diformyl chloride from renewable resources; the reaction conditions are mild, the 2, 5-furan dicarbonyl chloride can be prepared at high yield through a one-pot method, and the raw material 5-formyl furoic acid is converted into the 2, 5-furan dicarbonyl chloride at high selectivity.
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Paragraph 0024-0027
(2021/03/30)
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- Preparation method of 2, 5-furandicarboxylic acid
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The invention discloses a preparation method of 2, 5-furandicarboxylic acid, and belongs to the technical field of organic chemistry. According to the method, reaction gas is introduced into a reaction system to maintain the reaction system at a certain pressure, and raw materials in the reaction system are oxidized at a certain temperature to generate 2,5-furandicarboxylic acid, wherein the raw materials are 5-hydroxymethylfurfural or 5-hydroxymethylfurfural derivatives, the reaction gas contains carbon dioxide and oxygen in a molar ratio of (1-10):1, the solvent in the reaction system is organic acid, and halogen and a metal catalyst exist exist in the reaction system. According to the invention, by controlling the ratio of carbon dioxide to oxygen in reaction gas, combustion of a substrate in an oxidation process is effectively inhibited, the reaction safety is improved, and the selectivity and yield of FDCA are improved (can reach 93% or above).
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Paragraph 0034-0051
(2021/06/06)
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- Facile Production of 2,5-Furandicarboxylic Acid via Oxidation of Industrially Sourced Crude 5-Hydroxymethylfurfural
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The oxidation of 5-hydroxymethylfurfural (HMF) produces value-added chemicals such as 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). In this work, FDCA production was achieved by oxidation of crude HMF solution containing around 45 % HMF a
- Martin, Kevin J.,Subramaniam, Bala,Venkitasubramanian, Padmesh,Zuo, Xiaobin
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- Method for preparing 2, 5-furan dicarboxylic acid through efficient photocatalytic oxidation
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The invention discloses a method for preparing 2, 5-furan dicarboxylic acid through efficient photocatalytic oxidation, and belongs to the technical field of biomass energy and chemical industry. An octahedral Cu2O crystal and a cheap and nontoxic p-type semiconductor are prepared and used for preparing 2, 5-furan dicarboxylic acid through photocatalytic oxidation of 5-hydroxymethyl furfural, and 2, 5-furan dicarboxylic acid is obtained through illumination catalysis by taking 5-hydroxymethyl furfural as a raw material, utilizing a photocatalyst, taking water as a solvent and taking O2 as an oxidizing agent at normal temperature. According to the method, a noble metal catalyst is not used, the reaction condition is mild, the energy consumption is low, the reaction system is green and environment-friendly, the production cost is greatly reduced, byproducts are few, the yield is high, and the prepared 2, 5-furan dicarboxylic acid is good in purity.
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Paragraph 0023-0044
(2021/11/27)
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- Method and system for continuously synthesizing furandicarboxylic acid
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The invention discloses a method for continuously synthesizing furandicarboxylic acid. The method comprises the following steps: (1) dissolving sugars into an organic solvent to prepare a sugar solution with the mass concentration of 5 percent to 50 percent; reacting at 60 to 140 DEG C for 0.5 to 12h under the action of a solid acid dehydration catalyst; (2) adding an alkaline water solution and an oxidant into effluent liquid of step (1); reacting for 2 to 12h under the action of a loading type oxidization catalyst and under the conditions of 60 to 110 DEG C and 0.1 to 1MPa; (3) evaporating the effluent liquid of step (2) to remove a solvent; then adding an acidifying agent and adjusting the pH (Potential of Hydrogen) to be less than 2; precipitating to obtain a furandicarboxylic acid crude product; filtering, washing and recrystallizing to obtain the furandicarboxylic acid. The invention further discloses a system for continuously synthesizing the furandicarboxylic acid. According tothe method disclosed by the invention, an intermediate 5-hydroxymethylfurfural does not need to be separated and purified and the furandicarboxylic acid is synthesized in a high-yield manner under moderate conditions; the method can be continuously operated and has an important application prospect.
