- Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments
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Supported Fe-Ni catalysts have been reported for their activity and selectivity in the hydrogenation of unsaturated organic molecules. However, the control of the size and composition of the bimetallic nanoparticles remains a bottleneck when oxide-supported catalysts are prepared by impregnation, and alternative procedures should be investigated. Starting with Ni(II) and Fe(II) sulfates as precursor salts, deposition-precipitation with urea (DPU) on SiO2 in an inert atmosphere initially leads to the formation of an ill-crystallized Fe-containing Ni(II) 1:1 phyllosilicate, which reduces under hydrogen at 700 °C into bimetallic fcc Fe-Ni nanoparticles of 5.4 nm in average. Compared with the composition of the DPU solution (50 Fe at %, 50 Ni at %), an excess of Ni is detected on the catalyst (38 Fe at %, 62 Ni at %), due to the preferential reaction of Ni2+ ions with silica. In situ X-ray absorption spectroscopy and 57Fe M?ssbauer spectroscopy show that the reduction of Fe ions to the metallic state is triggered by the formation of reduced Ni centers above 350 °C, and, from then, proceeds progressively, resulting in an excess of Fe in the outer shells of the bimetallic particles. The composition of individual Fe-Ni particles evidences a standard deviation of 8%. The bimetallic Fe-Ni/SiO2 catalyst gives high yields in furfuryl alcohol in the hydrogenation of furfural, in contrast with an analog Ni/SiO2 catalyst that favours side-reactions of etherification, hydrogenolysis and hydrogenation of the furan ring.
- Shi, Dichao,Yang, Qifeng,Peterson, Christi,Lamic-Humblot, Anne-Félicie,Girardon, Jean-Sébastien,Griboval-Constant, Anne,Stievano, Lorenzo,Sougrati, Moulay T.,Briois, Valérie,Bagot, Paul A.J.,Wojcieszak, Robert,Paul, Sébastien,Marceau, Eric
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- Mechanistic insights into metal lewis acid-mediated catalytic transfer hydrogenation of furfural to 2-methylfuran
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Biomass conversion to fuels and chemicals provides sustainability, but the highly oxygenated nature of a large fraction of biomass-derived molecules requires removal of the excess oxygen and partial hydrogenation in the upgrade, typically met by hydrodeoxygenation processes. Catalytic transfer hydrogenation is a general approach in accomplishing this with renewable organic hydrogen donors, but mechanistic understanding is currently lacking. Here, we elucidate the molecular level reaction pathway of converting hemicellulose-derived furfural to 2-methylfuran on a bifunctional Ru/RuOx/C catalyst using isopropyl alcohol as the hydrogen donor via a combination of isotopic labeling and kinetic studies. Hydrogenation of the carbonyl group of furfural to furfuryl alcohol proceeds through a Lewis acid-mediated intermolecular hydride transfer and hydrogenolysis of furfuryl alcohol occurs mainly via ring-activation involving both metal and Lewis acid sites. Our results show that the bifunctional nature of the catalyst is critical in the efficient hydrodeoxygenation of furanics and provides insights toward the rational design of such catalysts.
- Gilkey, Matthew J.,Panagiotopoulou, Paraskevi,Mironenko, Alexander V.,Jenness, Glen R.,Vlachos, Dionisios G.,Xu, Bingjun
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- Exploiting H-transfer as a tool for the catalytic reduction of bio-based building blocks: The gas-phase production of 2-methylfurfural using a FeVO4 catalyst
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Over the past decade, a great deal of effort has been devoted to developing reductive processes in the field of biomass valorisation for the sustainable production of bio-fuel additives and chemicals. Catalytic transfer hydrogenation, which uses alcohol as the hydrogen source, is an interesting approach that avoids the use of both high H2 pressure and precious metal catalysts. In this work, the vapour-phase production of 2-methylfuran from biomass-derived furfural (FU), using methanol as the H-transfer agent and FeVO4 catalyst, was studied. At a temperature of 320°C it was possible to achieve 80% yield of 2-methylfuran, with small amounts of 2,5-dimethylfuran and 2-vinylfuran as by-products. Catalyst characterization highlighted that FeVO4 reduction took place under the studied conditions, leading to the in situ development of a true active phase. The study of the reaction network permitted us to infer on the relative contribution of H-transfer and hydrogenation, the latter from the in situ generated formaldehyde and H2, to 2-methylfuran, formation. The reported results indicate the potential application of H-transfer with FeVO4 catalysts as an efficient process for the selective de-oxygenation of biomass-derived molecules.
- Grazia,Bonincontro,Lolli,Tabanelli,Lucarelli,Albonetti,Cavani
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- Gas-Phase Heteroaromatic Substitution. 3. Electrophilic Methylation of Furan and Thiophene by CH3XCH3+ (X = F or Cl) Ions
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A previous radiolytic study on the gas-phase methylation of pyrrole and N-methylpyrrole by CH3XCH3+ (X = F or Cl) ions, from the γ radiolysis of CH3X, is extended to furan (3) and thiophene (4).The mechanism of the susbstitution and of the subsequent isomerization occuring via intramolecular 1,2 methyl-group shift is discussed and the substrate and positional selectivity of the selected electrophilic species evaluated.As for pyrroles, gas-phase CH3FCH3+ methylation of furan and thiophene is characterized by a scarce substrate discrimination (kS/kB = 1.2 (3), 0.8 (4), accompanied by an apprreciable positional selectivity toward those substrate positions with the highest negative net charge (O:α:β = 36percent:35percent:29percent for 3; S:α:β = 19percent:43percent:38percent for 4).On the contrary, CH3ClCH3+ confirm its inherent affinity toward n-type nucleophilic centers by attacking preferently the heteroatom of 3 and 4.In light of the previous results concerning CH3XCH3+ methylation of pyrroles, it is concluded that gas-phase attack of CH3XCH3+ on simple five-membered heteroaromatics is essentially regulated by the electrostatic interaction established within the encounter pair.A close correspondence does exist between this rationalization of the present gas-phase results and recent theoretical predictions.
- Angelini, Giancarlo,Lilla, Gaetano,Speranza, Maurizio
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- Healing by the Joule effect of electrically conductive poly(ester-urethane)/carbon nanotube nanocomposites
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Recent demands for polymers with autonomous self-healing properties are being constantly raised due to the need for high-performance and reliable materials. So far, the advances in this field are limited to the production of self-healing materials requiring a high energy input. Therefore there is an urgent need to develop self-healing polymer systems, in which healing can be easily and specifically induced by external stimuli for economical and viable applications. In the current work we demonstrate, for the first time to our knowledge, the possibility to heal local macroscopic damage by a confined temperature increase arising from the Joule effect. The damage healing is promoted by the resistance to an electrical current at the crack tip. This new concept is studied on thermo-reversible and electrically conductive poly(ester-urethane)/carbon nanotube nanocomposites derived from thermo-reversible Diels-Alder reactions between furfuryl- and maleimide-functionalized poly(ε-caprolactone) (PCL)-based precursors. Electrically conductive materials are then obtained after incorporating multi-walled carbon nanotubes into the thermo-reversible networks using reactive extrusion. Under mild electrical conditions, temperature in the range of the retro-Diels-Alder reaction can be obtained near the damaged site. The obtained results reveal the potential of this new approach for healing materials locally while maintaining the overall material properties.
- Willocq,Bose,Khelifa,Garcia,Dubois,Raquez
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- Conversion of furfuryl alcohol into 2-methylfuran at room temperature using Pd/TiO2 catalyst
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The selective hydrogenation of furfuryl alcohol into 2-methylfuran was investigated at room temperature using palladium supported catalysts. We have shown that Pd-TiO2 catalysts can be very effective for the synthesis of 2-methylfuran at room t
- Iqbal, Sarwat,Liu, Xi,Aldosari, Obaid F.,Miedziak, Peter J.,Edwards, Jennifer K.,Brett, Gemma L.,Akram, Adeeba,King, Gavin M.,Davies, Thomas E.,Morgan, David J.,Knight, David K.,Hutchings, Graham J.
