534-22-5Relevant articles and documents
Bimetallic Fe-Ni/SiO2 catalysts for furfural hydrogenation: Identification of the interplay between Fe and Ni during deposition-precipitation and thermal treatments
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
, p. 162 - 172 (2019)
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.
Mechanistic insights into metal lewis acid-mediated catalytic transfer hydrogenation of furfural to 2-methylfuran
Gilkey, Matthew J.,Panagiotopoulou, Paraskevi,Mironenko, Alexander V.,Jenness, Glen R.,Vlachos, Dionisios G.,Xu, Bingjun
, p. 3988 - 3994 (2015)
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.
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
Grazia,Bonincontro,Lolli,Tabanelli,Lucarelli,Albonetti,Cavani
, p. 4412 - 4422 (2017)
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.
Gas-Phase Heteroaromatic Substitution. 3. Electrophilic Methylation of Furan and Thiophene by CH3XCH3+ (X = F or Cl) Ions
Angelini, Giancarlo,Lilla, Gaetano,Speranza, Maurizio
, p. 7091 - 7098 (1982)
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.
Healing by the Joule effect of electrically conductive poly(ester-urethane)/carbon nanotube nanocomposites
Willocq,Bose,Khelifa,Garcia,Dubois,Raquez
, p. 4089 - 4097 (2016)
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.
Conversion of furfuryl alcohol into 2-methylfuran at room temperature using Pd/TiO2 catalyst
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.
, p. 2280 - 2286 (2014)
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
Single pot selective hydrogenation of furfural to 2-methylfuran over carbon supported iridium catalysts
Date, Nandan S.,Hengne, Amol M.,Huang,Chikate, Rajeev C.,Rode, Chandrashekhar V.
, p. 2027 - 2037 (2018)
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.
Molybdenum carbide as a highly selective deoxygenation catalyst for converting furfural to 2-methylfuran
Xiong, Ke,Lee, Wen-Sheng,Bhan, Aditya,Chen, Jingguang G.
, p. 2146 - 2149 (2014)
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.
Room temperature hydrogenation of furfuryl alcohol by Pd/titanate nanotube
Yuan, Qingqing,Ye, Feiyang,Xue, Teng,Guan, Yejun
, p. 26 - 33 (2015)
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.
Promotion effect of Ce or Zn oxides for improving furfuryl alcohol yield in the furfural hydrogenation using inexpensive Cu-based catalysts
Jiménez-Gómez, Carmen P.,Cecilia, Juan A.,Franco-Duro, Francisco I.,Pozo, Manuel,Moreno-Tost, Ramón,Maireles-Torres, Pedro
, p. 121 - 131 (2018)
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.
