109-99-9Relevant articles and documents
Anodization of bismuth doped TiO2 nanotubes composite for photocatalytic degradation of phenol in visible light
Ali, Imran,Kim, Seu-Run,Kim, Sung-Pil,Kim, Jong-Oh
, p. 31 - 37 (2017)
Bismuth doped TiO2 photocatalyst was synthesized in a one-step electrochemical anodization method. Bismuth nitrate Bi(NO3)3 was used as a bismuth source. The obtained samples were characterized by FE-SEM, XRD, EDX and XPS. The optimum synthesis conditions for bismuth doping were 1.0 M bismuth nitrate in an ethylene glycol electrolyte with anodization at 40 V for 2 h. Compared with undoped TiO2 nanotubes, bismuth doped TiO2 photocatalyst showed a higher photocatalytic activity by a factor of 4.0 for phenol degradation under visible light irradiation. The optimum phenol degradation using a photoelectrocatalytic method was observed at a 0.5 V external bias, and this degradation rate was 5.2 times faster than that observed for undoped TiO2 nanotubes. The doped bismuth TiO2 nanotubes are favorable for the separation of photo-induced electrons and holes, reducing the recombination of charges, and promoting the formation of hydroxyl radicals and superoxides that degrade phenol.
-
Klute,Walters
, p. 506,507 (1946)
-
Insights into the Oxidation State and Location of Rhenium in Re-Pd/TiO2 Catalysts for Aqueous-Phase Selective Hydrogenation of Succinic Acid to 1,4-Butanediol as a Function of Palladium and Rhenium Deposition Methods
Ly, Bao Khanh,Tapin, Beno?t,Aouine, Mimoun,Delichere, Pierre,Epron, Florence,Pinel, Catherine,Especel, Catherine,Besson, Michèle
, p. 2161 - 2178 (2015)
ReOx-Pd/TiO2 catalysts prepared from different 2 wt %Pd/TiO2 catalysts using two protocols for the deposition of the Re promoter (successive impregnation and catalytic reduction) were characterized by different techniques to better understand the nature of the active and selective sites implied in the aqueous-phase hydrogenation of succinic acid to 1,4-butanediol. Regardless of the support and Re introduction method, it was established that varying amounts of Pd and Re were in very close proximity without electronic interaction in the reduced catalysts. A high fraction of Re always remained partially oxidized to generate a bimetallic catalyst that can provide the necessary bifunctional sites to enable the selective hydrogenolysis of the intermediate γ-butyrolactone to 1,4-butanediol. Depending on the method of promotion, the ReOx species that interact with Pd were deposited as clusters with different spatial Re-Re interactions.
Hydrogenation of succinic acid to tetrahydrofuran (THF) over ruthenium-carbon composite (Ru-C) catalyst
Hong, Ung Gi,Kim, Jeong Kwon,Lee, Joongwon,Lee, Jong Kwon,Song, Ji Hwan,Yi, Jongheop,Song, In Kyu
, p. 466 - 471 (2014)
Ruthenium-carbon composite (Ru-XC) catalysts prepared by a single-step surfactant-templating method were pre-graphitized at different temperature (X = 200, 250, 300, 350, and 400 C), and they were applied to the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF). The effect of pre-graphitization temperature on the catalytic performance of Ru-XC catalysts (X = 200, 250, 300, 350, and 400 C) was investigated. It was observed that Ru-XC composite catalysts showed different textural properties depending on pre-graphitization temperature. In the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF), conversion of succinic acid and yield for THF showed volcano-shaped trends with respect to pre-graphitization temperature. In other words, an optimal pre-graphitization temperature was required to achieve maximum catalytic performance of Ru-XC catalysts. Yield for THF in the hydrogenation of succinic acid increased with decreasing ruthenium particle size of Ru-XC catalysts. Among the catalysts tested, Ru-300C, which had the smallest ruthenium particle size, showed the highest yield for THF.
