- One-pot catalytic reaction to produce high-carbon-number dimeric deoxygenated hydrocarbons from lignin-derived monophenyl vanillin using Al2O3-cogelled Ru nanoparticles
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Al2O3-cogelled Ru nanoparticle (Ru@Al) catalyst was prepared by a one-pot in-situ alumina gelation method using a PVP-stabilized Ru colloid solution. The Ru@Al catalyst exhibited excellent catalytic activity during the liquid-phase hydrodeoxygenation of vanillin, demonstrating 100% conversion, as well as significantly higher yields of fully deoxygenated compounds compared to other conventional alumina-supported Ru catalysts. We also observed better selectivity to deoxygenated dimers with the Ru@Al catalyst. The improved catalytic selectivity was attributed to the hypothesized three-dimensional structures of Al2O3 surrounding the Ru nanoparticles, which improved the two-step reaction, containing the dimerization of the phenolic compounds and the hydrodeoxygenation of phenolic dimers to produce deoxygenated high-carbon-number hydrocarbons.
- Yati, Indri,Dwiatmoko, Adid Adep,Yoon, Ji Sun,Choi, Jae-Wook,Suh, Dong Jin,Jae, Jungho,Ha, Jeong-Myeong
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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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- 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; 0098; 0100-0104
(2021/05/29)
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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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- 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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- 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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- Selective hydrogenation of lignin-derived compounds under mild conditions
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A key challenge in the production of lignin-derived chemicals is to reduce the energy intensive processes used in their production. Here, we show that well-defined Rh nanoparticles dispersed in sub-micrometer size carbon hollow spheres, are able to hydrogenate lignin derived products under mild conditions (30 °C, 5 bar H2), in water. The optimum catalyst exhibits excellent selectivity and activity in the conversion of phenol to cyclohexanol and other related substrates including aryl ethers.
- Chen, Lu,Van Muyden, Antoine P.,Cui, Xinjiang,Laurenczy, Gabor,Dyson, Paul J.
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supporting information
p. 3069 - 3073
(2020/06/17)
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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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- 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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- 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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- Bimetallic Nanoparticles in Supported Ionic Liquid Phases as Multifunctional Catalysts for the Selective Hydrodeoxygenation of Aromatic Substrates
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Bimetallic iron–ruthenium nanoparticles embedded in an acidic supported ionic liquid phase (FeRu@SILP+IL-SO3H) act as multifunctional catalysts for the selective hydrodeoxygenation of carbonyl groups in aromatic substrates. The catalyst material is assembled systematically from molecular components to combine the acid and metal sites that allow hydrogenolysis of the C=O bonds without hydrogenation of the aromatic ring. The resulting materials possess high activity and stability for the catalytic hydrodeoxygenation of C=O groups to CH2 units in a variety of substituted aromatic ketones and, hence, provide an effective and benign alternative to traditional Clemmensen and Wolff–Kishner reductions, which require stoichiometric reagents. The molecular design of the FeRu@SILP+IL-SO3H materials opens a general approach to multifunctional catalytic systems (MM′@SILP+IL-func).
- Offner-Marko, Lisa,Bordet, Alexis,Moos, Gilles,Tricard, Simon,Rengshausen, Simon,Chaudret, Bruno,Luska, Kylie L.,Leitner, Walter
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supporting information
p. 12721 - 12726
(2018/09/12)
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- Effective hydrodeoxygenation of lignin-derived phenols using bimetallic RuRe catalysts: Effect of carbon supports
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We have previously shown that an activated carbon-supported ruthenium catalyst promoted with ReOx (RuRe/AC) is highly active for the hydrodeoxygenation (HDO) of lignin-derived phenols (e.g., guaiacol). In this work, we have investigated the effect of carbon supports on the structure and HDO activity of bimetallic RuRe particles using three different carbon supports, i.e., activated carbon (AC), carbon black (Vulcan carbon, VC), multi-walled carbon nanotube (MWCNT). The MWCNT- and VC-supported catalysts show remarkably enhanced activity and hydrocarbon selectivity for the HDO of a range of phenolic molecules (i.e., guaiacol, eugenol, benzyl phenyl ether) compared to RuRe/AC. STEM-EDS and XPS analyses reveal that bimetallic RuRe particles are more common than monometallic Ru or Re particles in the VC- and MWCNT-supported catalysts, and hexavalent rhenium species are more easily reduced to tetravalent rhenium during the HDO reactions in these catalysts, suggesting that Ru and Re in close proximity are required for the efficient hydrogenolysis of phenols. The formation of bimetallic particles on the AC surface is likely hindered by high microporosity and high surface oxygen functionalities, both of which restrict the mobility of Re and Ru for assembly.
