- Organic modifiers promote furfuryl alcohol ring hydrogenation via surface hydrogen-bonding interactions
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Interactions between surface adsorbed species can affect catalyst reactivity, and thus, the ability to tune these interactions is of considerable importance. Deposition of organic modifiers provides one method of intentionally introducing controllable surface interactions onto catalyst surfaces. In this study, Pd/Al2O3 catalysts were modified with either thiol or phosphonic acid (PA) ligands and tested in the hydrogenation of furanic species. The thiol modifiers were found to inhibit ring hydrogenation (RH) activity, with the degree of inhibition trending with the thiol surface coverage. This suggests that thiols do not strongly interact with the reactants and simply serve to block active sites on the Pd surface. PAs, on the other hand, were found to enhance RH when furfuryl alcohol (FA) was used as the reactant. Density functional theory calculations suggested that this enhancement was due to hydrogen-bonding interactions between FA-derived surface intermediates and PA modifiers. Here, installation of hydrogen-bonding groups on the Pd surface served to preferentially stabilize RH product states. Furthermore, the promotional effect on the RH of FA was observed to be greater when a higher-coverage PA was used, providing a rate more than twice that of the unmodified Pd/Al2O3. The results of this work suggest that organic ligands can be designed to impart tunable surface interactions on heterogeneous catalysts, providing an additional method of controlling catalytic performance.
- Coan, Patrick D.,Farberow, Carrie A.,Griffin, Michael B.,Medlin, J. Will
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- Alkoxyl radicals from alcohols. Spectroscopic detection of intermediate alkyl and acyl hypoiodites in the Suarez and Beebe reactions
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Acetyl hypoiodite and a number of alkyl hypoiodites have been characterized as intermediates in the conversion of alcohols into alkoxyl radicals under Suarez (photostimulated iodosobenzenediactetate/iodine reagent) and Beebe (photolysed acetyl hypoiodite/alcohol) conditions.
- Courtneidge,Lusztyk,Page
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Read Online
- Platinum Single Atoms on Carbon Nanotubes as Efficient Catalyst for Hydroalkoxylation
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We report a facile synthesis of Pt single atoms on thiolated carbon nanotubes. To obtain Pt single atoms, it is crucial to treat thiol groups on carbon nanotubes. Pt single atoms on carbon nanotubes were used efficient catalyst for hydroalkoxylation of 3-buten-1-ol or 4-penten-1-ol. Hydroalkoxylation represents an atom-economic route to construct four or five- membered cyclic ethers through intramolecular addition of hydroxyl group. This catalyst exhibited higher catalytic activity than Pt complex and Pt nanoparticles on carbon nanotubes.
- Woo, Hyunje,Lee, Eun-Kyung,Yun, Su-Won,Park, Shin-Ae,Park, Kang Hyun,Kim, Yong-Tae
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Read Online
- Solvent effect on the rate and direction of furfural transformations during hydrogenation over the Pd/C catalyst
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The rate and directions of transformations during the liquid-phase hydrogenation of furfural with molecular hydrogen in the presence of the 5%Pd/C catalyst (at 423 K, 3 MPa) depend substantially on the chemical nature of the solvent. The main products of
- Belskaya, O. B.,Likholobov, V. A.,Mironenko, R. M.
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- Support Effect of Ru Catalysts for Efficient Conversion of Biomass-Derived 2,5-Hexanedione to Different Products
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Tuning the activity of supported metals by changing the properties of supports is a highly attractive strategy to realize some important reactions in biomass transformation. Herein, Ru nanoparticles supported on montmorillonite (MMT) and hydroxyapatite (HAP), denoted as Ru/MMT and Ru/HAP, were prepared. It was found that the activity of the Ru catalysts for different routes to convert biomass-derived 2,5-hexanedione (2,5-HD) could be controlled by the support materials. Ru/MMT was active for the synthesis of dimethyltetrahydrofuran from hydrogenation of 2,5-HD at 90 °C, while Ru/HAP showed excellent performance on the conversion of 2,5-HD into N-substituted tetrahydropyrroles at 30 °C via direct reductive amination. Systematic study revealed that the property of support materials influenced the activity of Ru/MMT and Ru/HAP for the different routes, affording different reaction pathways for conversion of 2,5-HD.
- Hua, Manli,Song, Jinliang,Huang, Xin,Hou, Minqiang,Fan, Honglei,Zhang, Zhaofu,Wu, Tianbin,Han, Buxing
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p. 7685 - 7693
(2021/06/30)
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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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- 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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- Mild reduction with silanes and reductive amination of levulinic acid using a simple manganese catalyst
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A manganese-based catalytic system using the commercially available complex [Mn(CO)5Br] was studied for the selective reduction of levulinic acid (LA) to 2-methyl-tetrahydrofuran (MTHF). We further studied the production of pyrrolidines via its reductive amination using silanes (phenylsilane and tetramethyldisiloxane). The results showed high efficiency and selectivity for this reaction leading to high yields using mild reaction conditions.
- Garcia, Juventino J.,Roa, Diego A.
