Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

Science.gov (United States)

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Activation and deactivation of neutral palladium(II) phosphinesulfonato polymerization catalysts

KAUST Repository

Rü nzi, Thomas; Tritschler, Ulrich; Roesle, Philipp; Gö ttker-Schnetmann, Inigo J.; Mö ller, Heiko Maa; Caporaso, Lucia; Poater, Albert; Cavallo, Luigi; Mecking, Stefan

2012-01-01

13C-Labeled ethylene polymerization (pre)catalysts [κ2-(anisyl)2P,O]Pd(13CH3)(L) (1-13CH3-L) (L = pyridine, dmso) based on di(2-anisyl)phosphine benzenesulfonate were used to assess the degree of incorporation of 13CH3 groups into the formed

Atom-transfer radical polymerization of methyl methacrylate (MMA) using CuSCN as the catalyst

NARCIS (Netherlands)

Singha, N.K.; Klumperman, B.

2000-01-01

The effect of CuSCN as a catalyst in atom-transfer radical polymerization (ATRP) was investigated. CuSCN can successfully be used for the ATRP of MMA. Substituted bipyridines as well as imines can be used to stabilize the copper complex in solution. CuSCN induces faster polymerization compared to

Highly active self-immobilized FI-Zr catalysts in a PCP framework for ethylene polymerization.

Science.gov (United States)

Li, He; Xu, Bo; He, Jianghao; Liu, Xiaoming; Gao, Wei; Mu, Ying

2015-12-04

A series of zirconium-based porous coordination polymers (PCPs) containing FI catalysts in the frameworks have been developed and studied as catalysts for ethylene polymerization. These PCPs exhibit good catalytic activities and long life times, producing polyethylenes with high molecular weights and bimodal molecular weight distribution in the form of particles.

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement; Bukhriakov, Konstantin; Bertrand, Olivier; Vu, Khanh B.; Gohy, Jean-Francois; Hadjichristidis, Nikolaos; Rodionov, Valentin

2016-01-01

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement

2016-03-22

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

Microwave-assisted Polymerization of D, L-Lactide with Stannous Octanoate as Catalyst

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening poly- merization of D, L-lactide with stannous octanoate (SnOct2) as catalyst. Its weight-average molar mass (Mw) ranged from 39000 to 67000 and the polydispersity index from 1.3 to 1.7. The polymerization rate was much faster than that of the conventional thermal polymerization. A degradation of newly formed PLA in reaction mixture by microwave irradiation was observed.

Effect of Mn doped-titania on the activity of metallocene catalyst by in situ ethylene polymerization

KAUST Repository

Abdul Kaleel, S. H.

2012-09-01

Ethylene polymerization was carried out using highly active metallocene catalysts (Cp 2ZrCl 2 and Cp 2TiCl 2) in combination with methylalumoxane. Titanium(IV) oxide containing 1% Mn as dopant was used as nanofillers. The influence of filler concentration, reaction temperature and pressure on the catalytic activity and polymer properties was investigated. There was a fourfold increase in the activity of zirconocene catalyst by addition of doped-titania. The morphology indicates that the doped-titania nanoparticles have a nucleus effect on the polymerization and caused a homogeneous PE shell around them. The optimum condition for polymerization was found to be 30°C. © 2012 The Korean Society of Industrial and Engineering Chemistry.

Synthesis,Characterization and Application of Benzyl-substituted Cyclopentadienyl lanthanide Complexes as Catalyst Precursors for the Syndiotactic Polymerization of Methyl Methacrylate

Institute of Scientific and Technical Information of China (English)

QIAN,Yan-Long(钱延龙); BALA,Muhammad D.; XIE,Xiao-Min(谢小敏); HUANG,Ji-Ling(黄吉玲)

2004-01-01

Benzyl-substituted cyclopentadienyl lanthanide complexes were synthesized and characterized by elemental analysis, MS and IR spectroscopy. The analytical data point out the formation of monomeric, unsolvated complexes.In conjunction with Al(Et)3 as co-catalyst, the title complexes are efficient catalysts for the syndiotactic polymerization of methyl methacrylate. For the complex (C6H5CH2C5H4)2YCI, under the optimum polymerization conditions (60 ℃, n(MMA):n(catalyst):n(co-catalyst)= 1000:1:10), a predominantly syndiotactic (rr=66%) polymer of high molecular weight (Mη = 105000) was obtained.

Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane Copper Complex Grafted Solid Catalyst for Oxidative Polymerization of 2,6-Dimethylphenol

Directory of Open Access Journals (Sweden)

Kei Saito

2016-01-01

Full Text Available A new solid phase catalyst, poly(N-4-vinylbenzyl-1,4,7-triazacyclononane copper(I complex, grafted onto polystyrene particles, has been employed for the oxidative polymerization of 2,6-dimethylphenol using an aqueous biphasic (water/toluene solvent system. The solid catalyst was synthesized by first grafting N-(4-vinylbenzyl-1,4,7-triaza-cyclononane onto polystyrene particles using a radical mediated polymerization method and next by creating the polymer-metal complex of copper-triazacyclononane with these modified particles. Poly(2,6-dimethyl-1,4-phenylene oxide was successfully obtained from the polymerization of 2,6-dimethylphenol using this new metal-organic solid phase catalyst.

Polyolefin polymerization catalyst and method of production use

Energy Technology Data Exchange (ETDEWEB)

Mitchell, K.E.; Hawley, G.R.; Godbehere, D.W.

1991-01-29

This patent describes a process for the preparation of a catalyst suitable for the polymerization of an {alpha}-olefin. It comprises: forming a first component by reacting reactants comprising a magnesium dihalide, a phenol, an alkylbenzoate, and a titanium tetrahydrocarbyloxide; reacting the first component with an organoaluminum halide comprising ethylaluminum sesquichloride to produce a solid product; and then contacting the resulting solid product with an activating liquid comprising titanium tetrachloride and trichlorosilane in a confined zone under pressure of at least about 70 psi.

The effect of temperature on nascent morphology of polyethylene polymerized over solution-phase flat model catalysts

NARCIS (Netherlands)

Jiang, S.D.; Kong, B.L.; Han, W.; Thune, P.C.; Yang, X.Z.; Loos, J.; Yan, S.K.

2009-01-01

The structure and morphology of polyethylene (PE) produced during solution polymerization using bis(imino)pyridyl metal catalysts supported by flat SiO2/Si(100) wafers were investigated by atomic force microscopy (AFM) and electron diffraction. Depending on the polymerization temperature, ranging

Proton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters

KAUST Repository

Hong, Miao

2016-01-18

This contribution presents a full account of experimental and theoretical/computational investigations into the N-heterocyclic carbene (NHC)-catalyzed proton-transfer polymerization (HTP) that converts common dimethacrylates (DMAs) containing no protic groups into unsaturated polyesters. This new HTP proceeds through the step-growth propagation cycles via enamine intermediates, consisting of the proposed conjugate addition–proton transfer–NHC release fundamental steps. This study examines the monomer and catalyst scopes as well as the fundamental steps involved in the overall HTP mechanism. DMAs having six different types of linkages connecting the two methacrylates have been polymerized into the corresponding unsaturated polyesters. The most intriguing unsaturated polyester of the series is that based on the biomass-derived furfuryl dimethacrylate, which showed a unique self-curing ability Four MeO– and Cl–substituted TPT (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) derivatives as methanol insertion products, RxTPT(MeO/H) (R = MeO, Cl; x = 2, 3), and two free carbenes (catalysts), OMe2TPT and OMe3TPT, have been synthesized, while OMe2TPT(MeO/H) and OMe2TPT have also been structurally characterized. The structure/reactivity relationship study revealed that OMe2TPT, being both a strong nucleophile and a good leaving group, exhibits the highest HTP activity and also produced the polyester with the highest Mn, while the Cl–substituted TPT derivatives are least active and efficient. Computational studies have provided mechanistic insights into the tail-to-tail dimerization coupling step as a suitable model for the propagation cycle of the HTP. The extensive energy profile was mapped out and the experimentally observed unicity of the TPT-based catalysts was satisfactorily explained with the thermodynamic formation of key spirocyclic species.

A "catalyst switch" Strategy for the sequential metal-free polymerization of epoxides and cyclic Esters/Carbonate

KAUST Repository

Zhao, Junpeng

2014-06-24

A "catalyst switch" strategy was used to synthesize well-defined polyether-polyester/polycarbonate block copolymers. Epoxides (ethylene oxide and/or 1,2-butylene oxide) were first polymerized from a monoalcohol in the presence of a strong phosphazene base promoter (t-BuP4). Then an excess of diphenyl phosphate (DPP) was introduced, followed by the addition and polymerization of a cyclic ester (ε-caprolactone or δ-valerolactone) or a cyclic carbonate (trimethylene carbonate), where DPP acted as both the neutralizer of phosphazenium alkoxide (polyether chain end) and the activator of cyclic ester/carbonate. This work has provided a one-pot sequential polymerization method for the metal-free synthesis of block copolymers from monomers which are suited for different types of organic catalysts. © 2014 American Chemical Society.

A "catalyst switch" Strategy for the sequential metal-free polymerization of epoxides and cyclic Esters/Carbonate

KAUST Repository

Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

2014-01-01

A "catalyst switch" strategy was used to synthesize well-defined polyether-polyester/polycarbonate block copolymers. Epoxides (ethylene oxide and/or 1,2-butylene oxide) were first polymerized from a monoalcohol in the presence of a strong phosphazene base promoter (t-BuP4). Then an excess of diphenyl phosphate (DPP) was introduced, followed by the addition and polymerization of a cyclic ester (ε-caprolactone or δ-valerolactone) or a cyclic carbonate (trimethylene carbonate), where DPP acted as both the neutralizer of phosphazenium alkoxide (polyether chain end) and the activator of cyclic ester/carbonate. This work has provided a one-pot sequential polymerization method for the metal-free synthesis of block copolymers from monomers which are suited for different types of organic catalysts. © 2014 American Chemical Society.

Olefin polymerization from single site catalysts confined within porous media

Science.gov (United States)

Kasi, Rajeswari M.

Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

Directory of Open Access Journals (Sweden)

Hatice Mutlu

2010-12-01

Full Text Available We report on the catalytic activity of commercially available Ru-indenylidene and “boomerang” complexes C1, C2 and C3 in acyclic diene metathesis (ADMET polymerization of a fully renewable α,ω-diene. A high activity of these catalysts was observed for the synthesis of the desired renewable polyesters with molecular weights of up to 17000 Da, which is considerably higher than molecular weights obtained using the same monomer with previously studied catalysts. Moreover, olefin isomerization side reactions that occur during the ADMET polymerizations were studied in detail. The isomerization reactions were investigated by degradation of the prepared polyesters via transesterification with methanol, yielding diesters. These diesters, representing the repeat units of the polyesters, were then quantified by GC-MS.

Exploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalysts

KAUST Repository

Neuwald, Boris

2013-11-21

Thirteen different symmetric and asymmetric phosphinesulfonato palladium complexes ([{(X1-Cl)-μ-M}n], M=Na, Li, 1= X(P^O)PdMe) were prepared (see Figure 1). The solid-state structures of the corresponding pyridine or lutidine complexes were determined for (MeO)21-py, (iPrO)21-lut, (MeO,Me2)1-lut, (MeO)31-lut, CF31-lut, and Ph1-lut. The reactivities of the catalysts X1, obtained after chloride abstraction with AgBF4, toward methyl acrylate (MA) were quantified through determination of the rate constants for the first and the consecutive MA insertion and the analysis of β-H and other decomposition products through NMR spectroscopy. Differences in the homo- and copolymerization of ethylene and MA regarding catalyst activity and stability over time, polymer molecular weight, and polar co-monomer incorporation were investigated. DFT calculations were performed on the main insertion steps for both monomers to rationalize the effect of the ligand substitution patterns on the polymerization behaviors of the complexes. Full analysis of the data revealed that: 1) electron-deficient catalysts polymerize with higher activity, but fast deactivation is also observed; 2) the double ortho-substituted catalysts (MeO)21 and (MeO)31 allow very high degrees of MA incorporation at low MA concentrations in the copolymerization; and 3) steric shielding leads to a pronounced increase in polymer molecular weight in the copolymerization. The catalyst properties induced by a given P-aryl (alkyl) moiety were combined effectively in catalysts with two different non-chelating aryl moieties, such as cHexO/(MeO)21, which led to copolymers with significantly increased molecular weights compared to the prototypical MeO1. Catalyst control: The influence of steric and electronic effects on the reactivity of phosphinesulfonato PdII catalysts in polymerization and copolymerization is explored through experimental and DFT methods. A comparison of thirteen different X(P O)PdMe catalysts ((P O)= κ2-P

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

Science.gov (United States)

Schäfer, Pascal M; Fuchs, Martin; Ohligschläger, Andreas; Rittinghaus, Ruth; McKeown, Paul; Akin, Enver; Schmidt, Maximilian; Hoffmann, Alexander; Liauw, Marcel A; Jones, Matthew D; Herres-Pawlis, Sonja

2017-09-22

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl 2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (M w =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k p . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isospecific propylene polymerization with in situ generated bis(phenoxy-amine)zirconium and hafnium single site catalysts.

Science.gov (United States)

Makio, Haruyuki; Prasad, Aitha Vishwa; Terao, Hiroshi; Saito, Junji; Fujita, Terunori

2013-07-07

Bis(phenoxy-imine) Zr and Hf complexes were activated with (i)Bu3Al or (i)Bu2AlH in conjunction with Ph3CB(C6F5)4 and tested as catalysts for propylene polymerization with emphasis on the enantioselectivity of the isospecific species and the single site polymerization characteristics. The isoselective species was identified as the in situ generated bis(phenoxy-amine) complex whose isoselectivity was sensitive to subtle changes in ligand structure. By employing specific substituents at certain key positions the isotacticity reached an extremely high level comparable to high-end commercial isotactic polypropylenes (Tm > 160 °C). Single site polymerization characteristics depended upon the efficiency and selectivity of the in situ imine reduction which is sensitive to the substituent on the imine nitrogen and the reaction conditions. By using (i)Bu2AlH as a reducing agent, quantitative imine reduction can be achieved with a stoichiometric amount of the reducing agent. This lower alkylaluminum loading is beneficial for the catalyst and significantly enhances the polymerization activity and the molecular weight of the resultant polymer.

Activation and deactivation of neutral palladium(II) phosphinesulfonato polymerization catalysts

KAUST Repository

Rünzi, Thomas

2012-12-10

13C-Labeled ethylene polymerization (pre)catalysts [κ2-(anisyl)2P,O]Pd(13CH3)(L) (1-13CH3-L) (L = pyridine, dmso) based on di(2-anisyl)phosphine benzenesulfonate were used to assess the degree of incorporation of 13CH3 groups into the formed polyethylenes. Polymerizations of variable reaction time reveal that ca. 60-85% of the 13C-label is found in the polymer after already 1 min polymerization time, which provides evidence that the pre-equilibration between the catalyst precursor 1-13CH3-L and the active species 1-13CH3-(ethylene) is fast with respect to chain growth. The fraction of 1-13CH3-L that initiates chain growth is likely higher than the 60-85% determined from the 13C-labeled polymer chain ends since (a) chain walking results in in-chain incorporation of the 13C-label, (b) irreversible catalyst deactivation by formation of saturated (and partially volatile) alkanes diminishes the amount of 13CH3 groups incorporated into the polymer, and (c) palladium-bound 13CH3 groups, and more general palladium-bound alkyl(polymeryl) chains, partially transfer to phosphorus by reductive elimination. NMR and ESI-MS analyses of thermolysis reactions of 1-13CH3-L provide evidence that a mixture of phosphonium salts (13CH3)xP+(aryl)4-x (2-7) is formed in the absence of ethylene. In addition, isolation and characterization of the mixed bis(chelate) palladium complex [κ2-(anisyl)2P,O]Pd[κ2-(anisyl) (13CH3)P,O] (11) by NMR and X-ray diffraction analyses from these mixtures indicate that oxidative addition of phosphonium salts to palladium(0) species is also operative. The scrambling of palladium-bound carbyls and phosphorus-bound aryls is also relevant under NMR, as well as preparative reactor polymerization conditions exemplified by the X-ray diffraction analysis of [κ2-(anisyl)2P,O] Pd[κ2-(anisyl)(CH2CH3)P,O] (12) and [κ2-(anisyl)2P,O]Pd[κ2-(anisyl) ((CH2)3CH3)P,O] (13) isolated from pressure reactor polymerization experiments. In addition, ESI-MS analyses of reactor

Mechanocatalytic polymerization and cross-linking in a polymeric matrix

NARCIS (Netherlands)

Jakobs, R.T.M.; Ma, Shuang; Sijbesma, R.P.