- Jung, Kyung Bin,Lee, Jinho,Ha, Jeong-Myeong,Lee, Hyunjoo,Suh, Dong Jin,Jun, Chul-Ho,Jae, Jungho
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p. 191 - 199
(2017/09/06)
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- Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts
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Super Lewis acids containing the triflate anion [e.g., Hf(OTf)4, Ln(OTf)3, In(OTf)3, Al(OTf)3] and noble metal catalysts (e.g., Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids.
- Wang, Hongliang,Wang, Huamin,Kuhn, Eric,Tucker, Melvin P.,Yang, Bin
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p. 285 - 291
(2017/11/20)
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- Stainless Steel-Mediated Hydrogen Generation from Alkanes and Diethyl Ether and Its Application for Arene Reduction
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Hydrogen gas can be generated from simple alkanes (e.g., n-pentane, n-hexane, etc.) and diethyl ether (Et2O) by mechanochemical energy using a planetary ball mill (SUS304, Fritsch Pulverisette 7), and the use of stainless steel balls and vessel is an important factor to generate the hydrogen. The reduction of organic compounds was also accomplished using the in-situ-generated hydrogen. While the use of pentane as the hydrogen source facilitated the reduction of the olefin moieties, the arene reduction could proceed using Et2O. Within the components (Fe, Cr, Ni, etc.) of the stainless steel, Cr was the metal factor for the hydrogen generation from the alkanes and Et2O, and Ni metal played the role of the hydrogenation catalyst.
- Sawama, Yoshinari,Yasukawa, Naoki,Ban, Kazuho,Goto, Ryota,Niikawa, Miki,Monguchi, Yasunari,Itoh, Miki,Sajiki, Hironao
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supporting information
p. 2892 - 2896
(2018/05/29)
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- Pyridine(diimine) Molybdenum-Catalyzed Hydrogenation of Arenes and Hindered Olefins: Insights into Precatalyst Activation and Deactivation Pathways
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Pyridine(diimine) molybdenum bis(olefin) and bis(alkyl) complexes were synthesized, characterized, and examined for their catalytic activity in the hydrogenation of benzene and a selection of substituted arenes. The molybdenum bis(alkyl) complex (4-tBu-iPrPDI)Mo(CH2SiMe3)2 (iPrPDI = 2,6-(2,6-(C(CH3)2H)2C6H3N=CMe)2C5H3N) exhibited the highest activity for the hydrogenation of benzene, producing cyclohexane in >98% yield at 23 °C under 4 atm of hydrogen after 48 h. Toluene and o-xylene were similarly hydrogenated to their respective cycloalkanes, with the latter yielding predominantly (79:21 dr) cis-1,2-dimethylcyclohexane. The molybdenum-catalyzed hydrogenation of naphthalene yielded tetralin exclusively, and this selectivity was maintained at higher H2 pressure. At 32 atm of H2, more hindered arenes such as monosubstituted benzenes, biphenyl, and m- and p-xylenes underwent hydrogenation with yields ranging between 20 and >98%. (4-tBu-iPrPDI)Mo(CH2SiMe3)2 was also a competent alkene hydrogenation catalyst, supporting stepwise reduction of benzene to cyclohexadiene and cyclohexene during molybdenum-catalyzed arene hydrogenation. Deuterium labeling studies for the molybdenum-catalyzed hydrogenation of benzene produced numerous isotopologues and stereoisomers of cyclohexane, indicating reversible hydride (deuteride) insertion/β-H(D) elimination, diene/olefin binding, and allylic C-H(D) activation during the reaction. The resting state of the catalyst under neat conditions was established as the η6-benzene complex (iPrPDI)Mo(η6-benzene). Under catalytic conditions, pyridine underwent C-H activation of the 2-position and furan underwent formal C-O oxidative addition to yield a "metallapyran". Both reactions were identified as important catalyst deactivation pathways for the attempted molybdenum-catalyzed hydrogenation of heteroarenes.
