- Niobium-containing lindqvist isopolyanions [NbxW6-xO19](2+x)- used as precursors for hydrodesulfurization catalysts with isomerization properties
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Lindqvist isopolyanions [NbxW6-xO19](2+x)- (x = 0-4 and 6) were prepared and their spectroscopic and thermal properties were determined by Raman and IR spectroscopy as well as TGA/DSC. The structure of the [NbW5O19]3- anion obtained as single crystal was determined. Ni-promoted alumina-supported hydrodesulfurization (HDS) catalysts were prepared from the best soluble NbW polyoxometalates. In the calcined catalysts, better dispersion of the metallic species is observed when using NbW isopolyanions instead of the conventional ammonium metatungstate. The presence of niobium was expected to introduce acidity leading to isomerization property in classical NiW HDS catalysts. In HDS reaction conditions (under hydrogen pressure and sulfided environment) the cyclohexane isomerization into methylcyclopentane activity of niobium-based catalysts was found up to 5 times superior to that of conventional NiW catalyst, showing the beneficial effect of niobium for this reaction. [NbxW6-xO19](2+x)- Lindqvist type isopolyanions were synthesized and characterized to prepared NbWNi-based alumina-supported hydrodesulfurization catalysts. Nb-containing catalysts showed improved CC6 isomerization properties under HDS conditions (H2 pressure and H2S presence) compared to those of a reference NiW catalyst related to the acid properties induced by niobium.
- Bouadjadja-Rohan, Karolina,Lancelot, Christine,Fournier, Michel,Bonduelle-Skrzypczak, Audrey,Hugon, Antoine,Mentré, Olivier,Lamonier, Carole
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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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- Highly Selective Hydrodeoxygenation of Lignin to Naphthenes over Three-Dimensional Flower-like Ni2P Derived from Hydrotalcite
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A strategy for low-temperature synthesis of hydrotalcite-based nickel phosphide catalysts (Ni2P-Al2O3) with flower-like porous structures was proposed. The in situ reduction of red phosphorus at 500 °C enables Ni2P catalysts with small particle size and abundant active and acidic sites, which facilitate the activation of substrates and H2. In the hydrodeoxygenation of guaiacol, a 100% conversion and 94.5% yield of cyclohexane were obtained over the Ni2P-Al2O3 catalyst under 5 MPa H2 at 250 °C for 3 h. Other lignin-derived phenolic compounds could also afford the corresponding alkanes with yields higher than 85%. Moreover, Ni2P-Al2O3 exhibited high hydrodeoxygenation activity in the deconstruction of more complex wood structures, including lignin oil and real lignin. Among the two different types of Ni sites of Ni(1) and Ni(2) in Ni2P, density functional theory (DFT) calculations showed that the Ni(2) site, highly exposed on the Ni2P-Al2O3 surface, possesses a stronger ability to break C-OH bonds during the hydrodeoxygenation of guaiacol in comparison with the Ni(1) site.
- Chen, Guanyi,Diao, Xinyong,Ji, Na,Jia, Zhichao,Li, Changzhi,Li, Xinxin,Liu, Caixia,Liu, Qingling,Lu, Xuebin,Ma, Longlong,Song, Chunfeng,Wang, Shurong,Zhao, Yujun
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p. 1338 - 1356
(2022/02/07)
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- Improved Hydrodeoxygenation of Phenol to Cyclohexane on NiFe Alloy Catalysts Derived from Phyllosilicates
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A phyllosilicate-derived NiFe/SiO2 catalyst (NiFe/SiO2?AE) was successfully prepared by the ammonia evaporation method and applied in the hydrodeoxygenation of phenol to cyclohexane. Another two catalysts were also prepared for a comparison by impregnation (NiFe/SiO2?IM) and deposition-precipitation (NiFe/SiO2?DP) methods, respectively. It was found that Ni?Fe alloy, the active sites for the hydrogenolysis of C?O bond, can be obtained by the reduction of NiFe2O4 (IM) or phyllosilicate (DP and AE) by H2. The AE strategy can generate more phyllosilicate structure, which improves the dispersion of both Ni?Fe alloy and metallic Ni sites and allows the formation of more interface between these two kinds of sites as well. Therefore, the NiFe/SiO2?AE exhibits a significantly high catalytic performance in the HDO of phenol to cyclohexane. Moreover, the turnover frequency of Ni?Fe alloy sites over NiFe/SiO2?AE catalysts is much higher than those of other two catalysts. It is suggested that the enhanced synergy between the two kinds of active sites in the adsorption of C?O groups and hydrogen molecules ensures the superior intrinsic activity in HDO process.
- Han, Qiao,Wang, Hui,Rehman, Mooeez Ur,Shang, Xin,Chen, Haijun,Ji, Na,Tong, Xinli,Shi, Hui,Zhao, Yujun
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supporting information
p. 5069 - 5076
(2021/12/14)
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- Influence of Nitrate and Phosphate on Silica Fibrous Beta Zeolite Framework for Enhanced Cyclic and Noncyclic Alkane Isomerization
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Phosphate and nitrate were loaded on silica BEA (P/HSi?BEA and N/HSi?BEA), which is fibrously protonated by the impregnation method for n-hexane and cyclohexane isomerization. The characterization analysis specified the removal of tetrahedral aluminum atoms in the framework, which was triggered by the existence of phosphate and nitrate groups in the catalyst. The exchanged role of Si(OH)Al to P-OH as active acidic sites in the P/HSi?BEA catalyst reduced its acidic strength, which was confirmed by the FTIR results. Lewis acidic sites of P/HSi?BEA performance are a significant part in the generation of high protonic acid sites, as proven by the in situ ESR study. However, FTIR evacuation and 27Al NMR revealed that the reduction in the amount of extraframework Al (EFAl) is due to its interaction with the nitrate group on the outside of the catalyst surface. The N/HSi?BEA catalyst exhibited high acidic strength because of the existence of more Si(OH)Al, which was initiated during the nitrate-incorporation process. Of significance is that the catalytic performance of n-hexane isomerization in the presence of hydrogen reached 50.3% product isomer yield at 250 °C, which might be ascribed to the presence of P-OH active sites that are responsible for accepting electrons, forming active protonic acid sites. NO3-EFAl interaction induced the formation of Br?nsted acid sites, and higher mesopore volume favors the production of cyclohexane isomers up to 48.4% at 250 °C. This fundamental study exhibits that significant interactions given by such phosphate and nitrate groups with the unique silica fibrous BEA support could enhance isomerization, which contributes to the high quality of fuel.