2013-01-01

A latent olefin metathesis catalyst, bearing two polymeric NHC ligands, was embedded in a semicrystalline polymer matrix containing cyclic olefins. The catalyst was activated by straining the solid material under compression, resulting in polymerization and cross-linking reactions of the monomers in

Ruthenium phosphine complexes as catalysts for alternating co-polymerization of ethylene and CO

International Nuclear Information System (INIS)

Gusev, O.V.; Kal'sin, A.M.; Peganov, T.A.; Petrovskij, P.V.; Belov, G.P.; Novikova, E.V.

2000-01-01

Ruthenium (2) complexes, [Ru(dppe) 2 (OTs) 2 ] and [Ru(PhP(CH 2 CH 2 CH 2 PPh 2 ) 2 )(OTs) 2 ], where dppe (diphenylphosphino)ethane; OTs = tosylate, were synthesized with the yield of 67 and 76%, respectively, and characterized by 31 P NMR. The properties of the above complexes as catalysts of alternating co-polymerization of ethylene and carbon monoxide were studied. A considerable increase in catalytic activity of the complexes was established in the presence of trifluoroacetic acid and 1,4-benzoquinone. These compounds are the first example of ruthenium complexes that catalyse co-polymerization of ethylene and CO [ru

Synthesis of New Silicon-linked Lanthanocene Complexes and Their High Catalytic Activity for Methyl Methacrylate Polymerization with Nanometric Sodium Hydride as Co-catalyst

Institute of Scientific and Technical Information of China (English)

谢小敏; 黄吉玲

2005-01-01

The synthesis and characterization of four new silicon-linked lanthanocene complexes with pendant phenyl groups on cyclopentadiene were reported. Based on the data of elemental analyses, MS and IR, the complexes were presumed to be unsolvated and dimeric complexes [Me2Si(C5H3CMe2C6H5)2LnC1]2 [Ln=Er (1), Gd (2), Sm (3), Dy (4)]. In conjunction with AlEt3 or sodium hydride as the co-catalyst, these complexes could efficiently catalyze the polymerization of methyl methacrylate (MMA). When the nanometric sodium hydride was used as a co-catalyst, the complexes were highly effective for the polymerization of MMA. At low temperature and in short time, in [MeESi(C5H3CMe2C6H5)2LnC1]2/NaH (nanometric) system, the polymer was obtained in more than 80% yield and the molecular weight was greater than 105. The activity reached that of organolanthanide hydride as a single-component catalyst. In ]MeESi(C5H3CMe2C6H5)2ErC1]2/Nail (nanometric) system, the effects of the molar ratio of MMA/catalyst and catalyst/co-catalyst, and the temperature on polymerization were studied.

Application of zeolite-based catalyst to hydrocracking of coal-derived liquids

Energy Technology Data Exchange (ETDEWEB)

Shimada, H.; Sato, T.; Yoshimura, Y.; Hinata, A.; Yoshitomi, S.; Castillo Mares, A.; Nishijima, A. (National Chemical Laboratory for Industry, Tsukuba (Japan))

1990-06-01

Y-zeolite supported catalysts were applied to the hydrocracking of coal-derived liquids. By the introduction of two-stage upgrading consisting of hydrotreating and hydrocracking, Wandoan coal-derived middle distillate was hydrocracked over Ni-Mo/Y-zeolite, producing a high gasoline fraction yield. Zeolite supported catalysts gave little hydrocracked compounds in the hydroprocessing of coal-derived heavy oils, even after hydrotreatment. The reaction inhibitors which seriously poison the active sites of zeolites were found to be small nitrogen-containing molecules. In the hydroprocessing of coal-derived heavy oils, zeolite supported catalysts were inferior to alumina supported catalysts. This is due to the high hydrocracking but low hydrogenation activity of zeolite supported catalysts. 22 refs., 5 figs., 11 tabs.

Reversible-Deactivation Radical Polymerization of Methyl Methacrylate Induced by Photochemical Reduction of Various Copper Catalysts

Directory of Open Access Journals (Sweden)

Jaroslav Mosnáček

2014-11-01

Full Text Available Photochemically mediated reversible-deactivation radical polymerization of methyl methacrylate was successfully performed using 50–400 ppm of various copper compounds such as CuSO4·5H2O, copper acetate, copper triflate and copper acetylacetonate as catalysts. The copper catalysts were reduced in situ by irradiation at wavelengths of 366–546 nm, without using any additional reducing agent. Bromopropionitrile was used as an initiator. The effects of various solvents and the concentration and structure of ligands were investigated. Well-defined polymers were obtained when at least 100 or 200 ppm of any catalyst complexed with excess tris(2-pyridylmethylamine as a ligand was used in dimethyl sulfoxide as a solvent.

Modeling intraparticle transports during propylene polymerizations using supported metallocene and dual function metallocene as catalysts: Single particle model

Directory of Open Access Journals (Sweden)

Li Hua-Rong

2014-01-01

Full Text Available Two improved multigrain models (MGMs for preparing homopolypropylene and long chain branched polypropylene via propylene polymerization using silica-supported metallocene or dual function metallocene as catalysts are presented in this paper. The presented models are used to predict the intraparticle flow fields involved in the polymerizations. The simulation results show that the flow field distributions involve dare basically identical. The results also show that both the two polymerization processes have an initiation stage and the controlling step for them is reaction-diffusion-reaction with the polymerization proceeding. Furthermore, the simulation results show that the intra particle mass transfer resistance has significant effect on the polymerization but the heat transfer resistance can be ignored.

NOVEL SLURRY PHASE DIESEL CATALYSTS FOR COAL-DERIVED SYNGAS

Energy Technology Data Exchange (ETDEWEB)

Dr. Dragomir B. Bukur; Dr. Ketil Hanssen; Alec Klinghoffer; Dr. Lech Nowicki; Patricia O' Dowd; Dr. Hien Pham; Jian Xu

2001-01-07

This report describes research conducted to support the DOE program in novel slurry phase catalysts for converting coal-derived synthesis gas to diesel fuels. The primary objective of this research program is to develop attrition resistant catalysts that exhibit high activities for conversion of coal-derived syngas.

Effect of Mn doped-titania on the activity of metallocene catalyst by in situ ethylene polymerization

KAUST Repository

Abdul Kaleel, S. H.; Bahuleyan, Bijal Kottukkal; De, Sadhankumar; Jabarulla Khan, Masihullah; Sougrat, Rachid; Al-Harthi, Mamdouh Ahmed

2012-01-01

Ethylene polymerization was carried out using highly active metallocene catalysts (Cp 2ZrCl 2 and Cp 2TiCl 2) in combination with methylalumoxane. Titanium(IV) oxide containing 1% Mn as dopant was used as nanofillers. The influence of filler

Polymerization of aliphatic alkynes with heterogeneous Mo catalysts supported on mesoporous molecular sieves

Czech Academy of Sciences Publication Activity Database

Balcar, Hynek; Topka, Pavel; Sedláček, J.; Zedník, J.; Čejka, Jiří

2008-01-01

Roč. 46, č. 7 (2008), s. 2593-2599 ISSN 0887-624X R&D Projects: GA ČR GA203/05/2194; GA AV ČR IAA4040411; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkyne polymerization * conjugated polymers * metathesis * Mo heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.821, year: 2008

Hydrogenation of citral into its derivatives using heterogeneous catalyst

Science.gov (United States)

Sudiyarmanto, Hidayati, Luthfiana Nurul; Kristiani, Anis; Aulia, Fauzan

2017-11-01

Citral as known as a monoterpene can be found in plants and citrus fruits. The hydrogenation of citral into its derivatives become interesting area for scientist. This compound and its derivatives can be used for many application in pharmaceuticals and food areas. The development of heterogeneous catalysts become an important aspect in catalytic hydrogenation citral process. Nickel supported catalysts are well known as hydrogenation catalyst. These heterogeneous catalysts were tested their catalytic activity in hydrogenation of citral. The effect of various operation conditions, in term of feed concentration, catalyst loading, temperature, and reaction time were also studied. The liquid products produced were analyzed by using Gas Chromatography-Mass Spectroscopy (GC-MS). The result of catalytic activity tests showed nickel skeletal catalyst exhibits best catalytic activity in hydrogenation of citral. The optimum of operation condition was achieved in citral concentration 0.1 M with nickel skeletal catalyst loading of 10% (w/w) at 80 °C and 20 bar for 2 hours produced the highest conversion as of 64.20% and the dominant product resulted was citronellal as of 56.48%.

New cobalt-mediated radical polymerization (CMRP of methyl methacrylate initiated by two single-component dinuclear β-diketone cobalt (II catalysts.

Directory of Open Access Journals (Sweden)

Feng Bao

Full Text Available Two dinuclear cobalt complexes based on bis-diketonate ligands (ligand 1: 3,3'-(1,3-phenylenebis(1-phenylpropane-1,3-dione; ligand 2: 3,3'-(1,4-phenylenebis(1-phenylpropane-1,3-dione were successfully synthesized. The two neutral catalysts all showed satisfactory activities in the cobalt-mediated radical polymerization (CMRP of methyl methacrylate (MMA with the common initiator of azodiisobutyronitrile (AIBN. The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities. Mono- or dicomponent low polydispersity polymers could be obtained by using the two dinuclear catalysts under proper reaction conditions. All these improvements facilitate the implementation of the acrylate CMRP and open the door to the scale-up of the syntheses and applications of the multicomponent low polydispersity polymers.

Synthesis, Characterization and Application of A Novel Carbon Bridged Half-metallocene Chromium Catalyst for Methyl Methacrylate Polymerization

Institute of Scientific and Technical Information of China (English)

CHENG Zhengzai; GONG Kai; WANG Yang; ZHOU Xue; ZHANG Weixing; LI Yin; SUN Junquan; LI Wenbing

2014-01-01

A new carbon bridged cyclopentadienyl chromium complex of the type [(C5H4)C(CH3)2 CH2(C5H4N)]CrCl2 was prepared by treatment of CrCl3•(THF)3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis(EA), and the crystal structure was determined by X-ray diffraction analysis. Activated by Al(i-Bu)3, the chromium complex displayed a very high activity for methyl methacrylate (MMA) polymerization. After 24 hours,more than 95.5%MMA was converted to polymethyl methacrylate (PMMA) with a viscosity average molecular weight (Wη) of 416000 g•mol-1 at 60℃for MMA/Al(i-Bu)3/chromium catalyst molar ratio of up to 2000:20:1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.

Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

Science.gov (United States)

Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

2018-03-06

We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

The Evaluation of Novel Camphor-derived Ligands as Catalysts in ...

African Journals Online (AJOL)

The evaluation of a series of camphor-derived ligands as catalysts in the asymmetric Henry reaction is reported. The synthesis of two novel derivatives is detailed and these molecules are also screened as catalysts in this reaction. The single crystal X-ray structure of one of the novel compounds is reported. The reaction is ...

Catalytic oxidation of n-hexane promoted by Ce1−xCuxO2 catalysts prepared by one-step polymeric precursor method

International Nuclear Information System (INIS)

Araújo, Vinícius D.; Lima, Maurício M. de; Cantarero, Andrés; Bernardi, Maria I.B.; Bellido, Jorge D.A.; Assaf, Elisabete M.; Balzer, Rosana; Probst, Luiz F.D.; Fajardo, Humberto V.

2013-01-01

Ceria-supported copper catalysts (Ce 1−x Cu x O 2 , with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N 2 -physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce 1−x Cu x O 2 systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce 0.97 Cu 0.03 O 2 and Ce 0.99 Cu 0.01 O 2 , respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO 2 , which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance

Effects of the Linking of Cyclopentadienyl and Ketimide Ligands in Titanium Half-sandwich Olefin Polymerization Catalysts

Czech Academy of Sciences Publication Activity Database

Varga, Vojtěch; Večeřa, M.; Gyepes, R.; Pinkas, Jiří; Horáček, Michal; Merna, J.; Lamač, Martin

2017-01-01

Roč. 9, č. 16 (2017), s. 3160-3172 ISSN 1867-3880 R&D Projects: GA ČR(CZ) GA14-08531S; GA ČR(CZ) GA17-13778S Institutional support: RVO:61388955 Keywords : ketimide ligands * olefin polymerization catalysts * cyclopentadienyl Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 4.803, year: 2016

Polymer-Supported Cinchona Alkaloid-Derived Ammonium Salts as Recoverable Phase-Transfer Catalysts for the Asymmetric Synthesis of α-Amino Acids

Directory of Open Access Journals (Sweden)

Carmen Nájera

2004-04-01

Full Text Available Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethyleneglycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee’s were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed.

One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a "catalyst switch" strategy

KAUST Repository

Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

2014-01-01

A "catalyst switch" strategy has been used to sequentially polymerize four different heterocyclic monomers. In the first step, epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator in the presence of a strong phosphazene base promoter (t-BuP4). Then, an excess of diphenyl phosphate (DPP) was introduced, followed by addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). DPP acted as both neutralizer of the phosphazenium alkoxide (polyether chain end) and activator of the cyclic carbonate/ester. Using this method, linear- and star-tetrablock quarterpolymers were prepared in one pot. This work is emphasizing the strength of the previously developed catalyst switch strategy for the facile metal-free synthesis of complex macromolecular architectures. © 2014 Wiley Periodicals, Inc.

One-pot synthesis of linear- and three-arm star-tetrablock quarterpolymers via sequential metal-free ring-opening polymerization using a "catalyst switch" strategy

KAUST Repository

Zhao, Junpeng

2014-08-06

A "catalyst switch" strategy has been used to sequentially polymerize four different heterocyclic monomers. In the first step, epoxides (1,2-butylene oxide and ethylene oxide) were successively polymerized from a monohydroxy or trihydroxy initiator in the presence of a strong phosphazene base promoter (t-BuP4). Then, an excess of diphenyl phosphate (DPP) was introduced, followed by addition and polymerization of a cyclic carbonate (trimethylene carbonate) and a cyclic ester (δ-valerolactone or ε-caprolactone). DPP acted as both neutralizer of the phosphazenium alkoxide (polyether chain end) and activator of the cyclic carbonate/ester. Using this method, linear- and star-tetrablock quarterpolymers were prepared in one pot. This work is emphasizing the strength of the previously developed catalyst switch strategy for the facile metal-free synthesis of complex macromolecular architectures. © 2014 Wiley Periodicals, Inc.

Solid-State Polymerization of Poly(ethylene furanoate Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase

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Nejib Kasmi

2017-11-01

Full Text Available In this work, we report the synthesis of poly(ethylene furanoate (PEF, catalyzed by three different catalysts, namely, titanium (IV isopropoxide (TIS, tetrabutyltitanate (TBT, and dibutyltin (IV oxide (DBTO, via the two-stage melt polycondensation method. Solid-state polymerization (SSP was conducted at different reaction times (1, 2, 3.5, and 5 h and temperatures 190, 200, and 205 °C, under vacuum. The resultant polymers were analyzed according to their intrinsic viscosity (IV, end groups (–COOH, and thermal properties, via differential scanning calorimetry. DSC results showed that the post polymerization process was favorable to enhance the melting point of the prepared PEF samples. As was expected, the intrinsic viscosity and the average molecular weight of PEF increased with the SSP time and temperature, whereas the number of carboxyl end-groups was decreased. A simple kinetic model was also developed and used to predict the time evolution of polymers IV, as well as the carboxyl and hydroxyl content of PEF during the SSP. From both the experimental measurements and the theoretical simulation results it was proved that the presence of the TIS catalyst resulted in higher transesterification kinetic rate constants and higher reaction rates. The activation energies were not much affected by the presence of different catalysts. Finally, using DBTO as a catalyst, the polyesters produced have higher crystallinity, and as a consequence, higher number of inactive carboxyl and hydroxyl groups.

Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

KAUST Repository

Widger, Peter C. B.; Ahmed, Syud M.; Coates, Geoffrey W.

2011-01-01

Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

Exploration of Cocatalyst Effects on a Bimetallic Cobalt Catalyst System: Enhanced Activity and Enantioselectivity in Epoxide Polymerization

KAUST Repository

Widger, Peter C. B.

2011-07-26

Organic ionic compounds were synthesized and investigated as cocatalysts with a bimetallic cobalt complex for enantioselective epoxide polymerization. The identities of both the cation and the anion were systematically varied, and the subsequent reactivity was studied. The nature of the ionic cocatalyst dramatically impacted the rate and enantioselectivity of the catalyst system. The ionic cocatalyst [P(N=P(N(CH2)4)3) 4 +][tBuCO2 -] in combination with a bimetallic cobalt complex produced a catalyst system that exhibited the greatest activity and selectivity for a variety of monosubstituted epoxides. © 2011 American Chemical Society.

Programmed photodegradation of polymeric/oligomeric materials derived from renewable bioresources.

Science.gov (United States)

Rajendran, Saravanakumar; Raghunathan, Ramya; Hevus, Ivan; Krishnan, Retheesh; Ugrinov, Angel; Sibi, Mukund P; Webster, Dean C; Sivaguru, Jayaraman

2015-01-19

Renewable polymeric materials derived from biomass with built-in phototriggers were synthesized and evaluated for degradation under irradiation of UV light. Complete decomposition of the polymeric materials was observed with recovery of the monomer that was used to resynthesize the polymers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metal-ion catalyzed polymerization in the eutectic phase in water-ice

DEFF Research Database (Denmark)

Monnard, Pierre-Alain; Szostak, Jack W.

2008-01-01

The emergence of an RNA world requires among other processes the non-enzymatic, template-directed replication of genetic polymers such as RNA or related nucleic acids, possibly catalyzed by metal ions. The absence of uridilate derivative polymerization on adenine containing templates has been...... the main issue preventing an efficient template-directed RNA polymerization. We report here the investigation of template-directed RNA polymerization in the eutectic phase in water-ice. In particular, it was found that activated Uridilate monomers in the presence of metal-ion catalysts could efficiently......-pairing opportunities. These results suggest that a template-directed RNA polymerization catalyzed by metal-ions could be carried out under eutectic phase in water-ice conditions....

Synthesis of High cis-Polybutadiene in Styrene Solution with Neodymium-Based Catalysts: Towards the Preparation of HIPS and ABS via In Situ Bulk Polymerization

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Ramón Díaz de León

2016-01-01

Full Text Available In a first step, 1,3-butadiene was selectively polymerized at 60°C in styrene as solvent using NdV3/DIBAH/EASC as the catalyst system. The catalyst system activation process, the addition order of monomers and catalyst components, and the molar ratios [Al]/[Nd] and [Cl]/[Nd] were studied. The catalyst system allowed the selective 1,3-butadiene polymerization, reaching conversions between 57.5 and 88.1% with low polystyrene contents in the order of 6.3 to 15.4%. Molecular weights ranging from 39,000 to 150,000 g/mol were obtained, while cis-1,4 content was found in the interval of 94.4 to 96.4%. On the other hand, the glass transition temperatures of synthesized materials were established in the range of −101.9 to −107.4°C, explained by the presence of polystyrene segments in the polybutadiene chains; in the same sense, the polybutadienes did not show the typical melting endotherm of high cis-polybutadienes. In a second step, the resulting styrene/high cis-1,4 polybutadiene solutions were used to synthesize ABS (adding a fraction of acrylonitrile monomer and HIPS via in situ bulk polymerizations and the results were discussed in terms of morphological development, molecular parameters, dynamical mechanical behavior, and mechanical properties.

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst.

Science.gov (United States)

Yeow, Jonathan; Xu, Jiangtao; Boyer, Cyrille

2016-06-08

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (λ = 460 nm, 0.7 mW/cm(2)), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

Polypropylene/graphite nanocomposites by in situ polymerization

International Nuclear Information System (INIS)

Milani, Marceo A.; Galland, Giselda B.; Quijada, Raul

2011-01-01

This work presents the synthesis of nanocomposites of polypropylene/graphite by in situ polymerization using metallocene catalyst and graphene nanosheets. Initially was analyzed which of the metallocene catalysts rac-Et(Ind) 2 ZrCl 2 or rac-Me 2 Si(Ind) 2 ZrCl 2 produces polypropylene with mechanical properties more relevant. Then it were performed the in situ polymerization reactions to obtain the nanocomposites. The polymeric materials were characterized by XRD, DSC, GPC and DMTA. (author)

Catalytic hydrotreatment of coal-derived naphtha using commercial catalysts

Energy Technology Data Exchange (ETDEWEB)

Liaw, S.-J.; Keogh, R.A.; Thomas, G.A.; Davis, B.H. (University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research)

Naphtha samples derived from the liquefaction of a bituminous Illinois No. 6 and a subbituminous Black Thunder coal were hydrotreated using commercial Co-Mo/Al[sub 2]O[sub 3], Ni-Mo/Al[sub 2]O[sub 3], and Ni-W/Al[sub 2]O[sub 3] catalysts. It was easier to remove the N, O and S heteroatoms from Illinois No. 6 naphtha than from the Black Thunder naphtha. Nitrogen and oxygen were more difficult to remove than sulfur in the temperature range 200-400[degree]C. Considerable differences in catalyst activity for the hydrodenitrogenation (HDN), hydrodeoxygenation (HDO), and hydrodesulfurization (HDS) reactions were observed. The Ni-Mo catalyst was found to be the most active catalyst for the HDN and HDO reactions and the least active catalyst for the HDS. The Co-Mo catalyst was the most active catalyst for the sulfur removal. For the Illinois No. 6 naphtha, a first-order reaction applies for the HDN and HDO reactions for all three catalysts. However, for the Black Thunder naphtha, the first-order reaction applies only at the lower space velocities; a large deviation is observed at higher space velocities. 11 refs., 15 figs., 4 tabs.

1-Hexene Polymerization Using Ziegler-Natta Catalytic System with Response Surface Methodology

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Maliheh Mazaheriyan

2017-07-01

Full Text Available The effects of process conditions and their interactions on the catalyst activity in 1-hexene polymerization were studied with design of experiments by response surface methodology (RSM using a commercial Ziegler-Natta (ZN catalyst in the form of TiCl4/MgCl2/Di-n-butyl phthalate. The effect of different operational variables on the catalyst activity was examined by performing the primary experiments of 1-hexene polymerization.  Among different operational variables, three variables including monomer concentration, polymerization temperature and cocatalyst/catalyst molar ratio (Al/Ti were considered as the main parameters which affected the catalyst activity in the 1-hexene polymerization. The Box-Behnken model with three main parameters in three level responses for each factor was applied to analyze the parameter relationships. After demonstrating the reproducibility of the experimental results, the statistical analysis of experimental data showed that the monomer concentration and Al/Ti molar ratio affected the catalyst activity significantly. It was found that, at room temperature, by increasing the monomer concentration from 80.0 mmol to 239.9 mmol, the activity of the studied ZN catalyst increased from 75.2 to 265.1 gpoly(1-hexene/gcat. In addition, by changing the Al/Ti ratio from 45.9 to 136.8, the catalyst activity increased from 145.2 to 265.1 gpoly(1-hexene/gcat. The maximum activity of catalyst was obtained at the polymerization temperature around 25°C, and by increasing the temperature the activity of studied catalyst decreased. Based on the RSM, the best polymerization condition was obtained at a polymerization temperature of about 35°C, Al/Ti ratio of 136.8, and monomer concentration of 239.9 mmol, which resulted in maximum productivity of the catalyst.

Modeling of molecular weight and molecular weight distribution in slurry polymerization of propylene by Ziegler-Natta catalysts

International Nuclear Information System (INIS)

Khorasani, R.; Pourmahdian, S.

2007-01-01

The Precise prediction of polypropylene synthesized by heterogeneous Ziegler-Natta catalysts needs good knowledge of parameters affecting on polymerization. molecular weight and molecular weight distribution are among important characteristics of a polymer determining physical-mechanical properties. broadening of molecular weight distribution is an important and well known characteristic of polypropylene synthesized by heterogeneous Ziegler-Natta catalysts, So it is important to understand the origin of broad molecular weight. Two main factors in broadening molecular weight, namely mass transfer resistances and multiplicity of active sites, are discussed in this paper and a model including these factors is presented. Then we calculate molecular weight and molecular weight distribution by the model and compare our results with

Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

Science.gov (United States)

Zhang, Yujing; Pang, Shaofeng; Wei, Zhihong; Jiao, Haijun; Dai, Xingchao; Wang, Hongli; Shi, Feng

2018-04-13

Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

Surface-initiated addition polymerization of norbornene by a Pd(II) catalyst bearing acetylacetone ligand on the glass slide

Science.gov (United States)

He, Xiaohui; Wang, Kaiti; Chen, Yiwang; Yuan, Bin

2012-02-01

A Pd catalyst bearing acetylacetone ligand [(CH3CO)2CHPdCl2] was covalently attracted onto the surface of glass slides, and then these Pd-terminated glass slides were immersed into a toluene solution of norbornene (NB) to produce a vinyl-type addition polynorbornene (PNB) layer on the surface of glass slides. It was found that the contract angles of the PNB-terminated glass slides surface increased with the increasing of polymerization time, and the thickness of the PNB layers were approximately 0-44.0 μm when the polymerization time was 0.5-24 h. The researching on etching also has been operated.

UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] hydrophobic catalyst beads in microfluidics

Energy Technology Data Exchange (ETDEWEB)

Wi, Jun; Li, Xiang; Song, Tong; Song, Zi Fan; Chang, Zhen Qi [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei (China); Meng, Da Qiao [Si Chuan Institute of Materials and Technology, Jiang You (China)

2015-10-15

The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] [Pt/poly(SDB-TPGDA)] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA) hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200-1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads.

UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] hydrophobic catalyst beads in microfluidics

International Nuclear Information System (INIS)

Wi, Jun; Li, Xiang; Song, Tong; Song, Zi Fan; Chang, Zhen Qi; Meng, Da Qiao

2015-01-01

The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] [Pt/poly(SDB-TPGDA)] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA) hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200-1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads

Enzymes as Green Catalysts for Precision Macromolecular Synthesis.

Science.gov (United States)

Shoda, Shin-ichiro; Uyama, Hiroshi; Kadokawa, Jun-ichi; Kimura, Shunsaku; Kobayashi, Shiro

2016-02-24

The present article comprehensively reviews the macromolecular synthesis using enzymes as catalysts. Among the six main classes of enzymes, the three classes, oxidoreductases, transferases, and hydrolases, have been employed as catalysts for the in vitro macromolecular synthesis and modification reactions. Appropriate design of reaction including monomer and enzyme catalyst produces macromolecules with precisely controlled structure, similarly as in vivo enzymatic reactions. The reaction controls the product structure with respect to substrate selectivity, chemo-selectivity, regio-selectivity, stereoselectivity, and choro-selectivity. Oxidoreductases catalyze various oxidation polymerizations of aromatic compounds as well as vinyl polymerizations. Transferases are effective catalysts for producing polysaccharide having a variety of structure and polyesters. Hydrolases catalyzing the bond-cleaving of macromolecules in vivo, catalyze the reverse reaction for bond forming in vitro to give various polysaccharides and functionalized polyesters. The enzymatic polymerizations allowed the first in vitro synthesis of natural polysaccharides having complicated structures like cellulose, amylose, xylan, chitin, hyaluronan, and chondroitin. These polymerizations are "green" with several respects; nontoxicity of enzyme, high catalyst efficiency, selective reactions under mild conditions using green solvents and renewable starting materials, and producing minimal byproducts. Thus, the enzymatic polymerization is desirable for the environment and contributes to "green polymer chemistry" for maintaining sustainable society.

System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed

Directory of Open Access Journals (Sweden)

Ahmmed Saadi Ibrehem

2011-11-01

Full Text Available In this work, system identification method is used to capture the reactor characteristics of production rate of polyethylene (PE based on published experimental data. The identification method is used to measure the percentage effect on the production rate of PE by measuring the effect of input factors of temperature of reaction, hydrogen concentration, and [Al]/[Ti] molar catalyst ratio. Temperature of reaction has big effects equal 52.4 % on the output of the system and 47.6 % on interaction of the system's parameters compare to other two factors. Also, hydrogen concentration has big effect equal 45.66 % on the output of the system and 14.7 % on interaction of the system's parameters. [Al]/[Ti] molar catalyst ratio has big effect on interaction of the system equal 28.6 and 1.94 % on the output of the system but less than the reaction temperature and hydrogen concentration. All these results depend on experiment results and these results are very important in industrial plants. ©2011 BCREC UNDIP. All rights reserved(Received: 13rd May 2011; Revised: 27th July 2011; Accepted: 22th September 2011[How to Cite: Ahmmed S. Ibrehem. (2011. System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 137-146. doi:10.9767/bcrec.6.2.874.137-146][How to Link / DOI: http://dx,doi.org/10.9767/bcrec.6.2.874.137-146 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/874 ] | View in 

Catalytic oxidation of n-hexane promoted by Ce{sub 1−x}Cu{sub x}O{sub 2} catalysts prepared by one-step polymeric precursor method

Energy Technology Data Exchange (ETDEWEB)

Araújo, Vinícius D., E-mail: dantas@ursa.ifsc.usp.br [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Lima, Maurício M. de [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Fundación General, Universitat de Valencia, Valencia (Spain); Cantarero, Andrés [Instituto de Ciencia de los Materiales, Universidad de Valencia, E-46071 Valencia (Spain); Bernardi, Maria I.B. [Instituto de Física, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Bellido, Jorge D.A. [CAP-Engenharia Química, Universidade Federal de São João Del-Rei – UFSJ, São João Del-Rei, MG (Brazil); Assaf, Elisabete M. [Instituto de Química, Universidade de São Paulo – USP, 13560-970 São Carlos, SP (Brazil); Balzer, Rosana; Probst, Luiz F.D. [Departamento de Química, Universidade Federal de Santa Catarina – UFSC, 88040-900 Florianópolis, SC (Brazil); Fajardo, Humberto V. [Departamento de Química, Universidade Federal de Ouro Preto – UFOP, 35400-000 Ouro Preto, MG (Brazil)

2013-11-01

Ceria-supported copper catalysts (Ce{sub 1−x}Cu{sub x}O{sub 2}, with x (mol) = 0, 0.01, 0.03, 0.05 and 0.10) were prepared in one step through the polymeric precursor method. The textural properties of the catalysts were investigated by X-ray diffraction (XRD), Rietveld refinement, N{sub 2}-physisorption (BET surface area), electron paramagnetic resonance (EPR), UV–visible diffuse reflectance and photoluminescence spectroscopies and temperature-programmed reduction (TPR). In a previous study ceria-supported copper catalysts were found to be efficient in the preferential oxidation of CO. In this study, we extended the catalytic application of Ce{sub 1−x}Cu{sub x}O{sub 2} systems to n-hexane oxidation and it was verified that the catalysts were highly efficient in the proposed reaction. The best performance (up to 95% conversion) was observed for the catalysts with low copper loads (Ce{sub 0.97}Cu{sub 0.03}O{sub 2} and Ce{sub 0.99}Cu{sub 0.01}O{sub 2}, respectively). The physicochemical characterizations revealed that these behaviors could be attributed to the copper species present in the catalysts and the interaction between CuO and CeO{sub 2}, which vary according to the copper content. - Highlights: • Synthesis of CuO/CeO2 catalysts by the one-step polymeric precursor method. • 95% n-hexane conversion on Ce0.97Cu0.03O2 catalyst. • Redox properties play a key role in the catalytic performance.