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Paragraph 0073-0101
(2021/01/24)
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- Method for synthesizing 2 and 5 - furandicarboxylic acid from furanecarboxylic acid and carbon dioxide
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The invention provides a method for synthesizing 2 and 5 - furandicarboxylic acid from furan formic acid and carbon dioxide, and belongs to the technical field 2 and 5 - furandicarboxylic acid synthesis. This process consists of furanecarboxylic acid. The inorganic base and the solvent are reacted to obtain 2 and 5 - furandicarboxylic acid under the condition of carbon dioxide, and 2 and 5 - furandicarboxylic acid are obtained by post-treatment. The solvent used is an aprotic compound. The aprotic compound is used as a solvent in the reaction process, the conversion rate of the furanecarboxylic acid can be greatly improved, 2 and 5 - furandicarboxylic acid yield is increased, and impurities are prevented from being generated. , By controlling the reaction conditions, the solubility in the solvent can be increased, and the reaction time is greatly shortened. Experimental results show that 2, 5 - furandicarboxylic acid yield prepared by the method can reach 99%.
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Paragraph 0045-0082
(2021/10/05)
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- Process for preparing 2-5 - furandicarboxylic acid from furfural
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The invention belongs to the technical field of organic synthesis and discloses a process for preparing 2, 5 - furandicarboxylic acid from furfural. The process comprises the following steps: (1) adjusting the acid-base regulator. The nano copper oxide powder is mixed with water to 60 - 100 °C, furfural is added, air is continuously introduced, the nano copper oxide is filtered and removed after reaction, the mother solution is cooled down to 0 - 10 °C, and potassium bran is filtered. (2) The mother liquor obtained after filtration through step (1) is continuously added with potassium carbonate and the nano copper oxide removed in step (1), the step (1) 0 - n is repeated, and the obtained potassium bran potassium is combined. (3) The obtained potassium chaff, the basic compound and the solvent are introduced into carbon dioxide to obtain 2 and 5 - furandicarboxylic acid after the reaction, and 2, 5 - furandicarboxylic acid is obtained after the reaction. The solvent and the catalyst used in the process are low in price, the solvent and the catalyst can be recycled, the reaction cost is low, the waste water waste is few, the process is simple, efficient, economical and environment-friendly, and is suitable for large-scale industrial production.
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Paragraph 0051-0073; 0077-0088; 0098-0107
(2021/10/27)
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- Method for preparing 2,5 - furandicarboxylic acid from furfural
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The method comprises 2,5 - steps of selective hydrogenation of furfural into furfuryl alcohol, first steps of furfuryl alcohol hydroxymethylation to second furan dimethanol, 2,5 - step of third furan dimethanol oxidation and 2,5 - 2,5 - furandicarboxylic acid. The biomass platform derived compound furfural has the advantages that the biomass platform derived compound furfural is a raw material and is wide in source. The process for hydroxymethylation of furfuryl alcohol is simple, and accords with the idea of sustainable development of green.
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- Mechanistic Studies on the Photooxidation of 5-Hydroxymethylfurfural by Polyoxometalate Catalysts and Atmospheric Oxygen
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Efficient oxidation of 5-hydroxymethylfurfural (HMF) to corresponding furanic products represents an important research focus of biomass valorization, recent research on polyoxometalates (POMs)-catalyzed aerobic oxidation of HMF usually requires high temperature and sometimes high O2/air pressure. In this work, we report a mild and green approach to photocatalytically transform HMF into various furanic products using atmospheric oxygen as oxidant and POMs as photocatalysts. The influence of different POMs, light sources, and additives were systematically investigated by various experimental and spectroscopic results. Under minimally optimized conditions, 88.0 % HMF can be efficiently photooxidized with as high as 70.2 % furanic yield by TBA-W10 catalyst after 2 h irradiation of 365 nm UV light when coupling with TEMPO and Na2CO3 as additives. Finally, detailed mechanistic pathways of HMF photooxidation have been proposed to illustrate the transformation of HMF to various furanic products. This work provides some insightful guidelines for photooxidation of biomass-derived platform chemicals to value-added products under efficient, mild, and green conditions, exhibiting potential practical applications in the future.
