- Heteromacrocycles from Ring-Closing Metathesis of Unsaturated Furanic Ethers
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New 2,5-bix(unsaturated alkyloxymethyl)-furan led to macrocyclic furanic derivatives in the presence of Grubb's catalyst via dimerization or direct intramolecular metathesis according to the length of the sidearm.
- Cottier, Louis,Descotes, Gerard,Soro, Yaya
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- Photo-induced reduction of biomass-derived 5-hydroxymethylfurfural using graphitic carbon nitride supported metal catalysts
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Photo-catalytic reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF) under visible light irradiation is achieved by using a platinum catalyst supported on graphitic carbon nitride (Pt/g-C3N4). Pt/g-C3N4 acts as a multifunctional and tandem catalyst to successively promote the photo-induced water splitting to form hydrogen and the successive activation of the produced hydrogen for HMF reduction, yielding DHMF yield of 6.5% with TOF of 0.457 h-1. This research provides a sustainable and green pathway for biomass conversion using solar radiation as a driving force.
- Guo, Yuanyuan,Chen, Jinzhu
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p. 101968 - 101973
(2016)
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- Hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over supported Pt-Co bimetallic catalysts under mild conditions
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Highly dispersed Pt-Co bimetallic catalysts were deposited on multi-walled carbon nanotubes (MWCNTs) by atomic layer deposition. High-resolution TEM and TPR analyses verified the formation of Pt-Co bimetallic particles. Catalysts were applied for the hydrogenolysis of 5-hydroxymethyfurfural (HMF) to 2,5-dimethyfuran (DMF). A high yield of DMF (>90%) was achieved in the hydrogenolysis of HMF over the optimized Pt-Co/MWCNTs catalyst after 8 h of reaction time under 10 bar H2 at 160 °C. Through a series of experiments and comparison, the synergistic effect among Pt, Co, and MWCNTs was investigated. The results revealed that the synergistic effect between Pt-Co and MWCNTs played an important role in the improvement of selectivity to DMF for Pt-Co/MWCNTs bimetallic catalysts. In addition, steric hindrance appeared when Co loading in Pt-Co/MWCNTs was high and it affected the activity of the Pt-Co bimetallic catalysts. However, moderate activity can inhibit the production of byproducts and thereby improve the yield of DMF.
- Wang, Xiaofeng,Liu, Yuzi,Liang, Xinhua
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- Efficient route for the construction of polycyclic systems from bioderived HMF
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The first synthesis of tricyclic compounds from biobased 5-hydroxymethylfurfural (HMF) is described. The Diels-Alder reaction was used to implement the transition from HMF to a non-planar framework, which possessed structural cores of naturally occurring biologically active compounds and building blocks of advanced materials. A one-pot, three-step sustainable synthesis in water was developed starting directly from HMF. The reduction of HMF led to 2,5-bis(hydroxymethyl)furan (BHMF), which could be readily involved in the Diels-Alder cycloaddition reaction with HMF-derived maleimide, followed by hydrogenation of the double bond. The described transformation was diastereoselective and proceeded with a good overall yield. The applicability of the chosen approach for the synthesis of analogous structures containing amine functionality on the side chain was demonstrated. To produce the target compounds, only platform chemicals were used with carbohydrate biomass as the single carbon source.
- Kucherov,Galkin,Gordeev,Ananikov
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- Bio-based furan polymers with self-healing ability
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We report the preparation of a furan polymer, poly(2,5-furandimethylene succinate) by means of a condensation reaction between bio-based monomers. A reversible Diels-Alder reaction between furan and maleimide groups allowed the formation of network polymers cross-linked by a bismaleimide. By controlling the amount of the bismaleimide, mechanical properties were varied widely. These network polymers healed well when their broken surfaces were activated by bismaleimide solutions or solvent. The polymers also displayed excellent self-healing ability without external stimulus. This polymer class offers a wide range of possibilities to produce materials from biomass that have both practical mechanical properties and healing ability. These materials have the potential to bring great benefits to our daily lives by enhancing the safety, performance, and lifetime of products.
- Zeng, Chao,Seino, Hidetake,Ren, Jie,Hatanaka, Kenichi,Yoshie, Naoko
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- Rhodium-Catalyzed Enantioselective Isomerization of meso-Oxabenzonorbornadienes to 1,2-Naphthalene Oxides
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Herein we describe a rhodium-catalyzed enantioselective isomerization of meso-oxabicyclic alkenes to 1,2-naphthalene oxides. These potentially useful building blocks can be accessed in moderate to excellent yields with impressive enantioselectivities. Additionally, experimental findings supported by preliminary computations suggest that ring-opening reactions of bridgehead disubstituted oxabicyclic alkenes proceed through the intermediacy of these epoxides and may point to a kinetically and thermodynamically favored reductive elimination as the origin for the observed enantioselectivities.
- Yen, Andy,Choo, Ken-Loon,Yazdi, Shabnam K.,Franke, Patrick T.,Webster, Robert,Franzoni, Ivan,Loh, Charles C. J.,Poblador-Bahamonde, Amalia I.,Lautens, Mark
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- Direct Conversion of 5-Hydroxymethylfurfural to Furanic Diether by Copper-Loaded Hierarchically Structured ZSM-5 Catalyst in a Fixed-Bed Reactor
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The highly-efficient conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(ethoxymethyl)furan (BEMF) was achieved over the copper-loaded hierarchically structured ZSM-5 (Cu/HSZ) catalysts in the continuous fixed-bed reactor. The main reaction path for BEMF synthesis on the Cu/HSZ catalysts was confirmed as following: HMF was firstly hydrogenated to BHMF intermediates over metal sites and then the formed BHMF was etherified by acid sites. Benefiting from the ammonia evaporation (AE) method promoted the dispersion of copper and reduced the acidity, the Cu/HSZ-AE catalyst exhibited more excellent BEMF yield and stability than the catalyst prepared by conventional incipient-wetness impregnation (Cu/HSZ-IW). Indeed, the inactivation of Cu/HSZ-IW catalyst was mainly attributed to the deactivation of copper by carbon species deposition.
- Hu, Hualei,Xue, Tingting,Zhang, Zhenxin,Gan, Jiang,Chen, Liangqi,Zhang, Jian,Qu, Fengzuo,Cai, Weijie,Wang, Lei
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- Highly selective supported gold catalyst for CO-driven reduction of furfural in aqueous media
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The reductive transformation of furfural (FAL) into furfuryl alcohol (FOL) is an attractive route for the use of renewable bio-sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst (Au/TiO2-R) that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel-derived H2, our process has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.
- Dong, Jing,Zhu, Mingming,Zhang, Gaoshuo,Liu, Yongmei,Cao, Yong,Liu, Su,Wang, Yangdong
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- Selective Conversion of 5-Hydroxymethylfuraldehyde Using Cp?Ir Catalysts in Aqueous Formate Buffer Solution
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The highly selective hydrogenation/hydrolytic ring-opening reaction of 5-hydroxymethylfuraldehyde (5-HMF) was catalyzed by homogeneous Cp?IrIII half-sandwich complexes to produce 1-hydroxy-2,5-hexanedione (HHD). Adjustment of pH was found to regulate the distribution of products and reaction selectivity, and full conversion of 5-HMF to HHD with 99 % selectivity was achieved at pH 2.5. A mechanistic study revealed that the hydrolysis/ring-opening reaction of 2,5-bis-(hydroxymethyl)furan is the important intermediate reaction step. In addition, an isolated yield of 85 % for HHD was obtained in a 10 g-scale experiment, and the reaction with fructose as the starting material also led to a 98 % GC yield (71.9 % to fructose) of HHD owing to the excellent tolerance of the catalyst under acidic conditions. pH dependent: A catalytic system is developed for the selective conversion of 5-hydroxymethylfuraldehyde to 1-hydroxy-2,5-hexanedione in high yield and selectivity. The Cp?IrIII half-sandwich catalysts have an excellent tolerance to acidic aqueous conditions and can transform 5-HMF in the hydrolysis solution of fructose in excellent yield, demonstrating a potential for a large-scale production.
- Wu, Wei-Peng,Xu, Yong-Jian,Zhu, Rui,Cui, Min-Shu,Li, Xing-Long,Deng, Jin,Fu, Yao
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- Efficient and Selective Electrochemical and Photoelectrochemical Reduction of 5-Hydroxymethylfurfural to 2,5-Bis(hydroxymethyl)furan using Water as the Hydrogen Source
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Reductive biomass conversion has been conventionally conducted using H2 gas under high-temperature and -pressure conditions. In this study, efficient electrochemical reduction of 5-hydroxymethylfurfural (HMF), a key intermediate for biomass conversion, to 2,5-bis(hydroxymethyl)furan (BHMF), an important monomer for industrial processes, was demonstrated using Ag catalytic electrodes. This process uses water as the hydrogen source under ambient conditions and eliminates the need to generate and consume H2 for hydrogenation, providing a practical and efficient route for BHMF production. By systematic investigation of HMF reduction on the Ag electrode surface, BHMF production was achieved with the Faradaic efficiency and selectivity nearing 100%, and plausible reduction mechanisms were also elucidated. Furthermore, construction of a photoelectrochemical cell (PEC) composed of an n-type BiVO4 semiconductor anode, which uses photogenerated holes for water oxidation, and a catalytic Ag cathode, which uses photoexcited electrons from BiVO4 for the reduction of HMF to BHMF, was demonstrated to utilize solar energy to significantly decrease the external voltage necessary for HMF reduction. This shows the possibility of coupling electrochemical HMF reduction and solar energy conversion, which can provide more efficient and environmentally benign routes for reductive biomass conversion.
- Roylance, John J.,Kim, Tae Woo,Choi, Kyoung-Shin
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- Dynamic combinatorial libraries of 2,5-diformylfuran-derived macrocycles
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A series of polyazamacrocycles, containing a furan moiety, have been prepared using the all-in-solution approach of dynamic combinatorial chemistry. The methodology involves the use of a range of simple, fully soluble inorganic salts as templates and fast imine-to-amine reduction followed by high-performance liquid chromatography screening for the best reaction conditions. It offers an elegant and labor-efficient alternative to the classical methodology of imine trapping via crystallization of complexes. For all the presented 2,5-diformylfuran-derived libraries, the templates provided control over the libraries behavior, which was reflected in increased isolated yields of the corresponding macrocyclic amines, compared to those of nontemplated libraries. The key parameters for achieving true thermodynamic control over the system, which are macrocyclization kinetics and imine reduction kinetics using NaBH4 accompanied by various protic additives, have been discussed.
