110-00-9Relevant articles and documents
Catalytic conversion of cellulose over mesoporous y zeolite
Park, Young-Kwon,Jun, Bo Ram,Park, Sung Hoon,Jeon, Jong-Ki,Lee, See Hoon,Kim, Seong-Soo,Jeong, Kwang-Eun
, p. 5120 - 5123 (2014)
Mesoporous Y zeolite (Meso-Y) was applied, for the first time, to the catalytic pyrolysis of cellulose which is a major constituent of lignocellulosic biomass, to produce high-quality bio-oil. A representative mesoporous catalyst Al-MCM-41 was also used t
Effects of thiol modifiers on the kinetics of furfural hydrogenation over Pd catalysts
Pang, Simon H.,Schoenbaum, Carolyn A.,Schwartz, Daniel K.,Will Medlin
, p. 3123 - 3131 (2014)
Thiolate self-assembled monolayers (SAMs) were used to block specific active sites on Pd/Al2O3 during the hydrogenation of furfural to elucidate site requirements for each process involved in this complex reaction network. Reactions were performed on uncoated, 1-octadecanethiol (C18) coated, and benzene-1,2-dithiol (BDT) coated catalysts. Selectivity among key reaction pathways was sensitive to the SAM modifier, with increasing sulfur density strongly suppressing furfural decarbonylation, less strongly suppressing furfural hydrogenation, and minimally affecting furfuryl alcohol hydrodeoxygenation to methylfuran. Diffuse reflectance infrared Fourier transform spectroscopy with CO was used to characterize site availability on the catalysts. The presence of a C18 modifier restricted the availability of Pd terrace sites, while accessibility to Pd edges and steps was practically unaffected with respect to the uncoated catalyst. The BDT modifier further restricted terrace accessibility but additionally restricted adsorption at particle edges and steps. Comparison between reaction rates and site availability suggested that decarbonylation occurred primarily on terrace sites, while hydrodeoxygenation occurred on particle steps and edges. Aldehyde hydrogenation, and its reverse process of alcohol dehydrogenation, was found to occur on both terrace or edge sites, with the dominant pathway dependent on surface coverage as determined by reaction conditions. The results of a detailed kinetic study indicate that in addition to changing the availability of specific sites, thiol monolayers can strongly affect reaction energetics and decrease the coverage of strongly adsorbed furfural-derived intermediates under reaction conditions. Ambient pressure X-ray photoelectron spectroscopy experiments indicated that the metal-sulfur bonds were not changed appreciably under reaction conditions. The results of this work show that HDO is not appreciably affected even with drastic decreases in the density of available sites as measured by CO adsorption, providing opportunities to design isolated catalyst sites for selective reaction.
Factors affecting thermally induced furan formation
Fan, Xuetong,Huang, Lihan,Sokorai, Kimberly J. B.
, p. 9490 - 9494 (2008)
Furan, a potential carcinogen, can be induced by heat from sugars, ascorbic acid, and fatty acids. The objective of this research was to investigate the effect of pH, phosphate, temperature, and heating time on furan formation. Heat-induced furan formation from free sugars, ascorbic acid, and linoleic acid was profoundly affected by pH and the presence of phosphate. In general, the presence of phosphate increased furan formation in solutions of sugars and ascorbic acid. In a linoleic acid emulsion, phosphate increased the formation of furan at pH 6 but not at pH 3. When an ascorbic acid solution was heated, higher amounts of furan were produced at pH 3 than at pH 6 regardless of phosphate's presence. However, in linoleic acid emulsion, more furan was produced at pH 6 than at pH 3. The highest amount of furan was formed from the linoleic acid emulsion at pH 6. In fresh apple cider, a product with free sugars as the major components (besides water) and little fatty acids, ascorbic acid, or phosphate, small or very low amounts of furan was formed by heating at 90-120 °C for up to 10 min. The results indicated that free sugars may not lead to significant amounts of furan formation under conditions for pasteurization and sterilization. Importantly, this is the first report demonstrating that phosphate (in addition to pH) plays a significant role in thermally induced furan formation.