- Joannou, Matthew V.,Bezdek, Máté J.,Chirik, Paul J.
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p. 5276 - 5285
(2018/05/15)
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- Catalytic Hydrogenation of Arenes in Water Over In Situ Generated Ruthenium Nanoparticles Immobilized on Carbon
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We describe a tandem process to generate active Ru nanoparticles (≈7 nm) immobilised in situ on carbon from an organometallic precursor and formic acid to afford the hydrogenation of a wide range of arenes and heteroarenes in yields up to 72 % with high conversions and selectivities for the desired products. The hydrogenation of several substrates analogous to lignin-derived fragments to the corresponding alicyclic products was also achieved. Our experimental investigations evidenced that the observed enhanced activity for arene hydrogenation was driven by the unique structural advantages of the organometallic precursor to activate formic acid, in which the presence of a nitrogen ligand is crucial to achieve a high catalytic activity. TEM analysis revealed the formation of Ru0 nanoparticles, and Hg0 poisoning experiments support the heterogeneous nature of the active catalyst.
- Dwivedi, Ambikesh Dhar,Rai, Rohit Kumar,Gupta, Kavita,Singh, Sanjay Kumar
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p. 1930 - 1938
(2017/06/13)
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- Highly selective catalytic hydroconversion of benzyloxybenzene to bicyclic cyclanes over bifunctional nickel catalysts
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An active bifunctional nickel catalyst was prepared by decomposing Ni(CO)4 to highly dispersed metallic Ni onto Hβ zeolite and first applied in hydroconverting benzyloxybenzene (BOB), which was used as a lignin-related model compound. Ni/Hβ proved to be effective for converting BOB to bicyclic cyclanes (BCCs) via Calk–O bond cleavage induced by H+ addition, benzylium addition to 2- and 4-positions in phenol, hydrogenation of benzene ring, dehydration, and H? abstraction. Compared to one-step conversion, the total BCC selectivity (TBCCS) significantly increases from catalytic hydroconversion of catalytically converted BOB by pretreatment under pressurized N2.
- Zhou, Xiao,Wei, Xian-Yong,Liu, Zhong-Qiu,Lv, Jing-Hui,Wang, Yue-Lun,Li, Zhan-Ku,Zong, Zhi-Min
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- One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y
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The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite.