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- Single pot selective hydrogenation of furfural to 2-methylfuran over carbon supported iridium catalysts
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Various iridium supported carbon catalysts were prepared and screened for the direct hydrogenation of furfural (FFR) to 2-methyl furan (2-MF). Amongst these, 5% Ir/C showed excellent results with complete FFR conversion and highest selectivity of 95% to 2-MF at a very low H2 pressure of 100 psig. Metallic (Ir°) and oxide (IrO2) phases of Ir catalyzed the first step hydrogenation involving FFR to FAL and subsequent hydrogenation to 2-MF, respectively. This was confirmed by XPS analysis and some control experiments. At a low temperature of 140 °C, almost equal selectivities of FAL (42%) and 2-MF (43%) were observed, while the higher temperature (220 °C) favored selective hydrodeoxygenation. At optimized temperature, 2-MF was formed selectively while higher pressure and higher catalyst loading favored ring hydrogenation of furfural rather than side chain hydrogenation. With the combination of several control experimental results and detailed catalyst characterization, a plausible reaction pathway has been proposed for the selective formation of 2-MF. The selectivity to various other products in FFR hydrogenation can be manipulated by tailoring the reaction conditions over the same catalyst.
- Date, Nandan S.,Hengne, Amol M.,Huang,Chikate, Rajeev C.,Rode, Chandrashekhar V.
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- Molybdenum carbide as a highly selective deoxygenation catalyst for converting furfural to 2-methylfuran
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Selectively cleaving the C = O bond outside the furan ring of furfural is crucial for converting this important biomass-derived molecule to value-added fuels such as 2-methylfuran. In this work, a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluation identified molybdenum carbide (Mo2C) as a highly selective deoxygenation catalyst for converting furfural to 2-methylfuran. These results indicate the potential application of Mo2C as an efficient catalyst for the selective deoxygenation of biomass-derived oxygenates including furanics and aromatics.
- Xiong, Ke,Lee, Wen-Sheng,Bhan, Aditya,Chen, Jingguang G.
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- Room temperature hydrogenation of furfuryl alcohol by Pd/titanate nanotube
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The liquid phase hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol at room temperature under 1 atm hydrogen was succeeded on a TiO2 nanotube (TNT) supported palladium catalyst. The palladium nanoparticles in size of 2-8 nm were loaded by the deposition-reduction method with NaBH4 as reducing reagent. The Pd/TNT catalyst showed high dispersion as revealed by CO chemisorption and improved catalytic performance in terms of both furfuryl alcohol conversion and tetrahydrofurfuryl alcohol selectivity, probably attributed to the unique electronic interaction between Pd metals and TNT surface containing sodium cations. Among the catalysts investigated, 5.8 wt.% Pd/TNT showed the best performance, with 98% conversion and 98% selectivity to tetrahydrofurfuryl alcohol in ethanol.
- Yuan, Qingqing,Ye, Feiyang,Xue, Teng,Guan, Yejun
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- Promotion effect of Ce or Zn oxides for improving furfuryl alcohol yield in the furfural hydrogenation using inexpensive Cu-based catalysts
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Kerolite/Mg-smectite mixed layer was used as inexpensive material to support metallic copper, with metal loadings (5–30 wt.%). These catalysts are active in gas-phase furfural hydrogenation, maintaining conversion values higher than 80 mol%, at 210 °C, after 5 h of time-on-stream, with high copper loading (15–30 wt.% Cu) catalysts, being furfuryl alcohol and 2-methylfuran the only detected products. The incorporation of Ce and Zn as promoters causes a decrease in the furfural conversion, although catalysts become much more selective toward furfuryl alcohol, reaching a maximum furfuryl alcohol yield above 80%, at 190 °C, after 5 h of TOS, after CeO2 addition.
- Jiménez-Gómez, Carmen P.,Cecilia, Juan A.,Franco-Duro, Francisco I.,Pozo, Manuel,Moreno-Tost, Ramón,Maireles-Torres, Pedro
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- High-Temperature Synthesis of Carbon-Supported Bimetallic Nanocluster Catalysts by Enlarging the Interparticle Distance
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Supported bimetallic nanoparticle catalysts with small size have attracted wide research attention in catalysis but are difficult to synthesize because high-temperature annealing required for alloying inevitably accelerates metal sintering and leads to larger particles. Here, we report a simple and scalable critical interparticle distance method for the synthesis of a family of bimetallic nanocluster catalysts with an average particle size of only 1.5 nm by using large-surface-area carbon black supports at high temperatures, which consist of 12 diverse combinations of 3 noble metals (Pt, Ru, and Rh) and 4 other metals (Cr, Fe, Zr, and Sn). In this strategy, high-temperature treatments ensure the formation of alloyed bimetallic nanoparticles and enlargement of the interparticle distance on high-surface-area supports significantly suppresses metal sintering. The prepared ultrafine Pt2Sn and RuSn nanocluster catalysts exhibited enhanced performance in catalyzing the synthesis of aromatic secondary amines and the selective hydrogenation of furfural, respectively.
- Zuo, Lu-Jie,Xu, Shi-Long,Wang, Ao,Yin, Peng,Zhao, Shuai,Liang, Hai-Wei
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supporting information
p. 2719 - 2723
(2022/02/16)
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- Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
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Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.
- Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
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supporting information
p. 9029 - 9039
(2021/06/28)
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- Heterogeneously Catalyzed Selective Decarbonylation of Aldehydes by CeO2-Supported Highly Dispersed Non-Electron-Rich Ni(0) Nanospecies
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Aldehyde decarbonylation has been extensively investigated, primarily using noble-metal catalysts; however, nonprecious-base-metal-catalyzed aldehyde decarbonylation has been hardly reported. We have established an efficient selective aldehyde decarbonylation reaction with a broad substrate scope and functional group tolerance utilizing a heterogeneous Ni(0) nanospecies catalyst supported on CeO2. The high catalytic performance is attributable to the highly dispersed and non-electron-rich Ni(0) nanospecies, which possibly suppress a side reaction producing esters and adsorbed CO-derived inhibition of the catalytic turnover, according to detailed catalyst characterization and kinetic evaluation.
- Matsuyama, Takehiro,Yatabe, Takafumi,Yabe, Tomohiro,Yamaguchi, Kazuya
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p. 13745 - 13751
(2021/11/17)
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- One-pot self-assembly synthesis of Ni-doped ordered mesoporous carbon for quantitative hydrogenation of furfural to furfuryl alcohol
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Ni-Doped ordered mesoporous carbon (Ni@OMC) was prepared by a one-pot solvent evaporation-induced self-assembly (EISA) process with sustainable biomass-derived gallic acid as the carbon precursor, F127 as the soft template and Ni2+as the cross-linker and catalytically active ingredient. Ni particles withca.7.8 nm diameter were uniformly dispersed in the carbon skeleton of the synthesized OMC due to the confinement effects of Ni particles in the carbon skeleton of OMC by coordination between gallic acid molecules and metal Ni2+ions in the EISA process. The as-synthesized Ni@OMC sample showed excellent catalytic performance for the hydrogenation of biomass-derived furfural into furfuryl alcohol (FFA), and a FFA yield as high as 98% could be achieved at 180 °C in 4 h reaction time in 1-propanol solvent in the presence of 3 MPa H2pressure. The prepared Ni@OMC exhibited good stability and recyclability. This work provides a green and simple one-pot strategy for the synthesis of metal-doped OMCs without using harmful phenolic and formaldehyde compounds, which should have many applications in fields such as catalysis, drug delivery and energy storage.
- Tang, Yiwei,Qiu, Mo,Yang, Jirui,Shen, Feng,Wang, Xiaoqi,Qi, Xinhua
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p. 1861 - 1870
(2021/03/09)
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- Furfural hydrodeoxygenation (HDO) over silica-supported metal phosphides – The influence of metal–phosphorus stoichiometry on catalytic properties
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The gas-phase hydrodeoxygenation (HDO) of furfural, a model compound for bio-based conversion, was investigated over transition metal phosphide catalysts. The HDO activity decreases in the order Ni2P ≈ MoP > Co2P ≈ WP ? Cu3P > Fe2P. Nickel phosphide phases (e.g., Ni2P, Ni12P5, Ni3P) are the most promising catalysts in the furfural HDO. Their selectivity to the gasoline additives 2-methylfuran and tetrahydro-2-methylfuran can be adjusted by varying the P/Ni ratio. The effect of P on catalyst properties as well as on the reaction mechanism of furfural HDO were investigated in depth for the first time. An increase of the P stoichiometry weakens the furan-ring/catalyst interaction, which contributes to a lower ring-opening and ring-hydrogenation activity. On the other hand, an increasing P content does lead to a stronger carbonyl/catalyst interaction, i.e., to a stronger η2(C, O) adsorption configuration, which weakens the C1[sbnd]O1 bond (Scheme 1) in the carbonyl group and enhances the carbonyl conversion. Phosphorus species can also act as Br?nsted acid sites promoting C1[sbnd]O1 (Scheme 1) hydrogenolysis of furfuryl alcohol, hence contributing to higher production of 2-methylfuran.