Importance of Zeolite Wettability for Selective Hydrogenation of Furfural over Pd@Zeolite Catalysts
Wang, Chengtao,Liu, Zhiqiang,Wang, Liang,Dong, Xue,Zhang, Jian,Wang, Guoxiong,Han, Shichao,Meng, Xiangju,Zheng, Anmin,Xiao, Feng-Shou
, p. 474 - 481 (2018)
The metal-catalyzed selective hydrogenation of biomass-derived molecules is in great demand but is challenging due to the complex reaction pathways. Herein, we report a persuasive example for achieving selective hydrogenation of furfural over Pd catalysts by controllable sorption of molecules in zeolite micropores. The key to this success is fixation of Pd nanoparticles inside of silicalite-1 zeolite with controllable wettability (Pd@S-1-OH) by functionalizing silanol groups into the zeolite framework. In the hydrogenation of furfural as a model reaction, the Pd@S-1-OH catalyst with appropriate hydrophilicity exhibits extraordinary selectivity for the formation of furan, giving furan selectivity as high as >99.9% with a complete conversion of furfural, outperforming the conventional Pd nanoparticles supported on zeolite crystals (Pd/S-1) and S-1 zeolite fixed Pd catalysts without an artificially functionalized silanol group (Pd@S-1). The extraordinary performance of Pd@S-1-OH is reasonably attributed to the controllable diffusion of molecules within the hydrophilic zeolite micropores, which favors the adsorption of furfural and a series of byproducts but promotes the desorption of furan. Very importantly, Pd@S-1-OH is stable and gives the furan productivity of ～583.3 g gPd-1 day-1 in a continuous test.
In situ DRIFTS for the mechanistic studies of 1,4-butanediol dehydration over Yb/Zr catalysts
Mi, Rongli,Hu, Zhun,Yang, Bolun
, p. 138 - 151 (2019)
To study the effect of acid-base properties of catalysts on 1,4-butanediol (BDO) dehydration to 3-buten-1-ol (BTO), Yb/Zr catalysts with different Yb content were synthesized by a wet impregnation method. The texture property, crystalline form and surface
The Elimination Kinetics of Methoxyalkyl Chlorides in the Gas Phase. Evidence for Neighboring Group Participation
Chuchani, Gabriel,Martin, Ignacio
, p. 431 - 433 (1986)
The rates of elimination of 3-methoxy-1-chloropropane and 4-methoxy-1-chlorobutane have been determined in a seasoned, static reaction vessel over the temperature range of 410-490 deg C and the pressure range of 56-181 torr.The reactions are homogeneous and unimolecular, follow a first-order rate low, and are invariant to the presence of a twofold or greater excess of the radical chain inhibitor toluene.The overall rate coefficients are given by the following Arrhenius equations: for 3-methoxy-1-chloropropane, logk1(s-1)=(12.92+/-0.48)-(226.0+/-6.8) kJ mol-1(2.303RT)-1; for 4-methoxy-1-chlorobutane, logk1(s-1)=(12. 9+/-0.26)-(218.1+/-3.5) kJ mol-1(2.303RT)-1.The CH3O group in 4-methoxy-1-chlorobutane has been found to assist anchimerically the elimination reaction, where dehydrochlorination and tetrahydrofuran formation arise from an intimate ion pair type of mechanism.The partial rates for these parallel eliminations have been determined and reported.Participation of the CH3O in 3-methoxy-1-chloropropane is barely detected.The present results give further evidence of intimate ion pair mechanism through neighboring group perticipation in the gas-phase elimination of certain types of organic molecules.