- Wang, Hongliang,Ruan, Hao,Feng, Maoqi,Qin, Yuling,Job, Heather,Luo, Langli,Wang, Chongmin,Engelhard, Mark H.,Kuhn, Erik,Chen, Xiaowen,Tucker, Melvin P.,Yang, Bin
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p. 1846 - 1856
(2017/04/27)
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- Conversion of lignin model compounds under mild conditions in pseudo-homogeneous systems
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To produce basic chemicals from lignin, depolymerization and removal of oxygen from lignin through C-O cleavage and hydrodeoxygenation (HDO) are crucial steps. In this study, a novel, pseudo-homogeneous catalyst system, consisting of uniformly stabilized noble metal nanoparticles (NPs) in ionic liquids is developed for the selective reductive cleavage of C-O and HDO. Phenol and guaiacol as lignin monomer model compounds are investigated to gain an insight into the possible HDO pathway, meanwhile, dimeric model compounds such as diphenyl ether and benzyl phenyl ether are studied for the cleavage of C-O bonds between aromatic units. Four types of NPs including Pd, Pt, Rh and Ru were synthesized in situ and well distributed in ILs without aggregation. These catalytic systems displayed almost 100% conversion for various monomeric and dimeric lignin model compounds at 130°C and were recycled several times without loss of activity. The catalytic selectivity of metals for HDO/C-O cleavage normally decreases in the order of Pt > Rh ~ Ru ? Pd, which is similar to the order of NP size, Pd ? Pt > Rh ~ Ru. With a mean diameter of 5.6 nm, Pt NPs in [Bmim]PF6 are identified as the best catalytic system for the transformation of lignin monomeric and dimeric model compounds with an almost 100% conversion and maximum 97% selectivity.
- Chen, Lu,Xin, Jiayu,Ni, Lingli,Dong, Huixian,Yan, Dongxia,Lu, Xingmei,Zhang, Suojiang
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p. 2341 - 2352
(2016/05/19)
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- Upgrading of aromatic compounds in bio-oil over ultrathin graphene encapsulated Ru nanoparticles
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Fast pyrolysis of biomass for bio-oil production is a direct route to renewable liquid fuels, but raw bio-oil must be upgraded in order to remove easily polymerized compounds (such as phenols and furfurals). Herein, a synthesis strategy for graphene encapsulated Ru nanoparticles (NPs) on carbon sheets (denoted as Ru@G-CS) and their excellent performance for the upgrading of raw bio-oil were reported. Ru@G-CS composites were prepared via the direct pyrolysis of mixed glucose, melamine and RuCl3 at varied temperatures (500-800 °C). Characterization indicated that very fine Ru NPs (2.5 ± 1.0 nm) that were encapsulated within 1-2 layered N-doped graphene were fabricated on N-doped carbon sheets (CS) in Ru@G-CS-700 (pyrolysis at 700 °C). And the Ru@G-CS-700 composite was highly active and stable for hydrogenation of unstable components in bio-oil (31 samples including phenols, furfurals and aromatics) even in aqueous media under mild conditions. This work provides a new protocol to the utilization of biomass, especially for the upgrading of bio-oil.
- Shi, Juanjuan,Zhao, Mengsi,Wang, Yingyu,Fu, Jie,Lu, Xiuyang,Hou, Zhaoyin
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supporting information
p. 5842 - 5848
(2016/05/24)
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- Hydrogen Self-Sufficient Arene Reduction to Cyclohexane Derivatives Using a Combination of Platinum on Carbon and 2-Propanol
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Various arenes have been hydrogenated using platinum on carbon in a 2-propanol-aqueous mixed solvent at 100 C without the addition of flammable hydrogen gas to give the corresponding cyclohexane derivatives. 2-Propanol plays a role as an efficient hydrogen source based on the platinum on carbon-catalyzed dehydrogenation.
- Sawama, Yoshinari,Mori, Misato,Yamada, Tsuyoshi,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 3667 - 3670
(2016/01/25)
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- Direct production of naphthenes and paraffins from lignin
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The utilization of lignin as a fuel precursor has attracted attention, and a novel and facile process has been developed for one-pot conversion of lignin into cycloalkanes and alkanes with Ni catalysts under moderate conditions. This cascade hydrodeoxygenation approach may open the route to a new promising technique for direct liquefaction of lignin to hydrocarbons.
- Kong, Jiechen,He, Mingyuan,Lercher, Johannes A.,Zhao, Chen
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supporting information
p. 17580 - 17583
(2015/12/08)
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- Biomass-derived lignin to jet fuel range hydrocarbons via aqueous phase hydrodeoxygenation
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A catalytic process, involving the hydrodeoxygenation (HDO) of dilute alkali extracted corn stover lignin catalysed by noble metal catalyst (Ru/Al2O3) and acidic zeolite (H+-Y), to produce lignin-substructure-based hydrocarbons (C7-C18), primarily C12-C18 cyclic structure hydrocarbons in the jet fuel range, was demonstrated.