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- Chemoselective and Tandem Reduction of Arenes Using a Metal–Organic Framework-Supported Single-Site Cobalt Catalyst
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The development of heterogeneous, chemoselective, and tandem catalytic systems using abundant metals is vital for the sustainable synthesis of fine and commodity chemicals. We report a robust and recyclable single-site cobalt-hydride catalyst based on a porous aluminum metal–organic framework (DUT-5 MOF) for chemoselective hydrogenation of arenes. The DUT-5 node-supported cobalt(II) hydride (DUT-5-CoH) is a versatile solid catalyst for chemoselective hydrogenation of a range of nonpolar and polar arenes, including heteroarenes such as pyridines, quinolines, isoquinolines, indoles, and furans to afford cycloalkanes and saturated heterocycles in excellent yields. DUT-5-CoH exhibited excellent functional group tolerance and could be reusable at least five times without decreased activity. The same MOF-Co catalyst was also efficient for tandem hydrogenation–hydrodeoxygenation of aryl carbonyl compounds, including biomass-derived platform molecules such as furfural and hydroxymethylfurfural to cycloalkanes. In the case of hydrogenation of cumene, our spectroscopic, kinetic, and density functional theory (DFT) studies suggest the insertion of a trisubstituted alkene intermediate into the Co–H bond occurring in the turnover limiting step. Our work highlights the potential of MOF-supported single-site base–metal catalysts for sustainable and environment-friendly industrial production of chemicals and biofuels.
- Akhtar, Naved,Begum, Wahida,Chauhan, Manav,Manna, Kuntal,Newar, Rajashree,Rawat, Manhar Singh
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supporting information
(2022/01/19)
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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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- 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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- 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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- The relevance of Lewis acid sites on the gas phase reaction of levulinic acid into ethyl valerate using CoSBA-xAl bifunctional catalysts
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A series of Co supported on Al-modified SBA-15 catalysts has been studied in the gas phase direct transformation of levulinic acid (LA) into ethyl valerate (EV) using a continuous fixed-bed reactor and ethanol as solvent. It was observed that once the intermediate product gamma-valerolactone (GVL) has been formed, the presence of aluminum is required for the selective transformation to EV. Three Lewis acid sites (LAS) are identified (from highest to lowest acid strength): aluminum ions in tetrahedral and octahedral coordination and Co2+sites. The intrinsic activity of these LAS for the key reaction, the GVL ring opening, decreases with the strength of these acid sites, but so does the undesirable formation of coke, also catalyzed by these centers. The best catalyst was that with the highest Al content, CoSBA-2.5Al, that reached an EV yield of up to 70%. This result is associated with the presence of LAS attributed to the presence of Co2+surface species that, although having low intrinsic activity in the selective GVL ring-opening reaction, are highly concentrated in this sample and also possess less activity in the undesirable and deactivating formation of coke. These Co2+LAS have been stabilized by incorporation of aluminum into the support, modifying the reducibility and dispersion of cobalt species. Additionally, the lower proportion of metallic Co species decreases the hydrogenating capacity of this catalyst. This decrease is a positive result because it prevents GVL hydrogenation to undesired products. This catalyst also showed promising stability in a 140 h on-stream run.
- Cecilia, J. A.,Dumesic, J. A.,Jiménez-Gómez, C. P.,López Granados, M.,Maireles-Torres, P.,Mariscal, R.,Mu?oz-Olasagasti, M.
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p. 4280 - 4293
(2021/06/30)
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- METHODS OF SYNTHESIZING 2-[4-[(2,3,4-TRIMETHOXYPHENYL)METHYL]PIPERAZIN-1-YL]ETHYL PYRIDINE-3-CARBOXYLATE
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The invention provides methods of chemical synthesis of the pharmacological agent 2-[4-[(2,3,4-trimethoxyphenyl)methyl]piperazin-1-yl]ethyl pyridine-3-carboxylate, also called CV-8972. The methods entail formation of a free base form of 2-[4-[(2,3,4-trimethoxyphenyl)methyl]piperazin-1-yl]ethanol, also called CV-8814, as intermediate without producing a salt form of CV-8814.
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- Unravelling the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol catalysed by supported RANEY Ni-Sn alloy catalysts
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Bimetallic Ni-Sn alloys have been recognised as promising catalysts for the transformation of furanic compounds and their derivatives into valuable chemicals. Herein, we report the utilisation of a supported bimetallic RANEY nickel-tin alloy supported on aluminium hydroxide (RNi-Sn(x)/AlOH; x is Ni/Sn molar ratio) catalysts for the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol (1,4-PeD). The as prepared RNi-Sn(1.4)/AlOH catalyst exhibited the highest yield of 1,4-PeD (78%). The reduction of RNi-Sn(x)/AlOH with H2 at 673-873 K for 1.5 h resulted in the formation of Ni-Sn alloy phases (e.g., Ni3Sn and Ni3Sn2) and caused the transformation of aluminium hydroxide (AlOH) to amorphous alumina (AA). The RNi-Sn(1.4)/AA 673 K/H2 catalyst contained a Ni3Sn2 alloy as the major phase, which exhibited the best yield of 1,4-PeD from furfural (87%) at 433 K, H2 3.0 MPa for 12 h and from levulinic acid (up to 90%) at 503 K, H2 4.0 MPa, for 12 h. Supported RANEY Ni-Sn(1.5)/AC and three types of supported Ni-Sn(1.5) alloy (e.g., Ni-Sn(1.5)/AC, Ni-Sn(1.5)/c-AlOH, and Ni-Sn(1.5)/γ-Al2O3) catalysts afforded high yields of 1,4-PeD (65-87%) both from furfural and levulinic acid under the optimised reaction conditions.