- Ziach, Krzysztof,Obrocka-Hrycyna, Aleksandra,Jurczak, Janusz
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- Modulation of Ru and Cu nanoparticle contents over CuAlPO-5 for synergistic enhancement in the selective reduction and oxidation of biomass-derived furan based alcohols and carbonyls
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Furfural (FAL) and 5-hydroxymethylfurfural (HMF) are important and sustainable platform chemicals. They are produced from lignocellulose biomass and attract significant attention as precursors for producing value-added chemicals and fuels. The selective conversion of these chemicals requires precise modulation of reaction parameters, solvent, and catalyst. In this study, FAL is selectively reduced to furfuryl alcohol (FOL), and HMF is selectively oxidized to 2,5-diformylfuran (DFF) over a Cu and Ru decorated copper aluminophosphate (CuAlPO-5) catalyst. A high FAL conversion (99.5%) and FOL selectivity (99.6%) are obtained in water under mild reaction conditions of 353 K and 1 MPa H2pressure. On the other hand, 94.0% HMF conversion and 99.9% DFF selectivity are obtained at 1 atm O2flow at 413 K. Both these processes are efficiently conducted over Cu and Ru nanoparticles supported CuAlPO-5 at optimized Cu and Ru contents and under different reaction conditions. The calculated activation energies for these processes are 21.5 kJ mol?1(for FAL hydrogenation) and 34.5 kJ mol?1(for HMF oxidation). The temperature-programmed reduction/oxidation (TPR/TPO) and adsorption results suggest the synergy between Cu and Ru, resulting in higher catalytic activity. Systematic and precise modulation of active metal contents and minimizing the Ru content in the Cu-Ru bimetallic catalyst system would be desirable from the industrial and academic perspective, especially for achieving oxidation/reduction capabilities in biomass conversion using a single catalyst.
- Bal, Rajaram,Kumar, Abhinav,Srivastava, Rajendra
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- Efficient and selective catalytic hydrogenation of furanic aldehydes using well defined Ru and Ir pincer complexes
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We report the homogeneous catalytic hydrogenation of biomass derived furanic aldehydes to furfuryl alcohols using low loadings of PNP metal complexes under mild conditions. Our strategy represents an efficient and selective approach to the direct hydrogenation of furan derivatives to promising platform chemicals. This journal is
- Koranchalil, Sakhitha,Nielsen, Martin,Padilla, Rosa
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- Identification and characterization of the furfural and 5-(hydroxymethyl)furfural degradation pathways of Cupriavidus basilensis HMF14
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The toxic fermentation inhibitors in lignocellulosic hydrolysates pose significant problems for the production of second-generation biofuels and biochemicals. Among these inhibitors, 5-(hydroxymethyl) furfural (HMF) and furfural are specifically notorious. In this study, we describe the complete molecular identification and characterization of the pathway by which Cupriavidus basilensis HMF14 metabolizes HMF and furfural. The identification of this pathway enabled the construction of an HMF and furfural-metabolizing Pseudomonas putida. The genetic information obtained furthermore enabled us to predict the HMF and furfural degrading capabilities of sequenced bacterial species that had not previously been connected to furanic aldehyde metabolism. These results pave the way for in situ detoxification of lignocellulosic hydrolysates, which is a major step toward improved efficiency of utilization of lignocellulosic feedstock.
- Koopman, Frank,Wierckx, Nick,De Winde, Johannes H.,Ruijssenaars, Harald J.
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- An integrated process for the production of 2,5-dihydroxymethylfuran and its polymer from fructose
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We report for the first time an integrated process for the selective production of 2,5-dihydroxymethylfuran (DHMF) from fructose via a two-step reaction in 1-butanol (BuOH). Fructose was initially dehydrated to 5-hydroxymethylfurfural in >95% yield using Amberlyst-15, and the resulting solution was directly transformed into DHMF in >97% yield by liquid-phase hydrogenation over a Cu(50)-SiO2 nanocomposite. This nanocomposite catalyst was demonstrated to be highly stable, with no Cu leaching or catalyst deactivation observed. The obtained DHMF/BuOH mixture was then transformed successfully into poly(2,5-furandimethylene succinate) by reaction with succinic acid. Thus, from both environmental and industrial perspectives, this protocol is a novel and effective method for producing a biomass-derived polymer from fructose.
- Upare, Pravin P.,Hwang, Young Kyu,Hwang, Dong Won
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- Pt-Carbon interaction-determined reaction pathway and selectivity for hydrogenation of 5-hydroxymethylfurfural over carbon supported Pt catalysts
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In this study, a series of Pt catalysts supported on carbon materials, including multi-walled carbon nanotubes (CNTs), reduced graphene oxide (rGO), graphitic carbon nitride (g-C3N4), and biochar (BC), were prepared by impregnation or atomic layer deposition (ALD) methods. The Pt content was around 2.5 wt% in all the Pt catalysts, and the average Pt particle size was 1.6-1.9 nm for the catalysts prepared by impregnation (IM), which was slightly larger than that for the Pt catalyst (~1.4 nm) synthesized by ALD (Pt/CNTs-ALD). All the catalysts were used in the HMF hydrogenation reaction to investigate the effects of different carbon materials and Pt-carbon interactions on the catalytic performance of catalysts. The main product was DHMF over all the Pt catalysts prepared by impregnation, and Pt/BC-IM showed the highest turnover frequency and the highest selectivity to DHMF (95.3%) with an HMF conversion of 94.6% after 10 h of reaction time, which could be due to the abundant functional groups on the surface of BC. Compared with the Pt/CNTs-IM catalyst, the main product over the Pt/CNTs-ALD catalyst was DMF with a yield of 47% due to the relatively strong Pt-CNT interaction. The interaction between Pt and CNTs is the dominant factor in determining the main product in the selective HMF hydrogenation reaction. After introducing Ni nanoparticles to Pt/CNTs-ALD, the yield of DMF reached 93.4% over the PtNi/CNTs-ALD bimetallic catalyst owing to the synergistic effect between Pt and Ni.
- Wang, Xiaofeng,Zhang, Chengcheng,Jin, Baitang,Liang, Xinhua,Wang, Qingfa,Zhao, Zhe,Li, Qingbo
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- Air-Stable and Reusable Cobalt Phosphide Nanoalloy Catalyst for Selective Hydrogenation of Furfural Derivatives
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While metal phosphides have begun to attract attention as electrocatalysts, they remain underutilized in the field of liquid-phase molecular transformations. Herein, we describe a supported cobalt phosphide nanoalloy (nano-Co2P) that functions as a highly efficient, reusable heterogeneous catalyst for the selective hydrogenation of furfural derivatives. The carbonyl moieties of several furfural derivatives were selectively hydrogenated to produce the desired products in high yields. In contrast to conventional nonprecious metal catalysts, nano-Co2P uniquely exhibited air stability, which enabled easy and safe handling and precluded the need for H2 pretreatment. Infrared and density functional theory studies revealed that the highly efficient hydrogenation is due to the favorable activation of the carbonyl moiety of furfural derivatives through the backdonation to its π? orbital from the Co d-electrons.
- Ishikawa, Hiroya,Sheng, Min,Nakata, Ayako,Nakajima, Kiyotaka,Yamazoe, Seiji,Yamasaki, Jun,Yamaguchi, Sho,Mizugaki, Tomoo,Mitsudome, Takato
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- Green synthesis of heterogeneous copper-alumina catalyst for selective hydrogenation of pure and biomass-derived 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan
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In this work novel copper-alumina catalysts were prepared through a solvent-free solid-state grinding method ― a low cost and green catalyst preparation method for selective hydrogenation of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(hydroxymethyl)furan (BHMF). Under the optimized reaction conditions (3 MPa H2, 130 °C, 1 h), >99 % 5-HMF conversion and 93 % BHMF yield were obtained by using a 20CA (20 mol%Cu-Al2O3) catalyst. The catalyst characterization results could reveal that the high catalytic activity and selectivity could be attributed to the presence of both metallic and electrophilic copper (Cu°/Cu2+) species and the uniformly distributed copper nanoparticles. Furthermore, an integrated catalytic process was demonstrated for the first time for direct conversion of mono, di, and polysaccharides into the corresponding BHMF, obtained overall BHMF yield in the range of 25 %–48 %.
- Hu, Yulin,Rao, Kasanneni Tirumala Venkateswara,Xu, Chunbao Charles,Yuan, Zhongsun,Zhang, Yongsheng
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- Efficient Cu catalyst for 5-hydroxymethylfurfural hydrogenolysis by forming Cu-O-Si bonds
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Selective hydrogenolysis of C-O bonds of biomass derived precursors has been identified as a promising and essential way to produce fuel additives. Supported transition metals were explored to give efficient reactivity commonly based on a bifunctionality strategy. Here, we report that covalent bonding between SiO2 and Cu features a homologous bifunctional catalyst with metallic Cu and Lewis acidic Cu cations. The catalyst gave superior reactivity for the conversion of 5-hydroxymethylfurfural into 2,5-dimethylfuran. Lewis acidic cations had more predominant roles than metallic sites for C-O hydrogenolysis by stretching and dissociating C-O bonds, whereas they remained inactive for CC bonds. The results rationalize the valence-state-sensitive catalysis for chemistry involving C-O cleavage. The covalent metal-O-Si bonding provides an alternative for developing efficient catalysts since silicates with such a feature are versatile in nature.
- Fang, Zhen,Kong, Xiao,Li, Luping,Peng, Bo,Zhu, Yifeng,Zhu, Yulei
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- Flow hydrogenation of 5-acetoxymethylfurfural over Cu-based catalysts
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5-Acetoxymethylfurfural (AMF) is a promising starting material for synthesis of the valuable furan derivatives. The catalytic properties of Cu-based catalysts obtained from layered double hydroxides were studied in flow hydrogenation of AMF to 5-(acetoxymethyl)-2-furanmethanol (AMFM) in the present work. The resulting product can be easily converted to 2,5-bis(hydroxymethyl)furan which has significant potential in the production of polymers and pharmaceuticals. It was found that hydrogenation of AMF gives AMFM with selectivity of 98 percent at the full conversion of the substrate under mild reaction conditions (90°C and 10 bar). The influence of the solvent nature, Cu/Al ratio and calcination temperature on the catalyst performance was investigated.
- Bukhtiyarova, Galina A.,Bukhtiyarova, Marina V.,Bulavchenko, Olga A.,Nuzhdin, Alexey L.
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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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- Tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural over a Ni3Fe intermetallic supported Pt single-atom site catalyst
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Single-atom site catalysts (SACs) have been used in multitudinous reactions delivering ultrahigh atom utilization and enhanced performance, but it is challenging for one single atom site to catalyze an intricate tandem reaction needing different reactive sites. Herein, we report a robust SAC with dual reactive sites of isolated Pt single atoms and the Ni3Fe intermetallic support (Pt1/Ni3Fe IMC) for tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural (5-HMF). It delivers a high catalytic performance with 99.0% 5-HMF conversion in 30 min and a 2, 5-dimethylfuran (DMF) yield of 98.1% in 90 min at a low reaction temperature of 160 °C, as well as good recyclability. These results place Pt1/Ni3Fe IMC among the most active catalysts for the 5-HMF hydrodeoxygenation reaction reported to date. Rational control experiments and first-principles calculations confirm that Pt1/Ni3Fe IMC can readily facilitate the hydrodeoxygenation reaction by a tandem mechanism, where the single Pt site accounts for C-O group hydrogenation and the Ni3Fe interface promotes the C-OH bond cleavage. This interfacial tandem catalysis over the Pt single-atom site and Ni3Fe IMC support may develop new opportunities for the rational structural design of SACs applied in other heterogeneous tandem reactions.