- Wang, Hongliang,Ruan, Hao,Pei, Haisheng,Wang, Huamin,Chen, Xiaowen,Tucker, Melvin P.,Cort, John R.,Yang, Bin
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supporting information
p. 5131 - 5135
(2015/12/08)
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- Solvothermal synthesis of MoS2 nanospheres in DMF-water mixed solvents and their catalytic activity in hydrocracking of diphenylmethane
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MoS2 nanospheres were successfully prepared via a solvothermal process using 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) in a mixed solvent of DMF-water. A probable [EMIM]Br aggregation in different mixed solvents and the formation mechanism of the MoS2 nanospheres are presented. The MoS2 nanospheres delivered high catalytic activity in hydrocracking of diphenylmethane.
- Du, Hui,Liu, Dong,Li, Min,Al Otaibi, Raja L.,Lv, Renqing,Zhang, Yadong
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p. 79724 - 79728
(2015/10/05)
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- Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations
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Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods.
- Mehta, Meera,Holthausen, Michael H.,Mallov, Ian,Pérez, Manuel,Qu, Zheng-Wang,Grimme, Stefan,Stephan, Douglas W.
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p. 8250 - 8254
(2015/07/07)
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- Reduction of aromatic compounds with Al powder using noble metal catalysts in water under mild reaction conditions
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In water, Al powder becomes a powerful reducing agent, transforming in cyclohexyl either one or both benzene rings of aromatic compounds such as biphenyl, fluorene and 9,10-dihydroanthracene under mild reaction conditions in the presence of noble metal catalysts, such as Pd/C, Rh/C, Pt/C, or Ru/C. The reaction is carried out in a sealed tube, without the use of any organic solvent, at low temperature. Partial aromatic ring reduction was observed when using Pd/C, the reaction conditions being 24 h and 60 °C. The complete reduction process of both aromatic rings required 12 h and 80 °C with Al powder in the presence of Pt/C.
- Rayhan, Ummey,Kwon, Hyeokmi,Yamato, Takehiko
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p. 952 - 957
(2014/08/18)
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- An improved method for the complete hydrogenation of aromatic compounds under 1 bar H2 with platinum nanowires
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A little pressure for a lot of gain: An efficient method has been developed for the controlled hydrogenation of phenol using a platinum nanowire catalyst under mild conditions (>98.4%, 1atm H2, 60°C). The catalyst also exhibited high levels of activity and selectivity towards other selected aromatic compounds bearing a variety of different substituents, demonstrating its generality towards the hydrogenation of aromatic compounds.
- Yu, Tingting,Wang, Jiaqing,Li, Xinming,Cao, Xueqin,Gu, Hongwei
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p. 2852 - 2855
(2013/10/21)
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- Dispersion and hydrogenation activity of surfactant-stabilized Rh(0) nanoparticles prepared on different mesoporous supports
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Supported Rh(0) colloidal particles were prepared by the reduction of Rh(III) ions by sodium borohydride in the presence of N-N-dimethyl-N-cetyl-N-(2- hydroxyethyl) ammonium chloride (HEA16Cl), usually used as a stabilizing agent in solution. Tested supports were Na-Al-SBA-15, SBA-15 and CMK-3. In each case, the influence of HEA16Cl was studied by comparison with blank samples. Surfactant and rhodium uptake were evaluated by means of elemental analysis and eventually thermogravimetry. Obtained materials were also characterized by XRD, N2 sorption and TEM. Given the results, it appears that HEA16Cl promotes rhodium uptake in all cases. Most significant effects on the size and dispersion of particles were observed for the system combining HEA16Cl and Na-Al-SBA-15. All the solids prepared in this study were tested in the room temperature hydrogenation of styrene as well as that of a more demanding substrate, diphenylmethane, at 0.1 MPa of H2. All of them were generally more active than their commercial analogue (5 wt.% Rh0/C). Best catalysts, i.e., those prepared from Na-Al-SBA-15 in the presence of HEA16Cl as well as CMK-3 without HEA16Cl, allowed almost 100% yield of dicyclohexylmethane within 6 h (molar substrate/Rh = 100).