Alum as a Catalyst for the Synthesis of Bispyrazole Derivatives

Directory of Open Access Journals (Sweden)

Mohammad Ali Zolfigol

2016-01-01

Full Text Available Compounds with pyrazolemoieties as nitrogen-containing heterocyclic systems have received attention owing to their diverse biological activities. Alum (KAl(SO42∙12H2O is an inexpensive, reusable and nontoxic catalyst used to synthesize 1H-pyrazole derivatives via the reaction of 3-methyl-1-phenyl-1H-pyrazol-5(4H-one and carbonyl compound under solvent-free conditions at 60 °C. The proposed method has been used for the preparation of 1H-pyrazole derivatives to yield green products for cleaning-in-place and to avoid toxic catalysts and hazardous solvents in accordance with the philosophy of sustainable chemistry.

Ziegler-Natta catalyst for polypropylene and polyethylene nanocomposites preparation

International Nuclear Information System (INIS)

Silvino, Alexandre C.; Dias, Marcos L.; Bezerra, Ana Beatriz F.

2009-01-01

Polypropylene and polyethylene nanocomposites are well known for their improved properties when compared with the neat polymers. In this work we report the preparation, characterization and the activity studies of a fourth generation Ziegler-Natta catalyst for the preparation of polyolefin/clay nanocomposites. The catalyst was prepared treating an organo-modified silicate with magnesium and titanium compounds. The content of titanium and that of the magnesium of the catalyst were determined by UV-vis spectroscopy and atomic absorption respectively. The first results show that the catalyst is active for propylene polymerization being suitable for polypropylene/clay nanocomposite preparation. The catalyst activity for ethylene polymerization was also investigated. The X-ray diffraction patterns of the polyethylene samples suggest the clay exfoliation occurs in the in situ polymerization, even with high clay loading (about 9 %) indicating that a nanocomposite was formed. (author)

Polymerization of Methyl Methacrylate with Samarocene Complex Supported on Mesoporous Silica

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

Samarocene complex was supported on a series of mesoporous silica with various pore sizes. Polymerization of methyl methacrylate (MMA) by these catalysts provide highly syndiotactic PMMAs with higher molecular weights compared with those obtained by solution polymerization with homogeneous catalyst system.

Stable hydrogen production from ethanol through steam reforming reaction over nickel-containing smectite-derived catalyst.

Science.gov (United States)

Yoshida, Hiroshi; Yamaoka, Ryohei; Arai, Masahiko

2014-12-25

Hydrogen production through steam reforming of ethanol was investigated with conventional supported nickel catalysts and a Ni-containing smectite-derived catalyst. The former is initially active, but significant catalyst deactivation occurs during the reaction due to carbon deposition. Side reactions of the decomposition of CO and CH4 are the main reason for the catalyst deactivation, and these reactions can relatively be suppressed by the use of the Ni-containing smectite. The Ni-containing smectite-derived catalyst contains, after H2 reduction, stable and active Ni nanocrystallites, and as a result, it shows a stable and high catalytic performance for the steam reforming of ethanol, producing H2.

Polypropylene obtained through zeolite supported catalysts

Directory of Open Access Journals (Sweden)

Queli C. Bastos

2004-01-01

Full Text Available Propylene polymerizations were carried out with f2C(Flu(CpZrCl2 and SiMe2(Ind2ZrCl2 catalysts supported on silica, zeolite sodic mordenite (NaM and acid mordenite (HM. The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]. The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f2C(Flu(CpZrCl2, SiO2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereoregularity.

Polypropylene obtained through zeolite supported catalysts

International Nuclear Information System (INIS)

Bastos, Queli C.; Marques, Maria de Fatima V.

2004-01-01

Propylene polymerizations were carried out with φ 2 C(Flu)(Cp)ZrCl 2 and SiMe 2 (Ind)2ZrCl 2 catalysts supported on silica, zeolite sodic mordenite (NaM) and acid mordenite (HM). The polymerizations were performed at different temperatures and varying aluminium/zirconium molar ratios ([Al]/[Zr]). The effect of these reaction parameters on the catalyst activity was investigated using a proposed statistical experimental planning. In the case of f 2 C(Flu)(Cp)ZrCl 2 , SiO 2 and NaM were used as support and the catalyst performance evaluated using toluene and pentane as polymerization solvent. The molecular weight, molecular weight distribution, melting point and crystallinity of the polymers were examined. The results indicate very high activities for the syndiospecific heterogeneous system. Also, the polymers obtained had superior Mw and stereo regularity. (author)

Activation of vanadium-based Ziegler-Natta catalysts by halocarbons for ethylene polymerization: results and mechanism

International Nuclear Information System (INIS)

Deffieux, A.; Amorin, C.; Fontanille, M.; Adisson, E.; Bujadoux, K.

1994-01-01

The reactions for the low productivity of the heterogeneous and homogenous V-based catalysts in the synthesis of LLDPE were discussed and some routes of improving their activity and stability were proposed. Ethylene polymerizations were performed in the isododecane solutions at 160 C and under constant ethylene pressure of 5 bars. One Ti-based catalytic system (TiCl 3 - 0.3 AlCl 3 ) and two V-based systems (TiCl 3 - 0.3 AlCl 3 and VCl 4 ) were investigated. The main reason of activity loss is a rapid reduction of V 4+ and V 3+ to inactive V 2+ form. AlR 3 cocatalysts are also involved in the deactivation process. The effect of addition to the system of various alkyl halides (a.o. of CCl 4 , CH 3 Cl 3 , CF 3 CCCl 3 , CHCl 3 , CHBr 3 , CH 2 Cl 2 , CH 2 BrCl and CH 2 Br 2 ) on the yield of polyethylene was investigated. The alkyl halides act as efficient activators for the heterogeneous and homogeneous vanadium catalysts in the high temperature ethylene polymerization and its copolymerization with 1-hexane. The effect of the presence of CHCl 3 on the short chain branching and the molecular weight distribution (GPC) of these copolymers was also investigated. Halocarbons do not act as chain transfer agents. The peak molecular weight remains almost unchanged but a narrowing of molecular weight distribution is observed due to the suppression of the amount of high-molecular-weight fraction in polymer. (author). 4 refs, 3 figs, 2 tabs

Correlation of Polymerization Conditions with Thermal and Mechanical Properties of Polyethylenes Made with Ziegler-Natta Catalysts

Directory of Open Access Journals (Sweden)

M. Anwar Parvez

2014-01-01

Full Text Available In this study, the synthesis of polyethylenes has been carried out with titanium-magnesium supported Ziegler-Natta catalysts in laboratory-scale reactors. A correlation of different polymerization conditions with thermal and mechanical properties of polyethylenes has been established. It is seen that there is lowering of molecular weight (Mw, polymer yield, and catalyst activity at high hydrogen pressure and high temperature. The Mw, polymer yield, and catalyst activity are improved with the increase in ethylene pressure. Dynamic mechanical analysis (DMA results show that the increase in temperature and hydrogen pressure decreases storage modulus. The samples with higher Mw showed high activation energy. The melting point decreases with the increase in hydrogen pressure but increases slightly with the increase in ethylene pressure. It is seen that the increase in reaction temperature, ethylene pressure, and hydrogen pressure leads to an increase in crystallinity. The tensile modulus increases with the increase in hydrogen pressure and can be correlated with the crystallinity of polymer. The Mw has a major influence on the flow activation energy and tensile strength. But the other mechanical and thermal properties depend on Mw as well as other parameters.

Three-site mechanism and molecular weight: Time dependency in liquid propylene batch polymerization using a MgCl2-supported Ziegler-Natta catalyst

NARCIS (Netherlands)

Shimizu, Fumihiko; Pater, J.T.M.; Weickert, G.

2001-01-01

This article demonstrates that the molecular weight of propylene homopolymer decreases with time, and that the molecular weight distribution (MWD) narrows when a highly active MgCl2-supported catalyst is used in a liquid pool polymerization at constant H2 concentration and temperature. To track the

Probing Stereoselectivity in Ring-Opening Metathesis Polymerization Mediated by Cyclometalated Ruthenium-Based Catalysts: A Combined Experimental and Computational Study

OpenAIRE

Rosebrugh, L. E.; Ahmed, T. S.; Marx, V. M.; Hartung, J.; Liu, P.; López, J. G.; Houk, K. N.; Grubbs, R. H.

2016-01-01

The microstructures of polymers produced by ring-opening metathesis polymerization (ROMP) with cyclometalated Ru-carbene metathesis catalysts were investigated. A strong bias for a cis,syndiotactic microstructure with minimal head-to-tail bias was observed. In instances where trans errors were introduced, it was determined that these regions were also syndiotactic. Furthermore, hypothetical reaction intermediates and transition structures were analyzed computationally. Combined experimental a...

Magnetic nanoparticle supported phosphotungstic acid: An efficient catalyst for the synthesis of xanthene derivatives

Science.gov (United States)

Patel, Nipun; Katheriya, Deepak; Dadhania, Harsh; Dadhania, Abhishek

2018-05-01

Magnetic nanoparticle supported phosphotungstic acid (Fe3O4@SiO2-HPW) was applied as a highly efficient catalyst for the synthesis of 14H-dibenzoxanthene derivatives via condensation reaction of 2-naphthol and aryl aldehydes. The catalyst was found highly efficient for the synthesis of xanthene derivatives under solvent free condition. The catalyst showed high activity and stability during the reaction and provided excellent yield of the corresponding products in short reaction time. All the synthesized compounds were characterized through FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. Furthermore, the catalyst is magnetically recoverable and can be reused several times without significant loss of its catalytic activity.

Polymerization Using Phosphazene Bases

KAUST Repository

Zhao, Junpeng

2015-09-01

In the recent rise of metal-free polymerization techniques, organic phosphazene superbases have shown their remarkable strength as promoter/catalyst for the anionic polymerization of various types of monomers. Generally, the complexation of phosphazene base with the counterion (proton or lithium cation) significantly improves the nucleophilicity of the initiator/chain end resulting in highly enhanced polymerization rates, as compared with conventional metalbased initiating systems. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges and perspectives being pointed out.

Phosphazene-promoted anionic polymerization

KAUST Repository

Zhao, Junpeng

2014-01-01

In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

Cascade synthesis of chiral block copolymers combining lipase catalyzed ring opening polymerization and atom transfer radical polymerization

NARCIS (Netherlands)

Peeters, J.W.; Palmans, A.R.A.; Veld, M.A.J.; Scheijen, F.J.E.; Heise, A.; Meijer, E.W.

2004-01-01

The enantioselective polymerization of methyl-substituted -caprolactones using Novozym 435 as the catalyst was investigated. All substituted monomers could be polymerized except 6-methyl--caprolactone (6-MeCL), which failed to propagate after ring opening. Interestingly, an odd-even effect in the

Dissolved oxygen removal in a column packed with catalyst

International Nuclear Information System (INIS)

Lee, Han Soo; Chung, Hong Suk; Cho, Young Hyun; Ahn, Do Hee; Kim, Eun Kee

1996-01-01

The dissolved oxygen removed by H 2 -O 2 reaction in column packed with various catalysts was examined. The catalysts employed were the prepared polymeric catalyst, platinum on activated carbon, and Lewatit OC-1045 which is available commercially. The column experiments with the prepared polymeric catalyst showed the dissolved oxygen reduced to 35 ppb which is below the limit in feel water of power plants. This implies the likely application of the prepared catalyst for practical use. The activated carbon required the pre-treatment for the removed of dissolved oxygen, since the surface of activated carbon contains much oxygen adsorbed initially. The Lewatit catalyst exposed the best performance, however, the aged one showed the gradual loss of catalytic activity due to degradation of resin catalyst. 14 refs., 6 figs., 2 tabs. (author)

TOTAL HYDROGENATION OF BIOMASS-DERIVED FURFURAL OVER RANEY NICKEL-CLAY NANOCOMPOSITE CATALYSTS

Directory of Open Access Journals (Sweden)

Rodiansono Rodiansono

2013-08-01

Full Text Available Inexpensive Raney Ni-clay composite (R-Ni/clay catalysts exhibited excellent activity and reusability in the total hydrogenation of biomass-derived furfural into tetrahydrofurfuryl alcohol under mild conditions. For the Raney Ni-bentonite (R-Ni/BNT catalysts, the complete reaction was achieved at 393 K, 180 min giving almost 99% yield of tetrahydrofurfuryl alcohol. The R-Ni/BNT catalyst was found to be reusable without any significant loss of activity and selectivity for at least six consecutive runs.

Enzymatically-Catalyzed Polymerization (ECP)- Derived Polymer Electrolyte for Rechargeable Li-Ion Batteries

National Research Council Canada - National Science Library

Chua, David

1998-01-01

Report developed under SBIR contract covers the syntheses and electrochemical characterizations of novel polymer electrolytes derived from compounds synthesized via enzyme-catalyzed polymerization(ECP) techniques...

CONVERSION OF (±-CITRONELLAL AND ITS DERIVATIVES TO (--MENTHOL USING BIFUNCTIONAL NICKEL ZEOLITE CATALYSTS

Directory of Open Access Journals (Sweden)

Indri Badria Adilina

2015-06-01

Full Text Available (±-Citronellal and its derivatives were converted to (--menthol by a one-pot reaction system using zeolite based nickel catalysts. The catalysts were prepared by immobilization of nickel on natural zeolite (NZ or synthetic zeolite (ZSM-5 by a simple cation exchange method. Calcination and hydrogen treatment procedures were able to significantly increase the surface area and pore volume of NZ based catalysts whereas negligible changes in the properties were observed for that of ZSM-5. Catalytic reactions were carried out at 70ºC by stirring the mixture in the air for cyclization of (±-citronellal to (±-isopulegol followed by hydrogenation towards the desired (--menthol at 2 Mpa of H2 pressure. The Ni/NZ catalyst was able to convert a (±-citronellal derivative yielding 9% (--menthol (36% selectivity with conversion up to 24%, whereas Ni/ZSM5 catalyst directly converted 65% (±-citronellal to give 4% menthol (6% selectivity. These zeolite based catalysts are therefore potential materials for the conversion of biomass feed stock to value-added chemicals.

Zn(OAc2-Catalyzing Ring-Opening Polymerization of N-Carboxyanhydrides for the Synthesis of Well-Defined Polypeptides

Directory of Open Access Journals (Sweden)

Yanzhao Nie

2018-03-01

Full Text Available Despite notable progress, the fabrication of well-defined polypeptides via controlled ring-opening polymerization (ROP of α-amino acid N-carboxyanhydrides (NCAs using convenient catalysts under mild conditions in a relatively short polymerization time is still challenging. Herein, an easily obtained catalyst system composed of zinc acetate and aniline was explored to mediate the fast ROP of γ-benzyl-l-glutamate-N-carboxyanhydride (BLG-NCA monomer, to produce poly(γ-benzyl-l-glutamates (PBLGs with controllable molecular weights and narrow dispersity. Considering the excellent cooperative action of zinc acetate and a broad scope of aniline derivatives with different functional groups to control ROP of BLG-NCA, this method may offer a useful platform enabling the rapid generation of end-functionalized PBLG and block copolymers for numerous biomedical applications.

Molecular weight control in emulsion polymerization by catalytic chain transfer : a reaction engineering approach

NARCIS (Netherlands)

Smeets, N.M.B.; Meda, U.S.; Heuts, J.P.A.; Keurentjes, J.T.F.; Herk, van A.M.; Meuldijk, J.