- Meng, Ge,Ji, Kaiyue,Zhang, Wei,Kang, Yiran,Wang, Yu,Zhang, Ping,Wang, Yang-Gang,Li, Jun,Cui, Tingting,Sun, Xiaohui,Tan, Tianwei,Wang, Dingsheng,Li, Yadong
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- Superior catalytic performance of Ce1-xBixO2-δ solid solution and Au/Ce1-xBixO2-δ for 5-hydroxymethylfurfural conversion in alkaline aqueous solution
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Porous Bi-doped ceria (Ce1-xBixO2-δ solid solution) was prepared by the easy citrate method and then used as a supporting material for Au nanoparticles (NPs) obtained by deposition-precipitation. In the presence of O2, Ce1-xBixO2-δ (0.08 ≤ x ≤ 0.5) efficiently catalyzed the conversion of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HFCA) and 2,5-bishydroxymethylfuran (BHMF) in alkaline aqueous solution without degradation of HMF. The excellent catalytic activity was attributed to the oxygen activation and hydride transfer enhanced by Bi doping and the large amount of oxygen vacancies. After Au NPs were supported on Ce1-xBixO2-δ (x ≤ 0.2), the presence of Auδ+ facilitated the activation of the C-H bond in the hydroxymethyl group and then the production of 2,5-furandicarboxylic acid (FDCA) as an end product, inhibiting the generation of BHMF.
- Miao, Zhenzhen,Zhang, Yibo,Pan, Xiqiang,Wu, Tianxiao,Zhang, Bin,Li, Jingwei,Yi, Ting,Zhang, Zhendong,Yang, Xiangguang
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- Electrocatalytic hydrogenation of 5-hydroxymethylfurfural in the absence and presence of glucose
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Electrocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) or other species, such as 2,5-dimethylfuran, on solid metal electrodes in neutral media is addressed, both in the absence and in the presence of glucose. The reaction is studied by combining voltammetry with on-line product analysis by using HPLC, which provides both qualitative and quantitative information about the reaction products as a function of electrode potential. Three groups of catalysts show different selectivity towards: (1) DHMF (Fe, Ni, Ag, Zn, Cd, and In), (2) DHMF and other products (Pd, Al, Bi, and Pb), depending on the applied potential, and (3) other products (Co, Au, Cu, Sn, and Sb) through HMF hydrogenolysis. The rate of electrocatalytic HMF hydrogenation is not strongly catalyst-dependent because all catalysts show similar onset potentials (-0.5±0.2 V) in the presence of HMF. However, the intrinsic properties of the catalysts determine the reaction pathway towards DHMF or other products. Ag showed the highest activity towards DHMF formation (up to 13.1 mM cm-2 with high selectivity> 85 %). HMF hydrogenation is faster than glucose hydrogenation on all metals. For transition metals, the presence of glucose enhances the formation of DHMF and suppresses the hydrogenolysis of HMF. On poor metals such as Zn, Cd, and In, glucose enhances DHMF formation; however, its contribution in the presence of Bi, Pb, Sn, and Sb is limited. Remarkably, in the presence of HMF, glucose hydrogenation itself is largely suppressed or even absent. The first electron-transfer step during HMF reduction is not metal-dependent, suggesting a non-catalytic reaction with proton transfer directly from water in the electrolyte. A clean sweep: The hydrogenation of HMF in neutral media has been studied on a wide range of solid metal electrodes both in the absence and in the presence of glucose. From HMF hydrogenation, three groups of catalysts show affinities towards (1) DHMF, (2) DHMF and other products, depending on applied potentials, and (3) other products. HMF hydrogenation is shown to be preferred to glucose hydrogenation on all metals. Copyright
- Kwon, Youngkook,De Jong, Ed,Raoufmoghaddam, Saeed,Koper, Marc T. M.
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- Novel catalysts for valorization of biomass to value-added chemicals and fuels
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Key furan compounds such as 5-hydroxymethylfurfural (HMF), 2,5-furandicarboxylic acid (FDCA) and 2,5-dimethylfuran (DMF) were synthesized from renewable feedstocks. Dehydration of fructose was carried out in biphasic conditions employing several solid acid catalysts by targeting selective formation of HMF. Its selectivity is linearly dependent on total acidity clearly revealing that lower acidity favours selective formation of HMF. Oxidation and hydrogenolysis of HMF has been explored using 2 wt% Ru-K-OMS-2. The catalysts used for each transformation were subjected to detailed characterization using XRD, BET surface area, temperature-programmed desorption and transmission electron microscopy. The effect of various reaction parameters was also investigated for obtaining high yields of desired chemical intermediates. High FDCA yields of 93.4 mol% and 66 mol% were achieved in alkaline and base-free conditions, respectively. The 2 wt% Ru-K-OMS-2 is a versatile catalyst as it also catalyses HMF hydrogenolysis giving 33 mol% of DMF. Thus, utility of various novel materials as catalysts has been demonstrated in the multistep transformations of hexoses to furan-based fuels and chemicals.
- Lucas, Nishita,Kanna, Narasimha Rao,Nagpure, Atul S.,Kokate, Ganesh,Chilukuri, Satyanarayana
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- A continuous flow strategy for the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural using lewis acid zeolites
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Hf-, Zr- and Sn-Beta zeolites effectively catalyze the coupled transfer hydrogenation and etherification of 5-(hydroxymethyl)furfural with primary and secondary alcohols into 2,5-bis(alkoxymethyl)furans, thus making it possible to generate renewable fuel
- Lewis, Jennifer D.,Van De Vyver, Stijn,Crisci, Anthony J.,Gunther, William R.,Michaelis, Vladimir K.,Griffin, Robert G.,Roman-Leshkov, Yuriy
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- Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol with Recyclable Al–Zr@Fe Mixed Oxides
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A series of magnetic, acid/base bifunctional Al–Zr@Fe3O4 catalysts were successfully prepared by a facile coprecipitation method and utilized in the catalytic transfer hydrogenation (CTH) of furfural to furfuryl alcohol with 2-propanol as hydrogen source. The physicochemical properties and morphologies of the as-prepared catalysts were characterized by various techniques, including XRD analysis, N2 physisorption, vibrating sample magnetometry, thermal gravimetry analysis, X-ray fluorescence spectroscopy, NH3/CO2 temperature-programmed desorption, SEM, and TEM. The Al7Zr3@Fe3O4(1/1) catalyst with a Al3+/Zr4+/Fe3O4 molar ratio of 21:9:3 was found to exhibit a high furfuryl alcohol yield of 90.5 % in the CTH from furfural at 180 °C after 4 h with a comparatively low activation energy of 45.3 kJ mol?1, as calculated from the Arrhenius equation. Moreover, leaching and recyclability tests confirmed Al7Zr3@Fe3O4(1/1) to function as a heterogeneous catalyst that could be reused for at least five consecutive reaction runs without significant loss of catalytic activity after simple recovery by an external magnet. Notably, the catalyst proved also efficient for hydrogenation of other biomass-derived furanic aldehydes.
- He, Jian,Li, Hu,Riisager, Anders,Yang, Song
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- Substrate and product role in the Shvo's catalyzed selective hydrogenation of the platform bio-based chemical 5-hydroxymethylfurfural
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The bio-based substrate and target product 2,5-bishydroxymethylfuran (BHMF) demonstrated to influence the reaction kinetics in the homogeneous reduction of 5-hydroxymethylfurfural (HMF) catalyzed by the Ru-based Shvo's catalyst. A combined experimental an
- Pasini, Thomas,Solinas, Gavino,Zanotti, Valerio,Albonetti, Stefania,Cavani, Fabrizio,Vaccari, Angelo,Mazzanti, Andrea,Ranieri, Silvia,Mazzoni, Rita
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- A non-noble bimetallic alloy in the highly selective electrochemical synthesis of the biofuel 2,5-dimethylfuran from 5-hydroxymethylfurfural
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The conversion of HMF to DMF has received great attention due to its potential as a gasoline alternative. Electrosynthesis is a powerful green tool due to its significant advantages and provides an efficient and environmentally friendly route. In this work, the process uses water as the hydrogen source in the electro-catalytic reduction of 5-hydromethylfurfural (HMF) for the synthesis of 2,5-dimethyl-furan (DMF). The performance of a non-noble CuNi bimetallic electrode was investigated in the electro-catalytic hydrogenation of HMF. The electrodes prepared were characterized using XRD, SEM, XPS, and BET techniques. 88.0% faradaic efficiency of DMF and 91.1% conversion selectivity of DMF were achieved. The CuNi bimetallic electrode also displayed a good stability during the reduction of HMF to DMF.
- Zhang, Yan-Ru,Wang, Bing-Xin,Qin, Lei,Li, Qiang,Fan, Yong-Ming
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- Selective hydrogenation of 2-hydroxymethyl-5-furfural to 2,5-bis(hydroxymethyl)furan over gold sub-nano clusters
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We report a gold sub-nano cluster supported on Al2O3 catalyzed hydrogenation of 2-hydroxymethyl-5-furfural without furan ring hydrogenation and its opening reaction, which resulted in excellent conversion to 2,5-bis(hydroxymethyl)furan (>96% yield), Fig. 1(a). The Royal Society of Chemistry 2013.
- Ohyama, Junya,Esaki, Akihiko,Yamamoto, Yuta,Arai, Shigeo,Satsuma, Atsushi
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- Influence of supports for selective production of 2,5-dimethylfuran via bimetallic copper-cobalt catalyzed 5-hydroxymethylfurfural hydrogenolysis
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The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass-derived furanic compounds to transportation fuels. One of these model reactions, namely conversion of 5-hydroxymethylfurfural (HMF) to the gasoline additive 2,5-dimethylfuran (DMF), is especially attractive. In this study, bimetallic Cu-Co catalysts supported on CeO2, ZrO2, and Al2O3 were used for the selective hydrogenolysis of HMF to DMF. The structures of the fresh and used catalysts were studied using X-ray diffraction, the Brunauer-Emmett-Teller method, transmission electron microscopy, temperature-programmed reduction by H2, temperature-programmed desorption of NH3, and CHNS analysis. The structures were correlated with the catalytic activities. The Cu-Co/CeO2 catalyst produced mainly 2,5-bis(hydroxymethyl)furan via reduction of C=O bonds on large Cu particles. The Cu-Co/Al2O3 catalyst gave the best selectivity for DMF, as a result of a combination of highly dispersed Cu, mixed copper–cobalt oxides, and suitable weak acidic sites. Cu-Co/ZrO2 had low selectivity for DMF and produced a combination of various over-hydrogenolysis products, including 2,5-dimethyltetrahydrofuran and 5,5-oxybis(methylene)-bis(2-methylfuran), because of the presence of strong acidic sites. The reaction pathways and effects of various operating parameters, namely temperature, H2 pressure, and time, were studied to enable optimization of the selective conversion of HMF to DMF over the Cu-Co/Al2O3 catalyst.
- Srivastava, Sanjay,Jadeja,Parikh, Jigisha
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- An integrated process for the production of 2,5-dimethylfuran from fructose
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2,5-Dimethylfuran was successfully produced in 92% overall yield from fructose in 1-butanol through a combination of dehydration over Amberlyst-15 and hydrogenolysis over the Ru-Sn/ZnO catalyst. The environmental favorability of this process, and its unprecedented efficiency, makes it promising from both a green chemistry and an industrial perspective.