- Boutros, Maya,Shirley, Guillaume,Onfroy, Thomas,Launay, Franck
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scheme or table
p. 158 - 165
(2012/01/02)
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- Catalytic double C-Cl bond activation in CHlby iron(III) salts with grignard reagents
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Cross-coupling of Grignard reagents with dichloromethane is achieved using iron(III) catalysts. Aryl- and benzylmagnesium bromides show a range of activity toward double C-Cl bond activation resulting in the insertion of methylene fragments between two equivalents of the nucleophilic partner. Georg Thieme Verlag Stuttgart.
- Qian, Xin,Kozak, Christopher M.
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experimental part
p. 852 - 856
(2011/06/21)
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- Rh(0) colloids supported on TiO2: A highly active and pertinent tandem in neat water for the hydrogenation of aromatics
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TiO2-supported Rh(0) nanoparticles were easily prepared in one step without calcination by a room temperature impregnation of the inorganic support with a prestabilized colloidal Rh(0) suspension. They are highly active and reusable catalysts for the hydrogenation of aromatics and chloroanisole derivatives in neat water with TOFs up to 33000 h-1. The comparison with the analogous silica system Rh@SiO2 was discussed showing higher catalytic selectivities and activities with Rh(0) colloids supported on TiO2.
- Hubert, Claudie,Bile, Elodie Guyonnet,Denicourt-Nowicki, Audrey,Roucoux, Alain
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experimental part
p. 1766 - 1771
(2011/09/19)
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- Nickel complexes of a pincer amidobis(amine) ligand: Synthesis, structure, and activity in stoichiometric and catalytic C-C bond-forming reactions of alkyl halides
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The synthesis, properties, and reactivity of nickel(II) complexes of a newly developed pincer amidobis(amine) ligand (McNN2) are described. Neutral or cationic complexes [(MeNN2)NiX] (X = OTf (6), OC(O)CH3 (7), CH3CN (8), OMe (9)) were prepared by salt metathesis or chloride abstraction from the previously reported [( MeNN2)NiCl] (1). The Lewis acidity of the {( McNN2)Ni) fragment was measured by the 1H NMR chemical shift of the coordinated CH3CN molecule in 8. Electrochemical measurements on 1 and 8 indicate that the electron-donating properties of NN2 are similar to those of the analogous amidobis(phosphine) (pnp) ligands. The solid-state structures of 6-8 were determined and compared to those of 1 and [(MeNN2)NiEt] (3). In all complexes, the MeNN2 ligand coordinates to the NiII ion in a mer fashion, and the square-planar coordination sphere of the metal is completed by an additional donor. The coordination chemistry of MeNN 2 thus resembles that of other three-dentate pincer ligands, for example, pnp and arylbis(amine) (ncn). Reactions of 2 with alkyl monohalides, dichlorides, and trichlorides were investigated. Selective C-C bond formation was observed in many cases. Based on these reactions, efficient Kumada-Corriu-Tamao coupling of unactivated alkyl halides and alkyl Grignard reagents with 1 as the precatalyst was developed. Good yields were obtained for the coupling of primary and secondary iodides and bromides. Double C-C coupling of CH2Cl2 with alkyl Grignard reagents by 1 was also realized. The scope and limitations of these transformations were studied. Evidence was found for a radical pathway in Ni-catalyzed C-C cross-coupling reactions, which involves NiIl alkyl intermediates.