- Hitam, Che Ku Nor Liana Che Ku,Izan, Siti Maryam,Jalil, Aishah Abdul,Nabgan, Walid
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p. 1723 - 1735
(2020/02/28)
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- Phospholane-Based Ligands for Chromium-Catalyzed Ethylene Tri- And Tetramerization
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Chromium complexes with bis(phospholane) ligands were synthesized and evaluated for ethylene tetramerization in a high-throughput reactor. Three ligand parameters - the phospholane substituent, the ligand backbone, and the type of phosphine (cyclic vs acyclic) - were investigated. The size of the phospholane substituent was found to impact the selectivity of the resulting catalysts, with smaller substituents leading to the production of larger proportions of 1-octene. Changing the ligand backbone from 1,2-phenylene to ethylene did not impact catalysis, but the use of acyclic phosphines in place of the cyclic phospholanes had a detrimental effect on catalytic activity. Selected phospholane-chromium complexes were evaluated in a 300 mL Parr reactor at 70 °C and 700 psi of ethylene pressure, and the ethylene oligomerization performance was consistent with that observed in the smaller, high-throughput reactor. MeDuPhos-CrCl3(THF) (MeDuPhos = 1,2-bis(2,5-dimethylphospholano)benzene; THF = tetrahydrofuran) gave activity and selectivity for 1-octene (54.8 wt %) similar to the state-of-the-art i-PrPNP-CrCl3(THF) (64.0 wt %) (PNP = bis(diphenylphosphino)amine), while EtDuPhos-CrCl3(THF) (EtDuPhos = 1,2-bis(2,5-diethylphospholano)benzene) exhibited even higher activity, with catalyst selectivity shifted toward 1-hexene production (90 wt %). These results are surprising, given the prevalence of the aryl phosphine motif in ligands used in ethylene oligomerization catalysts and the inferior performance of previously reported catalysts with alkyl phosphine-containing ligands.
- Boelter, Scott D.,Davies, Dan R.,Klosin, Jerzy,Margl, Peter,Milbrandt, Kara A.,Mort, Darrek,Rosen, Mari S.,Vanchura, Britt A.,Wilson, David R.,Wiltzius, Molly
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supporting information
(2020/02/27)
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- Ethylene Tetramerisation: A Structure-Selectivity Correlation
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The effect of ethylene tetramerisation ligand structures on 1-octene selectivity is well studied. However, by-product formation is less understood. In this work, a range of PNP ligand structures are correlated with the full product selectivity and with catalyst activity. As steric bulk on the N-substituent increases, the product selectivity shifts from >10 % to 3% of both C6 cyclics and C16+ by-products. 1-Octene peaks at ca. 70%. Thereafter, only 1-hexene increases. Similar selectivity changes were observed for ortho-Ph-substituted PNP ligands. The C10-14 selectivity was less affected by the ligand structure. The ligand effect on the changes in selectivity is explained mechanistically. Lastly, an increase in ligand steric bulk was found to improve catalyst activity and reduce polymer formation by an order of magnitude. It is proposed that steric bulk promotes formation of cationic catalytic species which are responsible for selective ethylene oligomerisation.
- Makume, Boitumelo F.,Holzapfel, Cedric W.,Maumela, Munaka C.,Willemse, J. Alexander,van den Berg, Jan A.
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p. 2308 - 2315
(2020/11/03)
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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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- 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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- Two-step catalytic conversion of lignocellulose to alkanes
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Direct conversion of lignocellulose to alkanes is challenged by the complex and recalcitrant nature of the starting material. Generally, alkanes are obtained from one of the main lignocellulose constituents (cellulose, hemicellulose or lignin) after their separation, and platform chemicals derived therein. Here we describe a two-step methodology, which uses unprocessed lignocellulose directly, targeting a mixture of alkanes. The first step involves the near-complete conversion of lignocellulose to alcohols, using a copper doped porous metal oxide (Cu-PMO) catalyst in supercritical methanol. The second step comprises a novel solvent exchange procedure and the exhaustive hydrodeoxygenation (HDO) of the complex mixture of aliphatic alcohols, obtained upon depolymerization, to C2-C10 alkanes by either HZSM-5 or Nafion at 180 °C in conjunction with Pd/C in dodecane. This describes an unprecedented two-step process from lignocellulose to hydrocarbons, with an overall carbon yield of 50%.
- Sun, Zhuohua,Buwalda, Daniel,Barta, Katalin
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p. 23727 - 23734
(2019/08/12)
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- Catalyst Systems and Ethylene Oligomerization Method
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Disclosed herein is a catalyst system comprising (i) a heterocyclic 2-[(phosphinyl)aminyl]imine transition metal compound complex having Structure I wherein T is oxygen or sulfur, R1 and R2 are each independently a C1 to C20 organyl group consisting essentially of inert functional groups, R3 is hydrogen or a C1 to C20 organyl group, L is a C1 to C20 organylene group consisting essentially of inert functional groups, MXp represents a transition metal compound where M is a transition metal, X is a monoanion, and p is an integer from 1 to 6, Q is a neutral ligand, and q ranges from 0 to 6, and (ii) an organoaluminum compound. Also disclosed herein is a process comprising contacting (i) ethylene, (ii) a catalyst system comprising (a) a heterocyclic transition metal compound complex having Structure I as described herein and (b) an organoaluminum compound, and (iii) optionally hydrogen to form an oligomer product.
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Paragraph 0170-0172
(2019/06/14)
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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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- Influence of calcination on metallic dispersion and support interactions for NiRu/TiO2 catalyst in the hydrodeoxygenation of phenol
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Bio-oil upgrading by hydrotreatment has been considered as a renewable route for fuels production and potential substitutes for fossil oil distillates. Traditional hydrodesulfurization catalysts (sulfided CoMo and NiMo) used in petroleum refining have been evaluated in hydrodeoxygenation reactions with high selectivity to aromatics. However, significant deactivation has been commonly observed, due to the low sulfur content in bio-oil. Thus, the development of different active and stable catalytic materials is needed. In this regard, we have previously reported a synergetic effect between Ni and Ru bimetallic materials supported on Al2O3, TiO2 and ZrO2 in phenol HDO with promising activity and selectivity results. In particular, materials supported TiO2 on displayed the highest activities. Therefore, the aim of this work was to evaluate the effect of calcination on dispersion and metal-support interactions and their impact on activity and selectivity for NiRu/TiO2 catalysts in HDO of phenol as a model compound for bio oil. Catalysts were characterized by hydrogen chemisorption, Temperature- programmed reduction, X-ray photoelectron spectroscopy, High resolution electron microscopy. Additionally, hydrogenation of benzene was used as a structure unsensitive reaction in order to obtain more information about metallic dispersion. A highly active NiRu catalyst was obtained when calcination was avoided prior to reduction. The calcination procedure induced the formation of metallic oxides and it provoked less dispersed NiRu species as compared with catalysts without this previous treatment. On the contrary, the formation of metallic species from direct reduction of precursor salts contributed to produce highly dispersed species.