Selective hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol over Ni/γ-Al2O3 catalysts
Sang, Shengya,Wang, Yuan,Zhu, Wei,Xiao, Guomin
, p. 1179 - 1195 (2017)
A series of nickel-based catalysts (with 2O3, x represents the Ni loading amount) were synthesized by the impregnation method, which was successfully applied for the catalytic hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol. The effects of reaction time, reaction temperature, nickel loading amount, solvent, and hydrogen pressure on conversion of furfural alcohol as well as selectivity for tetrahydrofurfuryl alcohol were investigated systematically. The conversion of furfural alcohol over 15?wt% Ni/γ-Al2O3 was up to 99.8?% with a selectivity of 99.5?% toward tetrahydrofurfuryl alcohol, when the reaction was carried out at 353?K with an initial H2 pressure of 4.0?MPa and reaction time of 2?h. In addition, there was an increase of turnover frequency (TOF) value with the decrease of Ni particle size. The features of the Ni/γ-Al2O3 catalysts were investigated by characterization of XRD, TPR, BET, and SEM.
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Cope,Keller
, p. 141 (1956)
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The Reaction of 5-Cyano and 5-Methoxycarbonyl-7-oxabicyclohept-2-enes with Chlorotrimethylsilane/Sodium Iodide Reagent
Kibayashi, Takao,Ishii, Yasutaka,Ogawa, Masaya
, p. 3627 - 3628 (1985)
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CHARACTERISTICS OF THE CATALYTIC HYDROGENATION OF 5-METHYLFURFURAL
Stonkus, V. V.,Yuskovets, Zh. G.,Shimanskaya, M. V.
, p. 1214 - 1218 (1990)
The hydrogenation of 5-methylfurfural in the vapor and liquid phases was studied in the presence of catalysts: Pd/C (KDF), Pd/Al2O3, copper-chromite (GIPKh-105) and Raney-Ni.The chief characteristics of the conversion of the aldehyde group of 5-methylfurfural depending on the nature of the catalyst and the reaction conditions were established.The greater reactivity of 5-methylfurfural in the hydrogenation reaction, compared with furfural, was revealed.
A magnetic CoRu-CoO: X nanocomposite efficiently hydrogenates furfural to furfuryl alcohol at ambient H2 pressure in water
Cao, Qiue,Fang, Wenhao,Lu, Yaowei,Wang, Yongxing
, p. 3765 - 3768 (2020)
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.
Production of renewable oleo-furan surfactants by cross-ketonization of biomass-derived furoic acid and fatty acids
Fu, Jiayi,Moglia, David,Nguyen, Hannah,Orazov, Marat,Vlachos, Dionisios G.,Wang, Yunzhu,Zheng, Weiqing
, p. 2762 - 2769 (2021)
Synthesis of 2-dodecanoyl furan is a crucial step in the formulation of oleo-furan sulfonates as bio-surfactants from biomass-derived furans and vegetable-oil-derived molecules. Herein, cross-ketonization of 2-furoic acid and lauric acid is proposed to produce the bio-surfactant precursor. Among the commonly reported metal oxide ketonization catalysts, the inexpensive and abundant iron oxides are demonstrated as effective and recyclable catalysts, enabling up to 77% selectivity to 2-dodecanoyl furan at 56% lauric acid conversion. Catalyst characterization by X-ray diffraction, H2temperature-programmed reduction, and X-ray photoelectron spectroscopy indicates that Fe3O4is the catalytically active and stable phase.13C isotopic tracing experiments suggest that cross-ketonization on Fe3O4proceedsviaa β-keto acid intermediate.
Infrared Study of the Adsorption of But-1-ene, Buta-1,3-diene, Furan and Maleic Anhydride on the Surface of Anhydrous Vanadyl Pyrophosphate
Puttock, Simon J.,Rochester, Colin H.