2007-01-01

For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on

The strange case of the "oscillating" catalysts

NARCIS (Netherlands)

Busico, [No Value; Cipullo, R; Kretschmer, W; Talarico, G; Vacatello, M; Castelli, VV

The field of stereoselective propene polymerization has been dramatically innovated by the discovery of homogeneous metallocene-based catalysts with well-defined and tunable molecular structure. Of all, "oscillating" metallocenes are probably the most ingenious and challenging example of catalyst

Synthesis and characterization of new chiral ketopinic acid-derived catalysts immobilized on polystyrene-bound imidazole

Directory of Open Access Journals (Sweden)

Hassan Yusuf

2017-02-01

Full Text Available Four new chiral ketopinic acid-derived catalysts were anchored on a polystyrene-bound imidazole via non-covalent bond. The resulting heterogeneous catalysts were successfully characterized using IR, SEM, and TGA analyses.

Transesterification of palm oil to biodiesel by using waste obtuse horn shell-derived CaO catalyst

International Nuclear Information System (INIS)

Lee, Seik Lih; Wong, Yong Chen; Tan, Yen Ping; Yew, Sook Yan

2015-01-01

Highlights: • Cost effective CaO catalyst derived from waste obtuse horn shells. • The optimum biodiesel yield, 86.75% can be achieved under mild reaction conditions. • The catalyst can be reused up to 3 times with biodiesel yield more than 70%. • Deactivation of catalyst was due to leaching of CaO and pores-filling. - Abstract: The calcium oxide catalysts derived from waste obtuse horn shells were utilized in the transesterification of palm oil into biodiesel. This environment-friendly catalyst is thermally activated at 800 °C for 3 h. The resulting CaO catalyst was characterized using thermogravimetric analysis (TGA), X-ray diffraction (XRD), temperature-programmed desorption of CO 2 (TPD-CO 2 ), Brunauer–Emmett–Teller (BET) surface area analysis, and scanning electron microscopy (SEM). XRD patterns of calcined catalyst showed intense peaks of calcium oxide, consistent with XRF results that revealed calcium is the major element present in the obtuse horn shells. High calcination temperature (800 °C) tended to promote agglomeration of fine crystals, resulted in a smaller surface area (0.07 m 2 /g) as examined by BET. Catalytic activities in the transesterification process had been investigated using one-variable-at-a-time technique. The optimum palm oil conversion was 86.75% under reaction conditions of 6 h, 5 wt.% of catalyst amount and methanol to oil ratio of 12:1. Reusability of this waste shell derived catalyst was examined and results showed that the prepared catalysts are able to be reused up to 3 times with conversion of more than 70% after the third cycles. Although the reusability may not be excellent at the moment, it is still in the exploratory study. More efforts were done to improve its properties and stability

Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

KAUST Repository

Chen, Xia; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2012-01-01

Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

KAUST Repository

Chen, Xia

2012-05-02

Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes

Science.gov (United States)

Tabernero, Vanessa; Camejo, Claudimar; Terreros, Pilar; Alba, María Dolores; Cuenca, Tomás

2010-01-01

In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet.

Polyolefin nanocomposites in situ polymerization

Energy Technology Data Exchange (ETDEWEB)

Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine, E-mail: griselda.barrera@ufrgs.br [Universidade Federal do Rio Grande de Sul - UFRGS, Porto Alegre, RS (Brazil); Basso, Nara R.S. [Pontificia Universidade Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil); Quijada, Raul [Universidad de Chile, Santiago (Chile)

2011-07-01

Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

Polyolefin nanocomposites in situ polymerization

International Nuclear Information System (INIS)

Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine; Basso, Nara R.S.; Quijada, Raul

2011-01-01

Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

Propene bulk polymerization kinetics: Role of prepolymerization and hydrogen

NARCIS (Netherlands)

Pater, J.T.M.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

2003-01-01

An experimental setup for the polymerization of liquid propylene was used to carry out main polymerizations with and without a prepolymerization step. Two types of prepolymerization are introduced: at a constant temperature and at rapidly increasing reactor temperatures. With the present catalyst

Rice husk-derived sodium silicate as a highly efficient and low-cost basic heterogeneous catalyst for biodiesel production

International Nuclear Information System (INIS)

Roschat, Wuttichai; Siritanon, Theeranun; Yoosuk, Boonyawan; Promarak, Vinich

2016-01-01

Graphical abstract: Rice husk-derived sodium silicate exhibits high potential as a low-cost solid catalyst for industrial biodiesel production. - Highlights: • Rice husk-derived sodium silicate was employed as a high performance catalyst for biodiesel production. • 97% yield of FAME was achieved in 30 min at 65 °C. • The room-temperature transesterification gave 94% yield of FAME after only 150 min. - Abstract: In the present work, rice husk-derived sodium silicate was prepared and employed as a solid catalyst for simple conversion of oils to biodiesel via the transesterification reaction. The catalyst was characterized by TG–DTA, XRD, XRF, FT-IR, SEM, BET and Hammett indicator method. Under the optimal reaction conditions of catalyst loading amount of 2.5 wt.%, methanol/oil molar ratio of 12:1, the prepared catalysts gave 97% FAME yield in 30 min at 65 °C, and 94% FAME yield in 150 min at room temperature. The transesterification was proved to be pseudo-first order reaction with the activation energy (Ea) and the frequency factor (A) of 48.30 kJ/mol and 2.775 × 10"6 min"−"1 respectively. Purification with a cation-exchange resin efficiently removed all soluble ions providing high-quality biodiesel product that meets all the ASTM and EN standard specifications. Rice husk-derived sodium silicate showed high potential to be used as a low-cost, easy to prepare and high performance solid catalyst for biodiesel synthesis.

Nanoparticle-Supported Molecular Polymerization Catalysts

OpenAIRE

Amgoune, Abderramane; Krumova, Marina; Mecking, Stefan

2008-01-01

Homogeneous molecular catalysts are immobilzed in a well-defined fashion on individual silica nanoparticles with a narrow particle size distribution by covalent attachment. This synthetic methodology is demonstrated with modified salicylaldiminato-substituted titanium(IV) complexes incorporating a trimethoxysilane-terminated linker: dichloro-bis[κ2-N,O-6-(3-(trimethoxysilyl)propoxyphenylimino)-2-tert-butyl-phenolato]titanium(IV) (3) and dichlorobis[κ2-N,O-6-(4-(trimethoxysilyl)propoxy-2,3,5,6...

A DFT study on the effect of hydrogen in ethylene and propylene polymerization using a Ti-based heterogeneous Ziegler–Natta catalyst

KAUST Repository

Bahri-Laleh, Naeimeh

2012-11-01

Hydrogenolysis of a series of model Ziegler-Natta (Z-N) catalysts to form Ti-H bond was studied within DFT. We focused our efforts on Ti species attached to the (110) lateral cut of MgCl 2 which exist as different centres including Ti-C 2H 5, Ti-CH 2CH(CH 3) 2, and Ti-CH(CH 3)CH 2CH 3 in ethylene and propylene polymerization. In the next step, reactivity of Ti-H bond towards ethylene and propylene (1,2- and 2,1-) insertion was investigated. Results showed that insertion of ethylene and propylene into Ti-H bond has less barrier, in comparison with their insertion in Ti-C bond, however, ethylene and propylene 2,1- insertion lead to Ti-C 2H 5 and Ti-CH(CH 3) 2 centres respectively, which were stable due to strong β-agostic interactions. Finally, by considering different possible reactions of active centre, activity depression in ethylene polymerization and activity increase in propylene polymerization were explained in detail. © 2012 Elsevier B.V.

Solid Catalyst Nanoparticles derived from Oil-Palm Empty Fruit Bunches (OP-EFB) as a Renewable Catalyst for Biodiesel Production

Science.gov (United States)

Husin, H.; Asnawi, T. M.; Firdaus, A.; Husaini, H.; Ibrahim, I.; Hasfita, F.

2018-05-01

Solid nanocatalyst derived from oil-palm empty fruit bunches (OP-EFB) fiber was successfully synthesized and its application for biodiesel production was investigated. The OPEFB was treated by burning, milling and heating methods to generate ashes in a nanoparticle size. The nanoparticle palm-bunch ash was characterized by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The effects of the calcination temperature and catalyst amounts for transesterification reactions were investigated. XRD analysis of palm bunch ash exhibited that the highest composition of peaks characteristic were potassium oxide (K2O). SEM analysis showed that the nano palm bunch ash have a particle size ranging of 150-400 nm. The highest conversion of palm-oil to biodiesel reach to 97.90% was observed by using of palm bunch ash nanocatalyst which heated at 600°C, 3 h reaction time and 1% catalyst amount. Reusability of palm bunch ash catalysts was also examined. It was found that of its high active sites, reusable solid catalyst was obtained by just heating of palm bunch ash. It has a capability to reduce not only the amount of catalyst consumption but also reduce the reaction time of transesterification process.

Ionic polymerization of p-methoxystyrene and other styrene derivatives by radiation. [Gamma radiation

Energy Technology Data Exchange (ETDEWEB)

Hayashi, K; Pepper, D C [Trinity Coll., Dublin (Ireland)

1976-01-01

Polymerization of p-methoxystyrene by radiation was studied in bulk. Upon drying the monomer, the rate of polymerization, Rsub(p), became greater, changing its dose rate dependence from 0.5 to 1. The molecular weight distribution of the obtained polymers failed to give a bimodal curve; however, the peak molecular weight increased with higher Rsub(p). These kinetic features can be explained by a coexistence of radical and cationic mechanisms, as has been established in styrene, though there remain ambiguities about the effects of additives. Copolymerizations with styrene and 2-chloroethyl vinyl ether also showed a cationic nature for the reaction. A survey of possibilities of ionic polymerization by radiation was also carried out in ten ring-substituted styrene derivatives.

Iron-Mediated Homogeneous ICAR ATRP of Methyl Methacrylate under ppm Level Organometallic Catalyst Iron(III Acetylacetonate

Directory of Open Access Journals (Sweden)

Jian Wu

2016-01-01

Full Text Available Atom Transfer Radical Polymerization (ATRP is an important polymerization process in polymer synthesis. However, a typical ATRP system has some drawbacks. For example, it needs a large amount of transition metal catalyst, and it is difficult or expensive to remove the metal catalyst residue in products. In order to reduce the amount of catalyst and considering good biocompatibility and low toxicity of the iron catalyst, in this work, we developed a homogeneous polymerization system of initiators for continuous activator regeneration ATRP (ICAR ATRP with just a ppm level of iron catalyst. Herein, we used oil-soluble iron (III acetylacetonate (Fe(acac3 as the organometallic catalyst, 1,1′-azobis (cyclohexanecarbonitrile (ACHN with longer half-life period as the thermal initiator, ethyl 2-bromophenylacetate (EBPA as the initiator, triphenylphosphine (PPh3 as the ligand, toluene as the solvent and methyl methacrylate (MMA as the model monomer. The factors related with the polymerization system, such as concentration of Fe(acac3 and ACHN and polymerization kinetics, were investigated in detail at 90 °C. It was found that a polymer with an acceptable molecular weight distribution (Mw/Mn = 1.43 at 45.9% of monomer conversion could be obtained even with 1 ppm of Fe(acac3, making it needless to remove the residual metal in the resultant polymers, which makes such an ICAR ATRP process much more industrially attractive. The “living” features of this polymerization system were further confirmed by chain-extension experiment.

A Comparative Study of Solvothermal and Sol-Gel-Derived Nanocrystalline Alumina Catalysts for Ethanol Dehydration

Directory of Open Access Journals (Sweden)

Mingkwan Wannaborworn

2015-01-01

Full Text Available The ethanol dehydration to ethylene over alumina catalysts prepared by solvothermal and sol-gel methods was investigated. Also, a commercial alumina was used for comparison purposes. The results showed that the catalytic activity depends on the properties of catalyst derived from different preparation methods and reaction temperature. The alumina synthesized by solvothermal method exhibited the highest activity. This can be attributed to the higher surface area and larger amount of acid site, especially the ratio of weak/strong acid strength as determined by N2 physisorption and NH3-TPD studies. The solvothermal-derived catalyst exhibited an excellent performance with complete ethanol conversion and 100% selectivity to ethylene at 350°C in comparison with other ones. In addition, we further studied the catalytic dehydration of alumina catalyst modified with Fe. The presence of 10 wt.% Fe decreased both conversion and ethylene selectivity. However, the acetaldehyde selectivity apparently increased. It was related to the dehydrogenation pathway that takes place on Fe species.

MOF derived Ni/Co/NC catalysts with enhanced properties for oxygen evolution reaction

Science.gov (United States)

Hu, Jiapeng; Chen, Juan; Lin, Hao; Liu, Ruilai; Yang, Xiaobing

2018-03-01

Designing efficient electrocatalysts for oxygen evolution reaction (OER) is very important for renewable energy storage and conversion devices. In this paper, we introduced a new strategy to synthesize Ni doped Co/NC catalysts (NC is the abbreviation of nitrogen-doped graphitic carbon), which were derived from ZIF-67. All catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and oxygen evolution reaction (OER). The results show that Ni was well doped in the Ni/Co/NC catalysts and the doping of Ni has great influence on the OER activity of Ni/Co/NC catalysts. Among these catalysts, 0.50Ni/Co/NC exhibits the highest OER activity. The onset potential of 0.50Ni/Co/NC is 1.47 V, which is superior than the onset potential of Co/NC (1.54 V), 0.25Ni/Co/NC (1.48 V), 1.00Ni/Co/NC (1.53 V). The excellent OER activity of 0.50Ni/Co/NC catalyst makes its potential to be used on renewable energy storage.

Catalytic wet air oxidation of 2-chlorophenol over sewage sludge-derived carbon-based catalysts

Energy Technology Data Exchange (ETDEWEB)

Tu, Yuting [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France); School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Xiong, Ya; Tian, Shuanghong [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275 (China); Kong, Lingjun [School of Environmental Science and Engineering, Sun Yat-Sen University, Guangzhou 510275 (China); Descorme, Claude, E-mail: claude.descorme@ircelyon.univ-lyon1.fr [Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON), CNRS – Université Claude Bernard Lyon 1, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex (France)

2014-07-15

Highlights: • A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared. • FeSC exhibited high catalytic activity in the wet air oxidation of 2-chlorophenol. • A strong correlation was observed between the 2-CP conversion, the iron leaching and the pH. • Using an acetate buffer, the iron leaching was suppressed while keeping some catalytic activity. • A simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst. - Abstract: A sewage sludge derived carbon-supported iron oxide catalyst (FeSC) was prepared and used in the Catalytic Wet Air Oxidation (CWAO) of 2-chlorophenol (2-CP). The catalysts were characterized in terms of elemental composition, surface area, pH{sub PZC}, XRD and SEM. The performances of the FeSC catalyst in the CWAO of 2-CP was assessed in a batch reactor operated at 120 °C under 0.9 MPa oxygen partial pressure. Complete decomposition of 2-CP was achieved within 5 h and 90% Total Organic Carbon (TOC) was removed after 24 h of reaction. Quite a straight correlation was observed between the 2-CP conversion, the amount of iron leached in solution and the pH of the reaction mixture at a given reaction time, indicating a strong predominance of the homogeneous catalysis contribution. The iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Upon four successive batch CWAO experiments, using the same FeSC catalyst recovered by filtration after pH adjustment, only a very minor catalyst deactivation was observed. Finally, based on all the identified intermediates, a simplified reaction pathway was proposed for the CWAO of 2-CP over the FeSC catalyst.

