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.
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.
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
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.
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Rice
, p. 3193 (1952)
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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
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.
Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
supporting information, p. 9029 - 9039 (2021/06/28)
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.
Heterogeneously Catalyzed Selective Decarbonylation of Aldehydes by CeO2-Supported Highly Dispersed Non-Electron-Rich Ni(0) Nanospecies
Matsuyama, Takehiro,Yatabe, Takafumi,Yabe, Tomohiro,Yamaguchi, Kazuya
, p. 13745 - 13751 (2021/11/17)
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.