, p. 3033 - 3039 (1986)
Broensted-acidic hydroxy groups on the surface of vanadyl pyrophosphate act as catalytically active sites for the isomerisation of but-1-ene to but-2-enes.Progressive poisoning of the reaction is attributed to the tormation of alkyl species, possibly alkoxy groups, on the (VO)2P2O7 surface.Adsorbed alkyl groups also result from buta-1,3-diene adsorption.Furan adsorbs on (VO)2P2O7 through coordinative interactions with Lewis-acidic surface sites.The presence of oxygen promotes the oxidation of furan to maleic anhydride.
Structure-dependent catalytic properties of mesoporous cobalt oxides in furfural hydrogenation
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
, (2019)
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.
Real-time product switching using a twin catalyst system for the hydrogenation of furfural in supercritical CO2
Stevens, James G.,Bourne, Richard A.,Twigg, Martyn V.,Poliakoff, Martyn
, p. 8856 - 8859 (2010)
"Vending machine" chemistry: A tandem flow-reactor setup can be used to generate a choice of five products in high yield from a single biorenewable feedstock, furfural (1). "Real-time" switching to any of the products can be achieved rapidly by simply changing the reactor conditions.
Understanding the Role of M/Pt(111) (M = Fe, Co, Ni, Cu) Bimetallic Surfaces for Selective Hydrodeoxygenation of Furfural
Jiang, Zhifeng,Wan, Weiming,Lin, Zhexi,Xie, Jimin,Chen, Jingguang G.
, p. 5758 - 5765 (2017)
Selectively cleaving the C=O bond of the aldehyde group in furfural is critical for converting this biomass-derived platform chemical to an important biofuel molecule, 2-methylfuran. This work combined density functional theory (DFT) calculations and temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) measurements to investigate the hydrodeoxygenation (HDO) activity of furfural on bimetallic surfaces prepared by modifying Pt(111) with 3d transition metals (Cu, Ni, Fe, and Co). The stronger binding energy of furfural and higher tilted degree of the furan ring on the Co-terminated bimetallic surface resulted in a higher activity for furfural HDO to produce 2-methylfuran in comparison to that on either Pt(111) or Pt-terminated PtCoPt(111). The 3d-terminated bimetallic surfaces with strongly oxophilic 3d metals (Co and Fe) showed higher 2-methylfuran yield in comparison to those surfaces modified with weakly oxophilic 3d metals (Cu and Ni). The effect of oxygen on the HDO selectivity was also investigated on oxygen-modified bimetallic surfaces, revealing that the presence of surface oxygen resulted in a decrease in 2-methylfuran yield. The combined theoretical and experimental results presented here should provide useful guidance for designing Pt-based bimetallic HDO catalysts.
Experimental and theoretical study of the homogeneous, unimolecular gas-phase elimination kinetics of 2-furoic acid
Ramirez, Beatriz C.,Dominguez, Rosa M.,Herize, Armando,Tosta, Maria,Cordova, Tania,Chuchani, Gabriel
, p. 298 - 306 (2007)
The kinetics of the gas-phase elimination kinetics of CO2 from furoic acid was determined in a static system over the temperature range 415-455°C and pressure range 20-50 Torr. The products are furan and carbon dioxide. The reaction, which is carried out in vessels seasoned with allyl bromide and in the presence of the free-radical suppressor toluene and/or propene, is homogeneous, unimolecular, and follows a first-order rate law. The observed rate coefficient is expressed by the following Arrhenius equation: log k1 (s-1) = (13.28 ± 0.16) - (220,5 ± 2.1) kJ mol-1 (2.303 RT)-1. Theoretical studies carried out at the B3LYP/6-31++G** computational level suggest two possible mechanisms according to the kinetics and thermodynamic parameters calculated compared with experimental values.
