- Nanoreactors based on hydrophobized tubular aluminosilicates decorated with ruthenium: Highly active and stable catalysts for aromatics hydrogenation
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Industrial hydrogenation catalysts must be not only selective and active but also resistant to feedstock impurities, including water. We report the strategy of preparing catalytic core-shell nanoreactors based on hydrophobized aluminosilicate nanotubes loaded with ruthenium. The modification of halloysite with alkyltriethoxysilanes enhances hydrophobicity of the clay nanotubes (water contact angle up to 122°) and enables their selective loading with 4-nm ruthenium particles. Such a core-shell tubular nanoreactors provide shielding of active sites from deactivation by admixed water and prevent metal leaching. Produced mesoscale catalysts were active in the hydrogenation of aromatics both in organic and aqueous media at 80 °C and a hydrogen pressure of 3 MPa. Benzene hydrogenation in the biphasic system with water resulted in a complete conversion with 100 % selectivity to cyclohexane over halloysite modified by C18-triethoxysilane supported ruthenium catalyst with turnover frequency (TOF) of 4371 h?1. This catalytic system remained stable after ten cycles of benzene hydrogenation, providing 98 % conversion. The demonstrated synthetic strategy is promising for the design of industrial catalysts for the hydroprocessing water-containing organic feedstock and may be upscaled due to the abundant availability of halloysite clay nanotubes.
- Glotov, Aleksandr,Novikov, Andrei,Stavitskaya, Anna,Nedolivko, Vladimir,Kopitsyn, Dmitry,Kuchierskaya, Alexandra,Ivanov, Evgenii,Stytsenko, Valentine,Vinokurov, Vladimir,Lvov, Yuri
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- Surfactant-stabilized aqueous iridium(0) colloidal suspension: An efficient reusable catalyst for hydrogenation of arenes in biphasic media
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Aqueous suspensions of iridium nanoparticles produced by the chemical reduction of IrCl3 assisted by sonication, in the presence of N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl)ammonium chloride salt as surfactant, have shown an efficient activity for the catalytic hydrogenation of various aromatic derivatives in biphasic media under mild conditions. These nanocatalysts can be reused for further runs with a total conservation of activity and provided significant catalytic lifetime for anisole hydrogenation in pure water with 3000 total turnover (TTO).
- Mevellec, Vincent,Roucoux, Alain,Ramirez, Esther,Philippot, Karine,Chaudret, Bruno
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- REACTIONS OF FREE RADICALS WITH MONOETHYLDICHLOROCHROMIUM(III) TRIS(TETRAHYDROFURANATE)
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?-Ethyl-chromium(III)dichloride * 3 THF reacts with free radicals by formation of a transient paramagnetic complex which decomposes giving the combination product of alkyl ligand and radical.
- Sustmann, Reiner,Altevogt, Rudolf
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- Catalytic dehydrogenation of cyclooctane with titanium, zirconium and hafnium metallocene complexes
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Metallocene complexes in combination with cocatalysts like methylalumoxane (MAO) are not only excellent catalysts for olefin polymerization but also appropriate catalysts for the activation of alkanes in homogeneous (autoclave) and heterogeneous (fixed be
- Taubmann, Sandra,Denner, Christine E.,Alt, Helmut G.
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- On the influence of diphosphine ligands on the chemical order in small RuPt nanoparticles: Combined structural and surface reactivity studies
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Diphenylphosphinobutane (dppb) stabilized bimetallic RuPt nanoparticles were prepared by co-decomposition of [Ru(COD)(COT)] [(1,5-cyclooctadiene)(1,3,5- cyclooctatriene)ruthenium] and [Pt(CH3)2(COD)] [dimethyl(1,5-cyclooctadiene) platinum(ii)] organometallic precursors under mild conditions (room temperature, 3 bar of dihydrogen) and in the presence of dppb. The determination of the nanoparticles' chemical composition was made possible thanks to a combination of several characterization techniques (HREM, STEM-HAADF, WAXS, EXAFS, IR, NMR) associated with surface reactivity studies based on simple catalytic reactions. The obtained nanoparticles display a ruthenium rich core and a disordered shell containing both ruthenium and platinum. The results were compared with those obtained on nanoparticles of similar size and composition but not containing ligands. The complexity observed in the present structure of these nanoparticles arises from the high chemical affinity of the diphosphine ligand used as a stabilizer for both metals.
- Lara, Patricia,Ayvali, Tugce,Casanove, Marie-Jose,Lecante, Pierre,Mayoral, Alvaro,Fazzini, Pier-Francesco,Philippot, Karine,Chaudret, Bruno
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- Small bite-angle 2-phosphinophosphinine ligands enable rhodium-catalysed hydroboration of carbonyls
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Two Rh complexes of the 2-phosphinophosphinine ligand 2-PPh2-3-Me-6-SiMe3-C5H2P (1) were prepared: dinuclear trans-[{Rh(CO)(Cl)(μ-1)}2] (2) and chelating [Rh(1)(COD)][B(ArF)4] (3). Despite the widespread use of Rh catalysts for the hydroboration of alkenes, 3 is reported to be the first Rh catalyst for ketone and ketimine hydroboration, with high activity observed at 0.1 mol% loading.
- Newland, Robert J.,Lynam, Jason M.,Mansell, Stephen M.
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- A Comparison of Ruthenium-Catalysed Arene Hydrogenation Reactions in Water and 1-Alkyl-3-methylimidazolium Tetrafluoroborate Ionic Liquids
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The hydrogenation of benzene and other arene substrates under biphasic conditions is evaluated using the catalyst precursor Ru(η6-C 10H14)(pta)Cl2 (pta = 1,3,5-triaza-7- phosphaadamantane) immobilised in water and 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids. The effect that contamination of the 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids with chloride has on the hydrogenation reaction has also been examined. Of the immobilisation solvents tested the optimum solvent was found to be chloride-free 1-butyl-3-methylimidazolium tetrafluoroborate. Catalytic turnovers in this solvent are highest, and in general, turnovers for the hydrogenation reactions follow the trend: chloride-free 1-butyl-3-methylimidazolium tetrafluoroborate > water > chloride-contaminated 1-butyl-3-methylimidazolium tetrafluoroborate.
- Dyson, Paul J.,Ellis, David J.,Henderson, William,Laurenczy, Gábor
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- Catalytic hydrogenation of aromatics under biphasic conditions: Isolation and structural characterisation of the cluster intermediate [(η6-C6Me6)2(η 6-C6H6)Ru3(μ2-H) 2(μ2-OH)(μ3-O)]+
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The water-soluble cluster cation [(η6-C6Me6)2(η 6-C6H6)Ru3(μ2-H) 3(μ3-O)]+ (2) catalyses the hydrogenation of benzene and benzene derivatives to give the corresponding cyclohexanes under biphasic conditions. The catalytic activity of 2 depends markedly on the substrate, an extremely high activity being observed for ethylbenzene. The cationic species present in the catalytic mixture of the ethylbenzene hydrogenation could be isolated as the tetrafluoroborate salt and characterised as the cation [(η6-C6Me6)2(η 6-C6H6)Ru3(μ2-H) 2(μ2-OH)(μ3-O)]+ (3). With 3 as the catalyst, the catalytic activity is also much higher for other benzene derivatives.
- Faure, Matthieu,Vallina, Ana Tesouro,Stoeckli-Evans, Helen,Süss-Fink, Georg
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- Alkyne-Functionalized Ruthenium Nanoparticles: Impact of Metal-Ligand Interfacial Bonding Interactions on the Selective Hydrogenation of Styrene
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In the present study, ruthenium nanoparticles functionalized with terminal and internal alkynes were prepared, and it was found that internal alkynes formed a η2 side-on configuration on the surface of ruthenium nanoparticles, in sharp contrast to the ruthenium-vinylidene interfacial bonds for terminal alkynes. For the nanoparticles capped with terminal alkyne, hydrogenation of both the vinyl moiety and phenyl ring occurred, whereas selective hydrogenation of the vinyl moiety was observed with internal alkyne-functionalized nanoparticles. This work highlights the importance of the metal-organic interface in the rational design and engineering of the nanoparticle catalyst for organic synthesis.
