- A High-Performance Base-Metal Approach for the Oxidative Esterification of 5-Hydroxymethylfurfural
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Exploring high-performance base-metal approaches for the sustainable production of chemicals from biomass is presently attracting immense interest and is truly important to promote their industrialized application. Herein, CoOx-N/C and α-MnO2 were combined as a base-metal catalyst that can achieve high yields of furan-2,5-dimethylcarboxylate (FDMC, 95.6 %) for the catalytic oxidative esterification of 5-hydroxymethylfurfural (HMF) without basic additive. The reaction proceeds through fast conversion of HMF to diformylfuran (DFF) with α-MnO2 and subsequent transformation of DFF to FDMC by CoOx-N/C. Quantitative X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculations indicated that the pyridinic-N present in doped carbon could behave as a Lewis base to promote the abstraction of hydrogen for the oxidative esterification reaction. Consequently, CoOx-N/C is a high performance catalyst for the synthesis of FDMC from DFF in a neutral medium.
- Sun, Yuxia,Ma, Hong,Jia, Xiuquan,Ma, Jiping,Luo, Yang,Gao, Jin,Xu, Jie
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- Aerobic oxidation of hydroxymethylfurfural and furfural by using heterogeneous CoxOy-N@C catalysts
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2,5-Furandicarboxylic acid (FDCA) is considered to be a promising replacement for terephthalic acid since they share similar structures and properties. In contrast to FDCA, 2,5-furandicarboxylic acid methyl (FDCAM) has properties that allow it to be easily purified. In this work, we reported an oxidative esterification of 5-hydroxymethylfurfural (HMF) and furfural to prepare corresponding esters over CoxOy-N@C catalysts using O2 as benign oxidant. High yield and selectivity of FDCAM and methyl 2-furoate were obtained under optimized conditions. Factors which influenced the product distribution were examined thoroughly. The CoxOy-N@C catalysts were recycled five times and no significant loss of activity was detected. Characterization of the catalysts could explain such phenomena. Using XPS and TGA, we made a thorough investigation of the effects of ligand and pyrolysis temperature on catalyst activity.
- Deng, Jin,Song, Hai-Jie,Cui, Min-Shu,Du, Yi-Ping,Fu, Yao
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- Oxidative Esterification of 5-Hydroxymethylfurfural under Flow Conditions Using a Bimetallic Co/Ru Catalyst
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Furanic di-carboxylate derivatives of 5-Hydroxymethylfurfural (HMF) are nowadays important in the polymer industry as they are used as building blocks for bio-based polyesters. The high reactivity of HMF compels to avoid harsh synthetic conditions. Therefore, developing mild catalytic processes for its selective oxidation is a challenging task. Herein, we report the first oxidative esterification of HMF to dimethyl furan-2,5-dicarboxylate (FDCM) under flow conditions using oxygen as oxidant. For that purpose, a new series of nitrogen-doped carbon-supported bimetallic Co/Ru heterogeneous catalysts were prepared and characterized by XRD, XPS and N2 physisorption. These analyses revealed that the porosity of the materials and order of impregnation of the metals to the carbon supports lead to varying catalytic activities. Under optimized conditions the flow reactor showed a 15-fold increase on the production of FDCM compared to batch conditions.
- Salazar, Abel,Linke, Alexander,Eckelt, Reinhard,Quade, Antje,Kragl, Udo,Mejía, Esteban
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p. 3504 - 3511
(2020/05/16)
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- Insights into the active sites and catalytic mechanism of oxidative esterification of 5-hydroxymethylfurfural by metal-organic frameworks-derived N-doped carbon
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Directly oxidative esterification of Biomass-derived 5-hydroxymethylfurfural (HMF) into dimethyl furan dicarboxylate (DMFDCA) is a promising route for the replacement of petroleum-derived commodity chemical terephthalic acid (TPA) extensively employed in polyester synthesis. Co-based N-doped carbon materials are one of the most promising applied catalysts for oxidative esterification reaction, however, the active sites and reaction pathway of these catalysts have not been clearly clarified, which is crucial to the practical application. Herein, we report that ZIF-67 (a zeolitic imidazolate framework (ZIF)-type cobalt-containing MOF) derived Co@C-N material is a highly effective catalyst for the selective conversion of HMF into DMFDCA in 95% yield. The high activity of the ZIF-67 derived nanocarbon composites Co@C-N can be attributed to the electron transfer between nitrogen-doped carbon shells and Co nanoparticles. The appropriate graphitic N and pyridinic N doping increases the electronic mobility and active sites. Density functional theory (DFT) simulations indicated that oxygen, HMF and methanol molecules are adsorbed and activated on C-N materials. Furthermore, no 2, 5-diformylfuran (DFF) was captured as an intermediate because the oxidative esterification of aldehyde preferentially occurred than the oxidation of hydroxyl group in HMF. We anticipate that these results can drive progress in the bio-based polymers sector and oxidative esterification reaction.