Furfural hydrodeoxygenation on iron and platinum catalysts
Zanuttini, M. Soledad,Gross, Martin,Marchetti, Gustavo,Querini, Carlos
, (2019)
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.
Dye-Sensitized Photooxygenation of 2,3-Dihydrofurans: Competing Cycloadditions and Ene Reactions of Singlet Oxygen with a Rigid Cyclic Enol Ether System
Gollnick, Klaus,Knutzen-Mies, Karen
, p. 4017 - 4027 (1991)
Singlet oxygen reacts with 2,3-dihydrofuran (1), 5-methyl (7), 4,5-dimethyl- (13), and 4-carbomethoxy-5-methyl-2,3-dihydrofuran (20), 5,6-dimethyl-3,4-dihydro-2H-pyran (26), and 3-methoxy-2-methyl-2-butene (32) in nonpolar and polar aprotic solvents to yield dioxetanes and allylic hydroperoxides, except 32, which gives only allylic hydroperoxides.The dioxetanes were isolated, but decompose slowly with weak chemiluminescence at room temperature to yield the corresponding dicarbonyl compounds.The allylic hydroperoxides produced by the cyclic enol ethers could not be isolated or separated by high vacuum distillation or by chromatography; the endocyclic allylic hydroperoxides arising from the dihydrofurans eliminate H2O2 to yield the corresponding furans while the exocyclic allylic hydroperoxides gives unknown products.Allylic hydroperoxides 28 and 29 and the dioxetane 27 obtained from 26 yield the same dicarbonyl compound 31.The proportion of dioxetanes to allylic hydroperoxides depends on ring size and substitution of the enol ethers and on solvent polarity.Smaller ring size, greater electron-donor substitution, and solvent polarity favor the formation of dioxetanes at the expense of allylic hydroperoxides.It is noteworthy that enol ether 20, an α,β-unsaturated ester, forms appreciable amounts of a dioxetane in polar solvents (44 percent in acetonitrile).Kinetic results show that the rate and product distribution of the ene reaction are independent of solvent polarity, whereas the rate of dioxetane formation increases with solvent polarity.It is suggested that cycloadditions and ene reactions occur via different transition states and intermediates, zwitterions and perepoxides, respectively.Furthermore, the remarkable propensity to dioxetane formation of dihydrofurans compared to that of dihydropyrans and the other enol ethers seems to be due to the rigidity of the five-membered ring in the transition state and intermediate zwitterion.
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Mowry
, p. 573 (1947)
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TERTIARY BUTYLATION OF FIVE MEMBERED HETEROCYCLES. A UPS STUDY
Nyulaszi, L.,Gyuricza, A.,Veszpremi, T.
, p. 5955 - 5960 (1987)
The reaction of 2-chloromercuryfuran and t-butylbromide was studied by UV photoelectron spectroscopy.During the reaction the formation of t-butylfuran, 2,5-di-t-butylfuran, t-butylchloride, isobutylene and furan were found.In accordance with the experimental observations a novel reaction mechanism has been proposed.The first fast and the second slow step of the reaction has been interpreted.The corresponding thiophene derivative gave similar results.
Carbon efficiency and the surface chemistry of the actinides: Direct formation of furan from acetylene over β-UO3
Idriss,Madhavaram
, p. 155 - 158 (2002)
Uranium oxide is a very good catalyst for oxidation reactions, and bare U atoms are very active for carbon-carbon coupling reactions. The direct oxidative coupling of two molecules of acetylene to furan (C4H4O) over the surface of pure polycrystalline β-UO3 was presented. For comparison, only traces of furan were formed over α-U3O8 and none on UO2 surfaces. Comparison to the reactions of other C2 compounds (ethanol, acetaldehyde, and ethylene) over β-UO3 showed the presence of two routes for making furan from C2 compounds, i.e., via aldolization and via oxidative coupling.
