3238-40-2Relevant articles and documents
Tunable mixed oxides based on CeO2 for the selective aerobic oxidation of 5-(hydroxymethyl)furfural to FDCA in water
Ventura, Maria,Nocito, Francesco,De Giglio, Elvira,Cometa, Stefania,Altomare, Angela,Dibenedetto, Angela
, p. 3921 - 3926 (2018)
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.
Salt-mediated synthesis of bimetallic networks with structural defects and their enhanced catalytic performances
Zhang, Pei,Zhang, Xiudong,Kang, Xinchen,Liu, Huizhen,Chen, Chunjun,Xie, Chao,Han, Buxing
, p. 12065 - 12068 (2018)
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.
Surface modification of ferrite nanoparticles with dicarboxylic acids for the synthesis of 5-hydroxymethylfurfural: A novel and green protocol
Shaikh, Melad,Sahu, Mahendra,Atyam, Kiran Kumar,Ranganath, Kalluri V. S.
, p. 76795 - 76801 (2016)
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.
Aerobic oxidation of 5-hydroxymethylfurfural (HMF) effectively catalyzed by a Ce0.8Bi0.2O2-δ supported Pt catalyst at room temperature
Miao, Zhenzhen,Wu, Tianxiao,Li, Jingwei,Yi, Ting,Zhang, Yibo,Yang, Xiangguang
, p. 19823 - 19829 (2015)
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
Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2-Supported Gold Catalyst
Kim, Minjune,Su, Yaqiong,Fukuoka, Atsushi,Hensen, Emiel J. M.,Nakajima, Kiyotaka
, p. 8235 - 8239 (2018)
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.
Poly-benzylic ammonium chloride resins as solid catalysts for fructose dehydration
Teong, Siew Ping,Yi, Guangshun,Cao, Xueqin,Zhang, Yugen
, p. 2120 - 2124 (2014)
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.
Hydrophilic mesoporous poly(ionic liquid)-supported Au-Pd alloy nanoparticles towards aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild conditions
Wang, Qian,Hou, Wei,Li, Shuai,Xie, Jingyan,Li, Jing,Zhou, Yu,Wang, Jun
, p. 3820 - 3830 (2017)
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.
One-pot FDCA diester synthesis from mucic acid and their solvent-free regioselective polytransesterification for production of glycerol-based furanic polyesters
Zhao, Deyang,Delbecq, Frederic,Len, Christophe
, (2019)
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.
The direct conversion of sugars into 2,5-furandicarboxylic acid in a triphasic system
Yi, Guangshun,Teong, Siew Ping,Zhang, Yugen
, p. 1151 - 1155 (2015)
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.
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
Niu, Wenqi,Wang, Ding,Yang, Guohui,Sun, Jian,Wu, Mingbo,Yoneyama, Yoshiharu,Tsubaki, Noritatsu
, p. 1124 - 1129 (2014)
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.