- Upare, Pravin P.,Hwang, Dong Won,Hwang, Young Kyu,Lee, U-Hwang,Hong, Do-Young,Chang, Jong-San
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- Synergism studies on alumina-supported copper-nickel catalysts towards furfural and 5-hydroxymethylfurfural hydrogenation
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The structure of alumina-supported copper-nickel catalysts prepared by impregnation method was studied by using a combination of various characterization techniques including XRD, N2-sorption, TEM, H2-TPR, NH3-TPD, XANES/EXAFS and CHNS methods. A series of characterizations revealed that dispersion of copper increases with an increase in nickel loading on ?-Al2O3 due to strong interaction between nickel and copper oxide particles. This also led to the formation of mixed copper-nickel oxides in calcined catalysts at the highest loading of nickel and copper (i.e. Cu/Ni = 1). In catalytic activity, both the monometallic Cu/?-Al2O3 and Ni/?-Al2O3 showed lower activity and selectivity towards hydrogenation of both Furfural and 5-Hydroxymethylfurfural to 2-methylfuran (2-MF) and 2, 5-dimethylfuran (DMF), respectively. However, with increase in nickel loading, the activity and the selectivity of Cu/?-Al2O3 drastically increased for both the cases and Cu-Ni/?-Al2O3 (Cu/Ni = 1) showed the highest catalytic activity. Furthermore, combination of Cu/Ni ratios and temperature plays a significant role in the product distribution, as in the case of furfural hydrogenation, at a lower temperature, furfuryl alcohol (FOL) appears as the main product while at a higher temperature, 2-methylfuran (2-MF) is found to be the dominant product over Cu-Ni/?-Al2O3 (Cu/Ni = 1) catalysts. Similarly, 2,5-bishydroxymethylfuran (BHF) is found to be the major product at a lower temperature and 2,5-dimethylfuran (DMF) is selectively produced at a higher temperature in the HMF hydrogenation. Furthermore, reaction pathways are discussed for both the reactions.
- Srivastava, Sanjay,Jadeja,Parikh, Jigisha
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- Gas phase hydrogenation of furaldehydes via coupling with alcohol dehydrogenation over ceria supported Au-Cu
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We have investigated the synthesis and application of Au-Cu/CeO2 (Cu: Au = 2) in the continuous gas phase (P = 1 atm; T = 498 K) coupled hydrogenation of 5-hydroxymethyl-2-furaldehyde (HMF) with 2-butanol dehydrogenation. STEM-EDX analysis revealed a close surface proximity of both metals in Au-Cu/CeO2 post-TPR. XPS measurements suggest (support → metal) charge transfer to form Auδ? and strong metal-support interactions to generate Cu0 and Cu+. Au-Cu/CeO2 promoted the sole formation of 2,5-dihydroxymethylfuran (DHMF) and 2-butanone in the HMF/2-butanol coupling with full hydrogen utilisation. Under the same reaction conditions, Au/CeO2 was fully selective to DHMF in standard HMF hydrogenation (using an external hydrogen supply), but delivered a lower production rate and utilised less than 0.2% of the hydrogen supplied. Exclusive -C=O hydrogenation and -OH dehydrogenation is also demonstrated for the coupling of a series of m-substituted (-CH3, -CH2CH3, -CH2OH, -CF3, -N(CH3)2, -H) furaldehydes with alcohol (1-propanol, 1-butanol, 2-propanol, 2-butanol, cyclohexanol) dehydrogenation over Au-Cu/CeO2, consistent with a nucleophilic mechanism. In each case, we observed a greater hydrogenation rate and hydrogen utilisation efficiency with a 3–15 times lower E-factor in the coupling process relative to standard hydrogenation. Our results demonstrate the feasibility of using hydrogen generated in situ through alcohol dehydrogenation for the selective hydrogenation of m-furaldehydes with important industrial applications.
- Pischetola, Chiara,Collado, Laura,Keane, Mark A.,Cárdenas-Lizana, Fernando
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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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- REDUCTION OF ALDEHYDES OF THE FURAN SERIES BY THE METHOD OF CATALYTIC HYDROGEN TRANSFER
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The intermolecular transfer of hydrogen from donor molecules to aldehydes of the furan series is studied in the presence of homogeneous, complex and heterogeneous (Pd/C) catalysts.A linear correlation is obtained between the reactivity of the furan aldehydes and the nature of the substituent.
- Yuskovets, Zh. G.,Shimanskaya, M. V.
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- Production of dimethylfuran from hydroxymethylfurfural through catalytic transfer hydrogenation with ruthenium supported on carbon
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RuCees' transfer: Transfer hydrogenation using alcohols as hydrogen donors and supported ruthenium catalysts results in the selective conversion of hydroxymethylfurfural to dimethylfuran (>80 % yield). During transfer hydrogenation, the hydrogen produced from alcohols is utilized in the hydrogenation of hydroxymethylfurfural. Copyright
- Jae, Jungho,Zheng, Weiqing,Lobo, Raul F.,Vlachos, Dionisios G.
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- Biocatalytic Reduction of HMF to 2,5-Bis(hydroxymethyl)furan by HMF-Tolerant Whole Cells
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Catalytic upgrading of 5-hydroxymethylfurfural (HMF), an important biobased platform chemical for high-value products, is currently of great interest. In this work, a new highly HMFtolerant yeast strain—Meyerozyma guilliermondii SC1103 was isolated, and biocatalytic reduction of HMF to 2,5-bis(hydroxymethyl)furan (BHMF) using its resting cells was reported. Cosubstrates exerted a significant effect on the catalytic activity and selectivity of microbial cells as well as their HMF-tolerant levels whereas the nitrogen source and mineral salts had no effects. In addition, M. guilliermondii SC1103 cells exhibited good catalytic performances within the range of pH 4.0–10.0. The yeast was highly tolerant to both HMF (up to 110 mm) and BHMF (up to 200 mm). In addition, 100 mm HMF could be selectively reduced to BHMF within 12 h by its resting cells in the presence of 100 mm glucose (as cosubstrate), with a yield of 86 % and selectivity of >99 %. The production of 191 mm of BHMF was realized within 24.5 h by using a fed-batch strategy, with a productivity of approximately 24 g L?1per day. In addition, this new biocatalytic approach was applied for the reduction of furfural and 5-methylfurfural, affording the corresponding furfuryl alcohols with yields of 83 and 89 %, respectively.
- Li, Yan-Mei,Zhang, Xue-Ying,Li, Ning,Xu, Pei,Lou, Wen-Yong,Zong, Min-Hua
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- Catalytic transfer hydrogenation of furfural into furfuryl alcohol over Ni–Fe-layered double hydroxide catalysts
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Layered double hydroxides (LDHs) and their derivatives have been reported to be widely used as heterogeneous catalysts in various reactions. Herein, Ni-Fe LDHs with the controlled Ni/Fe molar ratios (2:1, 3:1, 4:1) were synthesized via an easy hydrothermal method, which were used to catalyze the selective reduction of biomass-derived furfural into furfuryl alcohol using 2-propanol as a H-donor under autogenous pressure and characterized using FT-IR, XRD, TGA, BET, SEM, NH3-TPD, and CO2-TPD. It was found that the LDH with a Ni/Fe molar ratio of 3:1 demonstrated the best catalytic activity among the LDHs with different Ni/Fe molar ratios, which showed 97.0% conversion of furfural and 90.2% yield of furfuryl alcohol at 140°C for 5 hr. This was attributable to the synergistic effect of acidic sites and basic sites of the catalyst.
- Wang, Tao,Hu, Aiyun,Wang, Haijun,Xia, Yongmei
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- On the mechanism of selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over supported Pt and Au catalysts
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The mechanism of selective oxidation of aqueous 5-hydroxymethylfurfural (HMF) at high pH was studied over supported Pt and Au catalysts. Results from labeling experiments conducted with 18O2 and H 218O indicated that water was the source of oxygen atoms during the oxidation of HMF to 2-hydroxymethylfurancarboxylic acid (HFCA) and 2,5-furandicarboxylic acid (FDCA), presumably through direct participation of hydroxide in the catalytic cycle. Molecular oxygen was essential for the production of FDCA and played an indirect role during oxidation by removing electrons deposited into the supported metal particles. A reaction path for HMF oxidation to FDCA was proposed.
- Davis, Sara E.,Zope, Bhushan N.,Davis, Robert J.
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- Going Beyond the Limits of the Biorenewable Platform: Sodium Dithionite-Promoted Stabilization of 5-Hydroxymethylfurfural
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The lack of thermal and storage stability and occurrence of side reactions during the processing of 5-hydroxymethylfurfural (5-HMF) limits its potential as biorenewable platform molecule. The addition of small amounts of the readily available sodium dithionite has a remarkable effect on promoting the stability of 5-HMF and inhibiting side reactions, thus helping to circumvent such limitations. The addition of sodium dithionite led to improvements in thermal stability (120 °C, 4 h, neat; 100 % vs. 37 %), under distillation (yield: 85 % vs. 52 %), and in a wide range of reactions, including 5-HMF synthesis under biphasic conditions (yield: 98 % vs. 67 %; purity: 92 % vs. 83 %) and 5-HMF transformations, such as Knoevenagel condensation with Meldrum's acid (yield: 96 % vs. 74 %), Cannizaro reaction (yield: quantitative vs. 83 %), and condensation with primary diamines to give pyridinium salts (yield: 88 % vs. 60 %).
- Gomes, Rafael F. A.,Mitrev, Yavor N.,Simeonov, Svilen P.,Afonso, Carlos A. M.
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- Catalytic synthesis of 2,5-bis-methoxymethylfuran: A promising cetane number improver for diesel
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Efficient hydrogenation of 5-hydroxymethylfurfural (HMF) into 2,5-bis-hydroxymethylfuran (BHMF) was performed using a Cu/SiO2 catalyst, obtaining as high as 97% BHMF yield. In the presence of acidic ZSM-5 zeolite (HZSM-5), the synthesized BHMF further reacted with methanol, leading to 70% yield of corresponding 2,5-bis-methoxymethylfuran (BMMF). The target product BMMF was an excellent cetane number improver for diesel, proved by its cetane number of 80 (much higher than that of the commercial diesel), high flash point (90 °C) and low cold filter plugging point (-37 °C).
- Cao, Quan,Liang, Wenyuan,Guan, Jing,Wang, Lei,Qu, Qian,Zhang, Xinzhi,Wang, Xicheng,Mu, Xindong
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- Whole-cell biocatalytic selective oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2-furancarboxylic acid
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Currently, the catalytic upgradation of 5-hydroxymethylfurfural (HMF), an important bio-based platform chemical, is of great interest. In this work, we reported the biocatalytic oxidation of HMF to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) by using a newly isolated strain Comamonas testosteroni SC1588. Compared to growing cells, resting cells were found to be a better biocatalyst for the synthesis of HMFCA. This strain exhibited high tolerance to HMF (up to 180 mM). However, its catalytic performances were highly sensitive to pH. The product exerted a significant negative effect on the catalytic performances and viability of the cells, partially due to the acidity of this compound. The product inhibition and toxicity toward this strain were reduced considerably after adjusting the pH of the reaction mixtures to 7.0. Excellent substrate conversions (approximately 100%) and good HMFCA yields (88-99%) were obtained when the substrate concentrations were less than 130 mM. In addition, the HMFCA synthesis could be improved significantly by the combination of histidine addition with pH tuning at higher substrate concentrations. Catalytic activities of the cells increased markedly when they were cultivated in the presence of a low concentration of furfural and furfuryl alcohol. HMFCA was afforded in a yield of approximately 98% after 36 h at a substrate concentration of up to 160 mM. Besides, this strain was capable of selectively transforming other furfurals to the target acids with good yields of 90-93%.