- Zhang, Fengqi,Fang, Jingjing,Huang, Lin,Sun, Wenming,Lin, Zhang,Shi, Zhenqing,Kang, Xiongwu,Chen, Shaowei
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- Preparation of a PdRuNi/C tri-metallic nanocatalyst and its excellent catalytic performance for ethylbenzene hydrogenation reaction
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Herein, Ni/C was prepared at room temperature (RT) by liquid chemical reduction by using hydrazine hydrate as the reducing agent. The impregnation method was adopted to deposit precious metals on carbon black (C) to obtain the Pd/C, Ru/C monometallic and PdRu/C bimetallic catalysts. The PdNi/C, RuNi/C bimetallic and PdRuNi/C tri-metallic catalysts were obtained through a chemical replacement reaction method. The as-prepared catalysts were characterized by inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution TEM (HRTEM), high-angle annular dark-field scanning TEM (HAADF-STEM) and STEM energy dispersive X-ray spectroscopy (STEM-EDS) elemental mapping and line-scanning, scanning electron microscopy (SEM) and SEM-EDS, X-ray photoelectron spectroscopy (XPS) and high-sensitivity low-energy ion scattering spectroscopy (HS-LEIS) techniques, which proved that PdRu islands were supported on the Ni/Ni(OH)2 nanoparticles (NPs) (PdRu-on-Ni/Ni(OH)2 NPs) in PdRuNi/C. The results revealed that the PdRuNi/C catalyst showed the most excellent catalytic performance for ethylbenzene hydrogenation under mild reaction conditions mainly owing to the synergistic effect among the Pd, Ru and Ni related species. The PdRuNi/C catalyst also exhibited good stability in ethylbenzene hydrogenation.
- Pei, An,Ruan, Luna,Liao, Jianhua,Zhang, Huan,Wang, Jiexiang,Yang, Kai,Liu, Zhiping,Zhu, Lihua,Chen, Bing Hui
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- Enhancing the catalytic activity of Ru NPs deposited with carbon species in yolk-shell nanostructures
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The synthesis of metal NPs with a well-defined size, shape and composition provides opportunities for tuning the catalytic performance of metal NPs. However, the presence of a stabilizer on the metal surface always blocks the active sites of metal NPs. Herein, we report an efficient method to remove the stabilizer on the metal surface via H2 pyrolysis with Ru-poly(amindoamine) encapsulated in silica-based yolk-shell nanostructures as an example. The CO uptake amount of Ru NPs increases sharply after H2 pyrolysis, indicating that the exposure degree of Ru NPs is increased. No aggregation of the colloidal Ru NPs occurs after H2 pyrolysis, which could be mainly assigned to the protection effect of C and N species formed on Ru NPs. The overall activity of Ru NPs in the yolk-shell nanostructure after the pyrolysis could reach as high as 20 300 mmol per mmol Ru per h in the hydrogenation of toluene, which is much higher than that of most reported Ru-based solid catalysts. It was found that the yolk-shell nanostructure could efficiently prevent the leaching of Ru NPs during the catalytic process. Ru NPs in the yolk-shell nanostructure could also catalyze the hydrogenation of benzoic acid and Levulinic acid with high activity and selectivity.
- Guo, Miao,Lan, Guojun,Peng, Juan,Li, Mingrun,Yang, Qihua,Li, Can
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- Cellulose nanocrystals as non-innocent supports for the synthesis of ruthenium nanoparticles and their application to arene hydrogenation
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Ru nanoparticles were synthesized from RuCl3 under mild H2 pressure within a suspension of cellulose nanocrystals. X-ray photoelectron spectroscopy and transmission electron microscopy revealed that the small Ru(0) nanoparticles (3.3 ± 1 nm) were deposited onto their cellulosic support. This hybrid proved to be a highly efficient arene hydrogenation catalyst operational at 4 bars and room temperature.
- Kaushik, Madhu,Friedman, Hava Meira,Bateman, Mary,Moores, Audrey
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- Catalytic decomposition of 2,3-dihydrobenzofuran to monomeric cyclic compounds over Pd/XCs2.5H0.5PW12O 40/OMC (ordered mesoporous carbon) (X = 10-30 wt.%) catalysts
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A series of Pd/XCs2.5H0.5PW12O 40/OMC (ordered mesoporous carbon) (X = 10, 15, 20, 25, and 30 wt.%) catalysts with different Cs2.5H0.5PW12O 40 contents (X, wt%) were prepared by a sequential incipient wetness impregnation method for use in the catalytic decomposition of 2,3-dihydrobenzofuran to monomeric cyclic compounds. 2,3-Dihydrobenzofuran was used as a lignin model compound for representing β-5 linkage of lignin. Acidity of Pd/XCs2.5H0.5PW12O40/OMC catalysts served as an important factor determining the catalytic performance in the reaction. Conversion of 2,3-dihydrobenzofuran and total yield for main products (2-ethylphenol and ethylcyclohexane) increased with increasing acidity of Pd/XCs2.5H0.5PW12O40/OMC catalysts.
- Kim, Jeong Kwon,Park, Hai Woong,Hong, Ung Gi,Lee, Yoon Jae,Song, Ji Hwan,Song, In Kyu
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- Minor Modifications to the Ligands Surrounding a Ruthenium Complex Lead to Major Differences in the Way in which they Catalyse the Hydrogenation of Arenes
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The hydrogenation of benzene and other arenes under aqueous-organic biphasic conditions is evaluated using the ruthenium complexes Ru(η 6-C10H14)(pta)Cl2 (pta = 1,3,5-triaza-7-phosphaadamantane), Ru(η6-C10H 14)(tppts)Cl2 (tppts = tris-3-sulfonatophenylphosphine trisodium salt) and [Ru(η6-C10H14)(pta) 2Cl]+. The active catalysts formed during the hydrogenations correspond to a trinuclear cluster, a colloid and a mononuclear complex, respectively.
- Dyson, Paul J.,Ellis, David J.,Laurenczy, Gábor
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- Preparation of NiCu Alloy Catalyst for the Hydrodeoxygenation of Benzofuran
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A series of bimetallic NixCu(10-x)/SiO2 (where x is the mass fraction of Ni and the total metal loading was fixed at 10 wt%.) catalysts with different Ni/Cu mass ratio are prepared and characterized by X-Ray diffraction (XRD), N2 adsorption-desorption, inductively coupled plasma mass spectrometry (ICP-MS), H2 temperature-programmed reduction (H2-TPR) and transmission electron microscope (TEM). The benzofuran (BF) hydrodeoxygenation (HDO) performance of as-prepared catalysts are evaluated in a fixed flow reactor. The results showed that the incorporation of Cu to Ni/SiO2 catalyst can increase surface area of catalyst and improve the reducibility of nickel oxide species, which contributed to higher catalytic activity and total deoxygenated compounds yield. Moreover, the strong synergistic effect between Ni and Cu led to the formation of NiCu alloy at the Ni mass fraction of 5 wt% and thus induced smaller crystallite size and exposure of more active particles, which inevitably contributed to the improved HDO performance for Ni5Cu5/SiO2 catalyst. At 300 °C, 3.0 MPa, MHSV=3.0 h?1 and H2/oil = 500(v/v), the total yield of deoxygenated products over Ni5Cu5/SiO2 catalyst reached 86.0%, which is increased by 10.8% and 77.4% as compared to those of monometallic Ni/SiO2 (75.2%) and Cu/SiO2 catalysts (8.8%), respectively. Finally, a possible reaction network for HDO of BF on Ni5Cu5/SiO2 catalyst was proposed. Graphic Abstract: [Figure not available: see fulltext.]
- Zhu, Tianhan,Song, Hua,Li, Feng,Chen, Yanguang
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- Catalytic decomposition of 2,3-dihydrobenzofuran to monocyclic compounds over palladium catalysts supported on sulfonated ordered mesoporous carbon
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Ordered mesoporous carbon (OMC) was sulfonated at different temperature (OMC-SO3H-X, X =125, 150, 175, 200, and 225 °C) in order to provide acid sites to OMC. Palladium catalysts were then supported on OMC-SO3H-X by an incipient wetness impregnation method for use in the catalytic decomposition of 2,3-dihydrobenzofuran to monocyclic compounds. 2,3-Dihydrobenzofuran was used as a lignin model compound for representing β-5 linkage of lignin. In the catalytic decomposition of 2,3-dihydrobenzofuran over Pd/OMC-SO3H-X, ethylcyclohexane and 2-ethlyphenol were mainly produced. Conversion of 2,3-dihydrobenzofuran and total yield for main products (ethylcyclohexane and 2-ethylphenol) were closely related to the acidity of the catalysts. Conversion of 2,3-dihydrobenzofuran and total yield for main products increased with increasing acidity of Pd/OMC-SO3H-X catalysts. Among the catalysts tested, Pd/OMC-SO3H-150 with the largest acidity showed the highest conversion of 2,3-dihydrobenzofuran and the highest total yield for main products.