- Li, Zheng,Zhang, Mo,Xin, Xing,Lv, Hongjin
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p. 1389 - 1395
(2021/02/01)
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- Understanding the Roles of Electrogenerated Co3+ and Co4+ in Selectivity-Tuned 5-Hydroxymethylfurfural Oxidation
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The Co-based electrocatalyst is among the most promising candidates for electrochemical oxidation of 5-hydroxymethylfurfural (HMF). However, the intrinsic active sites and detailed mechanism of this catalyst remains unclear. We combine experimental evidence and a theoretical study to show that electrogenerated Co3+ and Co4+ species act as chemical oxidants but with distinct roles in selective HMF oxidation. It is found that Co3+ is only capable of oxidizing formyl group to produce carboxylate while Co4+ is required for the initial oxidation of hydroxyl group with significantly faster kinetics. As a result, the product distribution shows explicit dependence on the Co oxidation states and selective production of 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) and 2,5-furandicarboxylic acid (FDCA) are achieved by tuning the applied potential. This work offers essential mechanistic insight on Co-catalyzed organic oxidation reactions and might guide the design of more efficient electrocatalysts.
- Deng, Xiaohui,Fu, Xian-Zhu,Li, Jian-Feng,Luo, Jing-Li,Wang, Lei,Xu, Ge-Yang,Zhang, Jiujun,Zhang, Yue-Jiao
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supporting information
p. 20535 - 20542
(2021/08/12)
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- Highly selective oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over an α-MnO2 catalyst
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Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2, 5-diformylfuran (DFF) with molecular oxygen is realized with an α-MnO2 catalyst under mild conditions. In this work, α-MnO2 exhibited the best performance among the samples examined. Meanwhile, solvent shows a significant effect on the product selectivity and isopropanol is found good for improving the selectivity of DFF. 93.2 % conversion of HMF was achieved at 140 °C for 4 h with 84.3 % selectivity of DFF. Moreover, α-MnO2 catalyst keeps good reusability in recycling for five times. The reaction pathway indicated that the lattice oxygen species on α-MnO2 is involved in the selective oxidation of hydroxyl group in HMF molecule.
- Yu, Linhao,Chen, Hong,Wen, Zhe,Jin, Mengmeng,Ma, Zewei,Ma, Xueli,Sang, Yushuai,Chen, Mengmeng,Li, Yongdan
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- Preparation method of 2, 5-furandicarboxylic acid
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The invention discloses a preparation method of 2, 5-furandicarboxylic acid. The method comprises the step of reacting a material containing 2, 5-furandimethanol and an alkali source in the presence of a catalyst to obtain the 2, 5-furandicarboxylic acid, wherein the catalyst comprises an active component and a carrier, the active component is loaded on the carrier; and the active component is selected from noble metals. According to the invention, 2, 5-furandimethanol is taken as a raw material, 2, 5-furandicarboxylic acid is efficiently prepared by adjusting the alkali amount and the temperature, and the method has a relatively good industrial application prospect.
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Paragraph 0125-0169
(2021/06/06)
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- EFFICIENT PROCESS FOR PRODUCING 5-(ALKOXYCARBONYL)-FURAN-2-CARBOXYLIC ACIDS
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A process for preparing 5-(alkoxycarbonyl)furan-2-carboxylic acids (ACFC) by oxidizing various furcates in the presence of a catalyst containing cobalt, manganese, and bromine, and a solvent while simultaneously removing water vapor from the reaction chamber. The process can produce ACFC with high purity and low color, and in high yield.