- Vechorkin, Oleg,Csok, Zsolt,Scopelliti, Rosario,Hu, Xile
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experimental part
p. 3889 - 3899
(2009/12/26)
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- Rhodium/graphite-catalyzed hydrogenation of carbocyclic and heterocyclic aromatic compounds
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Rhodium on graphite (Rh/Gr, C24Rh) was prepared by reaction of anhydrous rhodium trichloride with potassium graphite (C8K, 3 equivalents) and used as a heterogeneous catalyst for the hydrogenation of carbocyclic and heterocyclic aromatic compounds at room temperature and 1 atm of hydrogen pressure. The effect of substitution on the benzene ring was examined in a variety of derivatives, including those with alkyl, hydroxy, alkoxy, aryloxy, carboxy, amino, nitro, acyl, chloro, or functionalized alkyl groups. Reduction of carbonyl functions of aromatic aldehydes and ketones occurred with complete or partial cleavage of the benzylic C-O bond; this cleavage also occurred in the hydrogenation of benzylic alcohols and esters. Georg Thieme Verlag Stuttgart.
- Falini, Giuseppe,Gualandi, Andrea,Savoia, Diego
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experimental part
p. 2440 - 2446
(2010/02/27)
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- Efficient and Practical Arene Hydrogenation by Heterogeneous Catalysts under Mild Conditions
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An efficient and practical arene hydrogenation procedure based on the use of heterogeneous platinum group catalysts has been developed. Rh/C is the most effective catalyst for the hydrogenation of the aromatic ring, which can be conducted in iPrOH under neutral conditions and at ordinary to medium H 2 pressures (10 atm). A variety of arenes such as alkylbenzenes, benzoic acids, pyridines, furans, are hydrogenated to the corresponding cyclohexyl and heterocyclic compounds in good to excellet yields. The use of Ru/C, less expensive than Rh/C, affords an effective and practical method for the hydrogenation of arenes including phenols. Both catalysts can be reused several times after simple filtration without any significant loss of catalytic activity.
- Maegawa, Tomohiro,Akashi, Akira,Yaguchi, Kiichiro,Iwasaki, Yohei,Shigetsura, Masahiro,Monguchi, Yasunari,Sajiki, Hironao
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experimental part
p. 6953 - 6963
(2010/02/28)
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- New method for the reduction of benzophenones with Raney Ni-Al alloy in water
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Raney Ni-Al alloy in a dilute alkaline aqueous solution has been shown to be a powerful reducing agent, which is highly effective in the reduction of benzophenones to the corresponding hydrocarbon derivatives, in the absence of any organic solvents. Copyright Taylor & Francis Group, LLC.
- Liu, Guo-Bin,Zhao, Hong-Yun,Zhu, Jia-Da,He, Hong-Jie,Yang, Hong-Jie,Thiemann, Thies,Tashiro, Hideki,Tashiro, Masashi
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p. 1651 - 1661
(2008/09/20)
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- Near-monodisperse tetrahedral rhodium nanoparticles on charcoal: The shape-dependent catalytic hydrogenation of arenes
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The shape of things to come? Monodisperse (4.9±0.4)-nm tetrahedral rhodium nanoparticles on charcoal (/C) are compared to (4.8±0.4)-nm spherical rhodium nanoparticles on charcoal(?/C) and commercial Rh/C as a catalyst for the hydrogenation of anthracene (see picture). The former is 5.8- and 109-times more active than the latter two, respectively. It also shows a higher selectivity and excellent activity in the hydrogenation of several other arenes. (Graph Presented).
- Park, Kang Hyun,Jang, Kwonho,Kim, Hae Jin,Son, Seung Uk
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p. 1152 - 1155
(2008/03/15)
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- A mild and facile method for complete hydrogenation of aromatic nuclei in water
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A mild and complete hydrogenation of aromatic rings catalyzed by heterogeneous 10% Rh/C proceeds at 80 °C in water under 5 atm of H 2 pressure. This method is applicable to the hydrogenation of various carbon and heteroaromatic compounds such as alkylbenzenes, biphenyls, pyridines and furans. Georg Thieme Verlag Stuttgart.