- Kim, Jeong Kwon,Park, Hai Woong,Hong, Ung Gi,Lee, Yoon Jae,Song, In Kyu
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- Fabricating nickel phyllosilicate-like nanosheets to prepare a defect-rich catalyst for the one-pot conversion of lignin into hydrocarbons under mild conditions
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The one-pot conversion of lignin biomass into high-grade hydrocarbon biofuels via catalytic hydrodeoxygenation (HDO) holds significant promise for renewable energy. A great challenge for this route involves developing efficient non-noble metal catalysts to obtain a high yield of hydrocarbons under relatively mild conditions. Herein, a high-performance catalyst has been prepared via the in situ reduction of Ni phyllosilicate-like nanosheets (Ni-PS) synthesized by a reduction-oxidation strategy at room temperature. The Ni-PS precursors are partly converted into Ni0 nanoparticles by in situ reduction and the rest remain as supports. The Si-containing supports are found to have strong interactions with the nickel species, hindering the aggregation of Ni0 particles and minimizing the Ni0 particle size. The catalyst contains abundant surface defects, weak Lewis acid sites and highly dispersed Ni0 particles. The catalyst exhibits excellent catalytic activity towards the depolymerization and HDO of the lignin model compound, 2-phenylethyl phenyl ether (PPE), and the enzymatic hydrolysis of lignin under mild conditions, with 98.3% cycloalkane yield for the HDO of PPE under 3 MPa H2 pressure at 160 °C and 40.4% hydrocarbon yield for that of lignin under 3 MPa H2 pressure at 240 °C, and its catalytic activity can compete with reported noble metal catalysts.
- Cao, Meifang,Chen, Bo,He, Chengzhi,Ouyang, Xinping,Qian, Yong,Qiu, Xueqing
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supporting information
p. 846 - 857
(2022/02/09)
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- Supported Pt-Ni bimetallic nanoparticles catalyzed hydrodeoxygenation of dibenzofuran with high selectivity to bicyclohexane
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Catalytic hydrodeoxygenation (HDO) is one of the most effective methods to upgrade the oxygen-containing compounds derived from coal tar to valuable hydrocarbons. Herein, an efficient bimetallic catalyst Pt1Ni4/MgO was prepared and applied in the HDO of dibenzofuran (DBF). High yield (95%) of the desired product bicyclohexane (BCH) was achieved at 240 °C and 1.2 MPa of H2. Superior catalytic performance could be ascribed to the “relay catalysis” of Pt sites and Ni sites, and the reaction pathway is proposed as well. Scale-up experiment and recyclability test were also performed, which demonstrated the recyclability and promising potential application of Pt1Ni4/MgO.
- Wu, Pengyu,Cai, Chun
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p. 234 - 238
(2021/07/10)
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- MOF-derived Ru@ZIF-8 catalyst with the extremely low metal Ru loading for selective hydrogenolysis of C–O bonds in lignin model compounds under mild conditions
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Lignin hydrogenolysis to produce chemicals and biofuels is a challenge due to the stable C–O ether bond structure. Metal–organic framework (MOF) materials with excellent structural and chemical versatility have received widespread attention. Herein, a highly dispersed Ru metal anchored in functionalised ZIF-8 was fabricated by a general host–guest and reduction strategy. The Ru@ZIF-8 catalyst with a high specific surface area could efficiently promote the C–O bond cleavage of a variety of lignin model compounds under mild conditions. Compared with previous studies, the extremely low metal Ru loading in the Ru@ZIF-8 catalyst achieved a relatively higher activity. The introduction of Ru metal not only improved the dispersion of Zn metal, but also enhanced the electron density on the Zn surface, suggesting a high catalytic performance. It was more conducive for the Ru@ZIF-8 catalyst to exhibit the C–O bond cleavage activity when in the presence of both H2 and isopropanol. An investigation of the mechanism revealed that the direct hydrogenolysis of benzyl phenyl ether was the main reaction pathway.
- Cao, Jing-Pei,Jiang, Wei,Xie, Jin-Xuan,Zhang, Chuang,Zhang, Jian-Li,Zhao, Liang,Zhao, Xiao-Yan,Zhao, Yun-Peng,Zhu, Chen
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p. 488 - 496
(2022/02/07)
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- Aromatic compound hydrogenation and hydrodeoxygenation method and application thereof
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The invention belongs to the technical field of medicines, and discloses an aromatic compound hydrogenation and hydrodeoxygenation method under mild conditions and application of the method in hydrogenation and hydrodeoxygenation reactions of the aromatic compounds and related mixtures. Specifically, the method comprises the following steps: contacting the aromatic compound or a mixture containing the aromatic compound with a catalyst and hydrogen with proper pressure in a solvent under a proper temperature condition, and reacting the hydrogen, the solvent and the aromatic compound under the action of the catalyst to obtain a corresponding hydrogenation product or/and a hydrodeoxygenation product without an oxygen-containing substituent group. The invention also discloses specific implementation conditions of the method and an aromatic compound structure type applicable to the method. The hydrogenation and hydrodeoxygenation reaction method used in the invention has the advantages of mild reaction conditions, high hydrodeoxygenation efficiency, wide substrate applicability, convenient post-treatment, and good laboratory and industrial application prospects.
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Paragraph 0094-0097; 0100-0104
(2021/05/29)
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- A regionally selective hydrogenation method for chromium-catalyzed thick cyclic aromatic hydrocarbons and olefins based on magnesium-activated ligands
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The present invention relates to the field of hydrogenation, specifically to a chromium-activated complex cyclic aromatic hydrocarbons and olefins promoted by magnesium-activated ligands regionally selective hydrogenation method, which is based on the in situ reduction strategy of magnesium, with biimides as ligands, CrCl2 as catalyst precursors, to construct an efficient low-costchromium hydrogenation system, under mild conditions, to achieve unilateral cyclic hydrogenation of thick ring aromatic hydrocarbons and high-selective hydrogenation of olefins. The system of the present invention is suitable for a variety of substrates of fused cyclic aromatic hydrocarbons, such as tetraphenyl, benzoanthracene, pentabenzo and alfalfa and the like. This provides a simple and efficient strategy and pathway for the synthesis of partially saturated thick cyclic aromatic hydrocarbon compounds.
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Paragraph 0020
(2022/01/10)
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- Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst
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The selective hydrogenation of functionalized olefins is of great importance in the chemical and pharmaceutical industry. Here, we report on a nanostructured nickel catalyst that enables the selective hydrogenation of purely aliphatic and functionalized olefins under mild conditions. The earth-abundant metal catalyst allows the selective hydrogenation of sterically protected olefins and further tolerates functional groups such as carbonyls, esters, ethers and nitriles. The characterization of our catalyst revealed the formation of surface oxidized metallic nickel nanoparticles stabilized by a N-doped carbon layer on the active carbon support.
- Klarner, Mara,Bieger, Sandra,Drechsler, Markus,Kempe, Rhett
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supporting information
p. 2157 - 2161
(2021/05/21)
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- RhNPs supported onN-functionalized mesoporous silica: effect on catalyst stabilization and catalytic activity
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Amine and nicotinamide groups grafted on ordered mesoporous silica (OMS) were investigated as stabilizers for RhNPs used as catalysts in the hydrogenation of several substrates, including carbonyl and aryl groups. Supported RhNPs on functionalized OMS were prepared by controlled decomposition of an organometallic precursor of rhodium under dihydrogen pressure. The resulting materials were characterized thoroughly by spectroscopic and physical techniques (FTIR, TGA, BET, SEM, TEM, EDX, XPS) to confirm the formation of spherical rhodium nanoparticles with a narrow size distribution supported on the silica surface. The use of nicotinamide functionalized OMS as a support afforded small RhNPs (2.3 ± 0.3 nm), and their size and shape were maintained after the catalyzed acetophenone hydrogenation. In contrast, amine-functionalized OMS formed RhNP aggregates after the catalytic reaction. The supported RhNPs could selectively reduce alkenyl, carbonyl, aryl and heteroaryl groups and were active in the reductive amination of phenol and morpholine, using a low concentration of the precious metal (0.07-0.18 mol%).
- Pulido-Díaz, Israel T.,Serrano-Maldonado, Alejandro,López-Suárez, Carlos César,Méndez-Ocampo, Pedro A.,Portales-Martínez, Benjamín,Gutiérrez-Alejandre, Aída,Salas-Martin, Karla P.,Guerrero-Ríos, Itzel
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p. 3289 - 3298
(2021/03/16)
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- Direct synthesis of a high-density aviation fuel using a polycarbonate
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High-density cyclic hydrocarbons were first synthesized with high carbon yields by a one-pot transfer hydrodeoxygenation of a polycarbonate (PC) using isopropanol as the solvent and hydrogen donor at the same time. RANEY nickel was found to be an effective catalyst for the conversion of the PC in isopropanol. Over it, the pure PC pellet was completely converted to a mixture of C6-C15oxygenates, aromatics and cycloalkanes after the reaction was carried out at 463 K for 1 h. The catalytic performance of RANEY Ni was further improved after the introduction of solid acids as co-catalysts. Among the investigated solid acids, ultrastable Y (USY), a commercial acidic zeolite, demonstrated the best promotion effect, which can be explained by its larger pore size and suitable acidity. Under the optimized conditions, an ~75% carbon yield of C6-C15cyclic hydrocarbons was achieved from the one-pot transfer hydrodeoxygenation of a chopped DVD disk under the co-catalysis of RANEY Ni and USY. According to our measurement, the C6-C15cyclic hydrocarbon mixture as obtained has a high density (0.94 g mL?1), good volumetric net heat of combustion (NHOC) (41.5 MJ L?1) and low freezing point (202 K-188 K). In real applications, it can be used as a potential substitute for currently used high-density aviation fuels.