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Paragraph 0140-0141
(2021/03/13)
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- Preparation method of 2,5-furandicarboxylic acid under mild condition
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The invention discloses a preparation method of 2,5-furandicarboxylic acid under a mild condition. The preparation method comprises reacting a mixed reaction system containing 5-hydroxymethylfurfural and/or 5-hydroxymethylfurfural derivatives, hydrogen peroxide, a catalyst, a hydrogen peroxide stabilizer, an alkali and water for 1-24 h at the temperature of 0-80 DEG C to prepare the 2,5-furandicarboxylic acid, with the pH value of the mixed reaction system being 7-13. The method provided by the invention is carried out in a water phase, a non-noble metal catalyst is used, the hydrogen peroxide is used as an oxygen source, and 2,5-furandicarboxylic acid is prepared with a high yield under a mild condition by adjusting the pH value and adding the hydrogen peroxide stabilizer. The method provided by the invention is green, pollution-free, convenient to operate and simple in process; the conversion rate of reactants and the selectivity of the product 2,5-furandicarboxylic acid are very high.
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Paragraph 0009; 0071-0072
(2021/05/26)
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- High yield electrooxidation of 5-hydroxymethyl furfural catalysed by unsaturated metal sites in CoFe Prussian Blue Analogue films
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Prussian Blue Analogues (PBAs) are promising electrocatalysts for oxidation reactions due to their binary metal composition and tuneable redox properties. Herein, we report the generation of coordinative unsaturated metal sites in pulse electrodeposited (PED) CoFe PBAs for the oxidation of 5-hydroxymethylfurfural (HMF). The high reactivity by unsaturated metal sites, thoroughly characterized by a suite of spectroscopic techniques, results in a catalyst with superior activity towards the oxidation of HMF to 2,5 furandicarboxylic acid (FDCA).
- Bedford, Nicholas M.,Chandra Hioe, Maria Veronica,Deng, Chen,Hadinata Lie, William,Tsounis, Constantine,Wang, Da-Wei,Wu, Kuang-Hsu,Yang, Yuwei
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p. 4333 - 4337
(2021/06/30)
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- Method for producing furandicarboxylic acid and derivatives thereof from furfural
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The invention discloses a method for producing furandicarboxylic acid and derivatives thereof from furfural. The method comprises the following steps: furfural is reduced to 2-methylfuran under the hydrogen condition; acetylation reaction is carried out on 2-methylfuran to obtain 5-methyl-2-acetylfuran; 5-methyl-2-acety furan reacts with ester to obtain methyl 5-methyl-2-furanformate, methyl 5-methyl-2-furanformate is oxidized into monomethyl 2,5-furandicarboxylate under the oxygen condition, and monomethyl 2,5-furandicarboxylate is hydrolyzed into monomethyl 2,5-furandicarboxylate or furtheresterified with methyl alcohol to generate dimethyl 2,5-furandicarboxylate. The cheap five-carbon furan compound furfural is used as a raw material, and the 2 5-furandicarboxylic acid and the derivatives thereof are prepared by a strategy of increasing a carbon chain, so that the cost of the raw material is greatly reduced. The product provided by the invention has high purity and can be directlyused as a polymerization monomer of PET polyester.
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- Synergistic chemo/biocatalytic synthesis of 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural
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2,5-Furandicarboxylic acid (FDCA) is a promising bio-based chemical in polymer industry. In this work, we constructed an oxidative cascade for one-pot synthesis of FDCA from 5-hydroxymethylfurfural (HMF) by exploiting Comamonas testosteroni SC1588 cells and laccase-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) system. HMF was oxidized to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) by the cells at neutral pH. The HMFCA formation shifted pH of the reaction mixture to acidic range, which favored laccase-TEMPO catalytic oxidation. 5-Formyl-2-furancarboxylic acid derived from HMFCA via laccase-TEMPO catalysis was converted to FDCA by the cells. FDCA was obtained in an 87% yield within 36 h, providing a productivity of around 0.4 g/L h.