- Valdés-Martínez,Santolalla-Vargas,Santes,de los Reyes,Pawelec,Fierro
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p. 149 - 155
(2018/11/30)
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- Breaking the Limit of Lignin Monomer Production via Cleavage of Interunit Carbon–Carbon Linkages
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Conversion of lignin into monocyclic hydrocarbons as commodity chemicals and drop-in fuels is a highly desirable target for biorefineries. However, this is severely hindered by the presence of stable interunit carbon–carbon linkages in native lignin and those formed during lignin extraction. Herein, we report a new multifunctional catalyst, Ru/NbOPO4, that achieves the first example of catalytic cleavage of both interunit C–C and C–O bonds in one-pot lignin conversions to yield 124%–153% of monocyclic hydrocarbons, which is 1.2–1.5 times the yields obtained from the established nitrobenzene oxidation method. This catalyst also exhibits high stability and selectivity (up to 68%) to monocyclic arenes over repeated cycles. The mechanism of the activation and cleavage of 5–5 C–C bonds in biphenyl, as a lignin model adopting the most robust C–C linkages, has been revealed via in situ inelastic neutron scattering coupled with modeling. This study breaks the conventional theoretical limit on lignin monomer production. The conversion of lignin into monocyclic hydrocarbons as commodity chemicals and drop-in fuels is essential for the future of biorefineries. State-of-the-art lignin depolymerization is primarily achieved via cleavage of interunit C–O bonds to form low-molecular-weight feedstocks. However, these processes can hardly cleave interunit C–C bonds in lignin, and thus, the yields of lignin monomers are heavily restricted. Here, we report a multifunctional catalyst, Ru/NbOPO4, that achieves the first example of catalytic cleavage of both interunit C–C and C–O bonds in lignin in one-pot reactions to yield 153% of monocyclic C6–C9 hydrocarbons from Kraft lignin, which is 1.5 times the theoretical yield obtained from the established nitrobenzene oxidation (NBO) method. Thus, significantly, this study successfully breaks the conventional limit on lignin monomer production. Lignin, containing a large volume of aromatic functionalities, is the most energy-dense fraction of renewable biomass. Particularly, conversion of lignin into monocyclic hydrocarbons as commodity chemicals is a highly desirable target. However, this is severally hindered by the presence of stable interunit carbon–carbon linkages in native lignin and those formed during lignin extraction. Here, we report a multifunctional Ru/NbOPO4 catalyst that achieves the first example of catalytic cleavage of both interunit C–C and C–O bonds in lignin in one-pot reactions.
- Dong, Lin,Lin, Longfei,Han, Xue,Si, Xiaoqin,Liu, Xiaohui,Guo, Yong,Lu, Fang,Rudi?, Svemir,Parker, Stewart F.,Yang, Sihai,Wang, Yanqin
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p. 1521 - 1536
(2019/06/14)
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- Comparative studies on enzyme activity of immobilized horseradish peroxidase in silica nanomaterials with three different shapes and methoxychlor degradation of vesicle-like mesoporous SiO2 as carrier
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In the present work, three differently shaped mesoporous silica nanoparticles, spherical nano-SiO2, tubular mesoporous SiO2 and vesicle-like mesoporous SiO2 (VSL), were prepared and used to immobilize Horse radish peroxida
- Yang, Yuxiang,Zhao, Min,Yao, Pingping,Huang, Yan,Dai, Zuocheng,Yuan, Hongming,Ni, Chaoying
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p. 2971 - 2978
(2018/01/10)
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- Effect of ketene additive and Si/Al ratio on the reaction of methanol over HZSM-5 catalysts
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The influence of ketene as possible intermediate for the reaction of methanol to aromatics was investigated over HZSM-5 catalysts (Si/Al ratio of 15 and 9) using diketene-acetone (2,2,6-trimethyl-4H-1,3-dioxin-4-one) as ketene precursor under atmospheric
- Hassanpour, Javad,Zamani, Mehdi,Dabbagh, Hossein A.
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- Accessing Alkyl- and Alkenylcyclopentanes from Cr-Catalyzed Ethylene Oligomerization Using 2-Phosphinophosphinine Ligands
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Desilylation of the 2-phosphinophosphinine 2-PPh2-3-Me-6-SiMe3-PC5H2 with HCl gave 2-PPh2-3-Me-PC5H3, demonstrating the late-stage modification of this bidentate heterocyclic lig
- Newland, Robert J.,Smith, Alana,Smith, David M.,Fey, Natalie,Hanton, Martin J.,Mansell, Stephen M.
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p. 1062 - 1073
(2018/03/30)
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- Heterolysis of Dihydrogen by Nucleophilic Calcium Alkyls
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β-Diketiminato (BDI) calcium alkyl derivatives undergo hydrogenolysis with H2 to regenerate [(BDI)CaH]2, allowing the catalytic hydrogenation of a wide range of 1-alkenes and norbornene under very mild conditions (2 bar H2, 298 K). The reactions are deduced to take place with the retention of the dimeric structures of the calcium hydrido-alkyl and alkyl intermediates via a well-defined sequence of Ca?H/C=C insertion and Ca?C hydrogenation events. This latter deduction is strongly supported by DFT calculations (B3PW91) performed on the 1-hexene/H2 system, which also indicates that the hydrogenation transition states display features which discriminate them from a classical σ-bond metathesis mechanism. In particular, NBO analysis identifies a strong second order interaction between the filled α-methylene sp3 orbital of the n-hexyl chain and the σ* orbital of the H2 molecule, signifying that the H?H bond is broken by what is effectively the nucleophilic displacement of hydride by the organic substituent.
- Wilson, Andrew S. S.,Dinoi, Chiara,Hill, Michael S.,Mahon, Mary F.,Maron, Laurent
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supporting information
p. 15500 - 15504
(2018/11/01)
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- In Situ Generation and Immobilization of an Activated Rh Complex Catalyst in a Metal–Organic Framework for Hydrogenation at Low H2 Pressure
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Hydrogenation reactions under low-pressure H2 atmosphere are highly relevant from the safety viewpoint, because H2 gas is highly flammable in air and explosions can be triggered by spark, heat, or sunlight. In this work, an Rh complex/MOF hybrid was synthesized and used as catalyst for the hydrogenation of alkene substrates. Thanks to the activation of the Rh complex catalyst during the immobilization process and the intrinsic gas-condensation property of MOFs, the resulting composite showed much higher catalytic activity than the complex catalyst itself. Moreover, the composite can maintain its catalytic activity even at low H2 pressures that cannot support the reaction with the complex catalyst alone. Furthermore, in contrast to the complex catalyst, the composite maintained its catalytic activity even without solvent, and thus provides an environmentally friendly approach to catalysis.