- Wang, Lulin,Han, Fengan,Li, Guangyi,Zheng, Min,Wang, Aiqin,Wang, Xiaodong,Zhang, Tao,Cong, Yu,Li, Ning
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supporting information
p. 912 - 919
(2021/02/09)
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- The solvent determines the product in the hydrogenation of aromatic ketones using unligated RhCl3as catalyst precursor
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Alkyl cyclohexanes were synthesized in high selectivity via a combined hydrogenation/hydrodeoxygenation of aromatic ketones using ligand-free RhCl3 as pre-catalyst in trifluoroethanol as solvent. The true catalyst consists of rhodium nanoparticles (Rh NPs), generated in situ during the reaction. A range of conjugated as well as non-conjugated aromatic ketones were directly hydrodeoxygenated to the corresponding saturated cyclohexane derivatives at relatively mild conditions. The solvent was found to be the determining factor to switch the selectivity of the ketone hydrogenation. Cyclohexyl alkyl-alcohols were the products using water as a solvent.
- Bartling, Stephan,Chakrabortty, Soumyadeep,De Vries, Johannes G.,Kamer, Paul C. J.,Lund, Henrik,Müller, Bernd H.,Rockstroh, Nils
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p. 7608 - 7616
(2021/12/13)
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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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- Metallic Barium: A Versatile and Efficient Hydrogenation Catalyst
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Ba metal was activated by evaporation and cocondensation with heptane. This black powder is a highly active hydrogenation catalyst for the reduction of a variety of unactivated (non-conjugated) mono-, di- and tri-substituted alkenes, tetraphenylethylene, benzene, a number of polycyclic aromatic hydrocarbons, aldimines, ketimines and various pyridines. The performance of metallic Ba in hydrogenation catalysis tops that of the hitherto most active molecular group 2 metal catalysts. Depending on the substrate, two different catalytic cycles are proposed. A: a classical metal hydride cycle and B: the Ba metal cycle. The latter is proposed for substrates that are easily reduced by Ba0, that is, conjugated alkenes, alkynes, annulated rings, imines and pyridines. In addition, a mechanism in which Ba0 and BaH2 are both essential is discussed. DFT calculations on benzene hydrogenation with a simple model system (Ba/BaH2) confirm that the presence of metallic Ba has an accelerating effect.
- Stegner, Philipp,F?rber, Christian,Zenneck, Ulrich,Knüpfer, Christian,Eyselein, Jonathan,Wiesinger, Michael,Harder, Sjoerd
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supporting information
p. 4252 - 4258
(2020/12/22)
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- Ambient Hydrogenation and Deuteration of Alkenes Using a Nanostructured Ni-Core–Shell Catalyst
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A general protocol for the selective hydrogenation and deuteration of a variety of alkenes is presented. Key to success for these reactions is the use of a specific nickel-graphitic shell-based core–shell-structured catalyst, which is conveniently prepared by impregnation and subsequent calcination of nickel nitrate on carbon at 450 °C under argon. Applying this nanostructured catalyst, both terminal and internal alkenes, which are of industrial and commercial importance, were selectively hydrogenated and deuterated at ambient conditions (room temperature, using 1 bar hydrogen or 1 bar deuterium), giving access to the corresponding alkanes and deuterium-labeled alkanes in good to excellent yields. The synthetic utility and practicability of this Ni-based hydrogenation protocol is demonstrated by gram-scale reactions as well as efficient catalyst recycling experiments.
- Beller, Matthias,Feng, Lu,Gao, Jie,Jackstell, Ralf,Jagadeesh, Rajenahally V.,Liu, Yuefeng,Ma, Rui
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supporting information
p. 18591 - 18598
(2021/06/28)
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- Catalytic transfer hydrogenation of 4-O-5 models in lignin-derived compounds to cycloalkanes over Ni-based catalysts
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There is an urgent need to develop a selective hydrogenolysis of Caryl-O bonds in lignin to produce valued-added chemicals and fuels. Recently, hydrogen has been used in the hydrogenation reaction, which hides inevitable danger and is not economical. Therefore, isopropanol, as a hydrogen-donor solvent, is employed for aryl ether hydrogenolysis in lignin models over nickel supported on a carbon nanotube (CNT). Except for aromatic ether (4-O-5), the Ni/CNT catalyst is also found to be suitable for alkyl-aryl ether (α-O-4 and β-O-4) cleavage in control experiments. The physicochemical characterizations were carried out by means of H2-temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses. The catalyst can be magnetically recovered and efficiently reused for five consecutive recycling tests in the transfer hydrogenation of aromatic ethers. A mechanism study indicated that the hydrogenolysis cleavage of the ether bond is the first step in the reaction process, and hydrogenation of aromatic rings is only a successive step in which phenol and benzene are intermediate states and are then further hydrogenated. Furthermore, it has been demonstrated that aryl groups play an important role in the hydrogenation of phenol in the competitive catalytic hydrogenation reaction of phenol.
- Chen, Changzhou,Liu, Peng,Xia, Haihong,Zhou, Minghao,Jiang, Jianchun
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p. 582 - 591
(2020/12/01)
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- Boosting homogeneous chemoselective hydrogenation of olefins mediated by a bis(silylenyl)terphenyl-nickel(0) pre-catalyst
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The isolable chelating bis(N-heterocyclic silylenyl)-substituted terphenyl ligand [SiII(Terp)SiII] as well as its bis(phosphine) analogue [PIII(Terp)PIII] have been synthesised and fully characterised. Their reaction with Ni(cod)2(cod = cycloocta-1,5-diene) affords the corresponding 16 VE nickel(0) complexes with an intramolecularη2-arene coordination of Ni, [E(Terp)E]Ni(η2-arene) (E = PIII, SiII; arene = phenylene spacer). Due to a strong cooperativity of the Si and Ni sites in H2activation and H atom transfer, [SiII(Terp)SiII]Ni(η2-arene) mediates very effectively and chemoselectively the homogeneously catalysed hydrogenation of olefins bearing functional groups at 1 bar H2pressure and room temperature; in contrast, the bis(phosphine) analogous complex shows only poor activity. Catalytic and stoichiometric experiments revealed the important role of the η2-coordination of the Ni(0) site by the intramolecular phenylene with respect to the hydrogenation activity of [SiII(Terp)SiII]Ni(η2-arene). The mechanism has been established by kinetic measurements, including kinetic isotope effect (KIE) and Hammet-plot correlation. With this system, the currently highest performance of a homogeneous nickel-based hydrogenation catalyst of olefins (TON = 9800, TOF = 6800 h?1) could be realised.
- Lücke, Marcel-Philip,Yao, Shenglai,Driess, Matthias
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p. 2909 - 2915
(2021/03/14)
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- Palladium-catalyzed synthesis of 4-cyclohexylmorpholines from reductive coupling of aryl ethers and lignin model compounds with morpholines
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This work describes the highly efficient Pd-catalyzed direct coupling of aryl ethers (including the typical lignin model compounds) and morpholines to produce 4-cyclohexylmorpholines, a useful class of fine chemicals. Without employing any acidic additives, various 4-cyclohexylmorpholines could be synthesized with good yields from a variety of aryl ethers using H2 as a hydrogen resource. A mechanism study revealed that the desired product was formed via the cleavage of the C(Ar)-O bonds to generate the corresponding cyclohexanones and subsequent reductive amination. This journal is
- Zheng, Bingxiao,Song, Jinliang,Wu, Haihong,Han, Shitao,Zhai, Jianxin,Zhang, Kaili,Wu, Wei,Xu, Caiyun,He, Mingyuan,Han, Buxing
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supporting information
p. 268 - 273
(2021/01/28)
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- Effects of steam on toluene hydrogenation over a Ni catalyst
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The catalytic toluene hydrogenation over Ni/SiO2 was carried out using H2 or a H2/H2O mixture. The toluene conversion and MCH selectivity were evaluated under partial steam pressures 0?10 kPa, at H2/t
- Atsumi, Ryosuke,Kobayashi, Keisuke,Xieli, Cui,Nanba, Tetsuya,Matsumoto, Hideyuki,Matsuda, Keigo,Tsujimura, Taku
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- Highly Efficient Cleavage of Ether Bonds in Lignin Models by Transfer Hydrogenolysis over Dual-Functional Ruthenium/Montmorillonite
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Cleavage of ether bonds is a crucial but challenging step for lignin valorization. To efficiently realize this transformation, the development of robust catalysts or catalytic systems is required. In this study, montmorillonite (MMT)-supported Ru (denoted as Ru/MMT) is fabricated as a dual-functional heterogeneous catalyst to cleave various types of ether bonds through transfer hydrogenolysis without using any additional acids or bases. The prepared Ru/MMT material is found to efficiently catalyze the cleavage of various lignin models and lignin-derived phenols; cyclohexanes (fuels) and cyclohexanols (key intermediates) are the main products. The synergistic effect between electron-enriched Ru and the acidic sites on MMT contributes to the excellent performance of Ru/MMT. Systematic studies reveal that the reaction proceeds through two possible reaction pathways, including the direct cleavage of ether bonds and the formation of intermediates with one hydrogenated benzene ring, for all examined types of ether bonds, namely, 4-O-5, α-O-4, and β-O-4.