- Yang, Zi-Yue,Wen, Mao,Zong, Min-Hua,Li, Ning
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-
- Effect of Gold Particles Size over Au/C Catalyst Selectivity in HMF Oxidation Reaction
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A series of gold nanoparticles in the 4–40 nm range were prepared, immobilized on activated carbon and further tested, at low base concentration, in the catalytic oxidation of 5-hydroxymethyl furfural (HMF) to 2,5-furandicarboxylic acid (FDCA). Gold particles size variation has no influence on HMF conversion but significantly affects product selectivity and carbon balance. This behavior is ascribed to the thermodynamically favorable oxygen reduction reaction on Au(100) faces. As the gold particle size decreases the Au(100)/Au(111) exposure ratio, estimated by using the van Hardeveld-Hartog model, increases as well as the FDCA selectivity. The smaller the gold particle size the smaller the 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) to FDCA ratio pointing to the gold size dependent behavior of the oxidation of the alcohol function of the HMF molecule.
- Megías-Sayago, Cristina,Lolli, Alice,Bonincontro, Danilo,Penkova, Anna,Albonetti, Stefania,Cavani, Fabrizio,Odriozola, José Antonio,Ivanova, Svetlana
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p. 1177 - 1183
(2020/01/22)
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- Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid over Holey 2 D Mn2O3 Nanoflakes from a Mn-based MOF
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The aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a promising renewable monomer to produce bio-based polymers such as polyethylene furanoate (PEF), has recently emerged as the subject of increasing interest. Here, holey 2 D Mn2O3 nanoflakes were obtained by a facile thermal treatment of a Mn-based metal–organic framework (MOF) precursor. The structural and morphological properties of the nanoflakes were characterized by powder XRD, FTIR, SEM and TEM to explore the formation process. It was inferred that the linker loss in the MOF precursor and the oxidation of the Mn cation induced by the heat-treatment in air were responsible for the formation of holey 2 D Mn2O3 nanoflakes. The specific morphology and redox cycle of the Mn cation on the surface endowed the synthesized nanoflakes with promising performance on the selective oxidation. The obtained nanoflakes calcined at 400 °C (M400) afforded over 99.5 % yield of FDCA at complete conversion of HMF, which is superior to the catalytic activity of commercial Mn2O3 and activated MnO2. To our knowledge, Mn2O3 exhibiting such a high performance on the aerobic oxidation of HMF to FDCA has not yet been reported. Based on the investigation of the experimental parameters, a plausible reaction mechanism was proposed.
- Bao, Liwei,Sun, Fang-Zhou,Zhang, Guo-Ying,Hu, Tong-Liang
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p. 548 - 555
(2019/12/27)
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- Two-dimensional metal-organic framework nanosheets for highly efficient electrocatalytic biomass 5-(hydroxymethyl)furfural (HMF) valorization
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To construct a green chemical synthesis system for a better future of human beings, the utilization of water as an oxygen source and electricity as the driving force for the oxygenation of biomass valorization is of great significance and essential. Here, we first investigated the possibility for 5-hydroxymethylfurfural (HMF) electrooxidation into 2,5-furandicarboxylic acid (FDCA) by Ni-based two-dimensional metal-organic frameworks (2D MOFs) as electrocatalysts. FDCA is a desirable alternative to fossil-based terephthalic acids for the production of environmentally friendly polymers. The as-prepared Co-doped 2D MOFs NiCoBDC (Ni2+, BDC = terephthalic acid) have a high FDCA yield of 99%, an excellent yield rate of 20.1 μmol cm-2 h-1 and a faradaic efficiency of 78.8% at 1.55 V vs. RHE, as performed in an electrolyte at pH 13, where the degradation of HMF was ignored. Benefitting from the accessible pores of HMF molecules, abundant exposed active sites and coupling effects between Ni and Co atoms, 2D NiCo-MOFs realized a high catalytic activity and a robust electrochemical durability. This work demonstrates 2D MOFs as promising electrocatalysts for highly efficient biomass valorization because of their porosity and rich active sites.
