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.
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-(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.
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.
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.
Encapsulation of ultrafine metal-oxide nanoparticles within mesopores for biomass-derived catalytic applications
Fang, Ruiqi,Tian, Panliang,Yang, Xianfeng,Luque, Rafael,Li, Yingwei
, p. 1854 - 1859 (2018)
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.
Thermoset coatings from epoxidized sucrose soyate and blocked, bio-based dicarboxylic acids
Kovash Jr., Curtiss S.,Pavlacky, Erin,Selvakumar, Sermadurai,Sibi, Mukund P.,Webster, Dean C.
, p. 2289 - 2294 (2014)
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.
Nanoscale center-hollowed hexagon MnCo2O4 spinel catalyzed aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid
Zhang, Shuang,Sun, Xiaozhu,Zheng, Zaihang,Zhang, Long
, p. 19 - 22 (2018)
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.
Efficient synthesis of diallyl esters of the furan series from fructose and preparation of copolymers on their basis
Klushin,Kashparova,Kashparov,Chus, Yu. A.,Chizhikova,Molodtsova,Smirnova
, p. 570 - 577 (2019)
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.
MnCo2O4 spinel supported ruthenium catalyst for air-oxidation of HMF to FDCA under aqueous phase and base-free conditions
Mishra, Dinesh Kumar,Lee, Hye Jin,Kim, Jinsung,Lee, Hong-Shik,Cho, Jin Ku,Suh, Young-Woong,Yi, Yongjin,Kim, Yong Jin
, p. 1619 - 1623 (2017)
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.
A novel magnetic palladium catalyst for the mild aerobic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid in water
Mei, Nan,Liu, Bing,Zheng, Judunn,Lv, Kangle,Tang, Dingguo,Zhang, Zehui
, p. 3194 - 3202 (2015)
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.
N-doped carbon supported Pt catalyst for base-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid
Han, Xuewang,Li, Chaoqun,Guo, Yong,Liu, Xiaohui,Zhang, Yongguang,Wang, Yanqin
, p. 1 - 8 (2016)
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.
Hydrogen-Binding-Initiated Activation of O?H Bonds on a Nitrogen-Doped Surface for the Catalytic Oxidation of Biomass Hydroxyl Compounds
Liu, Xin,Luo, Yang,Ma, Hong,Zhang, Shujing,Che, Penghua,Zhang, Meiyun,Gao, Jin,Xu, Jie
, p. 18103 - 18110 (2021)
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.
The one-pot synthesis of 2,5-diformylfuran, a promising synthon for organic materials in the conversion of biomass
Kashparova,Khokhlova,Galkin,Chernyshev,Ananikov
, p. 1069 - 1073 (2015)
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.
Dehydrogenase-Catalyzed Oxidation of Furanics: Exploitation of Hemoglobin Catalytic Promiscuity
Jia, Hao-Yu,Zong, Min-Hua,Yu, Hui-Lei,Li, Ning
, p. 3524 - 3528 (2017)
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.
Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural over Heterogeneous Silver-Gold Nanoparticle Catalysts
Schade, Oliver R.,Stein, Frederic,Reichenberger, Sven,Gaur, Abhijeet,Sara?i, Erisa,Barcikowski, Stephan,Grunwaldt, Jan-Dierk
, p. 5681 - 5696 (2020)
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.).
Efficient synthesis of 2,5-furandicarboxylic acid from biomass-derived 5-hydroxymethylfurfural in 1,4-dioxane/H2O mixture
Fang, Huayu,Ke, Xixian,Li, Tianyuan,Lin, Lu,Liu, Huai,Sun, Yong,Tang, Xing,Xie, Weizhen,Zeng, Xianhai
, (2021/12/17)
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.
Enabling Efficient Aerobic 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid in Water by Interfacial Engineering Reinforced Cu?Mn Oxides Hollow Nanofiber
Dong, Xuexue,Guo, Zengjing,Song, Hua,Wang, Qian,Wang, Xuyu,Yang, Fu,Yuan, Aihua,Zhang, Yue
, (2022/02/25)
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.
Oxidation of 2,5-bis(hydroxymethyl)furan to 2,5-furandicarboxylic acid catalyzed by carbon nanotube-supported Pd catalysts
Chen, Chunlin,Hao, Panpan,Huai, Liyuan,Li, Zhenyu,Wang, Yongzhao,Zhang, Bingsen,Zhang, Jian,Zhao, Xi
, p. 793 - 801 (2022/02/05)
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.