- Lan, Xuefang,Pestman, Robert,Hensen, Emiel J.M.,Weber, Thomas
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p. 181 - 193
(2021/02/27)
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- Interfacial effect of Pd supported on mesoporous oxide for catalytic furfural hydrogenation
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Highly dispersed Pd is loaded onto different types of mesoporous oxide supports to investigate the synergetic metal-support effect in catalytic furfural (FAL) hydrogenation. Ordered mesoporous Co3O4, MnO2, NiO, CeO2, and Fe2O3 are prepared by the nanocasting and the supported Pd on mesoporous oxide catalysts are obtained by the chemical reduction method. It is revealed that mesoporous oxides play an important role on Pd dispersion as well as the redox behavior of Pd, which determines the final FAL conversion. Among the catalysts used, Pd/Co3O4 shows the highest conversion in FAL hydrogenation and distinct product selectivity toward 2-methylfuran (MF). While FAL is converted via two distinct pathways to produce either furfuryl alcohol (FA) via aldehyde hydrogenation or MF via hydrogenolysis, MF as a secondary product is derived from FA via the hydrogenolysis of C–O over the Pd/Co3O4 catalyst. It is revealed that FAL is hydrogenated to FA preferentially on the Pd surface; then the secondary hydrogenolysis to MF from FA is further promoted at the interface between Pd and Co3O4. We confirm that the reaction pathway over Pd/Co3O4 is totally different from other catalysts such as Pd/MnO2, which produces FA dominantly. The characteristics of the mesoporous oxides influence the Pd-oxide interfaces, which determine the activity and selectivity in FAL hydrogenation.
- Lee, Hojeong,Nguyen-Huy, Chinh,Jeong Jang, Eun,Lee, Jihyeon,Yang, Euiseob,Lee, Man Sig,Kwak, Ja Hun,An, Kwangjin
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p. 291 - 300
(2020/03/05)
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- Highly selective reduction of biomass-derived furfural by tailoring the microenvironment of Rh@BEA catalysts
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Furfural is a renewable lignocellulose-derived platform molecule, which can be transformed into biofuels and value-added chemicals (e.g., furfuryl alcohol and 2-methylfuran over metal-supported catalysts). Despite a number of approaches proposed for designing hydrogenation catalysts, highly selective furfural hydrogenation towards furfuryl alcohol (FA) or 2-methylfuran (2-MF) is still challenging. Here, we report on selective transformation of furfural either to FA or 2-MF achieved over zeolite BEA-supported Rh catalysts by optimizing Si/Al ratio and charge-balancing cations of the support. Among studied H- and Na-exchanged aluminosilicate BEA zeolite supports (Si/Al = 12.5; 25; 68; 150), Rh@Na-BEA catalysts lacking Br?nsted and strong Lewis acidity showed enhanced selectivity towards FA (75 – 94% depending on the Si/Al ratio) at 74 – 84% conversion of furfural. In turn, selective formation of 2-MF (98% selectivity at 87% conversion) was observed over Al-rich Rh@H-BEA catalyst (Si/Al=12.5) with the highest concentration of Br?nsted acid sites. Weaker adsorption of FA on Na- vs. H-form of Rh@BEA-12.5 catalyst was verified by FTIR spectroscopy and is assumed a key factor governing selective hydrogenation of furfural to FA over Rh@Na-BEA catalysts.
- ?ejka, Ji?í,Kub?, Martin,Li, Ang,Shamzhy, Mariya,Zhang, Yuyan
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- Conversion of furfural to 2-methylfuran over CuNi catalysts supported on biobased carbon foams
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In this study, carbon foams prepared from the by-products of the Finnish forest industry, such as tannic acid and pine bark extracts, were examined as supports for 5/5% Cu/Ni catalysts in the hydrotreatment of furfural to 2-methylfuran (MF). Experiments were conducted in a batch reactor at 503 K and 40 bar H2. Prior to metal impregnation, the carbon foam from tannic acid was activated with steam (S1), and the carbon foam from pine bark extracts was activated with ZnCl2 (S2) and washed with acids (HNO3 or H2SO4). For comparison, a spruce-based activated carbon (AC) catalyst and two commercial AC catalysts as references were investigated. Compressive strength of the foam S2 was 30 times greater than that of S1. The highest MF selectivity of the foam-supported catalysts was 48 % (S2, washed with HNO3) at a conversion of 91 %. According to the results, carbon foams prepared from pine bark extracts can be applied as catalyst supports.
- Varila, Toni,M?kel?, Eveliina,Kupila, Riikka,Romar, Henrik,Hu, Tao,Karinen, Reetta,Puurunen, Riikka L.,Lassi, Ulla
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- Liquid phase hydrodeoxygenation of furfural over laponite supported NiPMoS nanocatalyst: Effect of phosphorus addition and laponite support
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Unsupported and laponite supported NiPMoS catalysts were prepared under the hydrothermal method and investigated for liquid-phase hydrodeoxygenation of furfural in a high-pressure batch reactor at 423 ?K ? 463 ?K under 20 ?bar H2 pressure. The reaction significantly produced 94% of furfural conversion with 75% yield of 2-MF on NiPMoS catalyst whereas, NiPMoS/Lap catalyst exhibited 28% of 2-MF yield with complete conversion at 463 ?K under 20 ?bar H2 pressure in toluene solvent. The influence of process parameters such as reaction temperature, reactant volume, catalyst compositions, and hydrogen pressure on furfural conversion and product yield was investigated in detail. The high reactivity and synergetic effect of the NiPMoS catalyst are due to added phosphorus, which has a profound influence on the structure of the catalyst, thereby increasing surface acidity, basicity, hydrogen consumption, and a number of MoS2 fringes and the dispersion of MoS2 on the surface of the support. The catalysts were characterized based on HRTEM, H2, CO2, and NH3 TPD, FT–IR, FT–Raman, DRS UV–Vis, XRD, N2–physisorption, and TGA. Recyclability, N2–physisorption, and XRD results confirm the stability and practical applicability of the catalyst for industrial applications.
- Krishnan, P. Santhana,Umasankar,Tamizhdurai,Mangesh,Shanthi
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- Catalytic Transfer Hydrogenation of Furfural over CuNi@C Catalyst Prepared from Cu–Ni Metal-Organic Frameworks
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Abstract: Cu/Ni-based metal-organic frameworks (CuNi@BTC) were prepared with benzene-1,3,5-tricarboxylate (H3BTC) as the organic ligand via the solvothermal method, and were then calcinated under N2 atmosphere to form C-coated CuNi catalysts (CuNi@C). TEM showed that carbon material on the surface of CuNi@C was a graphene-like structure. Then transfer hydrogenation of furfural catalyzed by CuNi@C was tested with alcohols as the hydrogen donor to optimize the Cu : Ni ratio, metal : organic ligand ratio, solvothermal synthesis, and calcination conditions. It was found that strong synergistic effect between Cu and Ni in the CuNi@C significantly enhanced the furfural transfer hydrogenation activity and raised the furfural selectivity. The reaction conditions of furfural transfer hydrogenation such as catalyst dosage, hydrogen donor, reaction temperature, and reaction time were studied. The catalytic mechanism for CTH of FF over CuNi@C catalyst was discussed.
- Feng Li,Jiang, Shanshan,Wang, Yue,Huang, Jin,Li, Cuiqin
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- Selective electrochemical hydrogenation of furfural to 2-methylfuran over a single atom Cu catalyst under mild pH conditions
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Furfural is regarded as one of the most promising bio-based feedstocks in the bio-refinery industry. Selective hydrogenation of the carbonyl bond in furfural plays a vital role in its conversion to downstream products. Electrochemical hydrogenation (ECH) method provides a green and sustainable way for this reaction. Yet, it still suffers from harsh pH conditions and low selectivity for highly reduced products, such as 2-methylfuran. In this study, high faradaic efficiencies of over 90% for furfuryl alcohol and 60% for 2-methylfuran were obtained in a near-neutral environment (pH = 5) at ?0.75 V and ?0.90 Vvs. the reversible hydrogen electrode, respectively. The key to this success is the integration of single atom copper active sites and the oxophilic phosphorus dopants in a single catalyst. Single atom Cu sites are found to be the active centers for this reaction and decreasing the size of Cu sites to a single atom enhances the efficiencies of the ECH reactions by suppressing the competing hydrogen evolution reaction. Phosphorus doping facilitates furfural hydrogenation to 2-methylfuranviaa sequential two-step reduction process. This study opens up possibilities for the selective electrochemical hydrogenation of furfural to 2-methylfuran under mild conditions.