- Ansyah, Fathur Razi,Astuti, Maria Dewi,Hara, Takayoshi,Husain, Sadang,Mustikasari, Kamilia,Rodiansono,Shimazu, Shogo
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p. 241 - 250
(2022/01/19)
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- Catalytic production of 1,4-pentanediol from furfural in a fixed-bed system under mild conditions
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Furfural is one of the most important biomass-derived chemicals. Its large-scale availability calls for the exploration of new transformation methods for further valorization. Here we report on the direct, one-step conversion of furfural into 1,4-pentanediols (1,4-PeDs) using a combination of Amberlyst-15 and Ru-FeOx/AC catalysts. It is interesting to find that the introduction of a suitable amount of FeOxresults in a great improvement in the dispersion of Ru and a decrease in the Lewis acidity. Both XPS and H2-TPR show that there is electron transfer from Ru to Fe, and the electronic interaction facilitates the reduction of both Ru and Fe species. When used in combination with Amberlyst-15, the Ru-6.3FeOx/AC catalyst afforded the best performance with a 1,4-PeD yield of 86%; by contrast, Ru/AC free of FeOxonly gave levulinic acid as the major product, demonstrating the key role of the acid/metal balance in the one-pot conversion of furfural to 1,4-PeD. Moreover, such a dual catalyst exhibited excellent durability within 175 h time-on-stream.
- Liu, Fei,Liu, Qiaoyun,Qiao, Botao,Su, Yang,Wang, Aiqin,Zhang, Leilei,Zhang, Tao
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supporting information
p. 3532 - 3538
(2020/08/28)
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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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- 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
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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.
- Gendler, T. A.,Mokhov, V. M.,Nebykov, D. N.,Popov, Yu. V.,Shemet, V. V.,Shirkhanyan, P. M.
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p. 931 - 935
(2020/07/27)
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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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- Dialkyl Ether Formation at High-Valent Nickel
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In this article, we investigated the I2-promoted cyclic dialkyl ether formation from 6-membered oxanickelacycles originally reported by Hillhouse. A detailed mechanistic investigation based on spectroscopic and crystallographic analysis revealed that a putative reductive elimination to forge C(sp3)-OC(sp3) using I2 might not be operative. We isolated a paramagnetic bimetallic NiIII intermediate featuring a unique Ni2(OR)2 (OR = alkoxide) diamond-like core complemented by a μ-iodo bridge between the two Ni centers, which remains stable at low temperatures, thus permitting its characterization by NMR, EPR, X-ray, and HRMS. At higher temperatures (>-10 °C), such bimetallic intermediate thermally decomposes to afford large amounts of elimination products together with iodoalkanols. Observation of the latter suggests that a C(sp3)-I bond reductive elimination occurs preferentially to any other challenging C-O bond reductive elimination. Formation of cyclized THF rings is then believed to occur through cyclization of an alcohol/alkoxide to the recently forged C(sp3)-I bond. The results of this article indicate that the use of F+ oxidants permits the challenging C(sp3)-OC(sp3) bond formation at a high-valent nickel center to proceed in good yields while minimizing deleterious elimination reactions. Preliminary investigations suggest the involvement of a high-valent bimetallic NiIII intermediate which rapidly extrudes the C-O bond product at remarkably low temperatures. The new set of conditions permitted the elusive synthesis of diethyl ether through reductive elimination, a remarkable feature currently beyond the scope of Ni.
- Le Vaillant, Franck,Reijerse, Edward J.,Leutzsch, Markus,Cornella, Josep
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p. 19540 - 19550
(2020/12/01)
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- Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton-Coupled Electron Transfer
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We report a catalytic, light-driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible-light irradiation in the presence of an IrIII-based photoredox catalyst, a Br?nsted base catalyst, and a hydrogen-atom transfer (HAT) co-catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O?H bonds through a proton-coupled electron-transfer mechanism. This method exhibits a broad substrate scope and high functional-group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented.
- Knowles, Robert R.,Metrano, Anthony J.,Tsuchiya, Yuto,Tsui, Elaine
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supporting information
p. 11845 - 11849
(2020/05/22)
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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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- One-pot dual catalysis for the hydrogenation of heteroarenes and arenes
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A simple dinuclear monohydrido bridged ruthenium complex [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] acts as an efficient and selective catalyst for the hydrogenation of various heteroarenes and arenes. The nature of the catalytically active species was investigated using a combination of techniques including in situ reaction monitoring, kinetic studies, quantitative poisoning experiments and electron microscopy, evidencing a dual reactivity. The results suggest that the hydrogenation of heteroarenes proceeds via molecular catalysis. In particular, monitoring the reaction progress by NMR spectroscopy indicates that [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] is transformed into monomeric ruthenium intermediates, which upon subsequent activation of dihydrogen and hydride transfer accomplish the hydrogenation of heteroarenes under homogeneous conditions. In contrast, carbocyclic aryl motifs are hydrogenated via a heterogeneous pathway, by in situ generated ruthenium nanoparticles. Remarkably, these hydrogenation reactions can be performed using molecular hydrogen under solvent-free conditions or with 1,4-dioxane, and thus give access to a broad range of saturated heterocycles and carbocycles while generating no waste.
- Chatterjee, Basujit,Kalsi, Deepti,Kaithal, Akash,Bordet, Alexis,Leitner, Walter,Gunanathan, Chidambaram
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p. 5163 - 5170
(2020/09/07)
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- Transformation of γ-valerolactone into 1,4-pentanediol and 2-methyltetrahydrofuran over Zn-promoted Cu/Al2O3catalysts
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The transformation of γ-valerolactone (GVL) into 1,4-pentanediol (1,4-PDO) and 2-methyltetra-hydrofuran (2-MTHF) in the presence of H2, one of the useful biomass conversion and utilization processes, was investigated with monometallic Cu/Al2O3 and bimetallic ZnCu/Al2O3 catalysts. A 10 wt% Cu-loaded monometallic catalyst produced 1,4-PDO and 2-MTHF in comparable quantities at a medium conversion (~50%). When Zn was added in a range of Zn/Cu molar ratios of up to 2, in contrast, the catalysts yielded 1,4-PDO in a high selectivity of about 97% at low and high conversion levels. In addition, the 1,4-PDO selectivity over the ZnCu/Al2O3 catalysts remained almost unchanged during recycled runs. That is, the addition of Zn to Cu/Al2O3 switched the product selectivity and improved the catalyst stability and reusability. Furthermore, the physicochemical properties of the catalysts were characterized by several methods including XRD, TEM, TPR, XPS, FTIR of adsorbed pyridine, and so on. On the basis of those results, the relationships between the catalytic performance (activity, selectivity, and reusability) and the catalyst structural features were discussed.