- Zhang, Xue-Ying,Zong, Min-Hua,Li, Ning
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- The effect of potassium on Cu/Al2O3 catalysts for the hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan in a fixed-bed reactor
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The highly efficient selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) was achieved in a fixed-bed reactor by using inexpensive potassium-doped Cu/Al2O3 catalysts, which were prepared via a successive incipient wetness impregnation method. The characterization results revealed that the introduction of potassium could adjust the size of the copper particles and modify the acid-base property of the catalyst, leading to a significant change in its performance for the selective hydrogenation of HMF to BHMF. The highest yield of BHMF (98.9%) was obtained over the 1.5K-Cu/Al2O3 catalyst under the reaction conditions of 120 °C, 2.0 MPa of H2, and a weight hourly space velocity (WHSV) of 1.0 h-1. The excellent performance could be explained by the fact that the addition of an appropriate amount of potassium facilitated the dispersion of copper and reduced the acidity of the catalyst, which improved the catalytic activity and suppressed unwanted side reactions, respectively.
- Hu, Danxin,Hu, Hualei,Zhou, Hao,Li, Guozheng,Chen, Chunlin,Zhang, Jian,Yang, Yong,Hu, Yaoping,Zhang, Yajie,Wang, Lei
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- Reductive Amination, Hydrogenation and Hydrodeoxygenation of 5-Hydroxymethylfurfural using Silica-supported Cobalt- Nanoparticles
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Efficient and selective conversion of renewable feedstocks to essential chemicals and fuels applying green and sustainable catalytic processes is of central importance and attracts scientific interest. Among different biomass-based feedstocks, 5-hydroxymethylfurfural (HMF) represents valuable platform compound widely used for the synthesis of valuable chemicals, fuels, and polymers. Here we report cobalt nanoparticles catalyzed reductive amination, hydrogenation and hydrodeoxygenation of HMF to produce furan based primary, secondary and tertiary amines including N-methylamines as well as 2,5-bis(hydroxymethyl)furan, (5-methylfuran-2-yl)methanol and selected N-, O-, and S-containing heterocycles. Key to success for this HMF valorization is the use of reusable silica supported cobalt-based nanoparticles, which have been prepared by the immobilization and pyrolysis of Co-terephthalic acid-piperazine MOF template on silica.
- Chandrashekhar, Vishwas G.,Natte, Kishore,Alenad, Asma M.,Alshammari, Ahmad S.,Kreyenschulte, Carsten,Jagadeesh, Rajenahally V.
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- MODIFIED ORGANOMETALLIC FRAMEWORK AND CATALYST FOR HYDROGENATION REACTION INCLUDING SAME
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The present disclosure relates to an organometallic framework modified using a compound having a hydroxyl group (—OH), a catalyst for a hydrogenation reaction including the same, and a method of manufacturing the same. The catalyst according to the present disclosure has high activity to the hydrogenation reaction even at a low temperature of 30 to 40° C., thus making low-grade waste heat usable.
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Paragraph 0202; 0208
(2022/03/14)
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- SUPPORTED COPPER CATALYST AND SELECTIVE HYDROGENATION OF FURAN-BASED COMPOUNDS USING THE SAME
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Disclosed are a catalyst including copper (Cu) particles having specific properties as an active metal dispersed and supported on an alumina support, a method of preparing the same, and a method of hydrogenating furan-based compounds such as 5-(hydroxymethyl)furfural (HMF) derived from biomass with a high selective conversion and high efficiency using the catalyst.
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Paragraph 0131; 0137; 0140; 0143; 0146
(2021/05/21)
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- Electrochemical and photoelectrochemical reduction of furfurals
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Electrochemical cells and photoelectrochemical cells for the reduction of furfurals are provided. Also provided are methods of using the cells to carry out the reduction reactions. Using the cells and methods, furfurals can be converted into furan alcohols or linear ketones.
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Page/Page column 6-14
(2021/05/19)
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- Method for preparing 2, 5-furandimethanol through transfer hydrogenation
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The invention discloses a method for preparing 2, 5-furandimethanol through transfer hydrogenation. The method comprises the following steps: adding a hydroxymethyl functionalized carbon-based compound, a nickel monatomic catalyst and ethanol into a stainless steel closed reactor, replacing air with nitrogen, and catalyzing 5-hydroxymethyl furfural to prepare 2, 5-furandimethanol, wherein the conditions for catalyzing the hydroxymethyl functionalized carbon-based compound are as follows: the reaction temperature is 130-190 DEG C, the stirring rotating speed is 400-800 rpm, and the reaction time is 1-10 hours, and the ratio of the 5-hydroxymethylfurfural to the nickel monatomic catalyst to the ethanol is 0.26 g:(0.03-0.3 g):(5-30 mL). According to the invention, a monatomic catalyst successfully catalyzes a carbon-based compound into alcohol in an ethanol system for the first time, and the used catalyst is simple in preparation method, cheap in raw material and easy to industrialize; and renewable and non-toxic ethanol is adopted as a hydrogen source to perform a reduction reaction, so that the reaction process is safe, green and environmentally-friendly, the product selectivity is high, the reaction activity conversion frequency (TOF) exceeds that of all non-noble metal catalysts reported at present, and the method has great industrial application value.
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Paragraph 0023-0036
(2021/06/22)
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- BIOMASS DERIVED DIKETONES AS EFFICIENT VISIBLE LIGHT PHOTOINITIATORS
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Isatin derivatives, and methods of using isatin and isatin derivatives as photoinitiators, are described.
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Paragraph 00192; 00214-00217
(2021/11/26)
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- Direct Reductive Amination of Biobased Furans to N-Substituted Furfurylamines by Engineered Reductive Aminase
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Furfurylamines are important building blocks for the synthesis of many pharmacologically active compounds and polymers. In this work, direct reductive amination of biobased furans to N-substituted furfurylamines by reductive aminase from Aspergillus oryzae (AspRedAm) was reported. Besides the reductive aminase activity, AspRedAm also showed a promiscuous, yet low alcohol dehydrogenase activity. The variant W210F proved to be a good catalyst for the synthesis of N-substituted furfurylamines. Furans were transformed to the target products with the conversions up to >99% and selectivities up to >99%. In addition, N-substituted furfurylamines were synthesized in the total turnover number (TTN) up to 3200 on a preparative scale, indicating the applicability of this biocatalytic route in synthetic chemistry. (Figure presented.).
- Chen, Qi,Hao, Ya-Cheng,Hu, Song-Qing,Li, Ning,Yang, Zi-Yue,Zong, Min-Hua
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supporting information
p. 1033 - 1037
(2021/01/18)
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- 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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- Electroreductive 5-Hydroxymethylfurfural Dimerization on Carbon Electrodes
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The electrochemical conversion of biomass-based compounds to fuels and fuel precursors can aid the defossilization of the transportation sector. Herein, the electrohydrodimerization of 5-hydroxymethylfurfural (HMF) to the fuel precursor 5,5’-bis(hydroxymethyl)hydrofuroin (BHH) was investigated on different carbon electrodes. Compared to boron-doped diamond (BDD) electrodes, on glassy carbon (GC) electrodes a less negative HMF reduction onset potential and a switch in product selectivity from BHH to the electrocatalytic hydrogenation product 2,5-di(hydroxymethyl)furan (DHMF) with increasing overpotential was found. On BDD, the electrohydrodimerization was the dominant process independent of the applied potential. An increase in the initial HMF concentration led to suppression of the competing hydrogen evolution reaction and DHMF formation, resulting in higher BHH faradaic efficiencies. In contrast, BHH selectivity decreased with higher initial HMF concentration, which was attributed to increased electrochemically induced HMF degradation. Finally, it was demonstrated that even a simple graphite foil can function as an active HMF electroreduction catalyst.
- Katsounaros, Ioannis,Kloth, Ricarda,Mayrhofer, Karl J. J.,Vasilyev, Dmitry V.
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p. 5245 - 5253
(2021/10/29)
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- Efficient and chemoselective hydrogenation of aldehydes catalyzed by well-defined PN3-pincer manganese(ii) catalyst precursors: An application in furfural conversion
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Well-defined and air-stable PN3-pincer manganese(ii) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.
- Gholap, Sandeep Suryabhan,Dakhil, Abdullah Al,Chakraborty, Priyanka,Li, Huaifeng,Dutta, Indranil,Das, Pradip K.,Huang, Kuo-Wei
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supporting information
p. 11815 - 11818
(2021/11/30)
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- Ni-Al/CoOx-catalyzed hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran at low temperatures without external hydrogen
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Catalytic hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran has received great interest in recent years. In this work, a ternary Ni-Al/CoOx-1 catalyst was fabricated, which provided 96% yield of DMF from in situ hydrodeoxygenation of HMF under mild reaction conditions. XRD, TEM and TPR revealed that the addition of Al to the Ni-Co bimetallic system could make the structure more stable and improve the dispersion of Ni and Co species. XPS, CO-DRIFTS and EPR verified that an enhanced electron transfer from Co species to Ni occurred on Ni-Al/CoOx-1. Reaction mechanism studies unraveled that the Al addition results in promoting in situ H2 production from 2-propanol and accelerating the aldehyde group hydrogenation to a hydroxymethyl group and the subsequent hydrogenolysis into a methyl group, due to the formation of a charge separated metal-couple-site (Niδ-Coδ+) and stronger Lewis acid sites in Ni-Al/CoOx-1. In addition, this ternary Ni-Al/CoOx-1 catalyst exhibits superior recyclability without significant loss of activity for 7 cycles.
- An, Yadan,Bai, Guoyi,Bian, Gang,Li, Tianming,Niu, Libo,Xia, Zhanghui
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p. 7763 - 7772
(2021/10/12)
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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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- Reductive Amination of 5-Hydroxymethylfurfural by the Hydrogenation of Intermediate Imines in the Presence of a Pt/Al2O3 Catalyst in a Flow Reactor
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Abstract: The catalytic properties of a platinum catalyst supported on γ-alumina in the hydrogenation of imines formed during the condensation of 5-hydroxymethylfurfural (HMF) with primary amines in methanol have been studied. The reaction has been run in a flow reactor at a hydrogen pressure of 5 bar and a temperature of 15–65oC. It has been found that the reductive amination of HMF with n-hexylamine; aniline; ortho-, meta-, and para-toluidines; and aniline derivatives containing F, Cl, Br, and I substituents at the para- or meta-positions leads to the formation of N-substituted 5-hydroxymethyl-2-furfuryl amines with high yields (90–99%). At the same time, the reaction of HMF with aromatic amines exhibiting weak nucleophilic properties (o-chloroaniline, p-aminoacetophenone) provides a target product yield that does not exceed 52%.[Equation not available: see fulltext.]