- Cai, Mengke,Li, Guangqin,Li, Yinle,Liu, Qinglin,Zhang, Yawei,Zhao, Yiyue
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supporting information
p. 20386 - 20392
(2020/11/03)
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- Scalable synthesis of hydroxymethyl alkylfuranoates as stable 2,5-furandicarboxylic acid precursors
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Hydroxymethyl furanoic acid and its derivatives have been synthesized in high yields and purity from gluconolactone. The reaction sequence allows the recovery of reagents and the use of bio-friendly chemicals and solvents, and can easily be scaled up. The reaction product on a >100 gram scale can be purified by a single purification method, such as distillation or precipitation. The overall yield is above 50%.
- Jurys, Arminas,Pedersen, Christian Marcus,Pedersen, Martin J?ger
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supporting information
p. 2399 - 2402
(2020/05/13)
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- Device and method for preparing 2, 5-furandicarboxylic acid from hexose diacid (hexose diacid salt) by coupling dehydration cyclization reaction and azeotropic distillation dehydration
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The invention discloses a device and a method for preparing 2, 5-furandicarboxylic acid from hexose diacid (hexose diacid salt) by coupling dehydration cyclization reaction and azeotropic distillationdehydration. The device integrates dehydration cyclization reaction and azeotropic distillation dehydration. The method comprises the following steps of 1) opening a reaction kettle for stirring anda reaction kettle jacket for heating steam, sequentially adding a reaction solvent, hexose diacid (salt), a catalyst and an entrainer into a dehydration cyclization reaction kettle, enabling water generated by reaction and the entrainer to form azeotrope, enabling the azeotrope to slip out of the tower top and reacting for 15-48h at the reaction temperature of 100-130 DEG C, and 2) after the reaction is finished, recovering the entrainer from a phase splitter, then cooling, neutralizing with alkali, recovering the reaction solvent by reduced pressure distillation, and then crystallizing and recrystallizing to obtain the 2, 5-furandicarboxylic acid product. By coupling azeotropic distillation, water generated in the reaction is removed in time, so that side reactions are reduced, and the yield of the product 2, 5-furandicarboxylic acid is greatly increased.
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Paragraph 0044-0047
(2020/07/24)
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- Synthesis of 2,5-furandicarboxylic acid by a TEMPO/laccase system coupled withPseudomonas putidaKT2440
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As a useful and renewable chemical building block from biomass, 2,5-furandicarboxylic acid (FDCA) has become an increasingly desirable platform chemical as a terephthalic acid replacement for polymerization. In this work, an efficient and highly selective biocatalytic approach for the synthesis of FDCA from 5-hydroxymethylfurfural (HMF) was successfully developed using a TEMPO/laccase system coupled withPseudomonas putidaKT2440. TEMPO/laccase afforded the selective oxidation of the hydroxymethyl group of HMF to form 5-formyl-2-furancarboxylic acid as a major product, which was subsequently oxidized to FDCA byP. putidaKT2440. Manipulating the reaction conditions resulted in a good conversion of HMF (100percent) and an excellent selectivity of FDCA (100percent) at substrate concentrations up to 150 mM within 50 h. The cascade catalytic process established in this work offers a promising approach for the green production of FDCA.