- Maegawa, Tomohiro,Akashi, Akira,Sajiki, Hironao
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p. 1440 - 1442
(2007/10/03)
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- Preferential catalytic hydrogenation of aromatic compounds versus ketones with a palladium substituted polyoxometalate as pre-catalyst
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A palladium-substituted polyoxometalate having a Keggin structure, supported on γ-alumina or active carbon, was used as a catalyst precursor for catalytic hydrogenation. The catalyst system enabled fast hydrogenation of arenes at 30 bar H2 and 230°C. Most interesting was the finding that arenes could be selectively reduced in the presence of distal ketone groups under similar conditions, 30 bar H2 and 200°C. For example, 1-phenyl-2-propanone yielded 1-cyclohexyl-2-propanone with no reduction of the ketone moiety. Additionally, aromatic compounds with vicinal (conjugated) ketone moieties underwent complete hydrogenation to saturated hydrocarbons and catalytic McMurry coupling was observed for aliphatic aldehydes.
- Kogan, Vladimir,Aizenshtat, Zeev,Neumann, Ronny
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p. 272 - 274
(2007/10/03)
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- Hydrogenation of Biphenyls over the Hydrogen Storage Alloy MmNi3.5Co0.7Al0.8H4
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Hydrogenation of biphenyl with the activated hydrogen storage alloy, MmNi3.5Co0.7Al0.8H4 (Mm: La, 30; Ce, 52; Pr, 5; Nd, 13 wtpercent), as a stoichiometric reductant proceeded effectively at 160 deg C for 3 h under nitrogen to give either phenylcyclohexane or bicyclohexyl selectively, according to the ratio of the alloy to biphenyl.
- Nakagawa, Shin-ichi,Murata, Satoru,Sakai, Tetsuo,Nomura, Masakatsu
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p. 431 - 432
(2007/10/02)
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- The Effect of Hydrogen Sulfide on Acridine Hydrodenitrogenation on a Sulfided NiMo/Al2O3 Catalyst
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The effect of hydrogen sulfide on acridine hydrodenitrogenation over a sulfided NiMo/Al2O3 catalyst at 280-380 deg C and 10.1 MPa total pressure was studied.The result showed that the presence of H2S depressed the total C-N hydrogenolysis at a low PH2S/PH2 ratio of 1.1-79x10-5, but that it rarely affected the C-N hydrogenolysis at a ratio above 0.003.
- Nagai, Masatoshi
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p. 330 - 332
(2007/10/02)
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- Active Sites of a Reduced Molybdena-Alumina Catalyst. A Transient Study of Hydrodenitrogenation of Carbazole and Acridine
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A response study of the hydrodenitrogenation of acridine and carbazole on a reduced MoO3/Al2O3 catalyst was performed at 300 deg C and 10.1 MPa total pressure.Acridine was strongly adsorbed on the acidic sites of the catalyst surface for hydrogenation, while carbazole was wakly adsorbed not only on the same sites as acridine, but also on the terminal oxygen anion sites in the presence in the presence of strong bases.
- Nagai, Masatoshi,Masunaga, Takashi
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p. 972 - 975
(2007/10/02)
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- EFFICIENCY OF TWO-STAGE HYDRODENITROGENATION OF AROMATIC NITROGEN COMPOUNDS
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A high hydrodenitrogenation (86 percent) of acridine on a Ni-Mo/Al2O3 catalyst was achieved by succesive reactions at 370 deg C for 2 h and 420 deg C for 3 h, respectively, while the single stage reaction at 420 deg C for 5 h removed only 67 percent nitrogen.The effective hydrodenitrogenation is postulated due to the extensive hydrogenation in the first stage and C-N bond fission in the second stage.
- Mochida, Isao,Sakanishi, Kinya,Korai, Yozo,Fujitsu, Hiroshi
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p. 909 - 912
(2007/10/02)
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