- Takashima, Yohei,Fukuhara, Yoshimasa,Sato, Yasushi,Tsuruoka, Takaaki,Akamatsu, Kensuke
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p. 5344 - 5349
(2017/12/04)
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- Copper-Catalyzed Dicarbofunctionalization of Unactivated Olefins by Tandem Cyclization/Cross-Coupling
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We present a strategy that difunctionalizes unactivated olefins in 1,2-positions with two carbon-based entities. This method utilizes alkyl/arylzinc reagents derived from olefin-tethered alkyl/aryl halides that undergo radical cyclization to generate C(sp3)-Cu complexes in situ, which are intercepted with aryl and heteroaryl iodides. A variety of (arylmethyl)carbo- and heterocycles (N, O) can be synthesized with this new method.
- Thapa, Surendra,Basnet, Prakash,Giri, Ramesh
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supporting information
p. 5700 - 5703
(2017/05/04)
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- Photochemical Production of Ethane from an Iridium Methyl Complex
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An iridium methyl complex, [Cp?Ir(bpy)(CH3)]+, was prepared by electrophilic methylation of Cp?Ir(bpy) with CH3I and characterized electrochemically, photophysically, crystallographically, and computationally. Irradiation of the MLCT transition of [Cp?Ir(bpy)(CH3)]+ in the presence of CH3I in acetonitrile produces ethane, methane, propionitrile, and succinonitrile. A series of mechanistic studies indicates that C-C bond formation is mediated by free methyl radicals produced through monometallic photochemical homolysis of the Ir-CH3 bond.
- Pitman, Catherine L.,Miller, Alexander J. M.
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supporting information
p. 1906 - 1914
(2017/06/14)
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- Hydrodeoxygenation of guaiacol on tungstated zirconia supported Ru catalysts
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Ru nanoparticles supported on tungstated zirconia (WZr) were prepared and used for the catalytic hydrodeoxygenation of guaiacol to deoxygenated hydrocarbon fuels. The tuning of tungsten, from 5 to 20?wt%, adjusted the number of acid sites on the tungstated zirconia and the size of the Ru nanoparticles. The optimum fraction of tungsten was determined for the optimum hydrodeoxygenation activity. The conversion of guaiacol reached a maximum of 96.8% for 10?wt% of tungsten. Increasing the tungsten fraction increased the number of acid sites and the dispersion of Ru, but the formation of tungsten oxide (WOx) particles with too large fraction of tungsten inhibited the formation of smaller Ru nanoparticles, thus reducing the catalytic activity.
- Dwiatmoko, Adid Adep,Kim, Inho,Zhou, Lipeng,Choi, Jae-Wook,Suh, Dong Jin,Jae, Jungho,Ha, Jeong-Myeong
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- Transfer Hydrogenation of Nitriles, Olefins, and N-Heterocycles Catalyzed by an N-Heterocyclic Carbene-Supported Half-Sandwich Complex of Ruthenium
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In the presence of KOBut, N-heterocyclic carbene-supported half-sandwich complex [Cp(IPr)Ru(pyr)2][PF6] (3) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) catalyzes transfer hydrogenation (TH) of nitriles, activated N-heterocycles, olefins, and conjugated olefins in isopropanol at the catalyst loading of 0.5%. The TH of nitriles leads to imines, produced as a result of coupling of the initially formed amines with acetone (produced from isopropanol), and showed good chemoselectivity. Reduction of N-heterocycles occurs for activated polycyclic substrates (e.g., quinoline) and takes place exclusively in the heterocycle. The TH also works well for linear and cyclic olefins but fails for trisubstituted substrates. However, the C = C bond of α,β-unsaturated esters, amides, and acids is easily reduced even for trisubstituted species, such as isovaleriates. Mechanistic studies suggest that the active species in these catalytic reactions is the trihydride Cp(IPr)RuH3 (5), which can catalyze these reactions in the absence of any base. Kinetic studies are consistent with a classical inner sphere hydride-based mechanism of TH.
- Mai, Van Hung,Nikonov, Georgii I.
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p. 943 - 949
(2016/05/09)
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- Dehydrocyclization of C6 Hydrocarbon with and Without Oxygen Containing Substituent over Pt/(Na)-Al2O3 Catalyst
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The presence of hydroxyl or keto functional group affects both activity and selectivity for dehydrocyclization of C6 hydrocarbon over Pt/(Na)-Al2O3 catalyst. Under similar reaction conditions, n-hexane produces benzene as the primary product (>40 %), whereas dehydration is a major reaction pathway for 2-hexanol and yields mainly hexenes (>70 %). However, 2-hexanone was found to be involved in a variety of reactions over Pt/(Na)-Al2O3 catalyst and produces lower hydrocarbons (C2-C5), 5-dodecanone, 2- And 5-nonanones, and 2-acetyl-3-propyl-2-cyclohexen-1-one. The presence of hydroxyl (-OH) or keto group (=C=O) at the C-2 position alters the interaction of C6 hydrocarbon with the catalyst surface which eventually controls the overall product selectivity.
- Gnanamani, Muthu Kumaran,Shafer, Wilson D.,Keogh, Robert A.,Davis, Burtron H.
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p. 424 - 432
(2016/02/23)
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- Evaluation of transition metal phosphides supported on ordered mesoporous materials as catalysts for phenol hydrodeoxygenation
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A series of transition metal phosphides (Ni2P, Co2P and MoP) have been synthesized by temperature programmed reduction of the corresponding metal phosphate precursors loaded over mesostructured Al-SBA-15, mesoporous γ-Al2O3 (m-Al2O3) and ordered mesoporous carbon (CMK-3). Both the dispersion and metal phosphide phases attained are strongly influenced by the support features, such as their acidic and textural properties. XRD, TEM and H2 chemisorption results revealed that the MoP phase was probably formed but it underwent a fast re-oxidation in air. On the other hand, metal phosphide formation was hindered over m-Al2O3 as only metallic Ni and Co were detected. All the materials prepared have been evaluated as catalysts in hydrodeoxygenation (HDO) using phenol as a bio-oil model compound. The highest phenol conversions were attained with the catalysts based on the acidic supports (Al-SBA-15 and m-Al2O3). Nevertheless, Co2P/Al-SBA-15, Ni2P/m-Al2O3 and Co2P/m-Al2O3 yielded cyclohexanol as the main product denoting very low HDO efficiency. In contrast, Ni2P/Al-SBA-15 showed remarkable catalytic properties, being the only catalyst that provided almost full phenol conversion and extremely high HDO efficiency, with cyclohexane selectivity higher than 90%. This may be due to a synergetic effect between the high electron deficiency, generated by the Niα+ (0 α 1) species owing to an electron transfer from Ni to P and the different acidic sites present in the catalyst.