Biodiesel production from palm oil using hydrated lime-derived CaO as a low-cost basic heterogeneous catalyst

International Nuclear Information System (INIS)

Roschat, Wuttichai; Siritanon, Theeranun; Yoosuk, Boonyawan; Promarak, Vinich

2016-01-01

Graphical abstract: Hydrated lime-derived CaO can be utilized as high efficient heterogeneous solid catalyst for transesterification of palm oil to biodiesel product. - Highlights: • CaO with high surface area and pore volume was successfully prepared from hydrated lime using a simple method. • Hydrated lime-derived CaO were used as a catalyst in transesterification of palm oil to biodiesel. • Over 97% FAME yield was achieved from transesterification of palm oil in 2 h. • This CaO has high potential for applications as green and low-cost catalyst. - Abstract: In this study, hydrated lime-derived calcium oxide (CaO) was used as a catalyst for the transesterification of palm oil. The catalysts were characterized by TG-DTA, XRD, XRF, FT-IR, SEM, Hammett indicator method, TPD-CO_2 and BET by N_2 adsorption. Under the optimal conditions at catalyst loading of 6 wt.%, methanol/oil molar ratio of 15:1, reaction temperature 65 °C, and stirring rate of 200 rpm; 97% yield of biodiesel could be achieved in 2 h. Effects of water amount were investigated and the catalyst could tolerate high water content of 5 wt.%. The kinetic of the reaction followed pseudo-first order with the activation energy (Ea) of 121.12 kJ/mol and frequency factor (A) of 1.203 × 10"1"7 min"−"1. After treatments, high quality biodiesel was obtained which indicated that the very cheap hydrated lime-derived CaO showed excellent catalytic activity and high potential for applications in biodiesel production.

NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

CERN Document Server

1998-01-01

The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

Tetramethylguanidine covalently bonded onto silica gel as catalyst for the addition of nitromethane to cyclopentenone

International Nuclear Information System (INIS)

Oliveira, Edimar de; Torres, Jocilene D.; Silva, Carlos C.; Luz, Afranio A.M.; Bakuzis, Peter; Prado, Alexandre G.S.

2006-01-01

A catalyst based on silica chemically modified with tetramethylguanidine (TMG) was synthesized by the co-condensation of tetraethyl orthosilicate with a new silylant agent derived from the reaction between the TMG molecule and (3-chloropropyl)trimethoxysilane. A neutral n-dodecylamine template was used to organize the polymerization of the inorganic-organic catalyst. Thermogravimetry showed that the number of active pendant groups in the catalyst was 1.35 mmol g -1 , with a surface area of 811±75 m 2 g -1 . Infrared spectroscopy and 13 C and 29 Si nuclear magnetic resonance data are in agreement with the proposed structure. This material has been used to catalyse the addition of nitromethane to cyclopentenone. The catalytic efficiency was followed and the nitromethylcyclopentanone conversion presented a yield of 98% at 3 h of reaction. The catalyst was recovered and reused 14 times, maintaining about 98% of its catalytic efficiency. (author)

Pentafluorosulfanyl Substituents in Polymerization Catalysis.

Science.gov (United States)

Kenyon, Philip; Mecking, Stefan

2017-10-04

Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

POLYMERIZATION OF METHYL METHACRYLATE WITH ETHYLENE BRIDGED HETERODINUCLEAR METALLOCENE OF SAMARIUM AND TITANIUM-STUDY ON SYNERGISM AND KINETICS

Institute of Scientific and Technical Information of China (English)

无

2001-01-01

Comparison of MMA polymerization results with samarocene chloride, titanocene chloride and the title heterodinuclear (Sm-Ti) catalyst, respectively, showed synergism in the Sm-Ligand-Ti system, which ob viously influenced the polymerization behaviors, for example, of yielding higher activity and higher molecular weight polymer. Kinetic studies on polymerization of MMA with ethylene bridged samarocene and titanocene chloride/M(i-Bu) 3 showed that the polymerization rate was first-order on the catalyst concentration, and 1.9- order on the monomer. The overall activation energy measured was 52.8 kJ/mol.

Polyethylene-waste tire dust composites via in situ polymerization

International Nuclear Information System (INIS)

Reyes A, Y. K.; Narro C, R. I.; Ramos A, M. E.; Neira V, M. G.; Diaz E, J.; Enriquez M, F.; Valencia L, L. A.; Saade C, H.; Diaz de L, R.

2014-01-01

Polyethylene/waste tire dust (WTD) composites were obtained by an in situ polymerization technique. The surface of the WTD was modified with deposition of polyethylene by using plasma polymerization. Ethylene polymerization was carried out using bis(cyclopentadienyl) titanium dichloride (Cp 2 TiCl 2 ) as homogeneous metallocenes catalyst, while diethylaluminum chloride (DEAC), ethyl aluminum sesquichloride (EASC) and methyl alumino xane (Mao) were used as co-catalysts at two different [Al]/[Ti] molar ratio. The main characteristics of the obtained polyethylenes were determined by size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry and wide-angle X-ray diffraction. The results showed that by using EASC and Mao the highest catalytic activities were presented at a [Al]/[Ti] molar ratio of 9.17 and 18.33 respectively. Even though it was possible to obtain polyethylene using WTD (modified or unmodified) the catalytic activity was lower than in the case in which no WTD was added in ethylene polymerization. Scanning transmission electronic microscopy images evidenced that the original morphology of the polyethylenes was not modified by the presence of WTD. (Author)

Polyethylene-waste tire dust composites via in situ polymerization

Energy Technology Data Exchange (ETDEWEB)

Reyes A, Y. K.; Narro C, R. I.; Ramos A, M. E. [Universidad Autonoma de Coahuila, Facultad de Ciencias Quimicas, Blvd. Venustiano Carranza s/n, 25280 Saltillo, Coahuila (Mexico); Neira V, M. G.; Diaz E, J.; Enriquez M, F.; Valencia L, L. A.; Saade C, H.; Diaz de L, R., E-mail: ramon.diazdeleon@ciqa.edu.mx [Centro de Investigacion en Quimica Aplicada, Blvd. Enrique Reyna Hermosillo No. 40, Col. San Jose de los Cerritos, 25293 Saltillo, Coahuila (Mexico)

2014-10-01

Polyethylene/waste tire dust (WTD) composites were obtained by an in situ polymerization technique. The surface of the WTD was modified with deposition of polyethylene by using plasma polymerization. Ethylene polymerization was carried out using bis(cyclopentadienyl) titanium dichloride (Cp{sub 2}TiCl{sub 2}) as homogeneous metallocenes catalyst, while diethylaluminum chloride (DEAC), ethyl aluminum sesquichloride (EASC) and methyl alumino xane (Mao) were used as co-catalysts at two different [Al]/[Ti] molar ratio. The main characteristics of the obtained polyethylenes were determined by size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry and wide-angle X-ray diffraction. The results showed that by using EASC and Mao the highest catalytic activities were presented at a [Al]/[Ti] molar ratio of 9.17 and 18.33 respectively. Even though it was possible to obtain polyethylene using WTD (modified or unmodified) the catalytic activity was lower than in the case in which no WTD was added in ethylene polymerization. Scanning transmission electronic microscopy images evidenced that the original morphology of the polyethylenes was not modified by the presence of WTD. (Author)

Tetramethylguanidine covalently bonded onto silica gel as catalyst for the addition of nitromethane to cyclopentenone

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Edimar de; Torres, Jocilene D.; Silva, Carlos C.; Luz, Afranio A.M.; Bakuzis, Peter; Prado, Alexandre G.S. [Brasilia Univ., DF (Brazil). Inst. de Quimica]. E-mail: agspradus@gmail.com

2006-09-15

A catalyst based on silica chemically modified with tetramethylguanidine (TMG) was synthesized by the co-condensation of tetraethyl orthosilicate with a new silylant agent derived from the reaction between the TMG molecule and (3-chloropropyl)trimethoxysilane. A neutral n-dodecylamine template was used to organize the polymerization of the inorganic-organic catalyst. Thermogravimetry showed that the number of active pendant groups in the catalyst was 1.35 mmol g{sup -1}, with a surface area of 811{+-}75 m{sup 2} g{sup -1}. Infrared spectroscopy and {sup 13}C and {sup 29}Si nuclear magnetic resonance data are in agreement with the proposed structure. This material has been used to catalyse the addition of nitromethane to cyclopentenone. The catalytic efficiency was followed and the nitromethylcyclopentanone conversion presented a yield of 98% at 3 h of reaction. The catalyst was recovered and reused 14 times, maintaining about 98% of its catalytic efficiency. (author)

Hydrodeoxygenation of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts derived from hydrotalcite-like precursors

Directory of Open Access Journals (Sweden)

Natalia Andrea Pino

2017-01-01

Full Text Available The aqueous phase hydrodeoxygenation (HDO of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts with different Mg/Al and Zn/Al molar ratios, were investigated. Mg-Al and Zn-Al mixed oxides derived from hydrotalcites precursors were used as supports, which were impregnated with an aqueous solution of copper nitrate by incipient wetness impregnation. The HDO reaction was carried out in a typical batch reactor at 5 MPa of H2 and 200 °C for 4 h. Among the catalysts studied, the Cu/MgAl-0.5 catalyst exhibited the higher furfuryl alcohol conversion (86% and yield of cyclopentanol (35%, which is the reaction product with the highest hydrogen-carbon (H/C ratio. With the Cu/MgAl-3 catalyst a high cyclopentanone yield (67% was achieved. The results obtained, showed that copper supported on mixed oxides catalysts derived from hydrotalcite precursors are a promising alternative to improve the bio-oil quality.

Survey and research on precision polymerization polymeric materials; Seimitsu jugo kobunshi zairyo ni kansuru chosa kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-03-01

Survey and research on the precision control of primary structure of polymeric materials and the precision evaluation technology have been conducted to develop advanced polymeric materials. It is proposed that the three basic processes of polymer synthesis, i.e., addition, condensation, and biomimesis, in forming the precision polymerization skeleton are to be covered through a centralized joint research effort with participation of industry, academia, and the government institute and under the leadership of researchers from academic institutions as the team leaders. For the study of technology trends, international conferences held in UK, Germany, and Hawaii are introduced, and domestic meetings, i.e., Annual Polymer Congress and Polymer Conference, are summarized. In addition, Precision Polymerization Forum and International Workshop on Precision Polymerization were held. The basic studies include a quantum-chemical elucidation of the elementary process in polymerization reaction, time-resolved analysis of polymerization process and polymer properties, synthesis of polymers with controlled microstructures by coordination polymerization using metal complexes, synthesis of polymer with controlled microstructures by precision polycondensation, molecular recognition in catalyst-reaction site, and synthesis of imprinting polymers. 246 refs., 117 figs., 14 tabs.

L-Threonine-derived novel bifunctional phosphine-sulfonamide catalyst-promoted enantioselective aza-morita-Baylis-Hillman reaction

KAUST Repository

Zhong, Fangrui

2011-03-18

A series of novel bifunctional phosphine-sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. l-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities. © 2011 American Chemical Society.

Mannich reactions of alkynes: the role of sub-stoichiometric amounts of stable polymeric alkynylcopper (I) compounds in the catalytic cycle (abstract)

International Nuclear Information System (INIS)

Khan, A.N.; Buckley, B.R.; Heaney, H.

2011-01-01

The rapid development of the use of organocopper reagents and catalysts in organic synthesis since the middle of the last century has been comprehensively documented. The advantages of using heterogeneous catalysts include ease of work-up and purification, reduction in waste disposal, and the ability to recycle catalysts. Reactions of terminal alkynes that involve copper(I) catalysts have been widely studied, in particular as a result of the search for atom efficiency. Ligand associated alkynylcopper(I) derivatives have been reported many times, for example in copper(I) catalysed alkyne-azide cycloaddition (CuAAC) reactions. Our interest in Mannich reactions, and also in alkynylcopper(I) pre-catalysts, prompted this study of reactions of alkynes with secondary amines with aldehydes. Early studies of Mannich reactions involving alkynes almost always involved formaldehyde, exceptions included imines and derivatives of glyoxylic esters. An efficient one-pot three-component coupling of an aldehyde, alkyne, and amine to generate propargyl amines has been effected by microwave heating in water using a polymeric alkynylcopper(I) complex as catalyst (Scheme 1). This reaction utilizes water as a solvent which provides a green-approach for such reactions. This method has proved to be applicable to a wide range of substrates. (author)

Micelle-derived catalysts for extended Schulz-Flory

Energy Technology Data Exchange (ETDEWEB)

Abrevaya, H.

1986-01-01

The objective of this program is to develop a synthesis gas conversion catalyst with higher selectivity to liquid fuels, while maintaining catalytic activity and stability at least equivalent relative to state-of-the-art precipitated iron catalysts. During this quarter, the emphasis in the program has been the investigation of the hydrocarbon cutoff hypothesis with supported ruthenium catalysts. An alumina-supported catalyst with smaller than 20[Angstrom] ruthenium particles was tested under conditions of maximal water gas shift activity. During this test more than 90% of the water made in the Fischer-Tropsch synthesis reaction was converted to H[sub 2]. However, the extent of ruthenium metal agglomeration was not reduced. Accordingly, it was not possible to conclude whether hydrocarbon cutoff occurs with smaller than 20[Angstrom] ruthenium particles on [gamma]-alumina. A ruthenium catalyst prepared on Y-type zeolite had 20[Angstrom] or smaller ruthenium particles according to STEM examination and a 15[Angstrom] average ruthenium metal particle size according to EXAFS examination. The ruthenium metal particle size was stable during the test with this catalyst. The hydrocarbon product distribution was Anderson-Schulz-Flory with no cutoff up to a carbon number of 160. A well-dispersed titania-supported ruthenium catalyst is going to be evaluated during the next quarter in order to determine whether hydrocarbon cutoff occurs.

Low cost guinea fowl bone derived recyclable heterogeneous catalyst for microwave assisted transesterification of Annona squamosa L. seed oil

International Nuclear Information System (INIS)

Singh, Veena; Sharma, Yogesh Chandra

2017-01-01

Highlights: • Discarded guinea fowl bone used to derive catalyst for biodiesel production. • High conversion of 95.82 ± 0.2% achieved in 20 min by microwave assisted transesterification of Annona Squamosa L. seed oil. • Catalyst was stable and can be reused up to five times by activation with >80% conversion. • Complete process is cheap, eco-friendly and fulfils ASTM standard limits. - Abstract: Guinea fowl bone derived heterogeneous catalyst was utilized for biodiesel production for the first time on microwave heating system from Annona squamosa (custard apple seed) oil. Synthesized catalyst was characterized by TGA, XRD, FTIR, SEM, EDS, BET surface area and basicity. Optimization for various reaction conditions on FAME conversion was explored. Maximum conversion of 95.82 ± 0.2% FAME was attained at 1:18 M ratio of oil: methanol, 4 wt% of catalyst at 800 W microwave power and 65 °C reaction temperatures for 20 min. Custard apple seed oil was studied by GCMS, whereas synthesized FAME was analysed by "1H FTNMR spectroscopy. Catalyst was reused up to five times with maximum conversion of >80%. Physicochemical properties of synthesized FAME were studied as per ASTM standards. Results displayed that catalyst derived from guinea fowl bone showed better reusability and has enormous potential to be used for biodiesel production under microwave irradiated transesterification of Annona squamosa L. (custard apple seed) oil within a short reaction time.

Two-step microalgal biodiesel production using acidic catalyst generated from pyrolysis-derived bio-char

International Nuclear Information System (INIS)

Dong, Tao; Gao, Difeng; Miao, Chao; Yu, Xiaochen; Degan, Charles; Garcia-Pérez, Manuel; Rasco, Barbara; Sablani, Shyam S.; Chen, Shulin

2015-01-01

Highlights: • Highly active catalyst was prepared using bio-char co-produced in Auger pyrolysis. • Catalyst inhibitors in crude oil were effectively removed by a practical refinery process. • Free fatty acids (FFA) content in refined microalgal oil was reduced to less than 0.5%. • A total fatty acid methyl ester (FAME) yield of 99% was obtained via a two-step process. • The inexpensive bio-char catalyst is superior to Amberlyst-15 in pre-esterification. - Abstract: An efficient process for biodiesel production from fast-refined microalgal oil was demonstrated. A low cost catalyst prepared from pyrolysis-derived bio-char, was applied in pre-esterification to reduce free fatty acid (FFA) content. Results showed that the bio-char catalyst was highly active in esterification; however, the performance of the catalyst significantly reduced when crude microalgal oil was used as feedstock. To solve the problem caused by catalyst-fouling, a fast and scalable crude oil refinery procedure was carried out to remove chlorophyll and phospholipids that might degrade the catalyst and the quality of biodiesel. The activity and reusability of bio-char catalyst were remarkably improved in the fast-refined oil. FFA content in the refined microalgal oil was reduced to less than 0.5% after pre-esterification. The bio-char catalyst could be reused for 10 cycles without dramatic loss in activity. The pre-esterification fits the first-order kinetic reaction with activation energy of 42.16 kJ/mol. The activity of bio-char catalyst was superior to commercial Amberlyst-15 under the same reaction condition. A total fatty acid methyl ester (FAME, namely biodiesel) yield of 99% was obtained following the second-step CaO-catalyzed transesterification. The cost-effective bio-char catalyst has great potential for biodiesel production using feedstocks having high FFA content.