- Arai, Masahiko,Cheng, Haiyang,Lin, Weiwei,Liu, Ke,Liu, Qiang,Shi, Ruhui,Wang, Zhuangqing,Wu, Peixuan,Zhang, Chao,Zhao, Fengyu,Zhao, Zhenbo
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p. 4412 - 4423
(2020/07/14)
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- Dual-Site-Mediated Hydrogenation Catalysis on Pd/NiO: Selective Biomass Transformation and Maintenance of Catalytic Activity at Low Pd Loading
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Creating a new chemical ecosystem based on platform chemicals derived from waste biomass has significant challenges: catalysts need to be able to convert these highly functionalized molecules to specific target chemicals and they need to be economical - not relying on large quantities of precious metals - and maintain activity over many cycles. Herein, we demonstrate how Pd/NiO is able to direct the selectivity of furfural hydrogenation and maintain performance at low Pd loading by a unique dual-site mechanism. Sol-immobilization was used to prepare 1 wt % Pd nanoparticles supported on NiO and TiO2, with the Pd/NiO catalyst showing enhanced activity with a significantly different selectivity profile; Pd/NiO favors tetrahydrofurfuryl alcohol (72%), whereas Pd/TiO2 produces furfuryl alcohol as the major product (68%). Density functional theory studies evidenced significant differences on the adsorption of furfural on both NiO and Pd surfaces. On the basis of this observation we hypothesized that the role of Pd was to dissociate hydrogen, with the NiO surface adsorbing furfural. This dual-site hydrogenation mechanism was supported by comparing the performance of 0.1 wt % Pd/NiO and 0.1 wt % Pd/TiO2. In this study, the 0.1 and 1 wt % Pd/NiO catalysts had comparable activities, whereas there was a 10-fold reduction in performance for 0.1 wt % Pd/TiO2. When TiO2 is used as the support, the Pd nanoparticles are responsible for both hydrogen dissociation and furfural adsorption and the activity is strongly correlated with the effective metal surface area. This work has significant implications for the upgrading of bioderived feedstocks, suggesting alternative ways for promoting selective transformations and reducing the reliance on precious metals.
- Botton, Gianluigi A.,Campisi, Sebastiano,Chan-Thaw, Carine E.,Chinchilla, Lidia E.,Chutia, Arunabhiram,Dimitratos, Nikolaos,Mohammed, Khaled M. H.,Villa, Alberto,Wells, Peter P.
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p. 5483 - 5492
(2020/09/02)
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- PROCESS FOR PRODUCING 2-BUTANOL FROM GAMMAVALEROLACTONE
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A process is disclosed for selectively producing 2-butanol from GVL by using at least one transition metal catalyst selected from the group consisting of iron, ruthenium, cobalt, rhodium and iridium.
- -
-
Paragraph 0082-0083; 0091
(2020/02/05)
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- One-pot direct conversion of levulinic acid into high-yield valeric acid over a highly stable bimetallic Nb-Cu/Zr-doped porous silica catalyst
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The direct conversion of levulinic acid (LA) to valeric biofuel is highly promising for the development of biorefineries. Herein, LA is converted into valeric acid (VA) via one-pot direct cascade conversion over non-noble metal-based Nb-doped Cu on Zr-doped porous silica (Nb-Cu/ZPS). Under mild reaction conditions (150 °C and 3.0 MPa H2 for 4 h), LA was completely converted into VA in high yield (99.8%) in aqueous medium with a high turnover frequency of 0.038 h-1. The Lewis acid sites of ZPS enhanced the adsorption of LA on the catalyst surface, and both the Lewis and Br?nsted acidity associated with Nb2O5 and the metallic Cu0 sites promoted catalysis of the cascade hydrogenation, ring cyclization, ring-opening, and hydrogenation reactions to produce VA from LA. The bimetallic Nb-Cu/ZPS catalyst was also effective for the conversion of VA into various valeric esters in C1-C5 alcohol media. The presence of Nb2O5 effectively suppressed metal leaching and coke formation, which are serious issues in the liquid-phase conversion of highly acidic LA during the reaction. The catalyst could be used for up to five consecutive cycles with marginal loss of activity, even without catalyst re-activation.
- Karanwal, Neha,Verma, Deepak,Butolia, Paresh,Kim, Seung Min,Kim, Jaehoon
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supporting information
p. 766 - 787
(2020/02/25)
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- Hydrogen-Bonding Catalyzed Ring-Closing C?O/C?O Metathesis of Aliphatic Ethers over Ionic Liquid under Metal-Free Conditions
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O-heterocycles have wide applications, and their efficient and green synthesis is very interesting. Herein, we report hydrogen-bonding catalyzed ring-closing metathesis of aliphatic ethers to O-heterocycles over ionic liquid (IL) catalyst under metal- and solvent-free conditions. The IL 1-butylsulfonate-3-methylimidazolium trifluoromethanesulfonate ([SO3H-BMIm][OTf]) is discovered to show outstanding performance, better than the reported catalysts. An interface effect plays an important role in mediating the reaction rate due to the immiscibility between the products and the IL catalyst, and the products can be spontaneously separated. NMR analysis and DFT calculation suggest that a pair of cation and anion of [SO3H-BMIm][OTf] could form three strong H-bonds with an ether molecule, which catalyze the ether transformation via a cyclic oxonium intermediate. A series of O-heterocycles including tetrahydrofurans, tetrahydropyrans, morpholines and dioxane can be obtained from their corresponding ethers in excellent yields (e.g., >99 %). This work opens an efficient and metal-free way to produce O-heterocycles from aliphatic ethers.