- Berenguer,Sankaranarayanan,Gómez,Moreno,Coronado,Pizarro,Serrano
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p. 1938 - 1951
(2016/04/19)
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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)
-
- Synthesis of biomass-derived methylcyclopentane as a gasoline additive via aldol condensation/hydrodeoxygenation of 2,5-hexanedione
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A novel approach to produce biomass-derived gasoline is the hydrolysis of 2,5-dimethylfuran (DMF) to produce 2,5-hexanedione followed by base-catalyzed intramolecular aldol condensation of this product to form 3-methylcyclopent-2-enone (MCP). By proper choice of catalysts and conditions, MCP yields of 98% can be achieved. We further show that hydrogenation of MCP over Pt/NbOPO4 gives methylcyclopentane with virtually quantitative yields. Methylcyclopentane is an attractive gasoline substitute for ethanol, since its octane number is similar to ethanol and its gravimetric energy density is 58% higher. This journal is
- Sacia, Eric R.,Deaner, Matthew H.,Louie, Ying Lin,Bell, Alexis T.
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p. 2393 - 2397
(2015/04/27)
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- Production of alkanes from lignin-derived phenolic compounds over in situ formed Ni catalyst with solid acid
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In situ formed Ni catalyst combined with added solid acids is highly active for the hydrodeoxygenation of lignin-derived phenolic compounds. In the heterogeneous catalysts, in situ formed Ni acts as the hydrogenation and hydrogenolysis catalyst and solid acid acts as the dehydration catalyst.
- Zhang, Xinghua,Wang, Tiejun,Zhang, Qi,Xu, Ying,Long, Jinxing,Chen, Lungang,Wang, Chenguang,Ma, Longlong
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supporting information
p. 648 - 650
(2015/05/20)
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- A novel route for the synthesis of alkanes from glycerol in a two step process using a Pd/SBA-15 catalyst
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Glycerol is produced as a valuable by-product in the transesterification of fatty acids, but it cannot be used directly as a fuel additive. In this study, we developed a systematic conversion for glycerol, which proceeds via synthesizing the key intermediate, 1,2,3-tribromopropane and using the Suzuki coupling reaction to introduce the alkyl group. A series of Pd/SBA-15 catalysts with different wt% of Pd (10%, 15% and 20%) was prepared by a one step sol-gel method. The structure and composition of the catalysts were characterized by X-ray diffraction analysis (XRD), N2 adsorption-desorption isotherms, transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectrometry (ICP-OES). The metallic state of dispersed palladium in SBA-15 is confirmed with X-ray photoelectron spectroscopy (XPS). Pd/SBA-15 with a Pd loading of 20 wt% shows good catalytic activity at 90 °C with methylboronic acid, allowing the complete conversion of 1,2,3-tribromopropane and 64% selectivity of 3-methylpentane. The optimized catalysts were also employed in coupling reactions between various alkylhalides and methylboronic acid, which obtained the desired product with an excellent selectivity. The catalyst can be successfully recycled five times. After the first cycle, we observed a drop in activity with 20% Pd/SBA-15, which was due to the leaching of palladium but in the later cycles, there was no significant decrease in activity.
- Udayakumar,Pandurangan
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p. 78719 - 78727
(2015/10/05)
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- A new approach for bio-jet fuel generation from palm oil and limonene in the absence of hydrogen
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The traditional methodology includes a carbon-chain shortening strategy to produce bio-jet fuel from lipids via a two-stage process with hydrogen. Here, we propose a new solution using a carbon-chain filling strategy to convert C10 terpene and lipids to jet fuel ranged hydrocarbons with aromatic hydrocarbon ingredients in the absence of hydrogen.
- Zhang, Jingjing,Zhao, Chen
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supporting information
p. 17249 - 17252
(2015/12/08)
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- PROCESS FOR SELECTIVE RING OPENING OF CYCLIC HYDROCARBONS
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PURPOSE: A process for ring opening is provided to obtain improved conversion ratio and selectivity in comparison with the case of using hydrogen as a reducing agent. CONSTITUTION: A cyclic hydrocarbon and a reducing agent are provided as supplying materials. The supplying materials are transferred into a reactor (5) and reacted under the presence of a catalyst. A product is separated from the effusion of reaction zone. The catalyst is a heterogeneous catalyst having both acid site and metallic component. The product is obtained by evaporating and heating a mixture containing 100 parts by weight of porous molecular sieve and 0.01-20 parts by weight of water soluble metallic salt. The cyclic hydrocarbon is a naphthene group cyclic hydrocarbon which is pentagonal or hexagonal compound, or an alkyl derivative thereof selected from cyclopentane and cyclohexane. The alkyl derivative is methyl, ethyl, profile, butyl, isopropyl or an isobutyl derivative.
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-
Paragraph 0078-0085
(2020/04/29)
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- Designed catalysts from Pt nanoparticles supported on macroporous oxides for selective isomerization of n-hexane
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Selective isomerization toward branched hydrocarbons is an important catalytic process in oil refining to obtain high-octane gasoline with minimal content of aromatic compounds. Colloidal Pt nanoparticles with controlled sizes of 1.7, 2.7, and 5.5 nm were deposited onto ordered macroporous oxides of SiO2, Al2O3, TiO2, Nb 2O5, Ta2O5, and ZrO2 to investigate Pt size-and support-dependent catalytic selectivity in n-hexane isomerization. Among the macroporous oxides, Nb2O5 and Ta2O5 exhibited the highest product selectivity, yielding predominantly branched C6 isomers, including 2-or 3-methylpentane, as desired products of n-hexane isomerization (140 Torr n-hexane and 620 Torr H2 at 360 °C). In situ characterizations including X-ray diffraction and ambient-pressure X-ray photoelectron spectroscopy showed that the crystal structures of the oxides in Pt/oxide catalysts were not changed during the reaction and oxidation states of Nb2O5 were maintained under both H2 and O2 conditions. Fourier transform infrared spectra of pyridine adsorbed on the oxides showed that Lewis sites were the dominant acidic site of the oxides. Macroporous Nb 2O5 and Ta2O5 were identified to play key roles in the selective isomerization by charge transfer at Pt-oxide interfaces. The selectivity was revealed to be Pt size-dependent, with improved isomer production as Pt sizes increased from 1.7 to 5.5 nm. When 5.5 nm Pt nanoparticles were supported on Nb2O5 or Ta 2O5, the selectivity toward branched C6 isomers was further increased, reaching ca. 97% with a minimum content of benzene, due to the combined effects of the Pt size and the strong metal-support interaction.
- An, Kwangjin,Alayoglu, Selim,Musselwhite, Nathan,Na, Kyungsu,Somorjai, Gabor A.