- Nuzhdin,Simonov,Bukhtiyarov
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p. 507 - 512
(2021/08/23)
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- Direct Visualization of Substitutional Li Doping in Supported Pt Nanoparticles and Their Ultra-selective Catalytic Hydrogenation Performance
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It has only recently been established that doping light elements (lithium, boron, and carbon) into supported transition metals can fill interstitial sites, which can be observed by the expanded unit cell. As an example, interstitial lithium (intLi) can block H filling octahedral interstices of palladium metal lattice, which improves partial hydrogenation of alkynes to alkenes under hydrogen. In contrast, herein, we report intLi is not found in the case of Pt/C. Instead, we observe for the first time a direct ‘substitution’ of Pt with substitutional lithium (subLi) in alternating atomic columns using scanning transmission electron microscopy-annular dark field (STEM-ADF). This ordered substitutional doping results in a contraction of the unit cell as shown by high-quality synchrotron X-ray diffraction (SXRD). The electron donation of d-band of Pt without higher orbital hybridizations by subLi offers an alternative way for ultra-selectivity in catalytic hydrogenation of carbonyl compounds by suppressing the facile CO bond breakage that would form alcohols.
- Chen, Tianyi,Foo, Christopher,Zheng, Jianwei J. W.,Fang, Huihuang,Nellist, Peter,Tsang, Shik Chi Edman
-
supporting information
p. 12041 - 12046
(2021/07/14)
-
- Formic acid enabled selectivity boosting in transfer hydrogenation of 5-hydroxymethylfurfural to 2,5-furandimethanol on highly dispersed Co-Nxsites
-
Catalytic transfer hydrogenation (CTH) reaction is considered as a potential route for upgrading bio-based carbonyl compounds to their corresponding alcohols. Herein, ordered mesoporous N-doped carbon confined Co-Nx(Co-NC) was adopted as a catalyst for converting cellulose-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandimethanol (FDM) using formic acid (FA) as a hydrogen donor. Different catalysts and preparation methods were screened, by varying cobalt phases and template removal procedures. It is found that highly dispersed N-confined Co species (Co-Nx) other than naked Co NPs acted as catalytic species for the CTH of HMF with FA, which gave 86% yield of FDM at 100% HMF conversion. Kinetic experiments revealed that, compared with molecular hydrogen, Co-NC could effectively accelerate HMF hydrogenation and suppress as-formed FDM hydrogenolysis in the presence of FA, which is ascribed to its superior activity toward hydrogen transfer from FA and fast desorption toward FDM. Mechanism studies indicated that C-H dissociation of FA could be the rate-determining step in the CTH reaction, and the hydrogenation of HMF could proceed through an intermolecular hydride transfer route. This work shows that the bifunctional nature of the catalyst is critical in the efficient CTH of biomass-derived carbonyl compounds and provides insights toward the rational design of such catalysts.
- Xu, Ling,Nie, Renfeng,Chen, Xujie,Li, Yanchen,Jiang, Yuxi,Lu, Xiuyang
-
p. 1451 - 1457
(2021/03/14)
-
- Multicatalysis from renewable resources: a direct route to furan-based polyesters
-
Here we present a multicatalytic route to produce 2,5-bis(hydroxymethyl)furan and the corresponding (co)polymers from stable 2,5-furanedicarboxylic acid. This approach combines the use of several commercial catalysts and in particular allows to quantitatively obtain two key furan intermediates, not contaminated by humins.
- Gauvin, Régis M.,Guillaume, Lucie,Marshall, Adam,Ni, Pingping,Niessen, Nicolas,Thomas, Christophe M.
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supporting information
p. 6931 - 6935
(2021/09/28)
-
- Ru/MnCo2O4 as a catalyst for tunable synthesis of 2,5-bis(hydroxymethyl)furan or 2,5-bis(hydroxymethyl)tetrahydrofuran from hydrogenation of 5-hydroxymethylfurfural
-
Manganese and cobalt metals-based mixed oxide (MnCo2O4) spinels supported ruthenium (Ru) nanoparticles, Ru/MnCo2O4, is found to be an active catalyst to execute outstandingly the hydrogenation of 5-hydroxymethylfurfural (HMF) to produce two useful furan diols such as 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) in highly selective fashion without any additive. It could found that Ru/MnCo2O4 was able to catalyze not only the oxidation but also the reduction of HMF due to the redox properties of the MnCo2O4. Moreover, the characterization details responsible for the high activity of this catalyst in the hydrogenation of HMF were investigated by several spectroscopic methods. In order to maximize the products yield and HMF conversion, the effect of reaction variables such as time, temperature, pressure, and various metal oxides supported Ru nanoparticles was also investigated. Furthermore, the reusability tests exhibited that Ru/MnCo2O4 catalyst could be reused at several consecutive cycles, retaining almost its original activity.
- Mishra, Dinesh Kumar,Lee, Hye Jin,Truong, Cong Chien,Kim, Jinsung,Suh, Young-Wong,Baek, Jayeon,Kim, Yong Jin
-
-
- Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol under Mild Conditions over Zr-MOFs: Exploring the Role of Metal Node Coordination and Modification
-
The catalytic transfer hydrogenation (CTH) reaction is considered as a potential route for upgrading bio-based carbonyls to their corresponding alcohols. Herein, a series of Zr-based metal-organic frameworks (Zr-MOFs) containing various types of metal node to ligand coordinations were synthesized and tested for CTH of furfural (FUR) to furfuryl alcohol (FOL). It was found that metal node coordination plays a more important role than porosity in Zr-MOFs. MOF-808 (synthesized using a scaled-up approach to achieve a higher batch yield), with the lowest metal node to ligand coordination (coordination number 6), was found to be the most active catalyst among the various tested Zr-MOFs. Furthermore, M-MOF-808, modified by simple methanol activation (M), outperformed the pristine MOF-808 in CTH of FUR to FOL even at 30 °C in the presence of 2-propanol (IPA) as the hydrogen source. The simple modification of the metal node in the Zr-MOF changed the acid-base properties of the MOF-808 surface through the development of coordinatively unsaturated sites (CUS), hydroxyl and methoxy groups in the framework of the Zr-MOF, which probably help to facilitate the adsorption of FUR and IPA onto the metal node surfaces of the catalyst. To evaluate the versatility of methanol activation in CTH, further substrates, including other types of biomass and representative carbonyl compounds over M-MOF-808, were tested. To demonstrate heterogeneous catalysis, the catalyst was recycled for five consecutive cycles, with little loss after the first cycle, and was fully characterized to observe any changes in its structure. Mechanistic insights were provided by isotopically labeled 2-propanol-d8 experiments, indicating FUR reduction through transfer hydrogenation. Finally, the reaction mechanism for CTH of FUR to FOL was proposed in detail using density functional theory (DFT) calculations over metal node modified model systems of a 6-connected Zr-MOF.
- Cha, Ga-Young,Chang, Jong-San,Hong, Do-Young,Hwang, Young Kyu,Jung, Jaehoon,Kwak, Jaesung,Kwon, Young-Uk,Lee, Minhui,Oh, Kyung-Ryul,Valekar, Anil H.,Yoon, Ji Woong
-
p. 3720 - 3732
(2020/04/15)
-
- Method of preparing 2,5-furandimethanol through solvent-free 5-hydroxymethylfurfural
-
The invention discloses a method of preparing 2,5-furandimethanol through solvent-free 5-hydroxymethylfurfural. According to the method, metal catalysts are adopted, and hydrogen is used as hydrogen donors; and by changing hydrogen-bond acceptors or regulating and controlling the molar ratio of the hydrogen-bond acceptors to 5-hydroxylfurfural (hydrogen-bond donors), the strength of hydrogen-bondinteraction between each hydrogen-bond acceptor and a substrate is changed, the purpose of stabilizing the substrate and a product under a high temperature is achieved, and hydrogenation synthesis ofthe 2,5-furandimethanol through the solvent-free 5-hydroxymethylfurfural is realized.
- -
-
Paragraph 0019-0033
(2020/02/10)
-
- CNN pincer ruthenium complexes for efficient transfer hydrogenation of biomass-derived carbonyl compounds
-
The ligand HCNNOMe (6-(4-methoxyphenyl)-2-aminomethylpyridine) is easily prepared from the commercially available 6-(4-methoxyphenyl)pyridine-2-carbaldehyde by the reaction of hydroxylamine and hydrogenation (H2, 1 atm) with Pd/C. The pincer complexes cis-[RuCl(CNNOMe)(PPh3)2] (1) and [RuCl(CNNOMe)(PP)] (PP = dppb, 2; and dppf, 3) are synthesized from [RuCl2(PPh3)3], HCNNOMe and PP (for 2 and 3) in 2-propanol with NEt3 at reflux and are isolated in 85-93% yield. Carbonylation of 1 (CO, 1 atm) gives [RuCl(CNNOMe)(CO)(PPh3)] (4) (79% yield) which cleanly reacts with Na[BArf4] and PCy3, affording the cationic trans-[Ru(CNNOMe)(CO)(PCy3)(PPh3)][BArf4] (5) (92% yield). These robust pincer complexes display remarkably high catalytic activity in the transfer hydrogenation (TH) of lignocellulosic biomass carbonyl compounds, using 2-propanol at reflux in a basic medium (NaOiPr or K2CO3). Thus, furfural, 5-(hydroxymethyl)furfural and Cyrene are reduced to the corresponding alcohols with 2 and 3, at S/C in the range of 10 000-100 000, within minutes or hours (TOF up to 1 500 000 h-1). The monocarbonyl complex 5 was found to be extremely active in the TH of cinnamaldehyde, vanillin derivatives and ethyl levulinate at S/C in the range of 10 000-50 000. Vanillyl alcohol is also obtained by the TH of vanillin with 5 (S/C = 500) in 2-propanol in the presence of K2CO3.
- Figliolia, Rosario,Cavigli, Paolo,Comuzzi, Clara,Del Zotto, Alessandro,Lovison, Denise,Strazzolini, Paolo,Susmel, Sabina,Zuccaccia, Daniele,Ballico, Maurizio,Baratta, Walter
-
supporting information
p. 453 - 465
(2020/01/21)
-
- Method for preparing 2, 5-furandimethanol from glucose through one-pot method under synergistic catalysis of metal halide and formic acid hydrogen supply
-
The invention discloses a method for preparing 2, 5-furandimethanol from the glucose through a one-pot method under the synergistic catalysis of metal halide and formic acid hydrogen supply. The method comprises the following steps: 1) preparing a mixed solvent from water and 1, 4-dioxane, adding the mixed solvent and glucose into a high-temperature and high-pressure reaction kettle with a stirring function, and then, adding metal halide, formic acid and a non-noble metal loaded aza-carbon catalyst; 2) starting stirring, heating to 120-200 DEG C, and carrying out a one-pot reaction for 30 min-15 h; and 3) after the reaction is finished, cooling to room temperature, filtering, and carrying out azeotropic distillation, crystallization and recrystallization on the filtrate to obtain the 2, 5-furandimethanol product, wherein the filter residues are recycled afterwashing and drying, a 1,4-dioxane-water azeotrope obtained through azeotropic distillation is recycled, and the crystallization mother liquor is recycled after membrane separation and impurity removal. The method has the advantages of simple and green process, cheap initial raw materials, high yield of the product 2,5-furandimethanol, and good industrialization prospect.