- Ouyang, Jia,Tan, Huanghong,Xu, Qianqian,Zheng, Zhaojuan,Zou, Lihua
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p. 21781 - 21788
(2020/07/03)
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- One-pot hydrothermal synthesis of ultrafine Pd clusters within Beta zeolite for selective oxidation of alcohols
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Highly dispersive and ultrafine Pd clusters were straightforwardly encapsulated within the crystals of Beta zeolite. This series of Pd&at;Beta material was hydrothermally synthesized by performing a unique acid co-hydrolysis of silica and Pd salt precursors in the early gelation stage, by virtue of which the interaction between Si and Pd species was strengthened to inhibit the potential phase separation in the following high pH alkali crystallization. The ultrafine Pd clusters within the wall of the zeolite framework enabled the catalysis to occur in the microchannels, resulting in a high and recyclable yield of above 95percent and a large turnover number of ~50?000 in the oxidation of benzyl alcohol under an O2 atmosphere in water, which can be extended to other microchannel-diffusive aromatic alcohols. Moreover, the catalyst also showed high activity in the aerobic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). The excellent activity is attributable to the synergistic effect of Pd clusters and preferential substrate adsorption behavior. Shape-selective catalysis and stable reusability were achieved. This result provides a novel straightforward synthesis route for fabricating zeolite encapsulated noble metal clusters that effectively and stably catalyze aerobic organic oxidation reactions with shape-selectivity.
- Chen, Lei,Liu, Peiwen,Liu, Xiaoling,Wang, Jun,Wen, Haimeng,Zhou, Yu,Zhuang, Wenxia
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supporting information
p. 4199 - 4209
(2020/07/14)
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- Deep eutectic solvent stabilised Co-P films for electrocatalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid
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The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) has been studied extensively. However, the short lifetime of catalytic electrodes remains a challenge for the electrocatalytic HMF oxidation reaction, and the high pH of the electrolyte causes denaturation of HMF during the reaction. Herein, deep eutectic solvents (DES) are employed for the preparation of efficient and durable catalytic electrodes for HMF oxidation. The catalytic electrode made up of DES avoided the complexity of multiple alkylations leading to 99% HMF conversion affording FDCA in 85.3% yield with high durability, due in part to the lower pH of the electrolyte.
- Kang, Myung Jong,Yu, Hye Jin,Kim, Hyun Sung,Cha, Hyun Gil
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p. 14239 - 14245
(2020/09/04)
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- Furan Carboxylic Acids Production with High Productivity by Cofactor-engineered Whole-cell Biocatalysts
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Furan carboxylic acids are useful chemicals in various industries. In this work, biocatalytic production of furan carboxylic acids was reported with high productivities by cofactor-engineered Escherichia coli cells. NADH oxidase (NOX) was introduced into E. coli harboring aldehyde dehydrogenases (ALDHs) to promote intracellular NAD+ regeneration, thus significantly enhancing ALDH-catalyzed oxidation. These engineered biocatalysts were capable of efficient aerobic oxidation of a variety of aromatic aldehydes. More importantly, they exhibited high substrate tolerance toward toxic furans. E. coli co-expressing vanillin dehydrogenase and NOX (E. coli_CtVDH1_NOX) enabled efficient oxidation of 250 mM of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), providing a productivity of 3.7 g/L h. With E. coli_CtVDH2_NOX as catalyst, up to 240 mM of furfural and 5-methoxymethylfurfural (MMF) could be smoothly oxidized. 2-Furoic acid (FCA, 227 mM) and 5-methoxymethyl-2-furancarboxylic acid (MMFCA, 287 mM) were produced in fed-batch synthesis, providing the productivities of 2.0 and 5.6 g/L h, respectively.