- Chaffee, Alan L.,Chen, Yu,Gu, Qinfen,Guo, Si-Xuan,Johannessen, Bernt,Luan, Peng,Mollah, Mamun,Turner, David R.,Yuan, Ziliang,Zhang, Jie,Zhang, Xiaolong,Zhou, Peng
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supporting information
p. 3028 - 3038
(2021/05/05)
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- Metal Catalyst and Hydrogen Gas-Free Selective Reduction of Biomass-Derived Substituted Furfuraldehyde to Alkyl Furan as a Key Biofuel Additive
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A metal catalyst and a hydrogen gas-free approach has been developed for selective reduction of aldehyde to an alkyl group of different substituted furan compounds. In this process, hydrazine hydrate under basic conditions at reflux temperature selectively participated in the reduction of the aldehyde moiety to the corresponding alkyl group of highly reactive furan compounds in a selective manner. The developed protocol was applied for selective and scalable reduction of 5-hydroxymethylfurfural (5-HMF) up to 250 g to 5-methylfurfuryl alcohol (MFA) in a 70% yield. Under the same process, furfuraldehyde was also tested in a 250 g reaction for 2-methylfuran (MF) synthesis in a highly selective manner and the product was distilled out from a single-pot reaction with gas chromatography (GC) purity ≥90%. The scope of the process was further extended for different substituted furfuraldehydes successfully. In addition, the protocol is found to be efficient for scalable production and easy separation of the product.
- Chauhan, Arvind Singh,Kumar, Ajay,Das, Pralay
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supporting information
p. 892 - 899
(2021/04/12)
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- METAL CATALYST AND HYDROGEN GAS FREE APPROACHES FOR SELECTIVE REDUCTION OF ALDEHYDE TO METHYL GROUP OF DIFFERENT SUBSTITUTED FURANS
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The present invention relates to 5-methyl substituted furan compounds of general formula (I) and process for the preparation thereof: OR1R2 R3CH3(I) Particularly, the present invention relates to a metal catalyst and hydrogen gas free, atom-economy, highly selective and low-cost process for the preparation of methyl substituted furan compounds from different aldehyde substituted furan compounds.
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Page/Page column 17-18
(2021/08/27)
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- Investigating hydrogenation and decarbonylation in vapor-phase furfural hydrotreating over Ni/SiO2 catalysts: Propylene production
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Furfural can be mass-produced from lignocellulose biomass and can be a platform chemical for producing valuable chemicals. In this study, we examine Ni/SiO2 catalysts for the conversion of furfural under a hydrogen atmosphere. The reactivity an
- Chen, Szu-Hua,Tseng, Ya-Chun,Yang, Sheng-Chiang,Lin, Shawn D.
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- Iodine-catalyzed alcohol disproportionation method
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The invention relates to the technical field of catalysis, in particular to an iodine-catalyzed alcohol disproportionation method which comprises the following steps: sequentially adding alcohol, iodine and a solvent into a high-temperature and high-pressure reaction kettle, introducing a certain amount of nitrogen, conducting reacting for a certain time, collecting an organic phase after the reaction is ended, and conducting fractionating to obtain corresponding alkane and aldehyde/ketone. Alcohol disproportionation is efficient and atom-economical conversion without any additional oxidizing agent and reducing agent, and hydrocarbon and aldehyde/ketone molecules which are easy to separate can be formed at the same time. Meanwhile, the method has wide functional group tolerance, various substrate samples including aryl alcohol derivatives, heterocyclic alcohol derivatives, allyl alcohol derivatives and dihydric alcohol are tested, and the result shows that most of the substrate samples show good or extremely good yield.
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Paragraph 0030-0031
(2021/06/13)
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- Efficient one-pot conversion of furfural into 2-methyltetrahydrofuran using non-precious metal catalysts
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2-methyltetrahydrofuran, a biomass-derived chemical, is an important solvent with broad applications in organic chemistry. In this study, one-pot conversion of furfural into 2-methyltetrahydrofuran over non-precious metal catalysts was achieved by two-stage packing in a single reactor. The first stage converted furfural into 2-methylfuran over Co-based catalysts, and the second stage converted 2-methylfuran into 2-methyltetrahydrofuran over Ni-based catalysts. In order to reveal the reaction pathway and mechanism of this process, the hydrogenation reactions of 2-methylfuran, furfuryl alcohol, and tetrahydrofurfuryl alcohol were also carefully investigated. It is discovered that the conversion of furfural into 2-methylfuran could be catalyzed by Lewis acid sites, which was confirmed by a correlation between 2-methylfuran production rate and Lewis acid site density. Also, a mechanism on the direct conversion of furfural into 2-methylfuran without forming furfuryl alcohol as the intermediate is proposed. The experimental results of 2-methylfuran, furfuryl alcohol, and tetrahydrofurfuryl alcohol hydrogenation/hydrodeoxygenation over various catalysts provided valuable information on the future design of 2-methyltetrahydrofuran catalyst.
- Jia, Xinxin,Li, Cuiqing,Liu, Ping,Song, Yongji,Sun, Luyang,Wang, Hong,Zhang, Chen,Zhang, Wei
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- A magnetic CoRu-CoO: X nanocomposite efficiently hydrogenates furfural to furfuryl alcohol at ambient H2 pressure in water
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A one-pot synthesized CoRu-CoOX nanocomposite was reported as a magnetically recoverable catalyst for selective hydrogenation of furfural to furfuryl alcohol in water at ambient H2 pressure.
- Cao, Qiue,Fang, Wenhao,Lu, Yaowei,Wang, Yongxing
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p. 3765 - 3768
(2020/04/10)
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- Selective Hydrogenation of Biomass-Derived Furfural: Enhanced Catalytic Performance of Pd?Cu Alloy Nanoparticles in Porous Polymer
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Here, the development of a new catalyst is reported for the selective furfural (FF) hydrogenation to furfuryl alcohol (FA) based on about 7 nm sized Pd?Cu alloy nanoparticles (NPs) formed in inexpensive, commercially available micro/mesoporous hypercrosslinked polystyrene (HPS). A comparison of the catalytic properties of as-synthesized and reduced (denoted “r”) catalysts as well as Pd?Cu alloy and monometallic palladium NPs showed a considerable enhancement of the catalytic performance of Pd?Cu/HPS-r compared to other catalysts studied, resulting in about 100 percent FF conversion, 95.2 percent selectivity for FA and a TOF of 1209 h?1. This was attributed to the enrichment of the NP surface with copper atoms, disrupting the furan ring adsorption, and to the presence of both zerovalent and cationic palladium and copper species, resulting in optimal hydrogen and FF adsorption. These factors along with exceptional stability of the catalyst in ten consecutive catalytic cycles make it highly promising in practical applications.
- Salnikova, Ksenia E.,Larichev, Yurii V.,Sulman, Esther M.,Bykov, Alexey V.,Sidorov, Alexander I.,Demidenko, Galina N.,Sulman, Mikhail G.,Bronstein, Lyudmila M.,Matveeva, Valentina G.