- -
-
Paragraph 0033-0164
(2020/12/29)
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- On demand production of ethers or alcohols from furfural and HMF by selecting the composition of a Zr/Si catalyst
-
Zr/Si mixed oxides with different amounts of silica (0-50 wt%) were prepared by a simple sol-gel method. These catalysts were tested in a cascade reaction of furfural and 5-hydroxymethyl furfural (HMF) with 2-butanol to form the corresponding alcohols or ethers through a combination of transfer hydrogenation and etherification processes under mild conditions. The selectivity can be finely tuned by changing the silica content which heavily impacts the acid-base properties. On pure ZrO2, featuring acid-base pairs, only the catalytic transfer hydrogenation occurs leading to alcohol products. In contrast, on ZrSi30 the etherification reaction is strongly favored owing to near one-to-one Lewis and Br?nsted acid sites. Ethers can thus be produced in high yields (≥90%), in particular the highly valuable diether of 5-hydroxymethyl furfural. The catalysts were characterized by N2 and CO2 absorption isotherms, FT-IR of adsorbed pyridine, 2-propanol TPD, and STEM-EDX mapping. For the first time we show that the tuning of acid-base properties by simple silica addition, with the somewhat unexpected rise of Br?nsted acidity, may represent the starting point for the development of cheap but highly active and selective catalysts for furfural and HMF transformation.
- Bossola, Filippo,Dal Santo, Vladimiro,Evangelisti, Claudio,Ravasio, Nicoletta,Scotti, Nicola,Zaccheria, Federica
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p. 7502 - 7511
(2020/12/01)
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- Assembly of Zr-based coordination polymer over USY zeolite as a highly efficient and robust acid catalyst for one-pot transformation of fructose into 2,5-bis(isopropoxymethyl)furan
-
It is highly desirable but challenging to develop a one-pot process for the transformation of fructose into 2,5-bis(isopropoxymethyl)furan (BPMF), a promising biofuel component, because a cascade sequence involving dehydration, reduction, and etherification requires multifunctional acid catalysts. Herein, we propose a facile and firm assembly of Zr/2-methylimidazole (2-MeIM) coordination polymer over USY zeolite (USY?ZrCP) through N-Al bonds formed by the condensation of 2-MeIM and the hydroxyls on USY surface at room temperature. USY?ZrCP possesses an abundance of strong Lewis acid sites with suitable amount of Bronsted acid sites, which are mainly attributed to the highly dispersed Zr(IV) species and the hydroxyls over USY?ZrCP, respectively. Unexpectedly, USY?ZrCP could offer BPMF yield up to 82.6% from fructose in isopropanol by the integration of dehydration, Meerwein–Ponndorf–Verley reduction and etherification in a one-pot strategy. This work proposes a novel approach to prepare highly efficient and robust solid acid catalyst for the catalytic valorization of biomass-derived carbohydrates and their derivatives.
- Lei, Tingzhou,Lin, Lu,Liu, Huai,Liu, Shijie,Liu, Yiqiang,Sun, Yong,Tang, Xing,Wang, Ting,Wei, Junnan,Zeng, Xianhai
-
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- Method for preparing furan-2,5-diyldimethanol from fructose by one-pot method under hydrogen supply of formic acid
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The invention discloses a method for preparing furan-2,5-diyldimethanol from fructose by a one-pot method under hydrogen supply of formic acid. The method comprises the following steps: 1) preparing amixed solvent from water and an organic solvent, adding the mixed solvent and fructose into a high-temperature and high-pressure reaction kettle with a stirring function, and then adding formic acidand a non-noble metal loaded aza-carbon catalyst; (2) starting to stir, replacing with nitrogen, introducing nitrogen of 0.5-1 MPa, heating to 120-200 DEG C, and reacting for 30-15 hours by a one-potmethod; and 3) cooling to room temperature after the reaction is finished, filtering, washing and drying filter residues to be reused as a catalyst; and rectifying a filtrate, crystallizing and recrystallizing to obtain a furan-2,5-diyldimethanol product. The method has the advantages of simple and green process, high target product yield, low cost and wide industrial prospect.
- -
-
Paragraph 0033-0146
(2020/06/02)
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- Conversion of Furfural Derivatives to 1,4-Pentanediol and Cyclopentanol in Aqueous Medium Catalyzed by trans-[(2,9-Dipyridyl-1,10-phenanthroline)(CH3CN)2Ru](OTf)2
-
The complex trans-[(2,9-dipyridyl-1,10-phenanthroline)(CH3CN)2Ru](OTf)2 was synthesized and tested as a homogeneous hydrodeoxygenation catalyst for the conversion of biomass-derived furfuryl alcohol and furfuryl acetate to 1,4-pentanediol (as the primary target compound) and cyclopentanol (formed by the competing Piancatelli rearrangement) in aqueous reaction medium at elevated temperature (150-200 °C) and hydrogen pressure (800 psi = 5.12 MPa). Catalytic reactions using furfuryl alcohol as a substrate were limited by the formation of solid resins with the product yields showing a strong negative correlation with increasing substrate concentration and maximum yields of 1,4-pentanediol and cyclopentanol being 23 and 41%, respectively. A two-level full factorial design of experiments study with four independent input variables (temp., time, [cat.], [substrate]) and a center point was carried out for the conversion of furfuryl acetate, showing good reproducibility between replicates and no humin formation. This enabled a full statistical analysis of the input variable impact on product distribution and yield. The maximum yields of 1,4-pentanediol and cyclopentanol using furfuryl acetate as a substrate are 68 and 35%, respectively. The decreased self-reactivity of furfuryl acetate versus furfuryl alcohol dramatically increases the yields of target products but still shows a strong negative correlation of the yield of the desired products with increasing substrate concentration.
- Banz Chung, Elise M.-J.,Da Cunha, Igor Tadeu,Magee, Megan,Moore, Cameron M.,Schlaf, Marcel,Soltanipanah, Parnian,Stones, Maryanne K.,Sullivan, Ryan J.,Sutton, Andrew D.,Umphrey, Gary J.
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p. 2667 - 2683
(2020/03/11)
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- Selective hydrogenation of 5-hydroxymethylfurfural and its acetal with 1,3-propanediol to 2,5-bis(hydroxymethyl)furan using supported rhenium-promoted nickel catalysts in water
-
The high reactivity of the formyl group of 5-hydroxymethylfurfural (5-HMF) is problematic, because it leads to undesired oligomerization reactions. This is usually countered by working in dilute non-aqueous solutions. Here, we present a novel approach to convert concentrated aqueous solutions of 5-HMF to 2,5-bishydroxymethylfuran (BHMF), which is a prospective monomer for polyesters and self-healing polymers. Our approach is based on the protection of the formyl group of 5-HMF using acetalization with 1,3-propanediol. Hydrogenation is carried out using an optimized bimetallic Ni-Re catalyst supported on TiO2 at a carefully controlled pH, resulting in balanced rates of deprotection and hydrogenation and high BHMF yield. Under optimized conditions at a benign temperature of 40 °C, hydrogenation of concentrated solutions (10-20 wt%) of protected 5-HMF in water gave 81-89% yields of BHMF without having to resort to platinum-group metals such as palladium or platinum.
- Wiesfeld, Jan J.,Kim, Minjune,Nakajima, Kiyotaka,Hensen, Emiel J. M.
-
supporting information
p. 1229 - 1238
(2020/03/11)
-
- Chemoenzymatic Synthesis of 5-Hydroxymethylfurfural (HMF)-Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification
-
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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- Self-tuned properties of CuZnO catalysts for hydroxymethylfurfural hydrodeoxygenation towards dimethylfuran production
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5-Hydroxymethylfurfural (HMF) is a very valuable platform molecule obtained from biomass. It can be catalytically transformed to many industrially relevant products of both oxidation and reduction reactions. In this work, we showed that robust CuZnO can be an efficient, self-tuned catalyst for 2,5-dimethylfuran (DMF) (biofuel additive) synthesis. We showed that CuZnO catalysts can be further activated in the reaction environment and this process depends strongly on the initial catalyst properties and therefore on the catalyst preparation method. Smaller copper particles are more active but more prone to carbon deposit formation. Based on activity tests and extensive characterization, we have concluded that both Cun+ and Cu0 sites are necessary for high HMF conversion. While these two sites favor high conversion and high 2,5-bishydroxymethylfuran (BHMF) yield, the in situ formation of Lewis acid sites is proposed to be necessary for achieving a high DMF yield.
- Brzezińska, Magdalena,Keller, Nicolas,Ruppert, Agnieszka M.
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p. 658 - 670
(2020/02/27)
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- Preparation of 1-Hydroxy-2,5-hexanedione from HMF by the Combination of Commercial Pd/C and Acetic Acid
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The development of a simple and durable catalytic system for the production of chemicals from a high concentration of a substrate is important for biomass conversion. In this manuscript, 5-hydroxymethylfurfural (HMF) was converted to 1-hydroxy-2,5-hexanedione (HHD) using the combination of commercial Pd/C and acetic acid (AcOH) in water. The influence of temperature, H2 pressure, reaction time, catalyst amount and the concentration of AcOH and HMF on this transformation was investigated. A 68% yield of HHD was able to be obtained from HMF at a 13.6 wt% aqueous solution with a 98% conversion of HMF. The resinification of intermediates on the catalyst was characterized to be the main reason for the deactivation of Pd/C. The reusability of the used Pd/C was studied to find that most of the activity could be recovered by being washed in hot tetrahydrofuran.
- Duan, Ying,Yang, Dexi,Yang, Yanliang,Zhang, Chi,Zheng, Min
-
-
- Method for preparing 2, 5-dialkoxy methyl furan by reducing and etherifying 5-hydroxymethylfurfural
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The invention belongs to the field of biomass energy chemical engineering and particularly relates to a method for preparing 2, 5-dialkoxy methyl furan by reducing and etherifying 5-hydroxymethylfurfural. Synthesized sulfonic functionalized inorganic/organic hybrid polymer catalysts simultaneously integrate Lewis acid sites/Lewis alkali sites and Br-nsted acid sites and can selectively reduce the5-hydroxymethylfurfural into an intermediate product of 2, 5-dihydroxymethyl furan and meanwhile efficiently etherify the 2, 5-dihydroxymethyl furan into the target product of 2, 5-dialkoxy methyl furan; through a step-by-step temperature adjusting method, the Lewis acid sites/Lewis alkali sites and the Br-nsted acid sites can give play to catalytic effects at appropriate temperatures to achieve step-by-step continuous production of the intermediate product and the target product and to avoid production of other by-products, thereby improving the selectivity and yield of the intermediate product and the target product.
- -
-
Paragraph 0042; 0043; 0044; 0045; 0046; 0047
(2019/05/22)
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- Method for preparing 2,5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural
-
The invention discloses a method for preparing 2,5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural, and the method comprises the following steps: adding the 5-hydroxymethylfurfural, catalyst CuNPs@ZIF-8 and ethanol to a stainless steel closed reactor, charging with H2, and reacting at thetemperature of 120-150DEG C and the pressure of 1-4 MPa for 0.1-5 h. The method adopts the CuNPs@ZIF-8 as the catalyst, and the catalyst not only has large specific surface area, high dispersion of nano copper and good hydrogen adsorption performance, but also has simple preparation, lowprice and reusability. The method overcomes the problem of expensive use of precious metals as catalysts and low efficiency of non-precious metals as catalysts in prior studies.