- Xue, Zhimin,Yu, Haitao,He, Jing,Zhang, Yibin,Lan, Xue,Liu, Rundong,Zhang, Luyao,Mu, Tiancheng
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p. 4579 - 4586
(2020/06/21)
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- Raney nickel-catalyzed hydrodeoxygenation and dearomatization under transfer hydrogenation conditions—Reaction pathways of non-phenolic compounds
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Catalytic reduction of oxygen-containing aromatic compounds has been studied under transfer hydrogenation (TH) conditions at 150 °C in 2-PrOH as a hydrogen donor. Raney nickel is used as a heterogeneous catalyst. The reaction of aromatic non-phenolic carbonyl compounds is most likely to proceed through the pathway “aromatic ketone (aldehyde)→aromatic alcohol→alkylaromatics→saturated alkylcyclohexane”. One of the main reactions under the TH conditions is a hydrodeoxygenation (HDO) process. Unexpectedly, the hydrodeoxygenation of aromatic ketones to alkylaromatics (C[dbnd]O → CH2) occurs faster than of corresponding aromatic alcohols (HC–OH → CH2) that means either additional reaction pathway of its hydrodeoxygenation missing for the corresponding aromatic alcohols or specific interaction of OH functionality with Raney nickel surface obstructing (hindering) the further reduction. Benzaldehyde is shown to be less reactive than the aromatic ketones under the same reaction conditions. The main reason is proposed to be carbon monoxide release resulted from the decarbonylation of the aldehyde. Carbon monoxide demonstrates a poisoning effect on Raney nickel surface that is evidenced in the catalyzed TH reaction of acetophenone. The HDO reaction of anisole under the same reaction conditions was a little slowly than of oxygen-containing non-phenolic aromatics.
- Philippov,Chibiryaev,Martyanov
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- One-Pot Conversion of Lignin into Naphthenes Catalyzed by a Heterogeneous Rhenium Oxide-Modified Iridium Compound
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The direct transformation of lignin into fuels and chemicals remains a huge challenge because of the recalcitrant and complicated structure of lignin. In this study, rhenium oxide-modified iridium supported on SiO2 (Ir-ReOx/SiO2) is employed for the one-pot conversion of various lignin model compounds and lignin feedstocks into naphthenes. Up to 100 percent yield of cyclohexane from model compounds and 44.3 percent yield of naphthenes from lignin feedstocks are achieved. 2 D HSQC NMR spectroscopy before and after the reaction confirms the activity of Ir-ReOx/SiO2 in the cleavage of the C?O bonds and hydrodeoxygenation of the depolymerized products. H2 temperature-programmed reduction, temperature-programmed desorption of NH3, IR spectroscopy of pyridine adsorption, X-ray photoelectron spectroscopy, X-ray absorption fine structure analysis, and control experiments reveal that a synergistic effect between Ir and ReOx in Ir-ReOx/SiO2 plays a crucial role in the high performance; ReOx is mainly responsible for the cleavage of C?O bonds, whereas Ir is responsible for hydrodeoxygenation and saturation of the benzene rings. This methodology opens up an energy-efficient route for the direct conversion of lignin into valuable naphthenes.
- Li, Xinxin,Zhang, Bo,Pan, Xiaoli,Ji, Jianwei,Ren, Yujing,Wang, Hua,Ji, Na,Liu, Qiying,Li, Changzhi
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p. 4409 - 4419
(2020/03/04)
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- An efficient bifunctional Ru-NbOPO4 catalyst for the hydrodeoxygenation of aromatic ethers, phenols and real bio-oil
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An efficient bifunctional NbOPO4 supported Ru catalyst (Ru-NbOPO4) was applied to the hydrodeoxygenation of aromatic ethers and phenols and the upgrading of bio-oil. Characterization results revealed that the Ru-NbOPO4 catalyst possessed strong acidity, including Lewis and Br?nsted acids. The Lewis acid sites originated from the Nb[sbnd]O bonding structures, including slightly distorted octahedral NbO6, regular tetrahedral NbO4 and highly distorted octahedral NbO6. In combination with the strong acidity of the Nb[sbnd]O species and excellent hydrogenation activity of the metallic Ru, the bifunctional Ru-NbOPO4 catalyst exhibited an excellent catalytic activity in the hydrodeoxygenation of aromatic ethers and phenols with different structures, and even real bio-oil to alkanes. The hydrocarbon yield after real bio-oil upgradation was up to 88.2 %. Carbon deposition and enlargement of the Ru nanoparticles resulted in slight deactivation of the catalyst. The catalytic activity could be mostly recovered after being calcined and reduced.
- Zhao, Hongye,Hu, Xun,Hao, Jianxiu,Li, Na,Zhi, Keduan,He, Runxia,Wang, Yunfei,Zhou, Huacong,Liu, Quansheng
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- Facile benzene reduction promoted by a synergistically coupled Cu-Co-Ce ternary mixed oxide
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Hydrogenation of aromatic rings promoted by earth-abundant metal composites under mild conditions is an attractive and challenging subject in the long term. In this work, a simple active site creation and stabilization strategy was employed to obtain a Cu+-containing ternary mixed oxide catalyst. Simply by pre-treatment of the ternary metal oxide precursor under a H2atmosphere, a Cu+-derived heterogeneous catalyst was obtained and denoted as Cu1Co5Ce5Ox. The catalyst showed (1) high Cu+species content, (2) a uniform distribution of Cu+doped into the lattices of CoOxand CeO2, (3) formation of CoOx/CuOxand CeO2/CuOxinterfaces, and (4) a mesoporous structure. These unique properties of Cu1Co5Ce5Oxendow it with pretty high hydrogenation activity for aromatic rings under mild conditions (100 °C with 5 bar H2), which is much higher than that of the corresponding binary counterparts and even exceeds the performance of commercial noble metal catalysts (e.g.Pd/C). The synergetic effect plays a crucial role in the catalytic procedure with CeO2functioning as a hydrogen dissociation and transfer medium, Cu+hydrogenating the benzene ring and CoOxstabilizing the unstable Cu+species. This will unlock a new opportunity to design highly efficient earth-abundant metal-derived heterogeneous catalystsviainterface interactions.
- Chen, Hao,Dai, Sheng,Fu, Jie,Jie, Kecheng,Lin, Wenwen,Yang, Shi-Ze,Yang, Zhenzhen,Zhang, Zihao
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p. 5766 - 5771
(2020/06/22)
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- Hydrogenation Performance of Acetophenone to 1-Phenylethanol on Highly Active Nano Cu/SiO2 Catalyst
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Abstract: In this work, highly active nano Cu/SiO2 catalysts with various copper content were prepared by urea homogeneous precipitation method. The catalysts were characterized by N2 adsorption, XRD, H2-TPR, XPS and TEM. It was found that the nano Cu/SiO2 catalyst displayed excellent catalytic performance for the selective hydrogenation of acetophenone (AP) to 1-phenylethanol (PhE) when copper content was 25?wt%. The Cu/SiO2 catalyst had well dispersed copper species, small particle size, high BET surface area (ca. 540?m2/g) and abundant pore structure. The influence of different reaction conditions on the hydrogenation process were also discussed. AP conversion and the PhE selectivity reached 99.8% and 99.08%, respectively, under the optimal reaction conditions (Temperature: 353?K; Pressure: 2.0?MPa, LHSV: 1.0?h?1 and the molar ratio of H2/AP:15). Besides, the above catalyst maintained a high catalytic performance in the duration of 500?h operation. The synergistic effect between Cu+ and Cu0 improved the activity and stability of Cu/SiO2 catalyst. The research indicated that the catalyst had a wide industrial prospect. Graphic Abstract: The Cu/SiO2 catalyst showed a good performance for AP hydrogenation. The reduced Cu/SiO2 catalyst contains both Cu+ and Cu0 consistent with XPS. Cu+ sties stabilize the methoxy and acyl species and Cu0 facilitates the decomposition of H2. Phenyl in AP and Cu had electrostatic repulsion, which was favorable for desorption of PhE.[Figure not available: see fulltext.].