-
Gillis
, p. 651,653 (1960)
-
Selective hydrogenolysis of 2-furancarboxylic acid to 5-hydroxyvaleric acid derivatives over supported platinum catalysts
Asano, Takehiro,Takagi, Hiroshi,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi
, p. 6133 - 6145 (2019)
The conversion of 2-furancarboxylic acid (FCA), which is produced by oxidation of furfural, to 5-hydroxyvaleric acid (5-HVA) and its ester/lactone derivatives with H2 was investigated. Monometallic Pt catalysts were effective, and other noble metals were not effective due to the formation of ring-hydrogenation products. Supports and solvents had a small effect on the performance; however, Pt/Al2O3 was the best catalyst and short chain alcohols such as methanol were better solvents. The optimum reaction temperature was about 373 K, and at higher temperature the catalyst was drastically deactivated by deposition of organic materials on the catalyst. The highest yield of target products (5-HVA, δ-valerolactone (DVL), and methyl 5-hydroxyvalerate) was 62%, mainly obtained as methyl 5-hydroxyvalerate (55% yield). The byproducts were mainly ring-hydrogenation compounds (tetrahydrofuran-2-carboxylic acid and its ester) and undetected ones (loss of carbon balance). The catalyst was gradually deactivated during reuses even at a reaction temperature of 373 K; however, the catalytic activity was recovered by calcination at 573 K. The reactions of various related substrates were carried out, and it was found that the O-C bond in the O-CC structure (1,2,3-position of the furan ring) is dissociated before CC hydrogenation while the presence and position of the carboxyl group (or methoxy carbonyl group) much affect the reactivity.
Catalytic conversion of furan to gasoline-range aliphatic hydrocarbons via ring opening and decarbonylation reactions catalyzed by Pt/γ-Al 2O3
Runnebaum, Ron C.,Nimmanwudipong, Tarit,Doan, Jonathan,Block, David E.,Gates, Bruce C.
, p. 664 - 666 (2012)
Conversion of furan in the presence of H2 catalyzed by Pt/γ-Al2O3 at 573 K and 1.4 bar leads to the formation of alkanes and alkenes, some in the gasolinerange, including C7 hydrocarbons, butenes, propene, and propane.
Hydro-Oxygenation of Furfural in the Presence of Ruthenium Catalysts Based on Al-HMS Mesoporous Support
Roldugina,Shayakhmetov,Maksimov,Karakhanov
, p. 1306 - 1315 (2019)
Ru-containing catalyst based on an Al-HMS mesoporous aluminosilicate was synthesized. The mesoporous support and the catalyst on its basis were characterized by the methods of low-temperature desorption/adsorption of nitrogen, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray photoelectron microscopy, and energy-dispersive X-ray fluorescence analysis. The synthesized catalyst was investigated in the hydrodeoxygenation of the model compound of bio-oil, furfural, in the presence of H2O. The reaction was carried out at initial hydrogen pressures of 1–7 MPa at 200°C–300°C temperature range. The results revealed that the synthesized catalyst displayed a high activity in the hydrotransformation of furfural. The conversion was 100% in 1 hr at a 5 MPa hydrogen pressure and 200°C.
Entropies of organolithium aggregation based on measured microsolvation numbers
Knorr, Rudolf,Menke, Thomas,Ferchland, Kathrin
, p. 468 - 472 (2013)
The recent measurement (J. Am. Chem. Soc.2008, 130, 14179-14188) of the microsolvation numbers of monodentate, nonchelating ethereal donor ligands coordinating to the monomers and dimers of two sterically shielded =C(aryl)-Li compounds permits the determination of well-founded dimerization enthalpies (ΔH0) and entropies (ΔS0) from properly formulated equilibrium constants, which must include the concentrations of the free donor ligands. The monomers are found to dimerize endothermically (ΔH0 > 0) in [D8]toluene solution in the presence of the donor tBuOMe or THF, but only slightly exothermically (ΔH 0 = -0.5 kcal per mol of dimer) with the donor Et2O. The dimerization entropies ΔS0 (in cal mol-1 K -1) with the respective equivalents of released donor ligands are 7.2 and 11.0 (with 2 equiv of tBuOMe in the two cases), 6.1 (with 2 Et 2O), and 34.1 (with 4 THF). It is shown that the improper omission of microsolvation from the equilibrium constant (a usual practice when the ligand numbers are not known) can lead to contaminated aggregation entropies ΔSψ, which may deviate considerably from the true entropies ΔS0. A method is provided for estimating the required microsolvation numbers from 13C/Li NMR coupling constants 1JC,Li for less congested organolithium types whose coordinated and free donor ligands cannot be distinguished by NMR integration.