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supporting information
p. 6830 - 6833
(2014/06/09)
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- Tailoring acid-metal functions in molybdenum oxides: Catalytic and XPS-UPS, ISS characterization study
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Formation of acid, metal and metal-acid (bifunctional) functions in titania-supported molybdena following controlled partial reduction of MoO 3 using hydrogen at different temperatures are monitored by a combination of surface XPS-UPS, ISS techniques. Addition of controlled amount of sodium or potassium alkali metals to the bifunctional MoO2-x(OH) y/TiO2 (MoTi) enabled to neutralize the Br?nsted acid Mo-OH functions. Sodium or potassium molybdenum bronze metallic function is formed following the addition of the alkali metal to the Mo salt following its calcination at 773 K. The catalytic functions of these MoTi and Na, KMoTi systems were evaluated for the dehydration/hydrogenation, oxidation reactions of isopropanol to acetone as well as the ring shortening of cyclohexane to methylcyclopentane MCP and its oxidative dehydrogenation to benzene.
- Al-Kandari,Al-Kandari,Mohamed,Al-Kharafi,Katrib
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p. 497 - 502
(2014/03/21)
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- Stabilized Ni-based catalysts for bio-oil hydrotreatment: Reactivity studies using guaiacol
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The development of catalysts possessing high activity and high stability in the catalytic hydrotreatment of pyrolysis oils (bio-oil) is of great interest. NiCu bimetallic catalytic systems are very attractive for use in hydrotreatment process due to their low price and high activity in hydrogenation, hydrodeoxygenation and hydrocracking reactions. In the present work P-/Mo-containing agents were used to modify bimetallic catalytic system NiCu/SiO2-ZrO2 to improve its mechanical strength and stability in acidic medium. The modified catalysts were tested in hydrodeoxygenation (HDO) of guaiacol - a well-known model compound of bio-oil. HDO process has been carried out in an autoclave at 320 C, 17 MPa initial hydrogen pressure, reaction time 1 h. It was shown that phosphorus and molybdenum addition to the catalysts composition results in the decrease of guaiacol conversion and deoxygenation degree. The yield of undesirable gaseous reaction products (mainly methane) and coking of the catalyst were lower for the modified catalysts in contrast to the initial NiCu/SiO2-ZrO 2 system. The catalysts treatment in glacial acetic acid at 118 C showed that modification by P and Mo gives a significant improvement of catalysts stability in acidic medium (mass loss decreases from 53 wt.% to 1 wt.%). Also a significant improvement of bulk crushing strength has been observed for PMo-modified samples (from 0.5 MPa to 1.2 MPa).
- Bykova,Ermakov,Khromova,Smirnov,Lebedev,Yakovlev
-
-
- Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts
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The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring resulting in cyclohexanone, which is subsequently converted to cyclohexanol and cyclohexane. Although aromatic ring hydrogenation has a higher rate for Pt and Pd-based catalysts, the rate of hydrogenation of the polar C=O moiety in cyclohexanone is faster for Ru/C. The complete HDO of phenol to cyclohexane on noble-metal catalysts can only be achieved in the presence of a Br?nsted acid co-catalyst. In guaiacol conversion, efficient demethoxylation and ring hydrogenation can be achieved within 0.5 h on Pt/C. Under acidic conditions, selectivity of nearly 90% to cyclohexane at a conversion of 75% was achieved in 4 h. To get an insight into the possibility to cleave covalent linkages between aromatic units in lignin under HDO conditions, the reactivity of dimeric model substances such as diphenyl ether, benzyl phenyl ether, diphenyl methane and biphenyl was investigated. Although dimeric oxygen-bridged model compounds such as benzylphenyl ether and diphenyl ether can be readily converted to monomeric species in the presence of noble metal catalysts, cleavage of C-C bonds in diphenyl methane and biphenyl was not observed. Plausible reaction mechanisms are proposed.
- Güvenatam, Burcu,Kur?un, Osman,Heeres, Erik H.J.,Pidko, Evgeny A.,Hensen, Emiel J.M.
-
-
- Selective ethylene oligomerization with chromium complexes bearing pyridine-phosphine ligands: Influence of ligand structure on catalytic behavior
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Chromium complexes bearing a series of pyridine-phosphine ligands have been synthesized and examined for their catalytic behavior in ethylene oligomerization. The choice of solvent, toluene versus methylcyclohexane, shows a pronounced influence on the catalytic activity for all these complexes. Variations of the ligand system have been introduced by modifying the phosphine substituents affecting ligand bite angles and flexibility. It has been demonstrated that minor differences in the ligand structure can result in remarkable changes not only in catalytic activity but also in selectivity toward α-olefins versus polyethylene and distribution of oligomeric products. Ligand PyCH2N(Me)PiPr2, in combination with CrCl3(THF)3 afforded selective ethylene tri- and tetramerization, giving 1-hexene and 1-octene with good overall selectivity and high purity, albeit with the presence of small amounts of PE.
- Yang, Yun,Gurnham, Joanna,Liu, Boping,Duchateau, Robbert,Gambarotta, Sandro,Korobkov, Ilia
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p. 5749 - 5757
(2015/02/19)
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- PROCESS FOR THE CONVERSION OF LIGNIN TO LIQUID HYDROCARBONS
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Process for the conversion of lignin to liquid hydro-carbons comprising: subjecting the lignin to hydrogenolysis in the presence of at least one hydrogenolysis catalyst, at a temperature ranging from 250° C. to 350° C., preferably ranging from 290° C. to 320 ° C., so as to obtain depolymerized lignin; subjecting said depolymerized lignin to hydrotreating so as to obtain a mixture of liquid hydrocarbons. Said liquid hydrocarbons can be used as such (biofuels) for the production of reformulated gasolines, or they can be used for the production of gasolines or of gas oils through conventional refining processes.
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-
Paragraph 0153-0176
(2013/03/26)
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- Catalytic conversion of cellulose into hydrocarbon fuel components
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The results of catalytic processing of cellulose to hydrocarbon fuel component are presented. Nanoscale Mo,Fe(III) catalytic systems have been formed from organic solutions of mono and bimetallic complex compounds on the surface of the substrate. Tetralin, an analogue of naphthenoaromatic compounds of crude oil and its refining products, has been used as a hydrogen donor. The effect of the precursor nature and catalyst activation method on the parameter of the process has been investigated. It has been shown that the cellulose conversion reaches 97-98% under optimal conditions, yielding up to 90% of liquid hydrocar- bons with the exhaustive deoxygenation. It has been found that the most efficient method of preliminary activation of both active components and cellulose is ultrasonic treatment leading to an increase of the rate of cellulose conversion into hydrocarbons. Pleiades Publishing, Ltd., 2013.