- Wang, Huan,Zhao, Yanfei,Zhang, Fengtao,Wu, Yunyan,Li, Ruipeng,Xiang, Junfeng,Wang, Zhenpeng,Han, Buxing,Liu, Zhimin
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supporting information
p. 11850 - 11855
(2020/05/16)
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- Strongly Lewis Acidic Metal-Organic Frameworks for Continuous Flow Catalysis
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The synthesis of highly acidic metal-organic frameworks (MOFs) has attracted significant research interest in recent years. We report here the design of a strongly Lewis acidic MOF, ZrOTf-BTC, through two-step transformation of MOF-808 (Zr-BTC) secondary building units (SBUs). Zr-BTC was first treated with 1 M hydrochloric acid solution to afford ZrOH-BTC by replacing each bridging formate group with a pair of hydroxide and water groups. The resultant ZrOH-BTC was further treated with trimethylsilyl triflate (Me3SiOTf) to afford ZrOTf-BTC by taking advantage of the oxophilicity of the Me3Si group. Electron paramagnetic resonance spectra of Zr-bound superoxide and fluorescence spectra of Zr-bound N-methylacridone provided a quantitative measurement of Lewis acidity of ZrOTf-BTC with an energy splitting (?E) of 0.99 eV between the ?x? and ?y? orbitals, which is competitive to the homogeneous benchmark Sc(OTf)3. ZrOTf-BTC was shown to be a highly active solid Lewis acid catalyst for a broad range of important organic transformations under mild conditions, including Diels-Alder reaction, epoxide ring-opening reaction, Friedel-Crafts acylation, and alkene hydroalkoxylation reaction. The MOF catalyst outperformed Sc(OTf)3 in terms of both catalytic activity and catalyst lifetime. Moreover, we developed a ZrOTf-BTC?SiO2 composite as an efficient solid Lewis acid catalyst for continuous flow catalysis. The Zr centers in ZrOTf-BTC?SiO2 feature identical coordination environment to ZrOTf-BTC based on spectroscopic evidence. ZrOTf-BTC?SiO2 displayed exceptionally high turnover numbers (TONs) of 1700 for Diels-Alder reaction, 2700 for epoxide ring-opening reaction, and 326 for Friedel-Crafts acylation under flow conditions. We have thus created strongly Lewis acidic sites in MOFs via triflation and constructed the MOF?SiO2 composite for continuous flow catalysis of important organic transformations.
- Ji, Pengfei,Feng, Xuanyu,Oliveres, Pau,Li, Zhe,Murakami, Akiko,Wang, Cheng,Lin, Wenbin
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supporting information
p. 14878 - 14888
(2019/10/02)
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- Continuous Hydrogenation of Ethyl Levulinate to 1,4-Pentanediol over 2.8Cu-3.5Fe/SBA-15 Catalyst at Low Loading: The Effect of Fe Doping
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Bimetallic Cu–Fe catalysts with low loading were prepared for hydrogenation of ethyl levulinate (EL) to 1,4-pentanediol (1,4-PDO). Among them, 2.8Cu-3.5Fe/SBA-15 (Cu/Fe molar ratio of 1:1.5) performed best, capable of converting EL to the key intermediate γ-valerolactone (GVL) at 140 °C with 97 % yield. It can also be used to hydrogenate GVL to 1,4-PDO with 92.6 % selectivity or convert EL to 1,4-PDO in one pot. The high activity of the catalyst at such a low loading was attributed to the highly dispersed metal species and the Fe doping effect. Various characterization methods indicated that Fe acted as both structural and electronic modifier to promote the chemical properties of the Cu species. Besides, the incorporation of Fe provided abundant Lewis acid sites and accelerated the reaction process. CuFeO2 was detected by energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and XRD. On the basis of a combination of characterization and reaction kinetics, synergistic catalysis by Cu0 and CuFeO2 is considered to be responsible for the excellent performance of the Cu–Fe catalysts.
- Deng, Tianyu,Yan, Long,Li, Xinglong,Fu, Yao
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p. 3837 - 3848
(2019/08/07)
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- Controlling product selectivity by surface defects over MoOx-decorated Ni-based nanocatalysts for γ-valerolactone hydrogenolysis
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Currently, highly efficient biomass upgrading over non-noble metal catalysts is of vital importance for reducing equipment and operation expenses in biorefinery industries. In this respect, the related heterogeneous catalysis demands the design and construction of mutual cooperative microstructure of catalysts to improve their catalytic performances. Here, an efficient catalytic process for selective hydrogenolysis of biomass-derived γ-valerolactone (GVL) to produce 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF) was developed by earth-abundant nickel-based catalysts, which were derived from a molybdate intercalated Ni-Al layered double hydroxide precursor. It was found that with the elevated reduction temperature, the amount of surface defective MoOx species (0 x/Al2O3 catalyst obtained at the reduction temperature of 600 °C delivered a 94.0% combined yield of 1,4-PDO and 2-MTHF under mild reaction conditions. It was demonstrated that over the present Ni-MoOx/Al2O3 catalyst system, surface defective MoOx species could greatly facilitate the adsorption and activation of carbonyl group in GVL and thus significantly promote the cleavage of C[dbnd]O bond and its adjacent C[sbnd]O bond. This finding opens a promising door to engineer surface defective structure of high-performance supported metal catalysts.