Ortho-directed lithiation of ω-phenoxy alcohols
Salteris, Constantinos S.,Kostas, Ioannis D.,Micha-Screttas, Maria,Heropoulos, George A.,Screttas, Constantinos G.,Terzis, Aris
, p. 5589 - 5592 (1999)
ω-Phenoxy alcohols, PhO(CH2)(n)OH (n = 2-7), have been subjected to metalation with 2 equiv of n-butyllithium in tetrahydrofuran/methylcyclohexane solvent. Reaction of the resulting lithiated compounds with carbon dioxide (n = 2-7), benzaldehyde (n = 2-6), benzophenone (n = 2, 3), dimethylformamide (n = 2), ethyl formate (n = 2), and chlorodiphenylphosphine (n = 3) afforded the corresponding ortho- substituted hydroxyalkoxybenzenes in yields ranging from 45 to 83%. The synthesis is also reported of five new bis[o-(ω-hydroxyalkoxy)phenyl]mercury compounds (n = 2-6), four crystal structures of which have been determined.
Catalytic transfer hydrogenation/hydrogenolysis for reductive upgrading of furfural and 5-(hydroxymethyl)furfural
Scholz, David,Aellig, Christof,Hermans, Ive
, p. 268 - 275 (2014)
The sequential transfer hydrogenation/hydrogenolysis of furfural and 5-hydroxymethylfurfural to 2-methylfuran and 2,5-dimethylfuran was studied over in situ reduced, Fe2O3-supported Cu, Ni, and Pd catalysts, with 2-propanol as hydrogen donor. The remarkable activity of Pd/Fe 2O3 in both transfer hydrogenation/hydrogenolysis is attributed to a strong metal-support interaction. Selectivity towards hydrogenation, hydrogenolysis, decarbonylation, and ring-hydrogenation products is shown to strongly depend on the Pd loading. A significant enhancement in yield to 62%, of 2-methylfuran and 2-methyltetrahydrofuran was observed under continuous flow conditions.
-
Heine,Siegfried
, p. 489 (1954)
-
Liquid phase chemo-selective catalytic hydrogenation of furfural to furfuryl alcohol
Sharma, Rajesh V.,Das, Umashankar,Sammynaiken, Ramaswami,Dalai, Ajay K.
, p. 127 - 136 (2013)
Novel Cu:Zn:Cr:Zr based catalysts were developed for the hydrogenation of furfural to furfuryl alcohol. Physio-chemical characterizations of the catalysts were performed by using XRD, BET, FTIR, TPR, NH3-TPD, ICP-MS, SEM, TEM, CO-chemisorption, and XANES techniques. Among all the catalysts prepared, the catalysts Cu(3):Zn(2):Cr(1):Zr(3) and Cu(3):Zn(2):Cr(1):Zr(4), referred as Cat-C and Cat-D, respectively are the best ones to demonstrate high activity and selectivity profile. Cat-C and Cat-D exhibited 100% conversion and 96% selectivity at 170 ± 2 °C and 2 MPa of hydrogen pressure. The role of constituent metals in the catalyst was delineated. Incorporation of Zn increases the activity for furfural conversion whereas Zr contributes significantly to the selectivity of furfuryl alcohol. It was also found that Zr loading not only increases the acidity of the catalyst but also helps in the dispersion of metallic Cu. The particle size of metallic Cu was found to be in the range of 17-19 nm as confirmed by TEM, XRD and CO chemisorption techniques. XANES analysis confirmed the presence of copper in Cu0 and Cu 2+ oxidation states in Cat-C (freshly reduced) and Cat-C (fresh), respectively. Hydrogenation of furfural to furfuryl alcohol follows a pseudo-first order reaction with an the apparent activation energy of 24.4 kcal/mol. Cat-C was recycled at least 4 times for the hydrogenation of furfural with no loss of activity and selectivity when compared to the fresh catalyst.