- Feng, Yunchao,Jia, Wenlong,Yan, Guihua,Zeng, Xianhai,Sperry, Jonathan,Xu, Binbin,Sun, Yong,Tang, Xing,Lei, Tingzhou,Lin, Lu
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p. 570 - 578
(2019/12/25)
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- METHOD FOR PREPARING 2, 5-FURANDIMETHYLCARBOXYLATE FROM HYDROXYMETHYLFURFURAL
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An embodiment of the present invention provides a method of preparing 2,5-furandimethylcarboxylate (FDMC), including preparing 2,5-furandimethylcarboxylate (FDMC) by subjecting a reaction mixture including 5-hydroxymethylfurfural (HMF), air, and an alcohol solvent to oxidative esterification in the presence of a gold (Au)-nanoparticle-supported catalyst, in which the gold (Au)-nanoparticle-supported catalyst includes a support and gold (Au) nanoparticles supported on the support.
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Paragraph 0080-0098; 0109-0110; 0117-0129
(2020/06/07)
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- Oxidative Esterification of 5-Hydroxymethylfurfural with an N-doped Carbon-supported CoCu Bimetallic Catalyst
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The direct fabrication of furan-2,5-dimethylcarboxylate (FDMC), a promising renewable monomer, from biomass-derived 5-hydroxymethylfurfural (HMF) is a cutting-edge process. In this contribution, an elaborately designed N-doped carbon-supported CoCu bimetallic catalyst (CoxCuy-NC; x/y=9:1, 7:3, 4:6, which represents the designed molar ratio of Co and Cu in the catalyst), which could offer a desirable FDMC yield of 95 percent under mild and base-free conditions (Co7Cu3-NC, 2 bar O2, 80 °C, 4 h) is described for the oxidative esterification of HMF. Notably, an FDMC formation rate of 6.1 molFDMC molCo?1 h?1 was achieved over Co7Cu3-NC, which represents the highest catalytic efficiency so far among Co-based catalytic systems. It has been demonstrated that Cu-doping in Co7Cu3-NC catalyst brings about more active sites (Co-Nx species) with stronger molecular oxygen activation ability. The increase of surface N content of Co7Cu3-NC also improves basicity of the catalyst, which favors the hydrogen abstraction process during the HMF oxidative esterification reaction. These findings may pave an efficient and green way for the synthesis of sustainable bio-based polymer monomers.
- Liu, Huai,Ding, Ning,Wei, Junnan,Tang, Xing,Zeng, Xianhai,Sun, Yong,Lei, Tingzhou,Fang, Huayu,Li, Tianyuan,Lin, Lu
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p. 4151 - 4158
(2020/07/10)
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- SYNTHESIS OF PRECURSORS OF 2,5-FURANDICARBOXYLIC ACID
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The present invention relates to a method for the manufacture of stable FDCA precursors from saccharide derived starting materials. More specific the invention relates to the synthesis of FDCA precursors such as alkyl 5-(hydroxymethyl)furan-2-carboxylates or 5-(hydroxymethyl)furan-2-carboxylic acid in an expedient, practical and environmental benign manner from e.g. D-glucono-δ-lactone. These bio-based monomer building blocks hold great potential in the manufacture of polymer materials.
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Page/Page column 16-18
(2019/10/01)
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- AuPd-Fe3O4 Nanoparticle-Catalyzed Synthesis of Furan-2,5-dimethylcarboxylate from 5-Hydroxymethylfurfural under Mild Conditions
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Efficient one-pot oxidative esterification of 5-hydroxymethylfurfural (HMF) to furan-2,5-dimethylcarboxylate (FDMC) was achieved under extremely mild reaction conditions by using AuPd alloy nanoparticles (NPs) supported on Fe3O4. A high yield of FDMC (92 %) was obtained at room temperature under atmospheric O2. The reaction proceeded through the synergistic effects of the AuPd heterobimetallic catalyst system. The most effective molar ratio of noble metal contents for HMF oxidation was 1.00:1.18. If Au-Fe3O4 NPs were used as the catalyst, selective synthesis of 5-hydroxymethylfuroic acid methyl ester (HMFE) was achieved. Additionally, the AuPd-Fe3O4 catalyst could be successfully reused.
- Cho, Ahra,Byun, Sangmoon,Cho, Jin Hee,Kim, Byeong Moon
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p. 2310 - 2317
(2019/04/30)
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- Method for preparation of 2, 5-furandicarboxylic acid diester compound from 5-hydroxymethylfurfural
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The invention discloses a method for preparation of a 2, 5-furandicarboxylic acid diester compound from 5-hydroxymethylfurfural. The method uses a cheap and specific non-noble metal as the catalyst, and adopts cheap and easily available oxygen or air as an oxygen source to prepare high purity dimethyl furan-2, 5-dicarboxylate at high efficiency under mild reaction conditions, thus solving the problems of low reaction efficiency, low product yield, high cost and the like in the prior art, and has good application prospects.
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Paragraph 0019-0024; 0027-0033
(2019/12/31)
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- Aerobic oxidative esterification of 5-hydroxymethylfurfural to dimethyl furan-2,5-dicarboxylate by using homogeneous and heterogeneous PdCoBi/C catalysts under atmospheric oxygen
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The conversion of platform molecule 5-hydroxymethylfurfural (HMF) into many value-added derivatives has attracted significant interest. FDCA and its esters are important derivatives of HMF, which can be used as polyester monomers and pharmaceutical intermediates. In this paper, oxidative esterification of 5-HMF has been carried out by using homogeneous and heterogeneous PdCoBi/C catalysts under atmospheric oxygen. The effect of reaction conditions on product distribution has been studied under both homogeneous and heterogeneous catalytic conditions. The highest yields of oxidative esterification products are obtained at 93% and 96% by using homogeneous and heterogeneous PdCoBi/C catalysts, respectively. The catalysts are characterized by X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (XRD). The catalytic system has better compatibility according to the expansion of the substrate. A reaction mechanism is proposed, and recycle experiments are also conducted.
- Li, Feng,Li, Xing-Long,Li, Chuang,Shi, Jing,Fu, Yao
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supporting information
p. 3050 - 3058
(2018/07/13)
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- Aerobic Oxidation and Oxidative Esterification of 5-Hydroxymethylfurfural by Gold Nanoparticles Supported on Nanoporous Polymer Host Matrix
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The aerobic oxidation and oxidative esterification of 5-hydroxymethylfurfural (HMF) catalyzed by gold nanoparticles (AuNPs) supported on a semicrystalline nanoporous multiblock copolymer matrix consisting of syndiotactic poly(styrene)-cis-1,4-poly(butadiene) (sPSB) have been investigated. Depending on the reaction parameters (support nanoporosity, presence of water, solvent, temperature, cocatalyst, oxygen pressure), the conversion of HMF can be finely addressed to the formation of the desired oxidation product, such as 2,5-diformylfuran (DFF), 5-formylfuran-2-carboxylic acid (FFCA), methyl 5-(hydroxymethyl)furan-2-carboxylate (MHMFC), dimethyl furan-2,5-dicarboxylate (DMFC), and furan-2,5-dicarboxylic acid (FDCA), under optimized reaction conditions. The AuNP–sPSB catalyst is highly effective and selective because the polymer support acts as a conveyor and concentrator of the reactants toward the catalytic sites.
- Buonerba, Antonio,Impemba, Salvatore,Litta, Antonella Dentoni,Capacchione, Carmine,Milione, Stefano,Grassi, Alfonso
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p. 3139 - 3149
(2018/09/14)
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- Selective mono-reduction of pyrrole-2,5 and 2,4-dicarboxylates
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Pyrrole-2,5-dicarboxylates were rapidly and selectively reduced to the corresponding mono-alcohol using 3 eq of diisobutylaluminum hydride at 0°C. Pyrrole-2,4-dicarboxylate showed the same reactivity; however, the selectivity decreased with pyrrole-3,4-dicarboxylate. When the nitrogen atom of the pyrrole-2,5-dicarboxylate is protected with a benzyl group, selective mono-reduction does not occur. Considering that furan-2,5-dicarboxylates did not give the corresponding mono-alcohol under the same conditions, the unprotected nitrogen atom of pyrrole apparently plays an important role in this selective mono-reduction.
- Yasui, Eiko,Tsuda, Jyunpei,Ohnuki, Satoshi,Nagumo, Shinji
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p. 1262 - 1267
(2016/09/09)
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- Biomass into chemicals: One pot-base free oxidative esterification of 5-hydroxymethyl-2-furfural into 2,5-dimethylfuroate with gold on nanoparticulated ceria
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2,5-Dimethylfuroate (DMF) is a valuable biomass derivative that can replace oil dependent PET polymers. 5-Hydroxymethyl-2-furfural (HMF) has been selectively converted into DMF (99 mol% yield) under mild conditions (65-130 °C, 10 bar O2) in the absence of any base, by using gold nanoparticles on nanoparticulated ceria. The catalyst can be reused several times without any loss of activity or selectivity. The absence of metal leaching has been checked by the three-phase test. A full reaction scheme has been established and it has been found that the rate-limiting step of the reaction is the alcohol oxidation into aldehyde. After this, the reaction proceeds via aldehyde conversion into hemiacetal and further oxidation into the corresponding ester. Additionally, the effect of temperature, substrate-to-catalyst ratio, alcohol and water has been studied in an attempt to explain the catalytic behaviour of the Au-CeO2.
- Casanova,Iborra,Corma
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experimental part
p. 109 - 116
(2009/09/24)
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