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p. 1697 - 1703
(2020/07/20)
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- Catalytic Activity of Ti-based MXenes for the Hydrogenation of Furfural
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Herein we report on the catalytic activity of Ti-based MXenes (Ti3CNTz and Ti3C2Tz) for biomass transformation. MXenes were found to be active catalysts for the hydrogenation of furfural using either
- Naguib, Michael,Tang, Wenjie,Browning, Katie L.,Veith, Gabriel M.,Maliekkal, Vineet,Neurock, Matthew,Villa, Alberto
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p. 5733 - 5742
(2020/10/12)
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- Structural evolution of ZIF-67-derived catalysts for furfural hydrogenation
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Zeolitic imidazolate framework-67 (ZIF-67) can be converted to metallic Co nanoparticles supported on N-doped carbon (Co/NC) through reduction. However, its unique properties, including extremely high surface area, isoreticular pore structure, and regular metal–organic network, disappear after high-temperature (>500 °C) reduction. Aggregated CoOx particles reduce the number of surface-active sites, resulting in poor catalytic activity. If the original ZIF-67 structure is maintained after the high-temperature reduction, promoting the uniform distribution of active sites in the porous carbon, the catalytic performance can be further improved. Herein, the correlation between the catalytic furfural hydrogenation performance, Co/NC morphology, and oxidation state of Co was investigated as a function of the H2 reduction temperature and time. The reduction of ZIF-67 at 400 °C for 6 h yields a highly dispersed Co/NC catalyst, while preserving the overall morphology. The resulting Co/NC-400-6 catalyst exhibits the highest activity, promoting high selectivity toward 2-methylfuran. The product selectivity can be further altered by incorporating Cu into ZIF-67 to produce furfuryl alcohol. With proper H2 treatment to minimize the damage to the intrinsic surface area and pore structure, metal–organic frameworks can be utilized as high-performance heterogeneous catalysts by maximizing the distribution of active sites.
- An, Kwangjin,Lee, Jae Hwa,Lee, Jun Gyeong,Moon, Hoi Ri,Song, Kyung,Yang, Euiseob,Yoon, Sinmyung
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p. 302 - 312
(2020/11/20)
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- Selective conversion of furfural into value-added chemical commodity in successive fixed-bed reactors
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Successive hydrogenation of furfural in two fixed-bed reactors connected in tandem with Cu/SiO2 and Ni/SiO2 as the catalysts was achieved under atmospheric pressure. Various targeting products including furfuryl alcohol (yield: 98.8%), 2-methylfuran (yield: 95.1%), 2-methyltetrahydrofuran (yield: 96.2%) and tetrahydrofurfuryl alcohol (yield: 78.2%) could be obtained by variation of the reactor configurations.
- Liu, Qianhe,Liu, Qing,Hu, Xun
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- Selective Activation of C-OH, C-O-C, or Ca? C in Furfuryl Alcohol by Engineered Pt Sites Supported on Layered Double Oxides
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The selective activation of targeted bonds in biomass-derived furfural or furfuryl alcohol with complex chemical linkages (C-C/C-H/C-O, Ca? C/Ca? O, or C-O-H/C-O-C) is of great challenge for biomass upgrading, expecting well-defined catalyst and definite catalytically active sites. This work demonstrates an efficient targeted activation to C-OH, C-O-C, or Ca? C by engineering the structure of catalytic Pt sites, affording 2-methylfuran (2-MF), tetrahydrofurfuryl alcohol (THFA), or 1,2-pentanediol (1,2-PeD) as product in the hydroconversion of furfuryl alcohol. The catalytic Pt sites have been engineered as atomic Pt, coordination unsaturated Pt-Pt in atom-thick dispersion, or coordination unsaturated 3D Pt-Pt by tailoring the Pt dispersion (single atom, 2D cluster, or 3D cluster) on Mg and Al-containing layered double oxide (Mg(Al)O) support. The selective activation of C-OH, C-O-C, or Ca? C has been traced with the FT-IR spectra recorded surface reaction. On atomic Pt, C-O-H is easily activated, with the assistance of Mg(Al)O support, with O-terminal adsorption without affecting furan C-O and Ca? C. However, Ca? C in the furan ring is easier to be activated on coordination-unsaturated Pt-Pt in atom-thick dispersion, resulting in a step-by-step hydrogenation to generate THFA. On coordination-unsaturated 3D Pt-Pt, the hydrogenolysis of furan ring is favored, resulting in the cleavage of furan C-O to produce 1,2-PeD. Also, the Mg(Al)O supports derived from Mg and Al layered double hydroxides (LDHs) here also play a key role in promoting the selectivity to 1,2-PeD by providing basic sites.
- An, Zhe,He, Jing,Jiang, Yitao,Ma, Xiaodan,Shu, Xin,Song, Hongyan,Xiang, Xu,Zhang, Jian,Zhang, Zhijun,Zhao, Wenfang,Zheng, Lirong,Zhu, Yanru
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p. 8032 - 8041
(2020/09/23)
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- Hydrogenation of furfural by noble metal-free nickel modified tungsten carbide catalysts
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Nickel-tungsten carbide catalysts convert furfural to high value products in a liquid phase catalytic reaction. The product distribution depends on the solvent and the Ni-W-ratio of the catalyst. In isopropyl alcohol a combination of Ni and WxC enables the opening of the furan ring to yield 1,2-pentanediol. Nickel accelerates the tungsten oxide reduction in the tungsten carbide catalyst synthesis and facilitates the carbon insertion. Nickel modified tungsten carbide is a promising, noble metal-free catalyst system for the upgrading of furfural based renewable resources. Its preparation is facilitated compared to unmodified tungsten carbide catalysts.
- Bretzler, Patrick,Huber, Michael,K?hler, Klaus,Nickl, Simon
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p. 27323 - 27330
(2020/09/01)
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- Highly Active Mesoporous Cu?Al2O3 Catalyst for the Hydrodeoxygenation of Furfural to 2-methylfuran
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While furfural has great potential as a platform chemical through diverse conversion pathways, 2-methylfuran is one of the key components as a fuel additive and a precursor of derived biofuels. However, catalyst design to control reactivity of active species to furfural has been challenging. Herein, we demonstrate that a mesoporous Cu?Al2O3 catalyst prepared by solvent-deficient precipitation shows the enhancement of furfural hydrodeoxygenation performance. Not only is the unique pore structure provided, but also the synergistic effects of improved Cu accessibility, co-existence of Cu0/Cu+ states, and strong metal-support interaction contribute to the superior activity and stability. Additionally, essential parameters for the synthesis and the test reaction are studied to improve the selectivity to 2-methylfuran. The employed catalyst preparation method opens a new channel for tailoring the bifunctionality of supported Cu catalysts.
- Park, Seyeon,Kannapu, Hari Prasad Reddy,Jeong, Cheonwoo,Kim, Jinsung,Suh, Young-Woong
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p. 105 - 111
(2019/11/25)
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- Ruthenium on phosphorous-modified alumina as an effective and stable catalyst for catalytic transfer hydrogenation of furfural
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Supported ruthenium was used in the liquid phase catalytic transfer hydrogenation of furfural. To improve the stability of Ru against leaching, phosphorous was introduced on a Ru/Al2O3 based catalyst upon impregnation with ammonium hypophosphite followed by either reduction or calcination to study the effect of phosphorous on the physico-chemical properties of the active phase. Characterization using X-ray diffraction, solid state 31P nuclear magnetic resonance spectroscopy, X-ray absorption spectroscopy, temperature programmed reduction with H2, infrared spectroscopy of pyridine adsorption from the liquid phase and transmission electron microscopy indicated that phosphorous induces a high dispersion of Ru, promotes Ru reducibility and is responsible for the formation of acid species of Br?nsted character. As a result, the phosphorous-based catalyst obtained after reduction was more active for catalytic transfer hydrogenation of furfural and more stable against Ru leaching under these conditions than a benchmark Ru catalyst supported on activated carbon.
- Campisi, Sebastiano,Ferri, Davide,Fovanna, Thibault,Kambolis, Anastasios,Kr?cher, Oliver,Nachtegaal, Maarten,Peng, Gael,Rentsch, Daniel,Villa, Alberto
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p. 11507 - 11516
(2020/04/03)
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- Chromium-free Cu?Mg/γ-Al2O3-an active catalyst for selective hydrogenation of furfural to furfuryl alcohol
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Development of a chromium (Cr)-free hydrogenation catalyst is very important to replace the existing hazardous Cr based catalyst used in the furfural hydrogenation to furfuryl alcohol. Herein, we report synthesis of well-dispersed copper nanoparticles supported on hydrothermally stable magnesium doped alumina (Cu?Mg/γ-Al2O3) for selective hydrogenation of furfural to furfuryl alcohol. The prepared catalyst was characterized by X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Powder X-ray Diffraction (PXRD), Surface Area Analysis (SAA), High Resolution-Transmission Electron Microscopy (HR-TEM), Temperature Programmed Reduction/Desorption (TPR/TPD) and Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) to understand textural properties of the catalyst. The prepared catalyst was found to be highly active and selective with 99% conversion of furfural and 94% selectivity for furfuryl alcohol under solvent free conditions at 443.15 K and 2 MPa of hydrogen pressure. It was also observed that the Cu?Mg/γ-Al2O3 catalyst is reusable (up to six runs) while maintaining its high activity and selectivity (≥94%) in the hydrogenation of furfural to furfuryl alcohol. This journal is
- Arundhathi, Racha,Newalkar, Bharat L.,Reddy, Panyala Linga,Samanta, Chanchal
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p. 41120 - 41126
(2020/11/23)
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- Hydroprocessing of furfural over in situ generated nickel phosphide based catalysts in different solvents
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The present work is dedicated to the nickel phosphide based catalysts, containing particles, generated in situ in the reaction medium from the different catalytic systems. The present catalytic systems exhibited high activity in the hydroprocessing of furfural. Full conversion of furfural depending on conditions was reached after 0.5?3 hours of reaction at 250?350 °C. 2-methylfuran was obtained as a main product in toluene with the highest selectivity of 77 %. Ethyl levulinate and 2-methylfuran with selectivity of 40 % and 38 % respectively were obtained as main products in ethanol under different conditions. Different reaction medium and nickel phosphide precursors had an influence on the obtained phases of catalysts. Ni12P5 and Ni2P were obtained in toluene from oil-soluble precursors and Ni12P5 was obtained in ethanol from water-soluble precursors.