Interfacial effect of Pd supported on mesoporous oxide for catalytic furfural hydrogenation
Lee, Hojeong,Nguyen-Huy, Chinh,Jeong Jang, Eun,Lee, Jihyeon,Yang, Euiseob,Lee, Man Sig,Kwak, Ja Hun,An, Kwangjin
, p. 291 - 300 (2021)
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.
Heine et al.
, p. 4778 (1953)
Synthesis and reactivity of naphthalene complexes of ytterbium
Bochkarev, M. N.,Trifonov, A. A.,Fedorova, E. A.,Emelyanova, N. S.,Basalgina, T. A.,et al.
, p. 217 - 224 (1989)
The complexes formulated as C10H8Ybx(THF)y (X = 1-2, y = 2-4) have been obtained as black pyrophoric powders by reactions of anhydrous ytterbium diiodide with a lithium naphthalide in THF.The reactions of samarium and europium iodide
Heterogeneous CaO-ZrO2 acid-base bifunctional catalysts for vapor-phase selective dehydration of 1,4-butanediol to 3-buten-1-ol
Zhang, Qian,Zhang, Yin,Li, Haitao,Gao, Chunguang,Zhao, Yongxiang
, p. 233 - 239 (2013)
A series of acid-base bifunctional CaO-ZrO2 catalysts was prepared simply by the impregnation method and evaluated for the vapour-phase dehydration of 1,4-butanediol (BDO). The effects of CaO content and calcination temperature on the catalytic properties of the CaO-ZrO2 catalysts were investigated. It was found that the catalyst with 12.5 wt% CaO and at a calcination temperature of 650°C exhibited favorable catalytic performance and good stability for the selective dehydration of BDO to 3-buten-1-ol (BTO). The maximum BTO selectivity and BDO conversion reached 68.9% and 94.6%, respectively. The formation of by-product, THF, was markedly suppressed. These catalysts were characterized by N2 physisorption, XRD, FT-IR spectra, NH3-TPD and CO2-TPD. The results indicated that the CaO-ZrO2 catalysts showed higher basicity density and similar acidity density compared to unmodified ZrO2 due to the formation of Ca-O-Zr Hetero-linkage by CaO introduction. The catalytic performance depended on the coexistence of acidic and basic sites on the surface of catalysts.
Preparation of Er2O3 nanorod catalyst without using organic additive and its application to catalytic dehydration of 1,4-butanediol
Sato, Fumiya,Yamada, Yasuhiro,Sato, Satoshi
, p. 593 - 594 (2012)
Er2O3 nanorods were successfully prepared with hydrothermal treatment without using organic additives such as surfactant, fatty acid, or alcohol. Er2 O3 nanorods were obtained under high temperature and/or long reaction times. Er2O3 nanorods mainly exposed {440} and {400} facets on the surface. Er2O3 nanorods showed excellent catalytic activity compared to commercial Er2O3 nanoparticles in the dehydration of 1,4-butanediol to produce 3-buten-1-ol.
Colloidal and Nanosized Catalysts in Organic Synthesis: XXIV. Study of Hydrogenation of Furan and Its Derivatives in the Presence of MgO-Supported Nickel and Cobalt Nanoparticles
Gendler, T. A.,Mokhov, V. M.,Nebykov, D. N.,Popov, Yu. V.,Shemet, V. V.,Shirkhanyan, P. M.