- Wang, Bing,Jin, Manman,An, Hao,Guo, Zhenmei,Lv, Zhiguo
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- Highly Active Superbulky Alkaline Earth Metal Amide Catalysts for Hydrogenation of Challenging Alkenes and Aromatic Rings
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Two series of bulky alkaline earth (Ae) metal amide complexes have been prepared: Ae[N(TRIP)2]2 (1-Ae) and Ae[N(TRIP)(DIPP)]2 (2-Ae) (Ae=Mg, Ca, Sr, Ba; TRIP=SiiPr3, DIPP=2,6-diisopropylphenyl). While monomeric 1-Ca was already known, the new complexes have been structurally characterized. Monomers 1-Ae are highly linear while the monomers 2-Ae are slightly bent. The bulkier amide complexes 1-Ae are by far the most active catalysts in alkene hydrogenation with activities increasing from Mg to Ba. Catalyst 1-Ba can reduce internal alkenes like cyclohexene or 3-hexene and highly challenging substrates like 1-Me-cyclohexene or tetraphenylethylene. It is also active in arene hydrogenation reducing anthracene and naphthalene (even when substituted with an alkyl) as well as biphenyl. Benzene could be reduced to cyclohexane but full conversion was not reached. The first step in catalytic hydrogenation is formation of an (amide)AeH species, which can form larger aggregates. Increasing the bulk of the amide ligand decreases aggregate size but it is unclear what the true catalyst(s) is (are). DFT calculations suggest that amide bulk also has a noticeable influence on the thermodynamics for formation of the (amide)AeH species. Complex 1-Ba is currently the most powerful Ae metal hydrogenation catalyst. Due to tremendously increased activities in comparison to those of previously reported catalysts, the substrate scope in hydrogenation catalysis could be extended to challenging multi-substituted unactivated alkenes and even to arenes among which benzene.
- Eyselein, Jonathan,F?rber, Christian,Grams, Samuel,Harder, Sjoerd,Knüpfer, Christian,Langer, Jens,Martin, Johannes,Thum, Katharina,Wiesinger, Michael
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supporting information
p. 9102 - 9112
(2020/03/30)
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- Anionic Amphiphilic Cyclodextrins Bearing Oleic Grafts for the Stabilization of Ruthenium Nanoparticles Efficient in Aqueous Catalytic Hydrogenation
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Oleic succinyl β-cyclodextrin was proved to be efficient for the stabilization of ruthenium nanoparticles (NPs) in aqueous medium. These NPs were characterized by FTIR spectroscopy and transition electron microscopy (TEM). The catalytic activity of these NPs was evaluated in the aqueous hydrogenation of petrosourced and biosourced unsaturated compounds such as benzene and furfural derivatives. The catalytic system can be easily recycled and reused up to nine runs without any loss of activity and selectivity, demonstrating its robustness.
- Cocq, Aurélien,Léger, Bastien,No?l, Sébastien,Bricout, Hervé,Djeda?ni-Pilard, Florence,Tilloy, Sébastien,Monflier, Eric
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p. 1013 - 1018
(2019/12/27)
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- One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
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The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).
- Coeck, Robin,De Vos, Dirk E.
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supporting information
p. 5105 - 5114
(2020/08/25)
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- Short time synthesis of titania modified-CMK-3 carbon mesostructure as support for Ir-catalyst applied in catalytic hydrotreating
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Ti-CMK-3 carbon mesoporous was prepared using a novel synthesis method. This new method avoids the hard template synthesis used commonly. The method developed here, allows to reduce time, energy consumptionand cost. Structural and textural characterization of the titanium modified-mesoporous carbonwas performed by N2 adsorption, XRD, UV–vis-DRS, Raman spectroscopy and TEM. The characterization results indicated that the textural and structural properties of the material synthesized by the short time method are comparable with the properties of the material prepared by the hard template method. Ti modified-mesoporous carbon was used as support of the iridium nanoparticles, in order to prepare a catalyst to be tested in model hydrotreating reactions. The catalyst obtained by wet impregnation with iridium acetylacetonate were characterized by ICP-AES, H2 chemisorption, TEM, XPS and FTIR of adsorbed pyridine. The high Ir dispersion and small particle size, along with the moderate Lewis acidity generated by the presence of titanium in the support, were responsible for the good performance and stability of the catalyst in the hydrogenation of tetralin in presence of nitrogen compounds. Main advantage of the present study is the reduction of time and cost in the synthesis of the new material and the applicability for HDT reactions.
- Beltramone, Andrea R.,Juárez, Juliana M.,Ledesma, Brenda C.
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p. 210 - 216
(2018/04/17)
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- Transfer hydrogenation of alkynes into alkenes by ammonia borane over Pd-MOF catalysts
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Ammonia borane with both hydridic and protic hydrogens in its structure acted as an efficient transfer hydrogenation agent for selective transformation of alkynes into alkenes in non-protic solvents. Catalytic synergy between the μ3-OH groups of the UiO-66(Hf) MOF and Pd active sites in Pd/UiO-66(Hf) furnished an elusive >98% styrene selectivity and full phenylacetylene conversion at room temperature. Such performance is not achievable by a Pd + UiO-66(Hf) physical mixture or by a commercial Pd/C catalyst.
- Bakuru, Vasudeva Rao,Samanta, Debabrata,Maji, Tapas Kumar,Kalidindi, Suresh Babu
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supporting information
p. 5024 - 5028
(2020/05/08)
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- Selective Hydrogenation and Hydrodeoxygenation of Aromatic Ketones to Cyclohexane Derivatives Using a Rh&at;SILP Catalyst
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Rhodium nanoparticles immobilized on an acid-free triphenylphosphonium-based supported ionic liquid phase (Rh&at;SILP(Ph3-P-NTf2)) enabled the selective hydrogenation and hydrodeoxygenation of aromatic ketones. The flexible molecular approach used to assemble the individual catalyst components (SiO2, ionic liquid, nanoparticles) led to outstanding catalytic properties. In particular, intimate contact between the nanoparticles and the phosphonium ionic liquid is required for the deoxygenation reactivity. The Rh&at;SILP(Ph3-P-NTf2) catalyst was active for the hydrodeoxygenation of benzylic ketones under mild conditions, and the product distribution for non-benzylic ketones was controlled with high selectivity between the hydrogenated (alcohol) and hydrodeoxygenated (alkane) products by adjusting the reaction temperature. The versatile Rh&at;SILP(Ph3-P-NTf2) catalyst opens the way to the production of a wide range of high-value cyclohexane derivatives by the hydrogenation and/or hydrodeoxygenation of Friedel–Crafts acylation products and lignin-derived aromatic ketones.
- Bordet, Alexis,Emondts, Meike,Leitner, Walter,Moos, Gilles
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supporting information
p. 11977 - 11983
(2020/06/02)
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- 2D and 3D Ruthenium Nanoparticle Covalent Assemblies for Phenyl Acetylene Hydrogenation
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The bottom-up covalent assembly of metallic nanoparticles (NP) represents one of the innovative tools in nanotechnology to build functional heterostructures, with the resulting assemblies showing superior collective properties over the individual NP for a broad range of applications. The ability to control the dimensionality of the assembly is one of the major challenges in designing and understanding these advanced materials. Here, two new organic linkers were used as building blocks in order to guide the organization of Ru NP into two- or three-dimensional covalent assemblies. The use of a hexa-adduct functionalized C60 leads to the formation of 3D networks of 2.2 nm Ru NP presenting an interparticle distance of 3.0 nm, and the use of a planar carboxylic acid triphenylene derivative allows the synthesis of 2D networks of 1.9 nm Ru NP with an interparticle distance of 3.1 nm. The Ru NP networks were found to be active catalysts for the selective hydrogenation of phenylacetylene, reaching good selectivity toward styrene. Overall, we demonstrated that catalyst performances are significantly affected by the dimensionality (2D vs. 3D) of the heterostructures, which can be rationalize based on confinement effects.
- Axet, M. Rosa,Barcenilla, María,Casu, Alberto,Coco, Silverio,Falqui, Andrea,Lecante, Pierre,Leng, Faqiang,Machado, Bruno F.,Martínez, Beatriz María Illescas,Martin, Nazario,Martinez, Hervé,Min, Yuanyuan,Roblin, Pierre,Serp, Philippe,Theussl, Thomas
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supporting information
p. 4069 - 4082
(2020/11/23)
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- Synthesis of Ni2P/Al2O3 utilizing triphenylphosphine (TPP) as the phosphorus source for hydrodeoxygenation of benzofuran
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A novel route to synthesize highly active Ni2P/Al2O3 (TPP) utilizing triphenylphosphine (TPP) as the phosphorus source at a low temperature of 573 K is described. The as-prepared catalysts were characterized by X-ray diffraction (XRD), CO uptake, Brunner-Emmett-Teller (BET) measurements, and X-ray photoelectron spectroscopy (XPS). The catalytic activity of the Ni2P/Al2O3 (TPP) catalyst and the role of the TPP phosphorus source were studied using hydrodeoxygenation (HDO) of benzofuran (BF) as a probe reaction. The results show that the use of TPP as the phosphorus source could suppress the strong interaction between phosphate and Al2O3, thereby the formation of AlPO4 was avoided. As compared to the Ni2P/Al2O3 prepared by using (NH4)2HPO4 as the phosphorus source, Ni2P/Al2O3 (TPP) possessed significantly higher surface area and smaller Ni2P particle size. The HDO activity and yield of O-free products over the Ni2P/Al2O3 (TPP) catalyst were increased by 17.2% and 36.0%, respectively, when compared with those found for Ni2P/Al2O3 prepared using (NH4)2HPO4. The use of TPP as the phosphorus source could effectively promote the dehydration of 2-ethylphenol (2-EtPh) to form ethylbenzene (EB), and the demethylation of ethylcyclohexane (ECH) to methylcyclohexane (MCH).