- Zhang, Guangcheng,Li, Wei,Fan, Guoli,Yang, Lan,Li, Feng
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p. 100 - 111
(2019/10/05)
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- Highly efficient hydrogenation of levulinic acid into 2-methyltetrahydrofuran over Ni-Cu/Al2O3-ZrO2 bifunctional catalysts
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Transformation of biomass or biomass-based feedstocks into fuels or valuable chemicals is of great importance for the sustainable development of our society. Mesoporous Al2O3-ZrO2 with different Al:Zr molar ratios was prepared by the sol-gel method, and Cu-Ni/Al2O3-ZrO2 catalysts were fabricated by the impregnation method. The catalytic performances of the bifunctional catalysts were studied in the selective hydrogenation of levulinic acid (LA) into 2-methyltetrahydrofuran (MTHF). It was demonstrated that both Cu:Ni and Al:Zr ratios affected the selectivity to MTHF significantly. The bimetallic catalysts Cu-Ni/Al2O3-ZrO2 containing 10 wt% Ni and 10 wt% Cu gave 99.8% MTHF selectivity at full conversion of LA when the Al:Zr ratio was 9:1. The outstanding catalytic performance of the catalyst is related to the mesoporous structure, the acidic properties of the support and the synergistic effect between Cu and Ni. The catalyst could be reused five times without a considerable loss of catalytic activity and selectivity.
- Xie, Zhenbing,Chen, Bingfeng,Wu, Haoran,Liu, Mingyang,Liu, Huizhen,Zhang, Jianling,Yang, Guanying,Han, Buxing
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supporting information
p. 606 - 613
(2019/02/14)
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- 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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p. 162 - 172
(2018/11/30)
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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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-
Paragraph 0045
(2019/12/30)
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- Iridium complex catalytic ring lactone hydrogenation [...] method
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The present invention provides one kind of iridium complex catalytic ring lactone hydrogenation [...] method, organic chemical technical field. The present invention is to ring lactone as raw materials, iridium complex as the catalyst hydrogenation reaction, in particular in accordance with the following steps: that the intrauterine lactone, iridium complex, the hydrogen gas as a reducing agent, the hydrogen reduction reaction, iridium complexes and ring lactone mass ratio is 0.00001 - 0.1; a hydrogen pressure of 1.0 - 10.0 mpa; the reaction temperature is 90 - 150 °C, the reaction time is: 0.5 - 72 h. The beneficial effects of the present invention: simple reaction operation, product selectivity and easy separation.
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Paragraph 0015-0027
(2019/07/04)
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- Preparation method 2 - methyltetrahydrofuran (by machine translation)
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The invention relates to a preparation method. 2 - methyltetrahydrofuran. The main steps are: mixing levulinic acid or ester compound, bimetallic supported catalyst and alkane solvent in a high-pressure reaction kettle, carrying out catalytic hydrogenation under certain reaction conditions to prepare 2 - methyltetrahydrofuran; and the catalytic reaction condition is: reaction temperature 160. o C- 220 o C, levulinic acid or ester compounds thereof and alkane solvent mass ratio (0.01 - 0.1): 1, hydrogen gas plenum 4 mpa type ?, reaction time 1 - 4 h; the bimetallic supported catalyst core metal used in the invention is copper and nickel bimetallic; the bimetallic catalyst has high activity, is matched with alkane solvent systems, obviously reduces reaction temperature, and promotes reaction conversion efficiency and yield. , The catalyst has the advantages of being easy to separate from the product and free of heavy metal pollution, and the like. (by machine translation)
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Paragraph 0021-0053
(2019/09/17)
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- Method for preparing n-amyl alcohol through gamma-valerolactone hydrogenation
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The invention provides a method for preparing n-amyl alcohol through gamma-valerolactone hydrogenation. The method comprises the following steps: pouring gamma-valerolactone, a hydrogenation catalystand a solid acid catalyst into a reactor, and carrying out catalytic reaction to generate the n-amyl alcohol and 2-methyltetrahydrofuran in the presence of hydrogen and under heating conditions. The hydrogenation catalyst contains active ingredients which are one or more of Ni, Ru, Cu, and Ag. The method for preparing the n-amyl alcohol through gamma-valerolactone hydrogenation, provided by the invention, has the advantages that the product yield is high and the catalyst is mechanically used for 20 times or above; the combined catalyst has long life and good industrial application prospect.
- -
-
Paragraph 0007; 0026-0052
(2019/01/17)
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- One-pot selective conversion of C5-furan into 1,4-pentanediol over bulk Ni-Sn alloy catalysts in an ethanol/H2O solvent mixture
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Inexpensive bulk Ni-Sn alloy-based catalysts demonstrated a unique catalytic property in the selective conversion of C5-furan compounds (e.g., furfuraldehyde (FFald), furfuryl alcohol (FFalc), and 2-methylfuran (2-MTF)) in an ethanol/H2O solvent mixture and selectively produced 1,4-pentanediol (1,4-PeD) in a one-pot reaction. The synergistic actions between the bulk Ni-Sn alloy catalyst, hydrogen gas, and the hydroxylated H2O or ethanol/H2O solvents are believed to play a prominent role in the catalytic reactions. Bulk Ni-Sn alloy catalysts that consisted of Ni3Sn or Ni3Sn2 alloy phases allowed an outstanding yield of 1,4-PeD up to 92% (from FFald), 67% (from FFalc), and 48% (from 2-MTF) in ethanol/H2O (1.5:2.0 volume ratio) at 433 K, 3.0 MPa H2 and 12 h. As the reaction temperature increased to 453 K, the yield of 1,4-PeD slightly decreased to 87% (from FFald), whereas it slightly increased to 71% (from FFalc). The bulk Ni-Sn alloy catalysts were reusable without any significant loss of selectivity.