, p. 931 - 935 (2020)
Abstract: The processes of hydrogenation of furan and its derivatives (2-methylfuran, furfuryl alcohol, and furfural) in plug-flow type reactor under atmospheric hydrogen pressure at 20–220°С in the presence of supported nickel nanoparticles prepared via chemical reduction have been investigated. It has been found that nickel nanoparticles supported on magnesium oxide surface are the most reactive and stable under the considered conditions. This catalyst allows the corresponding hydrogenation products with 100percent yield and complete conversion of the substrate.
-
Holtz et al.
, p. 3175,3178 (1973)
-
Reduction of Dicarboxylic Acid Anhydride with 2-Propanol over Hydrous Zirconium Oxide
Takahashi, Kyoko,Shibagaki, Makoto,Matsushita, Hajime
, p. 262 - 266 (1992)
The reduction of dicarboxylic acid anhydrides with 2-propanol proceeded efficiently over hydrous zirconium oxide to give the corresponding lactones and cyclic ethers.Secondary and primary alcohols, with the exception of methanol, are able to act as hydride donors in this reduction.The reduction proceeded as nearly second order concerning the concentration of 2-propanol and minus order concerning that of acid anhydride.These results suggest that the reduction was preferred under lower concentrations of acid anhydride and higher concentrations of 2-propanol.The selectivity of lactone or ether could be changed by the reaction temperature or the molar ratio of dicarboxylic acid anhydride to alcohol.
Hydrogenation of succinic acid to tetrahydrofuran (THF) over rhenium catalyst supported on H2SO4-treated mesoporous carbon
Hong, Ung Gi,Park, Hai Woong,Lee, Joongwon,Hwang, Sunhwan,Yi, Jongheop,Song, In Kyu
, p. 141 - 148 (2012)
Mesoporous carbon (MC) prepared by a surfactant-templating method was treated with different H2SO4 concentration (X = 0, 0.2, 0.4, 0.6, 0.8, and 1.0 M) for use as a support (MC-X) for rhenium catalyst. Rhenium catalysts supported on H2SO4-treated mesoporous carbons (Re/MC-X) were then prepared by an incipient wetness impregnation method, and they were applied to the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF). The effect of H2SO4 treatment on the physicochemical properties and catalytic activity of Re/MC-X catalysts (X = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) was investigated. It was observed that MC-X supports showed different pore characteristics depending on H2SO 4 concentration. As a result, Re/MC-X catalysts showed different rhenium particle size. In the liquid-phase hydrogenation of succinic acid to tetrahydrofuran (THF), conversion of succinic acid and yield for THF showed volcano-shaped curves with respect to H2SO4 concentration. Thus, an optimal H2SO4 concentration was required to achieve maximum catalytic performance of Re/MC-X. Yield for THF in the hydrogenation of succinic acid increased with decreasing rhenium particle size of Re/MC-X catalysts. Among the catalysts tested, Re/MC-0.4 with the smallest rhenium particle size showed the highest yield for THF.
PRODUCTION METHOD OF CYCLIC COMPOUND
-
Paragraph 0057-0058; 0062-0063, (2021/05/05)
PROBLEM TO BE SOLVED: To provide an industrially simple production method of a cyclic compound. SOLUTION: A production method of a cyclic compound includes a step to obtain a reduced form (B) by reducing an unsaturated bond in a ring structure of an aromatic compound (A) by means of catalytic hydrogenation of the aromatic compound (A) or its salt using palladium carbon as a catalyst under a normal pressure, in which the aromatic compound (A) has one or more ring structures selected from a group consisting of a five membered-ring, a six membered-ring, and a condensed ring of the five membered-ring or the six membered-ring with another six membered-ring, a hetero atom can be included in the ring structure, and the aromatic compound (A) can have one or two side chains bonded to the ring structure and does not have any carbon-carbon triple bond in the side chain. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