- Zhang, Xue-Ying,Wang, Xin,Li, Nan-Wei,Guo, Ze-Wang,Zong, Min-Hua,Li, Ning
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p. 3257 - 3264
(2020/05/25)
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- Sequential Connection of Mutually Exclusive Catalytic Reactions by a Method Controlling the Presence of an MOF Catalyst: One-Pot Oxidation of Alcohols to Carboxylic Acids
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A functionalized metal-organic framework (MOF) catalyst applied to the sequential one-pot oxidation of alcohols to carboxylic acids controls the presence of a heterogeneous catalyst. The conversion of alcohols to aldehydes was acquired through aerobic oxidation using a well-known amino-oxy radical-functionalized MOF. In the same flask, a simple filtration of the radical MOF with mild heating of the solution completely altered the reaction media, providing radical scavenger-free conditions suitable for the autoxidation of the aldehydes formed in the first step to carboxylic acids. The mutually exclusive radical-catalyzed aerobic oxidation (the first step with MOF) and radical-inhibited autoxidation (the second step without MOF) are sequentially achieved in a one-pot manner. Overall, we demonstrate a powerful and efficient method for the sequential oxidation of alcohols to carboxylic acids by employing a readily functionalizable heterogeneous MOF. In addition, our MOF in-and-out method can be utilized in an environmentally friendly way for the oxidation of alcohols to carboxylic acids of industrial and economic value with broad functional group tolerance, including 2,5-furandicarboxylic acid and 1,4-benzenedicarboxylic acid, with good yield and reusability. Furthermore, MOF-TEMPO, as an antioxidative stabilizer, prevents the undesired oxidation of aldehydes, and the perfect "recoverability"of such a reactive MOF requires a re-evaluation of the advantages of MOFs from heterogeneity in catalytic and related applications.
- Kim, Seongwoo,Lee, Ha-Eun,Suh, Jong-Min,Lim, Mi Hee,Kim, Min
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supporting information
p. 17573 - 17582
(2020/12/22)
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- PRODUCTION OF PURIFIED DIALKYL-FURAN-2,5-DICARBOXYLATE (DAFD) IN A RETROFITTED DMT PLANT
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Disclosed is a process to produce a purified vapor comprising dialkyl- furan-2,5-dicarboxylate (DAFD). Furan-2,5-dicarboxylic acid (FDCA) and an alcohol in an esterification zone to generate a crude diester stream containing dialkyi furan dicarboxylate (DAFD), unreacted alcohol, 5-(alkoxycarbonyl)furan-2- carboxylic acid (ACFC), and alkyl furan-2-carboxylate (AFC). The esterification zone comprises at least one reactor that has been previously used in an DMT process.
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Paragraph 0085
(2020/03/23)
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- Enhancing the electrocatalytic activity of CoO for the oxidation of 5-hydroxymethylfurfural by introducing oxygen vacancies
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The electrochemical oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a highly attractive strategy to generate valuable biomass-based oxygenated chemicals. Robust, stable and inexpensive electrocatalysts are crucial for this interesting reaction. In this work, we found that the electrocatalytic performance of cobalt oxide (CoO) could be significantly improved by introducing oxygen vacancies via Se doping. The resulting CoO-CoSe2 with a CoO/CoSe2 molar ratio of 23?:?1 showed excellent performance and stability for the electro-oxidation of HMF to FDCA, and a FDCA yield of 99% could be achieved with a faradaic efficiency of 97.9% at a potential of 1.43 V vs. RHE. A systematic study indicates that the introduction of rich oxygen vacancies could enhance the catalytic activity and the selectivity to FDCA by increasing the electrochemical surface area and reducing charge transfer resistance. As far as we know, this is the first work to develop a highly stable metal oxide as the active component for this reaction.
- Huang, Xin,Song, Jinliang,Hua, Manli,Xie, Zhenbing,Liu, Shuaishuai,Wu, Tianbin,Yang, Guanying,Han, Buxing
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supporting information
p. 843 - 849
(2020/02/21)
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- Method for catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid
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The invention relates to a method for catalytically oxidizing 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid by using methyltrioxorhenium. According to the method, 5-hydroxymethylfurfural isused as a reaction raw material, acetic acid is used as a reaction solvent, one or more than two selected from hydrogen peroxide, oxygen and tert-butyl hydroperoxide are used as oxidants, and 2,5-furandicarboxylic acid is obtained through a one-step catalytic oxidation process under mild conditions, wherein the yield is up to 99%. The catalytic method is environmentally friendly and has high atomeconomy and high reaction efficiency.
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Paragraph 0017-0049
(2020/06/17)
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