Ex situ catalytic upgrading of lignocellulosic biomass components over vanadium contained H-MCM-41 catalysts
Kim, Beom-Sik,Jeong, Chang Seok,Kim, Ji Man,Park, Su Bin,Park, Sung Hoon,Jeon, Jong-Ki,Jung, Sang-Chul,Kim, Sang Chai,Park, Young-Kwon
, p. 184 - 191 (2016)
H-V-MCM-41 catalysts containing 5, 10, and 30 wt% of vanadium were synthesized and applied to the ex situ catalytic pyrolysis (CP) of three polymeric components of lignocellulosic biomass for the first time. Characterization of the catalysts was performed using N2 adsorption-desorption, XRD, FT-IR, and NH3-TPD. The results of XRD analysis showed that 5 wt% and 10 wt% H-V-MCM-41 catalysts maintained the mesoporous structure, whereas the mesoporous structure was destroyed in 30 wt% H-V-MCM-41 with considerable amount of small V2O5 crystalline outside the framework. NH3-TPD showed that H-V-MCM-41 has mostly weak acid sites and that 10 wt% H-V-MCM-41 had the largest quantity of acid sites due to framework vanadium. In the case of CP of cellulose using Py-GC/MS, 10 wt% H-V-MCM-41 showed the highest catalytic activity for the production of valuable furanic compounds such as furfural because of the enhanced deoxygenation over the acid sites formed on framework vanadium. In the case of CP of xylan as well, 10 wt% H-V-MCM-41 led to the largest yield of mono-aromatics. The production of acetic acid was also promoted by H-V-MCM-41 catalysts. The CP of lignin over H-V-MCM-41 catalysts promoted substantially the production of important feedstock chemicals for the petrochemical industry: phenolics and mono-aromatics.
Study on the reaction pathway in decarbonylation of biomass-derived 5-hydroxymethylfurfural over Pd-based catalyst
Meng, Qingwei,Zheng, Hongyan,Zhu, Yulei,Li, Yongwang
, p. 76 - 82 (2016)
An extensive product distribution is firstly examined in the process of 5-hydroxymethylfurfural (HMF) decarbonylation over Pd-based catalysts and some interesting results are obtained. The main side reactions are due to the high activity of the furan ring-branched hydroxymethyl, which could go through hydrogenolysis, dehydrogenation and etherification. The H2 source was carefully explored and determined to be the hydroxymethyl dehydrogenation. The reactivity of the main intermediates was separately investigated and their evolution pathway was obtained. Noticeably, it is demonstrated that the elimination of the furanic ring-branched hydroxymethyl (in HMF or furfuryl alcohol) is completed by sequential dehydrogenation and decarbonylation via the intermediate of aldehyde (2, 5-diformylfuran or furfural). A comprehensive reaction pathway for HMF decarbonylation is proposed, which is significant for designing highly selective decarbonylation catalysts.
Study of the vacuum pyrolysis of 11-oxatricyclo[6.2.1.02,7]undeca-2,9-diene. The HeI ultraviolet photoelectron spectrum of 1,2-cyclohexadiene
Werstiuk,Roy,Ma
, p. 1903 - 1905 (1996)
A newly developed ultraviolet photoelectron spectrometer - CO2 laser apparatus that utilizes a 50-watt CW CO2 laser as a directed heat source is used to study the vacuum pyrolysis of 11-oxatricyclo[6.2.1.02.7]undeca-2,9-diene (4). We report the HeI photoelectron spectrum of the strained cyclic allene 1,2-cyclohexadiene (1) that correlates with the HAM/3 ionization energies calculated with the optimized C2 equilibrium structure obtained with AM1 and the molecular orbital energies of the optimized C2 equilibrium structure calculated at the ab initio HF/6-31G** level of theory.
Hydroprocessing of furfural over in situ generated nickel phosphide based catalysts in different solvents
Golubeva, Maria A.,Maximov, Anton L.
, (2020)
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.