- Tsodikov,Chudakova,Chistyakov,Maksimov
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p. 367 - 373
(2014/02/14)
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- High-performance ring-opening catalysts based on iridium-containing zeolite Beta in the hydroconversion of decalin
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Decalin was converted in a flow-type reactor under a hydrogen pressure of 5.2 MPa on Ir/H,A-Beta zeolite catalysts, where A stands for an alkali metal cation. In one series of catalysts, the Ir content was 3 wt.%, and the nature of A was varied from lithi
- Santi, Dominic,Holl, Tobias,Calemma, Vincenzo,Weitkamp, Jens
-
-
- Isomerization of n-Hexane Catalyzed by Supported Monodisperse PtRh Bimetallic Nanoparticles
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Composition and size of Pt x Rh1-x bimetallic nanoparticles were varied in order to study the effects in the catalytic reforming of n-hexane. Hexane isomerization, an analogue to the important industrial process of hydrocarbon reforming is a reaction in which we aim to investigate the molecular level details of catalysis. It is known, that in hydrocarbon isomerization, Pt atoms act to isomerize the reactants, while small amounts of promoter metal atoms (such as Rh, Ir, Re and Sn) provide C-C and C-H bond breaking activity. Herein, we report on the effect of composition and size in model bimetallic Pt x Rh1-x nanoparticle catalysts utilized in n-hexane reforming. Both nanoparticle composition and size were shown to influence catalytic turnover frequency and product selectivity. It was found, through ambient pressure X-ray photoelectron spectroscopy, that the surface of these nanoparticles is both dynamic, and Rh rich under relevant reaction conditions. The findings suggest that an ensemble effect exists, in which the highest isomer production occurs when Rh atoms are surrounded by Pt atoms on the metal surface. Graphical Abstract: [Figure not available: see fulltext.]
- Musselwhite, Nathan,Alayoglu, Selim,Melaet, Gerome,Pushkarev, Vladimir V.,Lindeman, Avery E.,An, Kwangjin,Somorjai, Gabor A.
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p. 907 - 911
(2013/10/08)
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- Effect of hydrohalogenation of PtRe/H-ZSM-5 for cyclohexene conversion
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Extended use of supported Pt catalysts causes thermal migration of Pt particles to form large agglomerates, thus decreasing the catalytic activity. The combination of Pt with Re protects Pt against migration. In addition, Cl- injection into the reactor assists Pt particles redispersion to prolong catalyst life. In this work, a PtRe/H-ZSM-5 catalyst was treated with either HCl or HF to investigate their role in activating or deactivating the catalyst. The conversion exceeded 90% in the whole temperature range with the PtRe/H-ZSM-5(HCl) catalyst, and its activity for the direct isomerization of cyclohexene to methylcyclopentenes (MCPEs) was the lowest but the activity for the hydrogenation of the MCPEs to methylcyclopentane was the highest. The reactivities of MCPEs and cyclohexadienes on the catalysts were similar because both are dehydrogenation reactions. Benzene production was significantly higher on the hydrochlorinated catalyst than on the other catalysts, and its hydrocracking activity was the lowest, which is a good characteristic for processing catalysts where cracking is undesired.
- Aboul-Fotouh, Sameh M.K.,Aboul-Gheit
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experimental part
p. 697 - 705
(2012/07/31)
-
- Tetraflic acid (1,1,2,2-Tetrafluoroethanesulfonic acid, HC 2F4SO3H) and gallium tetraflate as effective catalysts in organic synthesis
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Tetraflic acid offers ample acidity for various organic reactions that require high acidity. Its gallium(III) salt is an efficient catalyst under mild condtions for synthetic transformations such as the ketonic Strecker reaction for the synthesis of fluorinated α-amino nitriles and condensation- cyclzation reactions using suitable fluoro ketones and 1,2-disubstituted benzenes for the direct preparation of 5-membered or 6-membered fluorinated heterocycles. Copyright
- Prakash, G. K. Surya,Mathew, Thomas,Panja, Chiradeep,Kulkarni, Aditya,Olah, George A.,Harmer, Mark A.
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p. 2163 - 2171
(2012/11/07)
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- The catalytic properties of tungstated zirconia in n-heptane isomerization
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The catalytic properties of zirconia modified with different amounts of tungstate anions in the hydroisomerization of n-heptane and its mixtures with benzene or toluene have been studied. It has been found that at a low temperature of 170°C, the yield of isoheptanes reaches 62.8% with a fairly high selectivity of 87.6% on the Pt/WO24-/ZrO2 catalyst prepared by impregnation to contain 17.6 mol % tungstate anions. Under the same conditions, the yield of isoheptanes on a sulfated Pt/SO 24-/ZrO2 catalyst is as low as 14.0% with a selectivity of 20.3%. The hydroisomerization process effectively occurs on the tungstated catalyst in the presence of benzene or toluene. Pleiades Publishing, Ltd., 2012.
- Kuznetsova,Kazbanova,Kuznetsov
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experimental part
p. 86 - 90
(2012/09/08)
-
- Heterogenization of some PNP ligands for the oligomerization of ethylene
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Bis(diphenylphosphino)amine ligands were supported on Merrifield's resin and tested in catalytic ethylene oligomerization reactions with a chromium source. The supported ligands were characterized via IR, solid-state NMR, SEM and TGA-DSC. In order to compare activity of the supported and unsupported ligands, homogeneous bis(diphenylphosphino)amine ligands were synthesized and characterized via NMR, elemental analysis, IR and GC-MS. Oligomerization reactions were carried outina Parr pressure reactor using Cr(acac)3 as the precursor and MMAO-3A as the activator. The system with the homogeneous ligands proved active in the tetramerization of ethylene, with the selectivity of 1-octene in the C8 fraction being comparable with that mentioned in literature (>98 wt%). When comparing the homogeneous ligands with their heterogeneous counterparts, the latter showed a four-fold drop in activity compared to their homogeneous counterparts. The selectivity towards the main product, 1-octene, was less than 10 wt%. These supported ligands created a system that favoured the formation of C6 products more than any other product, with C6 cyclics (methylcyclopentane and methylenecyclopentane) being the most dominant, probably due to steric effects caused by the polymer chain.
- Shozi, Mzamo L.,Friedrich, Holger B.
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p. 214 - 222
(2013/01/15)
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- Sorbitol transformation in aqueous medium: Influence of metal/acid balance on reaction selectivity
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The effect of the metal/acid balance of Pt/SiO2-Al 2O3 catalysts on the catalytic transformation of sorbitol in aqueous medium was investigated, using four mechanical mixtures of Pt/SiO2-Al2O3 and SiO2-Al 2O3 (100:0; 50:50; 25:75; 0:100). The results show that the metal/acid balance has a strong impact on catalytic performances, tuning the yields in alkanes, alcohols, ketones and heterocycles. An optimum in the metal/acid balance is obtained with the 50:50 mechanical mixture: when the metallic function is introduced in higher quantity, the C-C cleavage pathway is favoured and leads to an important CO2 yield; on the contrary, a too low proportion of platinum atoms induces a lack of metallic sites for the hydrogenation reaction. Nevertheless many hydrocarbons containing 1-4 carbon atoms are still obtained with the best balanced catalyst, evidencing some C-C cleavage activity. Hydrocarbon selectivity could be improved by new more hydrogenating metallic phases and new supports with a stronger acidity in water.