- -
-
Paragraph 0030-0040
(2019/10/01)
-
- Simple basic zirconium carbonate: Low temperature catalysis for hydrogen transfer of biomass-derived carboxides
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A simple basic zirconium carbonate (BZC), which can be produced on a large scale in industry, was studied for hydrogen transfer of biomass-derived carboxides and exhibited excellent catalytic properties at low temperatures, especially for the conversion of furfural (FUR) to furfuryl alcohol (FFA). With the catalyst, the reduction reaction of FUR was efficiently performed at low temperatures (below 100 °C) and an FFA yield of 98.66% was obtained even at room temperature. When the temperature reached 180 °C, the yield of FFA quickly reached 90.29% within 15 minutes. During the reaction, the changes of the functional groups of the reactants and products were monitored by in situ ATR-IR spectroscopy in real time, which provided a basis for the proposed reaction mechanism. Further, the ATR-IR spectroscopy and XPS results of the different catalysts showed that BZC has the strongest acidity among all the comparative catalysts, which is consistent with its best catalytic performance. In addition, reaction kinetics were also studied.
- Ma, Mingwei,Hou, Pan,Cao, Jingjie,Liu, Hui,Yan, Xinyu,Xu, Xingliang,Yue, Huijuan,Tian, Ge,Feng, Shouhua
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p. 5969 - 5979
(2019/11/11)
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- A METHOD FOR PREPARING DI(HYDROXYMETHYL)FURAN FROM 5-HYDROXYMETHYLFURFURAL
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The present invention relates to a method for manufacturing dihydroxymethylfuran, a polymeric monomer, comprising a step of conducting a reaction of a butanol solution of 5-hydroxymethylfurfural with a Cu-based hydrogenation catalyst. According to the present invention, even though an environmentally friendly solvent and the inexpensive Cu-based hydrogenation catalyst are used, it is possible to manufacture dihydroxymethylfuran in high yield from fructose.COPYRIGHT KIPO 2019
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Paragraph 0069-0095
(2019/07/03)
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- Hydrogenation preparation method for formic acid hydrogen supply and non-5 - HMF noble metal loaded 2 nitrogen heterocarbon catalysis 5 - (CO-catalytic conversion reaction) (by machine translation)
-
The invention discloses a method for carrying out hydrogen production, non-noble metal loading of 5 - nitrogen heterocarbon to catalyze and 2 hydrogenate 5 - and hydrogenate and hydrogenate and hydrogenate methyl furfural, and a method for preparing furan dimethanol. After the reaction is finished, 1 the organic solvent obtained at the top of the catalytic transfer hydrogenation reaction 5 - is recycled, the crude product is obtained at the bottom of the catalyst transfer hydrogenation reaction, and the residue is recrystallized. 1 mpa 120~200 °C 30min~12h 2 5 - 2 5 . The method is simple in process, environment 2-5 - friendly, and low in cost, and has the advantages of high yield and low cost, and has a good industrial application prospect. (by machine translation)
- -
-
Paragraph 0030-0133
(2019/10/08)
-
- Method for preparing 2,5-furandimethanol by transfer hydrogenation of 5-hydroxymethylfurfural
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The invention discloses a method for preparing 2,5-furandimethanol by transfer hydrogenation of 5-hydroxymethylfurfural. The 5-hydroxymethylfurfural, a catalyst MnO@C-N and a lower alcohol are added into a stainless steel closed reactor for reaction at 150-200 DEG C for 1-30 h, and the materials are stirred at a rate of 300-900 rpm during the reaction. For the first time, the method of the invention uses the MnO@C-N as a catalyst to catalyze aldehyde to alcohol. The catalyst MnO@C-N used by the method uses renewable sucrose and urea as raw materials, and the preparation process is simple and environmentally friendly. The method uses the cheap lower alcohol as a hydrogen source for a reduction reaction, has the advantages of safe reaction process, simple operation and high product selectivity, and has great industrial application value.
- -
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Paragraph 0028-0038
(2019/10/01)
-
- Selective Room-Temperature Hydrogenation of Carbonyl Compounds under Atmospheric Pressure over Platinum Nanoparticles Supported on Ceria-Zirconia Mixed Oxide
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A Pt/CeO2-ZrO2 catalytic system was able to initiate an extremely intense hydrogen spillover providing a huge amount of activated hydrogen (12 mol/mol Pt) at temperatures –50°C - +25°C, which was not observed before. The idea was to use this activated hydrogen for reduction of carbonyl compounds under ambient conditions. Thus, the efficient and selective heterogeneous hydrogenation of carbonyl compounds of different structure, including 5-hydroxymethylfurfural and cinnamaldehyde, to the corresponding alcohols with quantitative yields was successfully performed over the Pt/CeO2-ZrO2 catalysts at room-temperature and atmospheric pressure of H2. The proposed catalysts afforded hydrogenation under significantly milder conditions with a much higher activity and selectivity compared to the commercial catalysts and reported catalytic systems. Hydrogenation of the C=O bond in the presence of a C=C bond proceeded with a high regioselectivity.
- Redina, Elena A.,Vikanova, Kseniia V.,Kapustin, Gennady I.,Mishin, Igor V.,Tkachenko, Olga P.,Kustov, Leonid M.
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supporting information
p. 4159 - 4170
(2019/07/12)
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- Surfactant-assisted synthesis of mesoporous hafnium- imidazoledicarboxylic acid hybrids for highly efficient hydrogen transfer of biomass-derived carboxides
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Catalytic transfer hydrogenations of biomass-derived carbonyl compounds to produce corresponding alcohols are important pathway for biomass transformation. Herein, a facile route was developed to synthesize the surfactant-assisted heterogeneous acid-base bifunctional 4,5-imidazoledicarboxylic acid-hafnium hybrid catalyst (Hf-H3IDC-T) by hydrothermal self-assembly method. The as-prepared Hf-H3IDC-T was characterized by SEM and TEM, FT-IR spectra, N2 adsorption-desorption, X-ray diffraction patterns (XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetry analysis (TG), NH3/CO2-TPD, NMR, GC[sbnd]MS, ICP-OES and elemental analysis. Hf-H3IDC-T hybrid had mesoporous structure and acid-base couple sites. A quantitative yield (99.2%) of furfuryl alcohol (FFA) was obtained from furfural (FUR) over Hf-H3IDC-T using 2-propanol as the hydrogen source under mild conditions. It's found that the amino groups on the imidazole ring is beneficial to enhance the base sites of catalyst. Meanwhile, the addition of hexadecyl trimethyl ammonium bromide (CTAB) as template agents can improve the specific surface area of the catalyst. Dynamic analysis showed that the apparent activation energy of FUR reduction was as low as 50.89 kJ / mol. The as-prepared catalyst has good stability and can be recycled. Finally, the catalyst also has a good catalytic effect on the hydrogenation reaction of aldehydes and ketones of biomass-derived compounds.
- Dai, Fanglin,Zhou, Shenghui,Qin, Xingzhen,Liu, Detao,Qi, Haisong
-
-
- A highly efficient Cu/AlOOH catalyst obtained by in situ reduction: Catalytic transfer hydrogenation of ML into Γ-GVL
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Catalytic transfer hydrogenation (CTH) of carbonyl compounds is considered as one of the most promising processes in the synthesis of fuels and chemicals. In this work, we propose a one-step strategy for catalyst preparation and CTH. Using the strategy, the production of γ-valerolactone (γ-GVL) was performed with isopropanol (2-PrOH) as solvent over in situ reduced nano-Cu/AlOOH catalyst from Cu2(OH)2CO3/AlOOH and the optimal reaction conditions for γ-GVL are 180 °C for 5 h using the in situ reduced catalyst with Cu/Al molar ratio 3/1 (90.51% yields of γ-GVL). Furthermore, it has been confirmed by different characterization methods (such as: SEM, TEM, XPS, etc.) that the catalyst is heterogeneous and exhibits high catalytic activity and stability which is attributed to the stability of the zero-valent copper in the catalyst and the nanosized particles of the catalyst. In addition, the catalysts also show general applicability to other carbonyl compounds.
- Ma, Mingwei,Liu, Hui,Cao, Jingjie,Hou, Pan,Huang, Jiahui,Xu, Xingliang,Yue, Huijuan,Tian, Ge,Feng, Shouhua
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- Porous Zr–Thiophenedicarboxylate Hybrid for Catalytic Transfer Hydrogenation of Bio-Based Furfural to Furfuryl Alcohol
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Furfural (FAL) is one of the most important biomass-derived platform compounds. The catalytic transformation of FAL was investigated with three porous Zr–thiophenedicarboxylate hybrids for the production of furfuryl alcohol (FOL). Three Zr-based catalysts, including DUT-67(Zr), DUT-68(Zr) and DUT-69(Zr) were synthesized through a facile assembly of 2,5-thiophenedicarboxylate acid with ZrCl4 using the acetic acid as a modulator under hydrothermal conditions. These catalysts were also characterized using FT-IR, XRD, SEM, TEM, N2 adsorption–desorption, XPS and TG. The specific surface area of the DUT-69(Zr) is smaller than that of the DUT-68(Zr) and slightly larger than that of the DUT-67(Zr), but it has a relatively large pore volume and pore diameter. Although all three catalysts showed excellent catalytic activity towards the catalytic transfer hydrogenation of FAL into FOL, the DUT-69(Zr) material has slightly higher catalytic activity than the other two catalysts. Besides, considering the cost of catalyst preparation, the DUT-69(Zr) material was used as the optimal catalyst and studied in detail. A high FOL yield of 92.2% at 95.9% FAL conversion was achieved at 120?°C for 4?h over DUT-69(Zr). Meanwhile, the DUT-69(Zr) could be reused more than six times with a minor decrease in catalytic activity. Finally, a plausible mechanism for catalytic transfer hydrogenation of carbonyl compounds to produce corresponding alcohols was presented based on the results of the experiments and previous reports. Graphical Abstract: [Figure not available: see fulltext.].
- Wang, Tao,Hu, Aiyun,Xu, Guangzhi,Liu, Chen,Wang, Haijun,Xia, Yongmei
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- Hierarchically constructed NiO with improved performance for catalytic transfer hydrogenation of biomass-derived aldehydes
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A 3D nano-/micrometer-scaled NiO material with urchin-like structure was prepared via a facile, green synthesis route, and served as a highly efficient and durable catalyst for catalytic transfer hydrogenation (CTH) of bio-based furfural (FF) to furfuryl alcohol (FAOL) using 2-propanol as H-donor and solvent. The as-prepared NiO possessed a good active-site accessibility owing to a high surface area and large amount of acid-base sites, resulting in high FF conversion of 97.3% with 94.2% FAOL yield at 120 °C and 3 h of reaction, which was a superior catalytic performance compared to commercial NiO nanoparticles. Besides, the excellent catalytic performance of the sea urchin-like NiO was validated for gram-scale FAOL synthesis, and recyclability test confirmed the catalyst to be reusable for multiple reaction runs without significant activity loss after intermediary calcination in air. Notably, the introduced catalytic system was also applicable to CTH of alternative bio-derived aldehydes.
- He, Jian,Nielsen, Monia Runge,Hansen, Thomas Willum,Yang, Song,Riisager, Anders
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p. 1289 - 1300
(2019/03/11)
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