A study on production of biodiesel using a novel solid oxide catalyst derived from waste.

Science.gov (United States)

Majhi, Samrat; Ray, Srimanta

2016-05-01

The issues of energy security, dwindling supply and inflating price of fossil fuel have shifted the global focus towards fuel of renewable origin. Biodiesel, having renewable origin, has exhibited great potential as substitute for fossil fuels. The most common route of biodiesel production is through transesterification of vegetable oil in presence of homogeneous acid or base or solid oxide catalyst. But, the economics of biodiesel is not competitive with respect to fossil fuel due to high cost of production. The vegetable oil waste is a potential alternative for biodiesel production, particularly when disposal of used vegetable oil has been restricted in several countries. The present study evaluates the efficacy of a low-cost solid oxide catalyst derived from eggshell (a food waste) in transesterification of vegetable oil and simulated waste vegetable oil (SWVO). The impact of thermal treatment of vegetable oil (to simulate frying operation) on transesterification using eggshell-derived solid oxide catalyst (ESSO catalyst) was also evaluated along with the effect of varying reaction parameters. The study reported that around 90 % biodiesel yield was obtained with vegetable oil at methanol/oil molar ratio of 18:1 in 3 h reaction time using 10 % ESSO catalyst. The biodiesel produced with ESSO catalyst from SWVO, thermally treated at 150 °C for 24 h, was found to conform with the biodiesel standard, but the yield was 5 % lower compared to that of the untreated oil. The utilization of waste vegetable oil along with waste eggshell as catalyst is significant for improving the overall economics of the biodiesel in the current market. The utilization of waste for societal benefit with the essence of sustainable development is the novelty of this work.

Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol.

Science.gov (United States)

Das, Vijay Kumar; Mazhar, Sumaira; Gregor, Lennon; Stein, Barry D; Morgan, David Gene; Maciulis, Nicholas A; Pink, Maren; Losovyj, Yaroslav; Bronstein, Lyudmila M

2018-06-14

Here, we report transfer hydrogenation of nitroarenes to aminoarenes using 2-propanol as a hydrogen source and Ag-containing magnetically recoverable catalysts based on partially reduced graphene oxide (pRGO) sheets. X-ray diffraction and X-ray photoelectron spectroscopy data demonstrated that, during the one-pot catalyst synthesis, formation of magnetite nanoparticles (NPs) is accompanied by the reduction of graphene oxide (GO) to pRGO. The formation of Ag 0 NPs on top of magnetite nanoparticles does not change the pRGO structure. At the same time, the catalyst structure is further modified during the transfer hydrogenation, leading to a noticeable increase of sp 2 carbons. These carbons are responsible for the adsorption of substrate and intermediates, facilitating a hydrogen transfer from Ag NPs and creating synergy between the components of the catalyst. The nitroarenes with electron withdrawing and electron donating substituents allow for excellent yields of aniline derivatives with high regio and chemoselectivity, indicating that the reaction is not disfavored by these functionalities. The versatility of the catalyst synthetic protocol was demonstrated by a synthesis of an Ru-containing graphene derivative based catalyst, also allowing for efficient transfer hydrogenation. Easy magnetic separation and stable catalyst performance in the transfer hydrogenation make this catalyst promising for future applications.

Ziegler-Natta catalysts for the preparation of polypropylene clay nanocomposites from magnesium ethoxide

International Nuclear Information System (INIS)

Marques, Maria de Fatima V.; Silva, Micheli G. da; Ferreira, Ana Luiza R.

2009-01-01

In the present work, the process for the preparation of Ziegler-Natta catalysts based on MgCl 2 /TiCl 4 was evaluated on the synthesis of isotactic polypropylene. The catalysts were produced by the chemical activation process aiming the morphology control, in order to obtain catalyst particles with spherical form. The synthesis of the catalytic support was accomplished from magnesium ethoxide at different preparation conditions. Commercial clays were also added in the preparation of ZN catalysts, which were employed in propylene polymerization. The purpose was to synthesizing polypropylene nanocomposites by in situ polymerization technique. The results indicated that the developed methods of catalyst preparation were effective, since they have shown high activities and they produced PP with high melting temperatures. It was possible to verify by XRD that the catalytic components were inserted in the clays galleries and the polymers obtained by means of those catalysts are possibly exfoliated nanocomposites. (author)

Halloysite nanotube supported Ag nanoparticles heteroarchitectures as catalysts for polymerization of alkylsilanes to superhydrophobic silanol/siloxane composite microspheres.

Science.gov (United States)

Li, Cuiping; Li, Xueyuan; Duan, Xuelan; Li, Guangjie; Wang, Jiaqiang

2014-12-15

Halloysite nanotube supported Ag nanoparticles heteroarchitectures have been prepared through a very simple electroless plating method. Robust Ag nanocrystals can be reproducibly fabricated by soaking halloysite nanotubes in ethanolic solutions of AgNO3 and butylamine. By simply adjusting the molar ratio of AgNO3 and butylamine, Ag nanoparticles with tunable size and quantity on halloysite nanotube are achieved. It reveals that the Ag nanoparticles are well-dispersed on the surface of halloysite nanotubes. The halloysite nanotube supported Ag nanoparticles heteroarchitectures can serve as active catalysts for the polymerization of an alkylsilane C18H37SiH3 with water to form silanol/siloxane composite microspheres and exhibit interesting superhydrophobicity ascribed to the micro/nanobinary structure. Copyright © 2014 Elsevier Inc. All rights reserved.

In situ cyclization modification in polymerization of butadiene by rare earth coordination catalyst

International Nuclear Information System (INIS)

Wang Chaoyang

2005-01-01

Butadiene was polymerized to a certain extent in the presence of a rare earth coordination catalyst, neodymium compound of neodymium chloride and i-propyl alcohol and triethyl aluminum (NdCl 3 ·3i-PrOH-AlEt 3 ) in toluene and the allyl chloride was then added to the reactive solution in order to in situ cyclize the formed polybutadiene and cyclopolymerize the unreacted butadiene monomers. Effects of molar ratio of allylchloride to AlEt 3 (Cl/Al), cyclization reaction time and temperature, butadiene and NdCl 3 ·3i-PrOH concentrations on the cyclization reaction have been investigated. The cyclization reaction is very quick, only several minutes. The cyclization reaction temperature has few effects on the properties of the cyclized product. Cl/Al is a very important condition for this reaction system. Cyclized polybutadiene has a low value of intrinsic viscosity, free gelling and high yield at high Cl/Al. The microstructures and properties of the cyclized products have been characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and gel permeation chromatography. The cyclization mechanism is put forward

Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst

International Nuclear Information System (INIS)

Yan, Kai; Chen, Aicheng

2013-01-01

Biomass-derived platform intermediate furfural and levulinic acid were efficiently hydrogenated to the value-added furfuryl alcohol and promising biofuel γ-valerolactone, respectively, using a noble-metal-free Cu–Cr catalyst, which was facilely and successfully synthesized by a modified co-precipitation method using the cheap metal nitrates. In the first hydrogenation of furfural, 95% yield of furfuryl alcohol was highly selectively produced at 99% conversion of furfural under the mild conditions. For the hydrogenation of levulinic acid, 90% yield of γ-valerolactone was highly selectively produced at 97.8% conversion. Besides, the physical properties of the resulting Cu–Cr catalysts were studied by XRD (X-ray diffraction), EDX (Energy-dispersive X-ray), TEM (Transmission electron microscopy) and XPS (X-ray photoelectron spectroscopy) to reveal their influence on the catalytic performance. Subsequently, different reaction parameters were studied and it was found that Cu 2+ /Cr 3+ ratios (0.5, 1 and 2), reaction temperature (120–220 °C) and hydrogen pressure (35–70 bar) presented important influence on the catalytic activities. In the end, the stability of the Cu–Cr catalysts was also studied. - Highlights: • A noble-metal-free Cu–Cr catalyst was successfully synthesized using metal nitrates. • Cu–Cr catalysts were highly selective hydrogenation of biomass-derived furfural to FA. • Cu–Cr catalysts were efficient for hydrogenation of biomass-derived LA to biofuel GVL. • The physical properties of the resulting Cu–Cr catalysts were systematically studied. • Reaction parameters and stability in the hydrogenation of furfural were studied in details

Ultrasonic-assisted production of biodiesel from transesterification of palm oil over ostrich eggshell-derived CaO catalysts.

Science.gov (United States)

Chen, Guanyi; Shan, Rui; Shi, Jiafu; Yan, Beibei

2014-11-01

In this study, waste ostrich eggshell-derived calcium oxide (denoted as CaO(OE)) particles were synthesized and explored as cost-effective catalysts for the ultrasonic-assisted transesterification of palm oil. The physicochemical properties of the resultant catalysts were characterized by XRD, N2 adsorption, XRF and Hammett indicator, while the catalytic activity was evaluated through transesterification of palm oil with methanol under ultrasonic conditions. More specifically, the CaO(OE) showed comparable catalytic activity to the one derived from commercial calcium carbonate (denoted as CaO(Lab)). Moreover, under ultrasonic conditions, the catalytic activity of CaO(OE) could be enhanced significantly. The maximum yield of fatty acid methyl esters could reach 92.7% under the optimal condition of reaction time of 60 min with ultrasonic power of 60% (120 W), methanol-to-oil ratio of 9:1, and catalyst loading of 8 wt.%. The results indicated that the CaO(OE) catalysts showed good catalytic performance and reusability, and may potentially reduce the cost of biodiesel production. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis, characterization and dielectric properties of polynorbornadiene–clay nanocomposites by ROMP using intercalated Ruthenium catalyst

International Nuclear Information System (INIS)

Yalçınkaya, Esra Evrim; Balcan, Mehmet; Güler, Çetin

2013-01-01

Polynorbornadiene clay nanocomposites were prepared for the first time by the ring opening metathesis polymerization (ROMP) using modified montmorillonite and polynorbornadiene the latter of which is used commonly in electric–electronic industry. The Na–MMT clay was modified by a quaternary ammonium salt containing Ruthenium complex as a suitable catalyst and intercalant as well. The norbornadiene monomers were polymerized within the modified montmorillonite layers by in-situ polymerization method in different clay loading degrees. Intercalation ability of the Ru catalyst and partially exfoliated nanocomposite structure were proved by powder X-ray Diffraction (XRD) Spectroscopy and Transmission Electron Microscopy (TEM) methods. The nanocomposite materials with high thermal degradation temperature and low dielectric constant compared to the pure polynorbornadiene were obtained. The dielectric constants decreased with the increase of the clay content. - Highlights: • Polynorbornadiene–clay nanocomposites were prepared for the first time. • Ruthenium complex was assigned as both suitable catalyst and intercalant. • The norbornadiene was polymerized by in-situ polymerization method. • Exfoliation/intercalation structures were found to be related with loading degree. • PNBD–MMT nanocomposites had a higher thermal degradation temperature and lower dielectric constant

Synthesis of vertical MnO2 wire arrays on hemp-derived carbon for efficient and robust green catalysts

Science.gov (United States)

Yang, MinHo; Kim, Dong Seok; Sim, Jae-Wook; Jeong, Jae-Min; Kim, Do Hyun; Choi, Jae Hyung; Kim, Jinsoo; Kim, Seung-Soo; Choi, Bong Gill

2017-06-01

Three-dimensional (3D) carbon materials derived from waste biomass have been attracted increasing attention in catalysis and materials science because of their great potential of catalyst supports with respect to multi-functionality, unique structures, high surface area, and low cost. Here, we present a facile and efficient way for preparing 3D heterogeneous catalysts based on vertical MnO2 wires deposited on hemp-derived 3D porous carbon. The 3D porous carbon materials are fabricated by carbonization and activation processes using hemp (Cannabis Sttiva L.). These 3D porous carbon materials are employed as catalyst supports for direct deposition of vertical MnO2 wires using a one-step hydrothermal method. The XRD and XPS results reveal the crystalline structure of α-MnO2 wires. The resultant composites are further employed as a catalyst for glycolysis of poly(ethylene terephthalate) (PET) with high conversion yield of 98%, which is expected to be expressly profitable for plastics recycling industry.

Broadening of molecular weight distribution of polymers synthesized by metallocene-based dual-site catalysts; Alargamento da distribuicao de massa molar de polimeros sintetizados com catalisadores metalocenicos dual-site

Energy Technology Data Exchange (ETDEWEB)

Santos, Joao H.Z. dos [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica]. E-mail: jhzds@iq.ufrgs.br; Fisch, Adriano G.; Cardozo, Nilo S.M.; Secchi, Argimiro R. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Dept. de Engenharia Quimica

2008-07-01

The main topics related to the use of dual-site catalysts in the production of polymers with broad molecular weight distribution are reviewed. The polymerization using dual-site catalysts is more economical and allows to produce a higher quality product than other processes, such as polymer blend and multistage reactors. However, the formulation of these catalysts is quite complicated since the same catalyst must produce distinct polymer grades. In addition, the release of patents concerning the combination of metallocenes and new technologies for polymerization shows that polymerization processes using dual-site catalysts are of current industrial interest. (author)

Effect of Inhibitors on Atom Transfer Radical Polymerization of MMA

Institute of Scientific and Technical Information of China (English)

张鸿; 徐冬梅; 张可达

2005-01-01

Effect of a series of inhibitors as additives on atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with FeCl2/PPh3 as catalyst system was studied, including 2,4,6-trinitrophenol (TNP), 4-methoxyphenol (4-MP), hydroquinone (HQ) and nitrobenzene (NB). It was found that TNP was the only. efficient additive for ATRP among these inhibitors. In the presence of small amounts of TNP, the polymerization proceeded rapidly after induction period to yield the polymers with controlled molecular weights and narrow molecular weight distributions (MWD). The initiating efficiency of the modified catalyst system with TNP was increased. The mechanism was proposed and confirmed by the end group analysis of the polymer.

Biomass Derived Chemicals: Furfural Oxidative Esterification to Methyl-2-furoate over Gold Catalysts

Directory of Open Access Journals (Sweden)

Maela Manzoli

2016-07-01

Full Text Available The use of heterogeneous catalysis to upgrade biomass wastes coming from lignocellulose into higher value-added chemicals is one of the most explored subjects in the prospective vision of bio-refinery. In this frame, a lot of interest has been driven towards biomass-derived building block molecules, such as furfural. Gold supported catalysts have been successfully proven to be highly active and selective in the furfural oxidative esterification to methyl-2-furoate under mild conditions by employing oxygen as benign oxidant. Particular attention has been given to the studies in which the reaction occurs even without base as co-catalyst, which would lead to a more green and economically advantageous process. The Au catalysts are also stable and quite easily recovered and represent a feasible and promising route to efficiently convert furfural to methyl-2-furoate to be scaled up at industrial level.