Unusual hydroxyl effect on fulvene endoperoxide decompositions
Erden, Ihsan,Basada, John,Poli, Daniela,Cabrera, Gabriel,Xu, Fupei,Gronert, Scott
, p. 2190 - 2193 (2016)
The thermal decomposition of fulvene endoperoxides ordinarily proceeds via an allene oxide intermediate affording oxepin-2(3H)-one derivatives. We have now uncovered new, unusual pathways in these decompositions where the presence of a hydroxyl group on the alkyl or aryl attached to the fulvene exocyclic double bond has a profound effect on the fate of the reactive intermediates derived from the unstable endoperoxides. Computational work supports the proposed mechanistic pathways.
Selective aqueous-phase hydrogenation of furfural to cyclopentanol over PdRu/C catalyst
Mironenko,Belskaya,Lavrenov,Likholobov
, p. 673 - 676 (2017)
The bimetallic PdRu catalyst supported on carbon nanotubes were found ot provide an efficient synthesis of cyclopentanol in aqueous-phase hydrogenation of furfural. Under the chosen reaction conditions (temperature of 473 K, total pressure of 8 MPa), the selectivity towards cyclopentanol reaches 77% at a complete conversion of furfural. A high activity of this catalyst can be associated with changes in the electronic state and dispersion of the supported metals caused by their mutual interaction and formation of PdRu alloy.
Biomass to drugs: Green production of salicylic acid from 2-furoic acid in two steps
Jiang, Jun,Li, Teng,Sun, Guangyu,Wang, Yantao,Xiong, Lu,Yang, Weiran,Yu, Pengxin,Zheng, Boying
, (2022/03/07)
Salicylic acid, generally produced by chemical synthesis based on petrochemical products, is a vital organic acid and widely used in the pharmaceutical synthesis. This work developed a new and green route for the production of salicylic acid from biomass-derived 2-furoic acid in two steps. Firstly, 2 mmol 2-furoic acid was creatively converted to 2,3-benzofuran using HZSM-5 (Si/Al=130) at 280 °C for 1.5 h under 100 psi N2; and then the oxidation of 2,3-benzofuran to salicylate was conducted with tert?butyl hydroperoxide under basic condition without metal catalyst at 120 °C for 1 h. The stability of the catalyst for the first step and the possible reaction pathway for the second step based on the control experiments was properly envisioned. Regardless of limited salicylic acid yield (16%) from 2-furoic acid, this work paves a potentially feasible pathway for the preparation of drugs from biomass.
Furfural hydrodeoxygenation (HDO) over silica-supported metal phosphides – The influence of metal–phosphorus stoichiometry on catalytic properties
Lan, Xuefang,Pestman, Robert,Hensen, Emiel J.M.,Weber, Thomas
, p. 181 - 193 (2021/02/27)
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.
H2-Free Selective Dehydroxymethylation of Primary Alcohols over Palladium Nanoparticle Catalysts
Yamaguchi, Sho,Kondo, Hiroki,Uesugi, Kohei,Sakoda, Katsumasa,Jitsukawa, Koichiro,Mitsudome, Takato,Mizugaki, Tomoo
, p. 1135 - 1139 (2020/12/29)
The dehydroxymethylation of primary alcohols is a promising strategy to transform biomass-derived oxygenates into hydrocarbon fuels. In this study, a novel, highly efficient, and reusable heterogeneous catalyst system was established for the H2-free dehydroxymethylation of primary alcohol using cerium oxide-supported palladium nanoparticles (Pd/CeO2). A wide range of aliphatic and aromatic alcohols including biomass-derived alcohols were converted into the corresponding one-carbon shorter hydrocarbons in high yields in the absence of any additives, accompanied by the production of H2 and CO. Pd/CeO2 was easily recovered from the reaction mixture and reused, retaining its high activity, thus, providing a simple and sustainable methodology to produce hydrocarbon fuels from biomass-derived oxygenates.