- Golubeva, Maria A.,Maximov, Anton L.
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- Synthesis method of 2,5-furandicarboxylic acid
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The invention discloses a synthesis method of 2,5-furandicarboxylic acid. The synthesis method comprises the following steps: 1, hydrogenation of furfural into methyl furan; 2, acetylation of methyl furan; 3, hydrogenation of 5-methyl-2-acetylfuran; and 4, oxidation of 2-methyl-5-ethylfuran. According to the invention, a green renewable bio-based platform compound furfural is used as a raw material; and compared with a process for preparing 2,5-furandicarboxylic acid by using 5-hydroxymethylfurfural as a raw material, the method disclosed by the invention has the advantages that the source ofthe used raw material is wider, the raw material is easy to produce, productivity is higher, the cost of the raw material is lower, the cost of a used oxidation catalyst is low, and large-scale production is facilitated. Compared with a noble metal complex catalyst used in a process adopting CO carbonylation for carbon chain growth, a carbon chain growth strategy catalyst used in the invention issolid acid, so cost is greatly reduced.
- -
-
Paragraph 0026-0030; 0040-0044; 0054-0058
(2020/06/09)
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- Method for producing furandicarboxylic acid and derivatives thereof from furfural
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The invention discloses a method for producing furandicarboxylic acid and derivatives thereof from furfural. The method comprises the following steps: furfural is reduced to 2-methylfuran under the hydrogen condition; acetylation reaction is carried out on 2-methylfuran to obtain 5-methyl-2-acetylfuran; 5-methyl-2-acety furan reacts with ester to obtain methyl 5-methyl-2-furanformate, methyl 5-methyl-2-furanformate is oxidized into monomethyl 2,5-furandicarboxylate under the oxygen condition, and monomethyl 2,5-furandicarboxylate is hydrolyzed into monomethyl 2,5-furandicarboxylate or furtheresterified with methyl alcohol to generate dimethyl 2,5-furandicarboxylate. The cheap five-carbon furan compound furfural is used as a raw material, and the 2 5-furandicarboxylic acid and the derivatives thereof are prepared by a strategy of increasing a carbon chain, so that the cost of the raw material is greatly reduced. The product provided by the invention has high purity and can be directlyused as a polymerization monomer of PET polyester.
- -
-
Paragraph 0034-0038; 0053-0057
(2020/06/05)
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- Highly dispersed Pd catalysts supported on various carbons for furfural hydrogenation
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Furfural (FAL), one of the important platform molecules derived from lignocellulosic biomass, can be converted into valuable chemicals such as furfuryl alcohol or cyclopentanone via hydrogenation. While carbon materials have been used as versatile catalyst supports for FAL hydrogenation, systematic studies on the structure of the catalytic performances are lacking. In this work, we prepare various types of carbon supports to investigate the impact of carbon structures for Pd-catalyzed FAL hydrogenation. Mesoporous carbons, including CMK-3, CMK-5, CMK-8, and MSU-F-C, as well as carbon nanotube and Vulcan XC are used as carbon supports. For the preparation of highly dispersed Pd-supported carbon (Pd/C) catalysts, chemical reduction by sodium borohydride is applied, in which trisodium citrate plays a critical role in anchoring small Pd clusters on the carbons. In the liquid-phase hydrogenation of FAL, CMK-5 with the largest surface area and hexagonal hollow tubular framework is proven to be the most efficient carbon support for Pd/C catalysts, with the highest conversion of FAL in both 2-propanol (100percent) and water (86.4percent) solvents. It is also demonstrated that the product selectivity in FAL hydrogenation over various Pd/C catalysts is changed dramatically depending on the type of solvent. The Pd/C catalysts exhibit similar fractions of product distributions containing furfuryl alcohol, cyclopentanol, tetrahydrofurfuryl alcohol, and minor products in 2-propanol. However, the production of cyclopentanone is increased when water is used as a solvent.
- Lee, Jihyeon,Woo, Jinwoo,Nguyen-Huy, Chinh,Lee, Man Sig,Joo, Sang Hoon,An, Kwangjin
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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
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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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- Pd/Lewis Acid Synergy in Macroporous Pd@Na-ZSM-5 for Enhancing Selective Conversion of Biomass
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Pd nanometal particles encapsulated in macroporous Na-ZSM-5 with only Lewis acid sites have been successfully synthesized by a steam-thermal approach. The synergistic effect of Pd and Lewis acid sites have been investigated for significant enhancement of the catalytic selectivity towards furfural alcohol in furfural hydroconversion.
- Liu, Jia-Wen,Wu, Si-Ming,Wang, Li-Ying,Tian, Ge,Qin, Yuan,Wu, Jing-Xian,Zhao, Xiao-Fang,Zhang, Yan-Xiang,Chang, Gang-Gang,Wu, Lu,Zhang, Yue-Xing,Li, Zhao-Fei,Guo, Cheng-Yu,Janiak, Christoph,Lenaerts, Silvia,Yang, Xiao-Yu
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p. 5364 - 5368
(2020/08/05)
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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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p. 7323 - 7330
(2020/11/25)
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- Integrating Biomass into the Organonitrogen Chemical Supply Chain: Production of Pyrrole and d-Proline from Furfural
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Production of renewable, high-value N-containing chemicals from lignocellulose will expand product diversity and increase the economic competitiveness of the biorefinery. Herein, we report a single-step conversion of furfural to pyrrole in 75 % yield as a key N-containing building block, achieved via tandem decarbonylation–amination reactions over tailor-designed Pd?S-1 and H-beta zeolite catalytic system. Pyrrole was further transformed into dl-proline in two steps following carboxylation with CO2 and hydrogenation over Rh/C catalyst. After treating with Escherichia coli, valuable d-proline was obtained in theoretically maximum yield (50 %) bearing 99 % ee. The report here establishes a route bridging commercial commodity feedstock from biomass with high-value organonitrogen chemicals through pyrrole as a hub molecule.
- Di, Lu,Fung Kin Yuen, Vincent,Song, Song,Sun, Qiming,Yan, Ning,Zhou, Kang
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supporting information
p. 19846 - 19850
(2020/09/02)
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- Decomposition of glucose with in situ deoxygenation in a low H2 pressure environment – Pt. II: Bimetallic catalysts
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Bimetallic catalysts, CoFe, NiFe, PdFe, and PtCo were studied for their ability to perform in situ deoxygenation of glucose decomposition production at 350 °C. Catalysts were prepared via co-impregnation and sequential impregnation methods on SiO2/s
- Rogers, Kyle A.,Zheng, Ying
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- Preparation of 5-methylfurfural from starch in one step by iodide mediated metal-free hydrogenolysis
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Starch is available in large quantities and at cheap price, especially that from stale rice, root and tuber crops, etc., which makes it desirable for conversion to value-added products. A metal-free approach to convert starch to 5-methylfurfural (5-MF) using hydrochloric acid, sodium iodide and hydrogen in a biphasic solvent system has been developed. 5-MF is an important fine chemical, widely used in food, medicine, pesticides, cosmetics and other industries, and is also considered to be an important bio-gasoline precursor. I- has superior nucleophilic substitution properties and high reactivity towards C-O bond cleavage, which is crucial for this transformation. Under optimal reaction conditions, 38.0% of 5-MF and 45.6% of total organic products can be obtained from starch with 22.5% levulinic acid as the main side product. Besides, 80.8% 5-MF can be directly obtained from 5-hydroxymethylfurfural (HMF) through the same process. To the best of our knowledge, this is the first reported example of a metal-free process to convert starch and HMF directly to 5-MF. The reaction mechanism was well studied. The catalyst system was proved to be stable and was recycled five times without loss of activity.