Synthesis of vertical MnO_2 wire arrays on hemp-derived carbon for efficient and robust green catalysts

International Nuclear Information System (INIS)

Yang, MinHo; Kim, Dong Seok; Sim, Jae-Wook; Jeong, Jae-Min; Kim, Do Hyun; Choi, Jae Hyung; Kim, Jinsoo; Kim, Seung-Soo; Choi, Bong Gill

2017-01-01

Highlights: • The three-dimensional nanocomposites based on vertical MnO_2 array on hemp-derived carbon (HDC) were prepared by hydrothermal method. • The 3D v-MnO_2/HDC nanocomposites showed well-defined porous nature with a high specific surface area of 382.3 m"2 g"−"1. • PET glycolysis was performed using the 3D v-MnO_2/HDC nanocomposites as a catalyst, leading to efficient catalytic performance. - Abstract: Three-dimensional (3D) carbon materials derived from waste biomass have been attracted increasing attention in catalysis and materials science because of their great potential of catalyst supports with respect to multi-functionality, unique structures, high surface area, and low cost. Here, we present a facile and efficient way for preparing 3D heterogeneous catalysts based on vertical MnO_2 wires deposited on hemp-derived 3D porous carbon. The 3D porous carbon materials are fabricated by carbonization and activation processes using hemp (Cannabis Sttiva L.). These 3D porous carbon materials are employed as catalyst supports for direct deposition of vertical MnO_2 wires using a one-step hydrothermal method. The XRD and XPS results reveal the crystalline structure of α-MnO_2 wires. The resultant composites are further employed as a catalyst for glycolysis of poly(ethylene terephthalate) (PET) with high conversion yield of 98%, which is expected to be expressly profitable for plastics recycling industry.

Dual Enantioselective Control using D-phenylglycine-L-proline-derived Catalysts for the Enantioselective Addition of Diethylzinc to Aldehyde

International Nuclear Information System (INIS)

Kang, Seock Yong; Park, Yong Sun

2016-01-01

Dipeptide-derived catalysts are of great interest in various asymmetric transformations because of their short and simple preparation and easy modification of their modular structure by using different α-amino acids. We recently reported the first example of dipeptide-catalyzed enantioselective addition of dialkylzinc to aldehydes. We have developed a novel D-Phg-L-Pro dipeptide-derived catalyst for the addition of diethylzinc to aromatic aldehydes. We also disclosed an effective chiral switching by simply modifying nonchiral part of D-Phg-L-Pro dipeptide.

STUDIES ON VINYL POLYMERIZATION WITH INITIATION SYSTEM CONTAINING AMINE DERIVATIVES

Institute of Scientific and Technical Information of China (English)

QIU Kunyuan; ZHANG Jingyi; FENG Xinde(S. T. Voong)

1983-01-01

Two main types of amine-containing initiation systems were studied in this work. In the case of MMA polymerization initiated by BPO-amine (DMT, DHET, DMA) redox systems, it was found that the polymerization rate and colour stability of the polymer for different amine systems were in the following order: DMT≈DHET＞DMA. Accordingly, BPO-DMT and BPO-DHET are effective initiators. In the case of MEMA polymerization by amine (DMT, DHET, DMA) alone, it was found that the polymerization rate and the percentage of conversion for these different amine systems were in the following order: DMT≥DHET＞DMA. The polymerization rate and the percentage of conversion also increased with the increase of DMT concentration. From the kinetic investigation the rate equation of Rp=K [DMT]1/2 [MEMA]3/2 was obtained, and the overall activation energy of polymerization was calculated to be 34.3 KJ/mol (8.2 Kcal/mol). Moreover, the polymerization of MEMA in the presence of DMT was strongly inhibited by hydroquinone, indicating the polymerization being free radical in nature. From these results, the mechanism of MEMA polymerization initiated by amine was proposed.

Liquid phase in situ hydrodeoxygenation of biomass-derived phenolic compounds to hydrocarbons over bifunctional catalysts

Science.gov (United States)

Junfeng Feng; Chung-yun Hse; Zhongzhi Yang; Kui Wang; Jianchun Jiang; Junming Xu

2017-01-01

The objective of this study was to find an effective method for converting renewable biomass-derived phenolic compounds into hydrocarbons bio-fuel via in situ catalytic hydrodeoxygenation. The in situ hydrodeoxygenation of biomass-derived phenolic compounds was carried out in methanol-water solvent over bifunctional catalysts of Raney Ni and HZSM-5 or H-Beta. In the in...

2-Methyl-2,4-pentanediol (MPD boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

Directory of Open Access Journals (Sweden)

Julia Kinzel

2017-07-01

Full Text Available Covering hydrophobic regions with stabilization agents to solubilize purified transmembrane proteins is crucial for their application in aqueous media. The small molecule 2-methyl-2,4-pentanediol (MPD was used to stabilize the transmembrane protein Ferric hydroxamate uptake protein component A (FhuA utilized as host for the construction of a rhodium-based biohybrid catalyst. Unlike commonly used detergents such as sodium dodecyl sulfate or polyethylene polyethyleneglycol, MPD does not form micelles in solution. Molecular dynamics simulations revealed the effect and position of stabilizing MPD molecules. The advantage of the amphiphilic MPD over micelle-forming detergents is demonstrated in the polymerization of phenylacetylene, showing a ten-fold increase in yield and increased molecular weights.

An optimization study of PtSn/C catalysts applied to direct ethanol fuel cell: Effect of the preparation method on the electrocatalytic activity of the catalysts

Science.gov (United States)

Almeida, T. S.; Palma, L. M.; Leonello, P. H.; Morais, C.; Kokoh, K. B.; De Andrade, A. R.

2012-10-01

The aim of this work was to perform a systematic study of the parameters that can influence the composition, morphology, and catalytic activity of PtSn/C nanoparticles and compare two different methods of nanocatalyst preparation, namely microwave-assisted heating (MW) and thermal decomposition of polymeric precursors (DPP). An investigation of the effects of the reducing and stabilizing agents on the catalytic activity and morphology of Pt75Sn25/C catalysts prepared by microwave-assisted heating was undertaken for optimization purposes. The effect of short-chain alcohols such as ethanol, ethylene glycol, and propylene glycol as reducing agents was evaluated, and the use of sodium acetate and citric acid as stabilizing agents for the MW procedure was examined. Catalysts obtained from propylene glycol displayed higher catalytic activity compared with catalysts prepared in ethylene glycol. Introduction of sodium acetate enhanced the catalytic activity, but this beneficial effect was observed until a critical acetate concentration was reached. Optimization of the MW synthesis allowed for the preparation of highly dispersed catalysts with average sizes lying between 2.0 and 5.0 nm. Comparison of the best catalyst prepared by MW with a catalyst of similar composition prepared by the polymeric precursors method showed that the catalytic activity of the material can be improved when a proper condition for catalyst preparation is achieved.

Study on supported binary sulfide catalysts for secondary hydrogenation of coal-derived liquids; Sekitan ekikayu niji suisoka shokubai no kenkyu

Energy Technology Data Exchange (ETDEWEB)

Shimada, H.; Matsubayashi, N.; Sato, T.; Imamura, M.; Yoshimura, Y.; Nishijima, A. [National Institute of Materials and Chemical Research, Tsukuba (Japan)

1995-07-28

To utilize the high performance of supported catalysts in coal liquefaction processes, one of the promising ways is to apply hydroprocessing sulfide catalysts to the secondary hydrogenation of coal-derived liquids which have undergone the solid separation unit. However, when the product yield from the first-stage liquefaction is maximized, the feed stocks in the secondary hydrogenation contain large amounts of residual fractions with preasphaltenes and metallic components. In this case, the development of a long-life catalyst is essential to establish the two-stage process as a practical one. From this viewpoint, the authors have investigated the deactivation causes of supported Ni-Mo sulfide catalysts through the analysis of the used catalysts in the secondary hydrogenation of coal-derived liquids for long periods. The major cause of the catalyst deactivation has been found to be metallic and carbonaceous deposition on the catalyst, which results thin layer which covers the catalyst particles. The catalysts located at the reactor inlet are more rapidly deactivated than those at the rector exit because of larger amounts of metallic foul ants and the above described shell-like layer. Hydrocracking active sites are much heavily deactivated compared with hydrogenation active sites. It is inferred that the basic or polar compounds contained in coal liquids are permanency adsorbed on the hydrocracking active sites. Spectroscopic analysis of the used catalysts clarified the destruction of the active phase of the binary sulfides, through the segregation and crystal growth. The structural changes of the catalysts are very likely caused by heteroatom compounds in the preasphaltenes. Thus, the primary cause of the catalyst deactivation is the preasphaltenes in the coal liquids. Hydroaromatic compounds in the coal liquids suppress the change of the deposited carbonaceous materials into inert coke which permanently deactivate the catalyst.

Investigation of properties of polyethylene/clay nanocomposites prepared by new in situ Ziegler-Natta catalyst

International Nuclear Information System (INIS)

Nikkhah, S. Javan; Ramazani, S.A.; Baniasadi, H.; Tavakolzadeh, F.

2009-01-01

This paper is devoted to investigation of morphological and physical-mechanical properties of polyethylene (PE)/clay nanocomposites prepared via in situ polymerization method using bi-supported Ziegler-Natta catalyst. Bentonite type clay and MgCl 2 (ethoxide type) were used as the support of TiCl 4 . Catalyst support and polymerization process have been done in slurry phase using Triisobutylaluminum as the co-catalyst. The microstructure of the nanocomposites was examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). XRD and TEM indicated that almost fully exfoliated PE/clay nanocomposites were produced successfully using this method. According to permeability measurements, it was found that oxygen permeability values of the nanocomposite samples prepared with in situ polymerization method were dropped more than 200% introducing only 1 wt% clay to polymeric matrix. Differential scanning calorimetry (DSC) results indicated that the crystallization temperatures of samples are significantly higher than that of virgin PE. Moderate thermal stability enhancement of in situ polymerized nanocomposites was confirmed using thermogravimetric analysis (TGA).The storage modulus, Young's modulus and tensile strength of prepared samples were increased where the toughness was declined slightly. It seems that good dispersion and exfoliation of clay during polymerization should be responsible to get more effective reinforcing properties for clay in this method comparing to melt blending method for preparation of polyethylene nanocomposites.

Calcium Oxide Derived from Waste Shells of Mussel, Cockle, and Scallop as the Heterogeneous Catalyst for Biodiesel Production

Directory of Open Access Journals (Sweden)

Achanai Buasri

2013-01-01

Full Text Available The waste shell was utilized as a bioresource of calcium oxide (CaO in catalyzing a transesterification to produce biodiesel (methyl ester. The economic and environmen-friendly catalysts were prepared by a calcination method at 700–1,000°C for 4 h. The heterogeneous catalysts were characterized by X-ray diffraction (XRD, X-ray fluorescence (XRF, scanning electron microscopy (SEM, and the Brunauer-Emmett-Teller (BET method. The effects of reaction variables such as reaction time, reaction temperature, methanol/oil molar ratio, and catalyst loading on the yield of biodiesel were investigated. Reusability of waste shell catalyst was also examined. The results indicated that the CaO catalysts derived from waste shell showed good reusability and had high potential to be used as biodiesel production catalysts in transesterification of palm oil with methanol.

Polymerization of N-(fluoro phenyl) maleimides

International Nuclear Information System (INIS)

Barrales-Rienda, J.M.; Ramos, J.G.; Chaves, M.S.

1979-01-01

Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by azobisisobutyronitrile in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. 6 figures, 8 tables

Polymerized Nile Blue derivatives for plasticizer-free fluorescent ion optode microsphere sensors.

Science.gov (United States)

Ngeontae, Wittaya; Xu, Chao; Ye, Nan; Wygladacz, Katarzyna; Aeungmaitrepirom, Wanlapa; Tuntulani, Thawatchai; Bakker, Eric

2007-09-05

Lipophilic H+-selective fluorophores such as Nile Blue derivatives are widely used in ISE-based pH sensors and bulk optodes, and are commonly dissolved in a plasticized matrix such as PVC. Unfortunately, leaching of the active sensing ingredients and plasticizer from the matrix dictates the lifetime of the sensors and hampers their applications in vivo, especially with miniaturized particle based sensors. We find that classical copolymerization of Nile Blue derivatives containing an acrylic side group gives rise to multiple reaction products with different spectral and H+-binding properties, making this approach unsuitable for the development of reliable sensor materials. This limitation was overcome by grafting Nile Blue to a self-plasticized poly(n-butyl acrylate) matrix via an urea or amide linkage between the Nile Blue base structure and the polymer. Optode leaching experiments into methanol confirmed the successful covalent attachment of the two chromoionophores to the polymer matrix. Both polymerized Nile Blue derivatives have satisfactory pH response and appropriate optical properties that are suitable for use in ion-selective electrodes and optodes. Plasticizer-free Na+-selective microsphere sensors using the polymerized chromoionophores were fabricated under mild conditions with an in-house sonic microparticle generator for the measurement of sodium activities at physiological pH. The measuring range for sodium was found as 10(-1)-10(-4) M and 1-10(-3) M, for Nile Blue derivatives linked via urea and amide functionalities, respectively, at physiological pH. The observed ion-exchange constants of the plasticizer-free microsphere were log K(exch) = -5.6 and log K(exch) = -6.5 for the same two systems, respectively. Compared with earlier Na+-selective bulk optodes, the fabricated optical sensing microbeads reported here have agreeable selectivity patterns, reasonably fast response times, and more appropriate measuring ranges for determination of Na+ activity

Radiation sterilization of polymeric implant materials

International Nuclear Information System (INIS)

Bruck, S.D.; Mueller, E.P.

1988-01-01

High-energy irradiation sterilization of medical devices and implants composed of polymeric biomaterials that are in contact with tissue and/or blood, may adversely affect their long-term mechanical and/or biological performance (tissue and/or blood compatibility). Since many polymeric implants may contain trace quantities of catalysts and/or other additives, the effect of high-energy radiation on these additives, and possible synergistic effects with the polymer chains under the influence of high-energy radiation, must be considered. It is essential to indicate whether polymeric implants are used in short-term (acute) or long-term (chronic) applications. Relatively small changes in their physicochemical, mechanical, and biological properties may be tolerable in the short term, whereas similar changes may lead to catastrophic failures in long-term applications. Therefore, polymeric implants which are to be sterilized by high-energy irradiation should be carefully evaluated for long-term property changes which may be induced by the radiation

Effect of pretreatment temperature on catalytic performance of the catalysts derived from cobalt carbonyl cluster in Fischer-Tropsch Synthesis

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Byambasuren O

2017-02-01

Full Text Available The monometallic cobalt-based catalysts were prepared by pretreating the catalysts derived from carbonyl cluster precursor (CO6Co2CC(COOH2 supported on γ-Al2O3 with hydrogen at 180, 220, and 260°C respectively. The temperature effect of the pretreatments on the structure evolution of cluster precursors and the catalytic performance of the Fischer-Tropsch (F-T synthesis was investigated. The pretreated catalyst at 220°C with unique phase structure exhibited best catalytic activity and selectivity among three pretreated catalysts. Moreover, the catalysts exhibited high dispersion due to the formation of hydrogen bonds between the cluster precursor and γ-Al2O3 support.

Pressure-induced polymerization of phenoxyethyl acrylate

Energy Technology Data Exchange (ETDEWEB)

Kaminski, K; Wrzalik, R; Paluch, M; Ziolo, J [Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice (Poland); Roland, C M [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States)

2008-06-18

Polymerization of phenoxyethyl acrylate was induced without catalyst or initiators by the application of hydrostatic pressure at elevated temperature. Broadband dielectric and infrared spectroscopy were employed to follow the course of the reaction, which reached a degree of conversion of 60%. The structure of the obtained polymer was determined from density functional theory calculations.

Synthesis of vertical MnO{sub 2} wire arrays on hemp-derived carbon for efficient and robust green catalysts

Energy Technology Data Exchange (ETDEWEB)

Yang, MinHo [Department of Materials Science and Engineering and Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana–Champaign, Urbana, IL 61801 (United States); Kim, Dong Seok; Sim, Jae-Wook [Department of Chemical Engineering, Kangwon National University, 346 Joongang-ro, Samcheok, Gangwon-do 25913 (Korea, Republic of); Jeong, Jae-Min; Kim, Do Hyun [Department of Chemical & Biomolecular Engineering, KAIST, 291 Daehak-ro, Yuseong-gu, Daejeon 34141 (Korea, Republic of); Choi, Jae Hyung [Department of Chemical Engineering, Kangwon National University, 346 Joongang-ro, Samcheok, Gangwon-do 25913 (Korea, Republic of); Department of Chemical Engineering, