- Bimetallic CuFe nanoparticles as active and stable catalysts for chemoselective hydrogenation of biomass-derived platform molecules
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Bimetallic CuFe nanoparticles covered by thin carbon layers were developed as a potential substitute for noble metal catalysts and have been used for chemoselective hydrogenation of 5-(hydroxymethyl)furfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF). Compared to Cu catalysts supported on conventional solid carriers prepared by impregnation, the CuFe@C nanoparticles are active and more stable catalysts. The spatial distribution of the immiscible Cu and Fe in the bimetallic CuFe@C nanoparticles is dependent on the Cu/Fe ratio, and moreover, an optimized Cu/Fe ratio has been found for hydrogenation of HMF. In the fresh Fe@C and CuFe@C catalysts, their surfaces are passivated and covered by FeOx, due to oxidation by air. Based on detailed structural characterization and catalytic studies, small Cu nanoparticles supported on Fe nanoparticles are proposed to be the key active sites for hydrogenation of HMF. These Cu nanoparticles can not only serve as the active sites for hydrogenation of HMF but also promote the reduction of FeOxinto metallic Fe, resulting in an increased number of active sites in the bimetallic CuFe@C catalyst compared to the monometallic Cu@C and Fe@C samples, resulting in significant promotion of the catalytic activity.
- Arias, Karen S.,Climent, Maria J.,Concepcion, Patricia,Corma, Avelino,Garcia-Ortiz, Andrea,Iborra, Sara,Liu, Lichen
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p. 3353 - 3363
(2021/06/06)
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- An efficient approach to synthesizing 2,5-bis(: N -methyl-aminomethyl)furan from 5-hydroxymethylfurfural via 2,5-bis(N -methyl-iminomethyl)furan using a two-step reaction in one pot
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In this study, an amination-oxidation-amination-reduction (AOAR) strategy was proposed for the synthesis of 2,5-bis(N-methyl-aminomethyl)furan (BMAF) from HMF via the intermediate 2,5-bis(N-methyl-iminomethyl)furan (BMIF). Firstly, an efficient synthesis of BMIF from HMF using a one-pot amination-oxidation-amination reaction was developed over α-MnO2 under an air atmosphere. A BMIF yield of 98.3% was obtained under mild reaction conditions. The conversion of HMF to BMIF underwent the fast amination of HMF to 5-(methyl-iminomethyl)furfuryl alcohol (MIFA), the subsequent rate-limiting oxidation of MIFA to 5-(methyl-iminomethyl)furfural (MIFF) and the final fast amination of MIFF to BMIF. The quick amination of MIFF to BMIF drove the oxidation reaction equilibrium toward MIFF from MIFA, which ensured the highly efficient conversion of HMF to BMIF. The investigation of the catalytic mechanism showed better lattice oxygen donating ability and oxygen coordination capacity, which made α-MnO2 retain the structural stability in the reaction. The higher ratio and better mobility of the lattice oxygen endowed α-MnO2 with excellent catalytic performance in the oxidation of MIFA to MIFF by the redox cycling of Mn4+/Mn3+, facilitating the conversion of HMF to BMIF. Eventually, a BMAF yield of 96.1% was achieved by the reduction of BMIF with Ru/C after the AOA reaction, realizing the synthesis of BMAF from HMF using a two-step reaction in one pot. This journal is
- Jia, Wenlong,Lin, Lu,Sun, Yong,Tang, Xing,Yang, Shuliang,Zeng, Xianhai,Zhang, Jie
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supporting information
p. 5656 - 5664
(2021/08/16)
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- Two-step one-pot reductive amination of furanic aldehydes using CuAlOx catalyst in a flow reactor
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Aminomethylhydroxymethylfuran derivatives are well known compounds which are used in the pharmaceutical industry. Reductive amination of 5-hydroxymethylfurfural (HMF) derived from available non-edible lignocellulosic biomass is an attractive method for the synthesis of this class of compounds. In the present study, the synthesis of N-substituted 5-(hydroxymethyl)-2-furfuryl amines and 5-(acetoxymethyl)-2-furfuryl amines was performed by two-step process, which includes the condensation of furanic aldehydes (HMF and 5-acetoxymethylfurfural) with primary amines in methanol on the first step and the reduction of obtained imines with hydrogen in a flow reactor over CuAlOx catalyst derived from layered double hydroxide on the second step. This process does not require isolation and purification of intermediate imines and can be used to synthesize a number of aminomethylhydroxymethylfurans in good to excellent yield.
- Bukhtiyarov, Valerii I.,Bukhtiyarova, Marina V.,Nuzhdin, Alexey L.
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- Chemoenzymatic Synthesis of 5-Hydroxymethylfurfural (HMF)-Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification
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Biobased plasticizers, as substitutes for phthalates, have been synthesized from 5-hydroxymethylfurfural (HMF) and carboxylic acids (or esters) through a chemoenzymatic cascade process that involves as its first step the reduction of 5-hydroxymethylfurfural into 2,5-bis(hydroxymethyl)furan (BHMF), followed by the esterification of BHMF with carboxylic acids (or esters) by using a supported lipase (Novozym 435). The reduction of HMF into BHMF is performed by using monodisperse metallic Co nanoparticles with a thin carbon shell (Co@C) with high activity and selectivity. After optimization of reaction conditions (temperature, hydrogen pressure, and solvent), it is possible to achieve 97 % conversion of HMF with 99 % selectivity to BHMF after 2 h reaction time. The reduction of HMF and esterification of BHMF using carboxylic acids or vinyl esters as acyl donors by lipase are optimized separately in batch and in fixed-bed continuous reactors. The coupling of two flow reactors (for reduction and subsequent esterification) working under optimized reaction conditions affords the diesters of BHMF in roughly 90 % yield with no loss of activity during 60 h of operation.
- Arias, Karen S.,Carceller, Jose M.,Climent, Maria J.,Corma, Avelino,Iborra, Sara
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p. 1864 - 1875
(2020/03/11)
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- Synthesis of a ZIF-derived hollow yolk-shell Co@CN catalyst for the oxidative esterification of 5-hydroxymethylfurfural
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A newly developed template protection-sacrifice (TPS) strategy is developed for the synthesis of hollow yolk-shell Co@CN with a large surface area and high pore volume. The catalyst exhibits excellent catalytic efficiency in base-free oxidative esterification of 5-hydroxymethylfurfural under mild conditions with excellent selectivity at a high concentration (2 M) of the reactant.
- Sun, Kang-Kang,Chen, Shu-Jie,Li, Ze-Lin,Lu, Guo-Ping,Cai, Chun
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p. 1602 - 1608
(2019/04/08)
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- Phosphotungstic acid heterogenized by assembly with pyridines for efficient catalytic conversion of fructose to methyl levulinate
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Solid acid-catalyzed sugar degradation has been considered to be an efficient approach to synthesize alkyl levulinates (which can be used as fuel additives and surfactants). However, those catalytic processes typically involve harsh reaction conditions and high cost for catalyst preparation. We prepared a series of phosphotungstic acid organic hybrids by a simple solvothermal method, and used them as heterogeneous catalysts for the selective degradation of fructose to methyl levulinate (ML) in methanol with high efficiency under mild reaction conditions. The catalysts were characterized systematically, and the effects of different substituents in pyridine, reaction temperature/time, catalyst dose, and fructose concentration studied. The 3-FPYPW hybrid prepared from 3-fluoropyridine and phosphotungstic acid exhibited superior catalytic activity for the synthesis of ML (82.5%) from fructose (97.8%). A possible reaction pathway was proposed. In addition, the catalyst could be separated from the reaction mixture readily, and reused without remarkable loss of reactivity.
- Fang, Chengjiang,Li, Yan,Zhao, Wenfeng,Wu, Weibo,Li, Hu,He, Chao,Yang, Song
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p. 16585 - 16592
(2018/05/23)
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- A bifunctional cerium phosphate catalyst for chemoselective acetalization
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Acid-base solid catalysts synthesized with structurally controlled uniform active sites can lead to unique catalysis. In this study, a CePO4 catalyst was synthesized using a hydrothermal method and found to exhibit high catalytic performance for the chemoselective acetalization of 5-hydroxymethylfurfural with alcohols, in sharp contrast to other homogeneous and heterogeneous acid and/or base catalysts. In the presence of CePO4, various combinations of carbonyl compounds and alcohols are efficiently converted into the corresponding acetal derivatives in good to excellent yields. Mechanistic studies show that CePO4 most likely acts as a bifunctional catalyst through the interaction of uniform Lewis acid and weak base sites with 5-hydroxymethylfurfural and alcohol molecules, respectively, which results in high catalytic performance.
- Kanai, Shunsuke,Nagahara, Ippei,Kita, Yusuke,Kamata, Keigo,Hara, Michikazu
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p. 3146 - 3153
(2017/04/04)
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- METHOD OF PRODUCING 5-HYDROXYMETHYLFURFURAL FROM CARBOHYDRATES
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Disclosed herein is a process for preparing 5-hydroxymethylfurfural comprising the step of contacting a carbohydrate and a Br?nsted acid in an alcoholic solvent comprising an alcohol selected from the group consisting of secondary alcohols, tertiary alcohols, aryl alcohols and combinations thereof under conditions to dehydrate the carbohydrate thereby forming a reaction product containing 5-hydroxymethylfurfural.
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Page/Page column 35; 36; 37
(2013/04/10)
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- The production of 5-hydroxymethylfurfural from fructose in isopropyl alcohol: A green and efficient system
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Solving problems: An isopropyl alcohol-mediated reaction system for the production of 5-hydroxymethylfurfural (HMF) from fructose reaches a yield of up to 87 %. The solvent can be easily recycled by evaporation, giving the HMF product. The system avoids the use of large amounts of organic solvent, has a minimal environmental impact, and offers a new route to large-scale economically viable processes.
- Lai, Linke,Zhang, Yugen
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experimental part
p. 1745 - 1748
(2012/03/27)
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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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