- Peng, Yang,Li, Xianghua,Gao, Tian,Li, Teng,Yang, Weiran
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p. 4169 - 4177
(2019/08/12)
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- Direct synthesis of furfuryl alcohol from furfural: Catalytic performance of monometallic and bimetallic Mo and Ru phosphides
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The catalytic properties of monometallic and bimetallic Ru and Mo phosphides were evaluated for their ability to selectively hydrogenate furfural to furfuryl alcohol. Monometallic MoP showed high selectivity (98%) towards furfuryl alcohol, while RuP and Ru2P exhibited lower selectivity at comparable conversion. Bimetallic promotional effects were observed with Ru1.0Mo1.0P, as the pseudo-first order reaction rate constant for furfural hydrogenation to furfuryl alcohol, k1, was at least 5× higher than MoP, RuP, and Ru2P, while maintaining a 99% selectivity. Composition-directed catalytic studies of RuxMo2-xP (0.8 1, but not the selectivity. The rate constant ratio k1/(k2 + k3) for furfuryl alcohol production compared to methyl furan (k2) and tetrahyrofurfuryl alcohol (k3) followed the trend of Ru1.0Mo1.0P > Ru1.2Mo0.8P > MoP > Ru0.8Mo1.2P > RuP > Ru2P. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to examine the configuration of adsorbed furfural on the synthesized catalysts, but the results were inconclusive and no correlation could be found with the selectivity due to the possible IR inactive surface modes with furfural adsorption. However, gas phase density functional theory calculations suggested the x = 1.0 material in RuxMo2-xP (0.8 1 after 3 cycles without any regeneration, but the activity could be fully recovered through a re-reduction step.
- Bonita, Yolanda,Jain, Varsha,Geng, Feiyang,O'Connell, Timothy P.,Wilson, Woodrow N.,Rai, Neeraj,Hicks, Jason C.
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p. 3656 - 3668
(2019/07/22)
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- In-situ hydrogenation of furfural conversion to furfuryl alcohol via aqueous-phase reforming of methanol
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It is a promising pathway to reduce the dependence on fossil fuels and obtain the bio-fuels or chemicals production from biomass derivatives. The conversion from furfural (FFR) to furfuryl alcohol (FFA) is an important industrial technology using the liquid-phase hydrogenation method with external hydrogen gas. However, the natural environment is threatened by the security of external hydrogen gas, toxicant catalyst, and the high energy consumption. Recently, in-situ hydrogenation is a novel method to converse FFR to FFA at mild reaction conditions to replace the dangerous external hydrogen gas. In this paper, we reported an efficient in-situ hydrogenation method via aqueous-phase reforming of methanol using Pt loading MgTiO3 (perovskite-type material) at mild conditions. Pt nanoparticles were high dispersion on the nano-MgTiO3-450 surface, and CH3OH and H2O were reformed to produce hydrogen gas on the catalyst surface through the action of Pt nanoparticles. A part of active hydrogen could be involved in the reduction of Pt2+ to Pt0, resulting in the perfect recyclability of the Pt@MT-450 catalyst. The other part of active hydrogen were participated in the hydrogenation of FFR conversion to FFA under the interaction of Pt and Mg elements. The in-situ hydrogenation of FFR to FFA using Pt@MT-450 is an effectively pathway to reduce the reaction conditions than that with external hydrogen gas.
- Zhang, Shiqiu,Yang, Xue,Zheng, Kui,Xiao, Ruihao,Hou, Qidong,Liu, Bangjun,Ju, Meiting,Liu, Le
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p. 103 - 110
(2019/06/18)
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- Method and System for Hybrid Catalytic Biorefining of Biomass to Methylated Furans and Depolymerized Technical Lignin
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A method is disclosed for converting biomass into a fuel additive, the method comprising: liquefying the biomass to form a liquor; neutralizing the liquor; precipitating lignin out of the liquor; extracting furfural (FF) and 5-hydroxymethylfurfural (HMF) from the liquor; and hydrodeoxygenating (HDO) the extracted furfurals over a Cu—Ni/TiO2 catalyst. The catalyst for hydrodeoxygenating (HDO) furfural (FF) and 5-hydroxymethylfurfural (HMF) to methylated furans comprises copper-nickel (Cu—Ni) particles supported on titanium dioxide (TiO2), and wherein the copper-nickel particles form core-shell structures in which copper (Cu) is enriched at a surface of the catalyst.
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- Mesoporous mixed CuCo oxides as robust catalysts for liquid-phase furfural hydrogenation
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A series of highly ordered mesoporous CuCo oxide catalysts with a controlled composition are successfully synthesized by nanocasting from mesoporous silica, KIT-6 template. Liquid-phase furfural (FAL) hydrogenation is carried out to find the optimal composition of the CuCo oxide catalysts to achieve the best catalytic performance. As-prepared mesoporous mixed CuCo oxides exhibit a high surface area (60?135 m2 g?1) and a well-defined ordered mesostructure with homogenous dispersion of Cu and Co. Among various compositions of CuxCoy oxides (x = 1–9, y = 1–x) studied, the Cu1Co5 oxide catalyst shows the highest conversion in the hydrogenation of FAL, which is superior to those achieved with mesoporous monometallic oxides, CuO and Co3O4. While 2-methylfuran is produced from furfuryl alcohol via aldehyde hydrogenation and subsequent hydrogenolysis, the formation of 2-methylfuran increased with a decrease in the Cu/Co ratio of the CuCo oxide catalyst. The mixed CuCo oxide catalyst is readily reduced under the reaction environment to produce metallic CuCo as the active species. The synergistic interactions between Cu and Co in the mixed CuCo oxide catalysts play an important role in the outstanding catalytic performance for FAL hydrogenation, which could not be achieved with either of the monometallic catalysts or their physical mixtures. The excellent stability and recyclability of mesoporous mixed CuCo oxide catalysts as well as the exceptionally high activity, surpassing those of the monometallic oxides, render them promising as a low-cost and efficient catalyst for the industrial upgrading of biomass-derived FAL.
- Nguyen-Huy, Chinh,Lee, Hojeong,Lee, Jihyeon,Kwak, Ja Hun,An, Kwangjin
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p. 118 - 126
(2019/01/04)
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- Structure-dependent catalytic properties of mesoporous cobalt oxides in furfural hydrogenation
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As the development of noble metal free catalysts became important in the biomass conversion, catalytic hydrogenation of furfural (FAL) is investigated over ordered mesoporous cobalt oxide (m-Co3O4). When m-Co3O4 is reduced at 350 and 500 °C in hydrogen, the original crystal structure of Co3O4 is changed to CoO and Co, respectively. Here we examine the effect of the structure, porosity, and oxidation state of m-Co3O4 to identify catalytically active species for hydrogenation of FAL. Among cobalt oxide catalysts having different crystal structures and symmetry, m-CoO having p6mm symmetry exhibits the highest activity. In product selectivity, the CoO phase induces FAL hydrogenolysis by selective production of 2-methyl furan (MF), while the Co3O4 and Co phases promote preferential hydrogenation of side chain (carbonyl group) of FAL to furfuryl alcohol. Density functional theory calculations also reveal that the adsorption of FAL on CoO(111) is higher than Co(111). Overall, these studies demonstrate that CoO as the most active phase is responsible for the high FAL conversion and the distinct pathway of FAL to MF.