- Rodiansono,Dewi Astuti, Maria,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
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supporting information
p. 2307 - 2315
(2019/05/21)
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- Glycerin and the laevulinic acid one-step process for preparing 1, 3 - propylene glycol and γ - e lactone method
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The invention relates to a method for preparing 1,3-propylene glycol and gamma-valerolactone from glycerin and acetylpropionic acid by a one-step method. According to the method, a stainless steel high-pressure reactor with a volume of 50 ml is adopted; a catalyst used in the invention is Ru/C with its catalytic amount of 0.04g and with its composition by weight of Ru%=5%; and the rest is a carrier, namely activated carbon. A reaction material is a glycerin-acetylpropionic acid solution (concentration of acetylpropionic acid is 20 wt% and concentration ratio of acetylpropionic acid to glycerin is 1:1-10:1), and volume of the solution is 5 ml. A reaction solvent is water. Reaction temperature is 120-200 DEG C; reaction H2 pressure is 2-4 MPa; and reaction time is 0.5-12 h. In comparison with existing technologies for preparing 1,3-propylene glycol from glycerin, the invention is different in the following aspects: an acid reactant is added into the glycerin system; and by the utilization of a metal catalyst, the catalyst can cooperate with the acid reactant to selectively convert glycerin to 1,3-propylene glycol on one hand, and the acid reactant is simultaneously converted to a more valuable product on the other hand. The method provided by the invention has a wide application prospect.
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Paragraph 0019-0027
(2019/06/14)
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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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- Hydro-Oxygenation of Furfural in the Presence of Ruthenium Catalysts Based on Al-HMS Mesoporous Support
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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.
- Roldugina,Shayakhmetov,Maksimov,Karakhanov
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p. 1306 - 1315
(2019/11/03)
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- Aqueous Hydrogenation of Levulinic Acid to 1,4-Pentanediol over Mo-Modified Ru/Activated Carbon Catalyst
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A highly efficient and green process was developed for direct conversion of levulinic acid into 1,4-pentanediol over Mo-modified Ru/activated carbon (AC) catalyst in a continuous fixed-bed reactor. The Ru–MoOx/AC catalyst was found to be efficient for the aqueous-phase hydrogenation of levulinic acid to 1,4-pentanediol, whereby a high yield (96.7 mol %) of 1,4-pentanediol was obtained under mild reaction conditions (70 °C, 4 MPa H2).
- Cui, Jinglei,Tan, Jingjing,Zhu, Yulei,Cheng, Fangqin
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p. 1316 - 1320
(2018/03/21)
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- Pd anchored on C3N4 nanosheets/reduced graphene oxide: An efficient catalyst for the transfer hydrogenation of alkenes
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In this work, a porous g-C3N4 nanosheets/reduced graphene oxide (rGO) composite was synthesized via the hydrothermal co-assembly of GO and g-C3N4 nanosheets (g-C3N4 NS). Compared with g-C3N4 NS, rGO and bulk g-C3N4/rGO, the g-C3N4 NS/rGO supported Pd nanocatalyst displayed a remarkable catalytic activity for the hydrogenation of alkenes with formic acid and formates as the hydrogen source at atmospheric pressure. Among all the as-prepared Pd-g-C3N4 NS/rGO catalysts, the optimized Pd-g-C3N4 NS/rGO20 exhibited the highest turnover frequency of 133 mol mol-1 Pd h-1, which is among the highest value reported in documents. 99% conversion and 99% selectivity were achieved after 30 min reaction at 30 °C for the hydrogenation of nitrobenzene. In addition, Pd-g-C3N4 NS/rGO20 exhibited an excellently high stability after five successive cycles without significant loss of its catalytic activity.
- Li, Jie,Cheng, Saisai,Du, Tianxing,Shang, Ningzhao,Gao, Shutao,Feng, Cheng,Wang, Chun,Wang, Zhi
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p. 9324 - 9331
(2018/06/08)
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- Nitrogen-enriched porous carbon supported Pd-nanoparticles as an efficient catalyst for the transfer hydrogenation of alkenes
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Ultrafine palladium nanoparticles were immobilized on nitrogen-enriched porous carbon nanosheets (NPC), which were fabricated with g-C3N4 as a nitrogen source and a self-sacrificial template. The prepared Pd@NPC exhibited superior catalytic activity and chemoselectivity for the catalytic transfer hydrogenation of alkenes under mild conditions with formic acid as a hydrogen donor. Moreover, the catalyst displays high structure stability, and can be reused for five runs without any significant decrease of its catalytic activity and obvious leaching of Pd species. This work provides a facile and feasible approach to fabricate nitrogen-enriched carbon nanosheets and to construct advanced Pd supported heterogeneous catalysts for achieving high catalytic activity.