- Jiang, Bolong,Jiang, Nan,Han, Chunbao
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p. 7577 - 7582
(2020/06/19)
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- Selective hydrogenation of fluorinated arenes using rhodium nanoparticles on molecularly modified silica
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The production of fluorinated cyclohexane derivatives is accomplished through the selective hydrogenation of readily available fluorinated arenes using Rh nanoparticles on molecularly modified silica supports (Rh?Si-R) as highly effective and recyclable catalysts. The catalyst preparation comprises grafting non-polar molecular entities on the SiO2 surface generating a hydrophobic environment for controlled deposition of well-defined rhodium particles from a simple organometallic precursor. A broad range of fluorinated cyclohexane derivatives was shown to be accessible with excellent efficacy (0.05-0.5 mol% Rh, 10-55 bar H2, 80-100 °C, 1-2 h), including industrially relevant building blocks. Addition of CaO as scavenger for trace amounts of HF greatly improves the recyclability of the catalytic system and prevents the risks associated to the presence of HF, without compromising the activity and selectivity of the reaction.
- Bordet, Alexis,Emondts, Meike,Kacem, Souha,Leitner, Walter
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p. 8120 - 8126
(2020/12/28)
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- Metal-Organic Framework Nodes Support Single-Site Nickel(II) Hydride Catalysts for the Hydrogenolysis of Aryl Ethers
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Herein we report that the Ti8-BDC (MIL-125) (BDC is 1,4-benzenecarboxylate) metal-organic framework (MOF) supports single-site solid NiII-hydride catalyst for the hydrogenolysis of aryl ethers containing α-O-4, β-O-4, and 4-O-5 linkages to exclusively afford hydrocarbons under mild conditions without the addition of a base. The catalytic activity of Ti8-BDC-NiH is highly dependent on the reduction of Ti8(μ2-O)8(μ2-OH)4 nodes. Density functional theory (DFT) calculations revealed two key steps of σ-bond metathesis in the catalytic cycle of Ti8-BDC-NiH catalyzed hydrogenolysis. This work highlights the potential of MOF-supported single-site catalysts in aryl ether bond scission and other processes for the efficient production of biofuels and chemical feedstocks.
- Song, Yang,Li, Zhe,Ji, Pengfei,Kaufmann, Michael,Feng, Xuanyu,Chen, Justin S.,Wang, Cheng,Lin, Wenbin
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p. 1578 - 1583
(2019/02/05)
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- Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts
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Selective hydrogenolysis of the Caryl-O bonds in lignin is a key strategy for the generation of fuels and chemical feedstocks from biomass. Currently, hydrogenolysis has been mainly conducted using hydrogen, which is flammable and not sustainable or economical. Herein, an external hydrogen-free process for aryl ethers hydrogenolysis in lignin models and dioxasolv lignin over nickel nanoparticles supported on Al2O3, is reported. Kinetic studies reveal that the transfer hydrogenolysis activity of the three model compounds decreased in the following order: benzyl phenyl ether (α-O-4), 2-phenylethyl phenyl ether (β-O-4) and diphenyl ether (4-O-5), which linearly corresponds to their binding energies and the activation energies. The main reaction route for the three model compounds was the cleavage of the ether bonds to produce aromatic alkanes and phenol, and the latter was further reduced to cyclohexanol. Dioxasolv lignin depolymerization results exhibit a significant Caryl-O decrease over the Ni nanoparticles supported on Al2O3 with iso-propanol as the hydrogen source through 2D-HSQC-NMR analysis, which confirmed the transfer hydrogenolysis conclusion in the model study. This work provides an economical and environmentally-friendly method for the selective cleavage of lignin and lignin model compounds into value-added chemicals.
- Jiang, Liang,Guo, Haiwei,Li, Changzhi,Zhou, Peng,Zhang, Zehui
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p. 4458 - 4468
(2019/04/29)
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- Solvent and substituent effects in hydrogenation of aromatic ketones over Ru/polymer catalyst under very mild conditions
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The paper reports on the solvent and the substituent effects in hydrogenation of aromatic ketones (acetophenone and its derivatives) in the presence of Ru catalyst supported on functionalized gel-type methacrylate-styrene resin under very mild conditions
- Duraczyńska,Serwicka,Drelinkiewicz,Socha,Zimowska,Lityńska-Dobrzyńska,Bukowska
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p. 145 - 151
(2019/04/13)
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- Platinum Nanosheets between Graphite Layers
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Two-dimensional platinum nanosheets were obtained by the hydrogen reduction of platinum tetrachloride intercalated between graphite layers, the latter was prepared by the treatment of the mixture of platinum tetrachloride and graphite powder under chlorine atmosphere. The size of platinum nanosheets was 1–3 nm in thickness with a width in the range of 5–300 nm. These nanosheets contain a number of hexagonal holes and edges with an angle of 120°. This review discusses the reduction and oxidation behavior of platinum species and structure of platinum nanosheets between graphite layers. The selective hydrogenation catalyzed by these platinum nanosheets entrapped between the graphite layers is also demonstrated.
- Shirai, Masayuki
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p. 1263 - 1271
(2018/11/27)
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- Potassium Yttrium Ate Complexes: Synergistic Effect Enabled Reversible H2 Activation and Catalytic Hydrogenation
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A potassium yttrium benzyl ate complex was generated simply by mixing an yttrium amide and potassium benzyl. The benzyl ate complex could undergo peripheral deprotonation to produce a cyclometalated complex or hydrogenation to give a hydride ate complex. The latter hydride ate complex features a (KH)2 structure protected by two yttrium amide complexes. The synergistic effect between potassium hydride and the amide ligand enables the complex to deprotonate a methyl C-H bond. The combination of intramolecular deprotonation of the hydride ate complex and hydrogenation of the cyclometalated complex constitutes a reversible H2 activation process. Using this process involving formal addition and elimination of H2, we accomplished the catalytic hydrogenation of alkenes, alkynes, and imines.
- Zhai, Dan-Dan,Du, Hui-Zhen,Zhang, Xiang-Yu,Liu, Yu-Feng,Guan, Bing-Tao
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p. 8766 - 8771
(2019/09/30)
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- Rhodium nanoparticles stabilized by ferrocenyl-phosphine ligands: Synthesis and catalytic styrene hydrogenation
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A series of ferrocenylphosphine-stabilized rhodium nanoparticles has been prepared in one pot from the organometallic [Rh(η3-C3H5)3] precursor. This complex has been decomposed by hydrogen treatment (3 bar) in dichloromethane in the presence of five different ferrocene-based phosphine ligands. Very small rhodium nanoparticles in the size range of 1.1-1.7 nm have been obtained. These nanoparticles have shown activity in a model catalytic reaction, namely the hydrogenation of styrene. These results evidence that the metal surface is not blocked despite the steric bulk of the stabilizing ligands. Moreover, certain selectivity has been observed depending on the ligand employed. To the best of our knowledge, such a type of compound has not yet been used for stabilizing metal nanoparticles and our findings highlight the interest to do so.
- Ibrahim,Wei,Deydier,Manoury,Poli,Lecante,Philippot
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p. 6777 - 6786
(2019/05/27)
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- A nickel-iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins
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Nickel and iridium supported on SiO2 (Ni-Ir/SiO2) acted as an effective and reusable heterogeneous catalyst for hydrogenation of olefins, and it showed higher activity and selectivity than the monometallic counterparts. The Ni-Ir/SiO2 catalyst has small Ni-Ir alloy and monometallic Ni particles, and the high catalytic performance can be attributed to the isolated Ni atom in the Ni-Ir alloys.
- Bai, Jia-qi,Tamura, Masazumi,Nakagawa, Yoshinao,Tomishige, Keiichi
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supporting information
p. 10519 - 10522
(2019/09/06)
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- Mesoporous Silica Doped with Dysprosium and Modified with Nickel: A Highly Efficient and Heterogeneous Catalyst for the Hydrogenation of Benzene, Ethylbenzene and Xylenes
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The catalytic activity of synthesized by the template method mesoporous silica doped with dysprosium and modified with nickel (Dy-Ni/MPS) in the hydrogenation of benzene, ethylbenzene and xylenes has been studied. The catalyst is characterized by various techniques such as TEM, SEM, BET, XRD, ICP, XRF analyses. It is shown that the presence of dysprosium in the MPS structure increases the activity of the catalyst. The catalytic activity of the catalyst (Dy-Ni/MPS) has been explored in hydrogenation reaction of benzene derivatives with excellent conversion (96–100%) at low pressure. Graphical Abstract: [Figure not available: see fulltext.].