- Nguyen-Huy,Lee, Jihyeon,Seo, Ji Hui,Yang, Euiseob,Lee, Jaekyoung,Choi, Keunsu,Lee,Kim, Jae Hyung,Lee, Man Sig,Joo, Sang Hoon,Kwak, Ja Hun,Lee, Jun Hee,An, Kwangjin
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- Hydrodeoxygenation Using Magnetic Induction: High-Temperature Heterogeneous Catalysis in Solution
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Magnetic heating has recently been demonstrated as an efficient way to perform catalytic reactions after deposition of the heating agent and the catalyst on a support. Here we show that in solution, and under mild conditions of mean temperature and pressure, it is possible to use magnetic heating to carry out transformations that are otherwise performed heterogeneously at high pressure and/or high temperature. As a proof of concept, we chose the hydrodeoxygenation of acetophenone derivatives and of biomass-derived molecules, namely furfural and hydroxymethylfurfural. These reactions are difficult, require heterogeneous catalysts and high pressures, and, to the best of our knowledge, have no precedent in standard solution. Here, hydrodeoxygenations are fully selective under mild conditions (3 bar H2, moderate mean temperature of the solvent). The reason for this reactivity is the fast heating of the particles well above the boiling temperature of the solvent and the local creation of hot spots surrounded by a vapor layer, in which high temperature and pressure may be present. This technology may be practicable for many organic transformations.
- Asensio, Juan M.,Miguel, Ana B.,Fazzini, Pier-Francesco,van Leeuwen, Piet W. N. M.,Chaudret, Bruno
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supporting information
p. 11306 - 11310
(2019/07/12)
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- Furfural hydrodeoxygenation on iron and platinum catalysts
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Furfural can be converted into a wide range of high-octane products like 2-methylfuran (2-MF) through hydrodeoxygenation (HDO). Iron-based catalyst (Fe/SiO2), has shown high selectivity for gas phase conversion of furfural to 2-MF at atmospheric pressure and 573 K. However, it showed rapid deactivation. Furfural is the main coke precursor, although coke is also formed when 2-MF and furan are used as reactants, but in lower quantities. Coke profiles along the catalytic bed suggest that tetra-hydrofuran is an important coke precursor. The addition of a second metal like platinum, even in very low proportions, generates hydrogen spillover leading to an important improvement in the stability of the catalyst. The Fe/Pt ratio on the surface regulates the amount of coke deposited because it modifies the iron particle sizes, the interaction with the support and the amount of hydrogen available for the reactions. These phenomena influence the reaction, coke formation and regeneration mechanisms.
- Zanuttini, M. Soledad,Gross, Martin,Marchetti, Gustavo,Querini, Carlos
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- Sustainable hydrocarbon production via simultaneous condensation-hydrodeoxygenation of propionic acid with furfural over red mud-supported noble metal catalysts
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A new catalytic system for single-step alkane synthesis from furans and carboxylic acids was investigated using noble metals-supported red mud (RM) catalysts. Maximum alkane selectivities were 100%, 87%, and 56% over Pt/RM, Pd/RM, and Ru/RM respectively. Potassium doping prolonged the catalyst life by suppressing methanation reaction, decreased coking, and enhancing the stability of noble metals towards oxidation. Five functionalities were accomplished on the modified catalysts: partial reduction of propionic acid on noble metals; moderating coking reactions on K, suppressing methanation on K, ketonization of acid on RM, and condensation-hydrodeoxygenation reaction on RM. Magnetite played significant role in catalyzing ketonization reaction.
- Castille, Antonie,Bessette, Claudie,Thomas, Francois,Etemad, Mania
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- Catalyst-free synthesis of biodiesel precursors from biomass-based furfuryl alcohols in the presence of H2O and air
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Production of biodiesel from biomass resources usually requires elongation of carbon numbers from typical C5 and C6 platform molecules through C-C coupling reactions, which were catalyzed by acid, base or metal catalysts traditionally. Herein, a catalyst-free method was developed to produce bis(furan-2-yl)methane derivatives (BFMs) from furfuryl alcohol derivatives (FAs) in the presence of H2O and air without any other additional catalysts. An 81% yield of bis(5-methylfuran-2-yl)methane (BMFM) can be obtained from 5-methylfurfuryl alcohol (5-MFA) and a 59% total yield of C11 biodiesel was obtained from 5-methylfurfural (5-MF). In addition, a H2O and air mediated free radical decarboxylation mechanism was proposed based on the detailed mechanistic studies. This strategy offers a green, low-cost and environmentally friendly approach to synthesize biodiesel precursors from biomass based platform molecules.
- Qin, Shengxiang,Li, Teng,Zhang, Man,Liu, Hongyu,Yang, Xin,Rong, Nianxin,Jiang, Jun,Wang, Yalin,Zhang, Hua,Yang, Weiran
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p. 6326 - 6334
(2019/12/03)
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- Accelerated decarbonylation of 5-hydroxymethylfurfural in compressed carbon dioxide: A facile approach
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Herein, decarbonylation of biomass-based 5-hydroxymethylfurfural (HMF) in compressed CO2 with an unexpected acceleration of the reaction rate and excellent catalytic activity is reported. Without any additive, CO surrogates, or any organic solvents, via the developed method, an excellent conversion of 99.8% and highest selectivity of furfuryl alcohol (99.6%) in 4 h at 145 °C were achieved using an alumina-supported Pd catalyst (Pd/Al2O3). The superior activity is due to the unique characteristics (miscibility of reactant gases and high diffusivity) of compressed CO2 and the synergy between CO2 and Pd/Al2O3, where CO2 plays an interesting role in accelerating the reaction by enhancing the diffusion of CO and furfuryl alcohol (both products have high solubilities in CO2), consequently shifting the equilibrium to the forward direction. Characterisation of the catalyst suggested its direct interaction with the substrate and provided an indication of the possible reaction path. Thus, a mechanism was outlined. Compared to the results obtained using organic solvents, the results obtained using compressed CO2 were superior in terms of activity, selectivity, and reaction rate. This strategy highlights easy product separation, improved catalyst life, and a simple sustainable process. The efficiency of this protocol is confirmed by its potential application to a series of aldehydes with various substituents to produce decarbonylated products in good to excellent yields.
- Chatterjee, Maya,Ishizaka, Takayuki,Kawanami, Hajime
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p. 2345 - 2355
(2018/06/01)
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- Batch versus Continuous Flow Performance of Supported Mono- and Bimetallic Nickel Catalysts for Catalytic Transfer Hydrogenation of Furfural in Isopropanol
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Furfural takes an important position in hemicelluloses biorefinery platforms. It can be converted into a wide range of chemicals. One important valorization route is the catalytic hydrogenation. Whereas molecular hydrogen is mostly used in industrial hydrogenation processes, recent studies also showed that alcohols can be used as reductants from which hydrides can be transferred catalytically to furfural. This process is often assisted by the formation of significant amounts of side products, in despite of high yields to the hydrogenolysis product 2-methylfuran. The present work explores the catalytic behavior in batch and continuous flow of mono- and bimetallic nickel catalysts supported on activated carbon for the catalytic transfer hydrogenation of furfural in isopropanol.
- Wang, Yantao,Prinsen, Pepijn,Triantafyllidis, Konstantinos S.,Karakoulia, Stamatia A.,Yepez, Alfonso,Len, Christophe,Luque, Rafael
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p. 3459 - 3468
(2018/08/07)
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- Solvent Tunes the Selectivity of Hydrogenation Reaction over α-MoC Catalyst
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Selective activation of chemical bonds in multifunctional oxygenates on solid catalysts is a crucial challenge for sustainable biomass upgrading. Molybdenum carbides and nitrides preferentially activate C=O and C-OH bonds over C=C and C-C bonds in liquid-phase hydrogenation of bioderived furfural, leading to highly selective formations of furfuryl alcohol (FA) and its subsequent hydrogenolysis product (2-methyl furan (2-MF)). We demonstrate that pure-phase α-MoC is more active than β-Mo2C and γ-Mo2N for catalyzing furfural hydrogenation, and the hydrogenation selectivity on these catalysts can be conveniently manipulated by alcohol solvents without significant changes in reaction rates (e.g., > 90% yields of FA in methanol solvent and of 2-MF in 2-butanol solvent at 423 K). Combined experimental and theoretical assessments of these solvent effects unveil that it is the hydrogen donating ability of the solvents that governs the hydrogenation rate of the reactants, while strong dissociative adsorption of the alcohol solvent on Mo-based catalysts results in surface decoration which controls the reaction selectivity via enforcing steric hindrance on the formation of relevant transient states. Such solvent-induced surface modification of Mo-based catalysts provides a compelling strategy for highly selective hydrodeoxygenation processes of biomass feedstocks.
- Deng, Yuchen,Gao, Rui,Lin, Lili,Liu, Tong,Wen, Xiao-Dong,Wang, Shuai,Ma, Ding
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p. 14481 - 14489
(2018/11/30)
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