- Vilcocq,Cabiac,Especel,Lacombe,Duprez
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experimental part
p. 117 - 122
(2012/09/08)
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- Synthesis, reactivity, and catalytic application of a nickel pincer hydride complex
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The nickel(II) hydride complex [(MeN2N)Ni-H] (2) was synthesized by the reaction of [(MeN2N)Ni-OMe] (6) with Ph2SiH2 and was characterized by NMR and IR spectroscopy as well as X-ray crystallography. 2 was unstable in solution, and it decomposed via two reaction pathways. The first pathway was intramolecular N-H reductive elimination to give MeN2NH and nickel particles. The second pathway was intermolecular, with H2, nickel particles, and a five-coordinate Ni(II) complex [(MeN2N)2Ni] (8) as the products. 2 reacted with acetone and ethylene, forming [( MeN2N)Ni-OiPr] (9) and [(MeN 2N)Ni-Et] (10), respectively. 2 also reacted with alkyl halides, yielding nickel halide complexes and alkanes. The reduction of alkyl halides was rendered catalytically, using [(MeN2N)Ni-Cl] (1) as catalyst, NaOiPr or NaOMe as base, and Ph2SiH2 or Me(EtO)2SiH as the hydride source. The catalysis appears to operate via a radical mechanism.
- Breitenfeld, Jan,Scopelliti, Rosario,Hu, Xile
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experimental part
p. 2128 - 2136
(2012/06/01)
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- Cross coupling reactions of multiple CCl bonds of polychlorinated solvents with Grignard reagent using a pincer nickel complex
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The nickel(II) complex of a bulky pincer-type ligand, N,N′-bis(2,6- diisopropylphenyl)-2,6-pyridinedicarboxamido, was examined for sp 3-sp3 coupling of Grignard reagents with polychlorinated solvents. The nickel(II) complex catalyzed CC coupling of polychlorinated alkyl halides, such as dichloromethane (CH2Cl2), chloroform (CHCl3), and carbon tetrachloride (CCl4), with various Grignard reagents. The effective activation of multiple CCl bonds proceeded under ambient reaction conditions and within a short time (20 min). This catalyst displays the highest activity yet reported for this reaction type, with catalyst loading as low as 0.4 mol% and turnover frequency (TOF) as high as 724 h-1. The catalyst is capable of replacing all chlorine atoms with CC bond formations for all of the polychlorinated solvents under investigation. The catalytic process could prove to be an efficient method of remediation of toxic polychlorinated solvents while generating synthetically and commercially important chemicals.
- Gartia, Yashraj,Nasini, Udaya Bhasker,Ghosh, Anindya,Biswas, Abhijit,Stadler, Matthew
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p. 322 - 327,6
(2020/07/30)
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- A novel iron complex for cross-coupling reactions of multiple C-Cl bonds in polychlorinated solvents with grignard reagents
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A novel iron(III) complex (2) of a pincer ligand [1, N2,N6-bis(2,6- diisopropylphenyl)pyridine-2,6-dicarboxamide] was developed and used for remediation of polychlorinated solvents via sp3-sp3 coupling of Grignard reagents with C-Cl bonds. The use of an iron catalyst for such coupling reactions is highly desirable due to its greener and more economical nature. Complex 2 was characterized using various spectroscopic techniques: electrospray ionization mass spectrometer (ESI-MS, m/z 575.1), cyclic voltammetry (E 1/2, 0.03 V and ΔE, 0.97 V), and ultraviolet visible (UV/Vis) spectroscopic techniques. The iron(III) complex showed efficient activation of multiple C-Cl bonds and catalyzing C-C coupling of polychlorinated alkyl halides, such as dichloromethane (CH2Cl2), chloroform (CHCl3), and carbon tetrachloride (CCl4), with various Grignard reagents under ambient reaction conditions. Complex 2 showed exceptional activity with reactions approaching near completion in about 5 min. With the required catalyst loading as low as 0.2 mol%, considerably high turnover numbers (TON = 483) and turnover frequency (TOF = 5,800 h-1) were obtained. None of the products detected during the reaction contained any chlorine, indicating an efficient dechlorination method while synthesizing products of synthetic and commercial interest. Interestingly, the catalyst was capable of replacing all chlorine atoms in each polychlorinated solvent under the investigations with high conversion. Springer Science+Business Media, LLC 2012.
- Gartia, Yashraj,Pulla, Sharon,Ramidi, Punnamchandar,Farris, Carolina Costa,Nima, Zeid,Jones, Darin E.,Biris, Alexandru S.,Ghosh, Anindya
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p. 1397 - 1404
(2013/01/15)
-
- Zeolite supported platinum catalysts for benzene hydrogenation and naphthene isomerization
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Benzene hydrogenation over zeolite supported platinum catalysts; particularly the effect of catalyst preparation procedures was studied. It was found that Pt/zeolite prepared with wet solution ion exchange procedure using cationic platinum precursors showed the best catalytic performances. The potential of Pt/beta in catalyzing benzene hydrogenation-naphthene isomerization cascaded reaction was demonstrated, showing the highest methyl-cyclopentane to cyclohexane product ratio comparable to the thermodynamic equilibrium value, the lowest cracking gas yield and a maximum octane barrel number.
- Tsai, Kun-Yeh,Wang, Ikai,Tsai, Tseng-Chang
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experimental part
p. 73 - 78
(2012/02/03)
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- PHOSPHINYL AMIDINE COMPOUNDS, METAL COMPLEXES, CATALYST SYSTEMS, AND THEIR USE TO OLIGOMERIZE OR POLYMERIZE OLEFINS
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N2-phosphinyl amidine compounds, N2-phosphinyl amidinates, N2-phosphinyl amidine metal salt complexes, N2-phosphinyl amidinate metal salt complexes are described. Methods for making N2-phosphinyl amidine compounds, N2-phosphinyl amidinates, N2-phosphinyl amidine metal salt complexes, and N2-phosphinyl amidinate metal salt complexes are also disclosed. Catalyst systems utilizing the N2-phosphinyl amidine metal salt complexes and N2-phosphinyl amidinate metal salt complexes are also disclosed along with the use of the N2-phosphinyl amidine compounds, N2-phosphinyl amidinates, N2-phosphinyl amidine metal salt complexes, and N2-phosphinyl amidinate metal salt complexes for the oligomerization and/or polymerization of olefins.
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Page/Page column 356-359; 369
(2011/07/30)
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