- Shafigulin,Filippova,Shmelev,Bulanova
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p. 916 - 928
(2019/02/14)
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- Cobalt-Nanoparticles Catalyzed Efficient and Selective Hydrogenation of Aromatic Hydrocarbons
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The development of inexpensive and practical catalysts for arene hydrogenations is key for future valorizations of this general feedstock. Here, we report the development of cobalt nanoparticles supported on silica as selective and general catalysts for such reactions. The specific nanoparticles were prepared by assembling cobalt-pyromellitic acid-piperazine coordination polymer on commercial silica and subsequent pyrolysis. Applying the optimal nanocatalyst, industrial bulk, substituted, and functionalized arenes as well as polycyclic aromatic hydrocarbons are selectively hydrogenated to obtain cyclohexane-based compounds under industrially viable and scalable conditions. The applicability of this hydrogenation methodology is presented for the storage of H2 in liquid organic hydrogen carriers.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Alshammari, Ahmad S.,Altamimi, Rashid M.,Kreyenschulte, Carsten,Pohl, Marga-Martina,Lund, Henrik,Jagadeesh, Rajenahally V.,Beller, Matthias
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p. 8581 - 8591
(2019/09/12)
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- Synthesis of jet fuel range high-density polycycloalkanes with polycarbonate waste
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Jet fuel range high-density polycycloalkanes were first synthesized with polycarbonate waste by a two-step method which was conducted under mild conditions. In the first step, polycarbonate waste was converted to bisphenol by methanolysis. Subsequently, bisphenol was further converted to polycycloalkanes by hydrodeoxygenation.
- Tang, Hao,Hu, Yancheng,Li, Guangyi,Wang, Aiqin,Xu, Guoliang,Yu, Cong,Wang, Xiaodong,Zhang, Tao,Li, Ning
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supporting information
p. 3789 - 3795
(2019/07/31)
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- Efficient hydrodeoxygenation of lignin-derived phenols and dimeric ethers with synergistic [Bmim]PF6-Ru/SBA-15 catalysis under acid free conditions
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Selective catalytic hydrotreatment of lignin-derived phenols and dimeric ethers into alkanes is crucial for utilization of lignin and its fragments. Herein, we developed an efficient catalytic system with well-dispersed metal nanoparticles supported on SBA-15 synergistic with an ionic liquid. The catalytic system could catalyze the hydrodeoxygenation (HDO) of various monomeric and dimeric lignin-derived phenols into the corresponding alkanes under acid free conditions. The synergistic [Bmim]PF6-Ru/SBA-15 (1-butyl-3-methylimidazolium hexafluorophosphate) catalysis exhibited the best HDO activity for lignin-derived phenols and dimeric ethers with >99.0% conversion and maximum >98.0% selectivity of the corresponding alkanes. The yield of cyclohexane from diphenyl ether was 97.7% with 100% conversion under 2 MPa H2 at 130 °C for 6 h. The mechanism investigation confirmed that the Ru/SBA-15 catalyst and the anion of [Bmim]PF6 played crucial roles in the hydrogenation process and deoxidization process, respectively. The catalytic system was reused six times for HDO of diphenyl ether to test its stability.
- Yang, Shaoqi,Lu, Xingmei,Yao, Haoyu,Xin, Jiayu,Xu, Junli,Kang, Ying,Yang, Yongqing,Cai, Guangming,Zhang, Suojiang
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p. 597 - 605
(2019/02/14)
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- Method for using ionic liquid to catalyze deoxygenation in hydrodeoxygenation process of lignin derivative
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The invention discloses a method for preparing high-calorific-value alkanes by using an ionic liquid to catalyze deoxygenation in hydrodeoxygenation process of a lignin derivative aromatic compound. According to the method, a negative ion is selected as a proton type ionic liquid catalyst of trifluoromethanesulfonic acid, under the conditions that the temperature is 100-150 DEG C, the hydrogen pressure is 1-5 MPa, and the time is 2-20 hours, the high-efficiency deoxygenation process of a lignin derivative aromatic compound is catalyzed by the ionic liquid in a batch kettle, so that biomass alkane gasoline can be efficiently prepared. According to the method, the reaction conditions are mild, the energy consumption is low, the heat stability of the catalyst is good, the selectivity of product cycloparaffin is high, the conversion rate of the lignin derivative reaches 100%, and the selectivity of the product cycloparaffin is up to more than 98%. According to the method, the addition of protonic acid in a conventional catalytic system is avoided, the low pressure of the reaction system is ensured by the low vapor pressure of the ionic liquid, and the requirement for equipment is reduced. Meanwhile, the ionic liquid used in the process is easy to separate from the product, and the catalytic system is good in cycle performance and has good industrial application potential.
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Paragraph 0041; 0042
(2019/05/15)
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- Ru/hydroxyapatite as a dual-functional catalyst for efficient transfer hydrogenolytic cleavage of aromatic ether bonds without additional bases
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Cleavage of aromatic ether bonds is a key step for lignin valorization, and the development of novel heterogeneous catalysts with high activity is crucial. Herein, bifunctional Ru/hydroxyapatite has been prepared via ion exchange and subsequent reduction. The obtained Ru/hydroxyapatite could efficiently catalyze the cleavage of various compounds containing aromatic ether bonds via transfer hydrogenolysis without additional bases. Systematic studies indicated that the basic nature of hydroxyapatite and electron-enriched Ru sites resulted in the high activity of the catalyst. A mechanism study revealed that the direct cleavage of aromatic ether bonds was the main reaction pathway.
- Hua, Manli,Song, Jinliang,Xie, Chao,Wu, Haoran,Hu, Yue,Huang, Xin,Han, Buxing
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supporting information
p. 5073 - 5079
(2019/09/30)
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- Selective C?C Hydrogenolysis of Alkylbenzenes to Methylbenzenes with Suppression of Ring Hydrogenation
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Selective reduction of alkylbenzenes, which are supplied by refining heavy hydrocarbons, to methylbenzenes by selective C?C hydrogenolysis was accomplished by Ru/CeO2 catalyst. Hydrogenolysis of ethylbenzene was carried out with gas-phase fixed-bed flow reactor and various noble metal catalysts. The catalyst with high Ru loading (4 wt%) on CeO2 support pre-calcined at high temperature (1073 K; Ru(4)/CeO21073 catalyst) showed both good activity and selectivity to toluene. The yield of toluene reached 65 %-C in the conditions of 533 K and H2 partial pressure of 0.075 MPa. Hydrogenolysis of other alkylbenzenes including p-ethyltoluene, propylbenzene and cumene was also carried out. Hydrogenolysis of Caryl-Calkyl bond and hydrogenation of benzene ring was slow in all substrate cases. Hydrogenolysis of p-ethyltoluene can give p-xylene as the main product (highest yield: 53 %-C). These high yields of methylbenzenes make a marked contrast to the traditional bifunctional hydrocracking systems which preferably dissociate Caryl-Calkyl bond in alkylbenzenes. Characterization of Ru catalysts suggests that the block-shaped Ru particles with small size (21073 give good catalytic performance. Too strong interaction between Ru species and CeO2 support induced by decreasing the loading amount rather gives ring-hydrogenation activity and decreases methylbenzenes selectivity.
- Yanatake, Shin,Nakaji, Yosuke,Betchaku, Mii,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi
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p. 4172 - 4181
(2018/09/06)
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- Effect of preparation temperature on the structures and hydrodeoxygenation performance of Ni2P/C catalysts prepared by decomposition of hypophosphites
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A novel method for preparing Ni2P/C-x (x = preparation temperature, °C) catalysts in a flowing N2 atmosphere by decomposition of hypophosphites was proposed, and the effect of preparation temperature on the hydrodeoxygenation performance of the catalysts was further investigated. X-ray diffraction (XRD), N2-adsorption specific surface area measurements, CO uptake, and X-ray photoelectron spectroscopy (XPS) were applied. The performances of the Ni2P/C-x catalysts prepared at different preparation temperatures were tested in the benzofuran hydrodeoxygenation (BF HDO) reaction. The diffraction peaks related to Ni2P can be seen when x ≧ 400 °C. With increasing x, the Ni2P crystallite size and CO uptake amount of the Ni2P/C-x catalysts increased, and the amount of phosphorous decreased. The BF conversion and yield of total O-free products over the Ni2P/C-x catalysts increased with increasing preparation temperature. The Ni2P/C-550 catalyst showed a BF HDO conversion of 91.6% and a yield of total O-free products of 70.2% under the reaction conditions of 300 °C, 3.0 MPa, a H2/oil ratio of 500 (V/V), and a weight hourly space velocity (WHSV) of 4.0 h?1.
- Dai, Xueya,Song, Hua,Yan, Zijin,Li, Feng,Chen, Yanguang,Wang, Xueqin,Yuan, Dandan,Zhang, Jiaojing,Wang, Yuanyuan
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p. 19917 - 19923
(2018/12/13)
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