- Li, Jie,Zhou, Xin,Shang, Ning-Zhao,Feng, Cheng,Gao, Shu-Tao,Wang, Chun
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p. 16823 - 16828
(2018/10/23)
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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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supporting information
p. 2027 - 2037
(2018/05/24)
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- Method for preparing 2-methyltetrahydrofuran by taking 4-pentene-1-ol as raw material in one step through high-efficiency catalyst
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The invention discloses a method for preparing 2-methyltetrahydrofuran by taking 4-pentene-1-ol as a raw material in one step through a high-efficiency catalyst. The 2-methyltetrahydrofuran is prepared by taking the 4-pentene-1-ol as the raw material, catalyzing through a magnetic loaded cation lanthanum series complex catalyst and carrying out intramolecular hydrogen alkylation; the magnetic loaded cation lanthanum series complex catalyst is obtained by connecting a cation lanthanum series complex and hydroxyl on the surface of a functionalized magnetic nano-carrier; the functionalized magnetic nano-carrier is obtained by carrying out surface silanization treatment on silica sol covered ferroferric oxide nanoparticles. According to the method disclosed by the invention, the catalyst doesnot contain noble metal; the method has the advantages of low preparation cost, low reaction pressure and moderate temperature which is about 80 DEG C, and has the characteristics of simplicity and convenience for operation, high yield, low byproducts, easiness for recycling the catalyst and the like, so that an efficient and green synthesis method for rapidly and safely separating the catalyst isrealized.
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Paragraph 0009; 0048
(2018/05/16)
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- Facile synthesis of furfuryl ethyl ether in high yield: Via the reductive etherification of furfural in ethanol over Pd/C under mild conditions
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The one-pot synthesis of furfuryl ethyl ether (FEE) over Pd nanoparticles supported on TiO2, Al2O3, SiO2, and active carbon via the catalytic reductive etherification of furfural in ethanol was systematically studied. The Pd nanoparticles supported on SiO2, TiO2 and active carbon are all active for this novel process under mild reaction conditions, with Pd/C showing the highest selectivity to FEE. The effects of palladium loading, reaction temperature, and hydrogen pressure on the activity and selectivity of Pd/C have been investigated in detail. The results demonstrate that suitable Pd amount, low reaction temperature of about 60 °C, and low H2 pressure of about 0.3 MPa are favorable for the formation of the desired ether product. Under the optimized conditions, an unprecedented high yield of up to 81% of FEE was firstly obtained with the major by-products being furfuryl alcohol and 2-methyltetrahydrofuran. Compared with the conventional hydrogenation-etherification route via furfural alcohol as a reaction intermediate, the reductive etherification shows significant advantage in product yield because of its much lower reaction temperature that is required.
- Wang, Yun,Cui, Qianqian,Guan, Yejun,Wu, Peng
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p. 2110 - 2117
(2018/05/24)
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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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- Supported cobalt catalysts for the selective hydrogenation of ethyl levulinate to various chemicals
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A highly active and selective cobalt catalyst was developed for the hydrogenation of biomass-derived ethyl levulinate (EL) to γ-valerolactone (GVL), ethyl 4-hydroxypentanoate (EHP), 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF), which are considered to be value-added chemicals and important biofuels. The effects of reaction time, reaction temperature, catalyst amount and solvent on its catalytic performance were investigated. In addition, the reaction pathway was studied as well. It was found that the selectivity of GVL, 1,4-PDO and 2-MTHF on Co/ZrO2 can be easily tuned by changing reaction conditions, and can reach as high as 94%, 78% and 77%, respectively. The product selectivity is also significantly affected by the catalyst support. With SBA-15 as the support, the selectivity of EHP can reach 90%. Moreover, Co/ZrO2 gave an extraordinarily high GVL productivity of 1.50 mol gmetal-1 h-1 and displayed excellent stability and reusability. Interestingly, coke has a positive effect on the enhancement of GVL yield. AL dimers and trimers were identified as the coke species in the hydrogenation of EL. As far as we know, this is the first work conducting the flexible transformation of EL on cobalt catalysts.
- Cen, Youliang,Zhu, Shanhui,Guo, Jing,Chai, Jiachun,Jiao, Weiyong,Wang, Jianguo,Fan, Weibin
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p. 9152 - 9160
(2018/03/21)
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- Palladium–Ruthenium Catalyst for Selective Hydrogenation of Furfural to Cyclopentanol
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Bimetallic Pd–Ru/C catalyst was shown to be much more active in the aqueous-phase hydrogenation of furfural (473 K, 8 MPa) in comparison with both Pd/C and Ru/C catalysts. The enhanced hydrogenation activity manifested itself as an increased yield of cyclopentanol (77%) at a complete conversion of furfural. The observed synergistic effect between palladium and ruthenium in the tested reaction can be related to changes in the electronic state and particle size of supported metals upon interaction with each other and the Pd–Ru alloy formation.
- Mironenko,Belskaya,Lavrenov,Likholobov
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p. 339 - 346
(2018/06/11)
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- Selective hydrogenolysis of furfuryl alcohol to 1,5- and 1,2-pentanediol over Cu-LaCoO3 catalysts with balanced Cu0-CoO sites
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Selective hydrogenolysis of biomass-derived furfuryl alcohol (FFA) to 1,5- and 1,2-pentanediol (PeD) was conducted over Cu-LaCoO3 catalysts with different Cu loadings; the catalysts were derived from perovskite structures prepared by a one-step citrate complexing method. The catalytic performances of the Cu-LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions. The catalyst with 10 wt% Cu loading exhibited the best catalytic performance after prereduction in 5%H2-95%N2, achieving a high FFA conversion of 100% and selectivity of 55.5% for 1,5-pentanediol (40.3%) and 1,2-pentanediol (15.2%) at 413 K and 6 MPa H2. This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity. Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs, especially to 1,5-PeD, while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol (THFA). Therefore, it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5-/1,2-pentanediol selectivity ratio during FFA hydrogenolysis.
- Gao, Fangfang,Liu, Hailong,Hu, Xun,Chen, Jing,Huang, Zhiwei,Xia, Chungu
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p. 1711 - 1723
(2018/08/21)
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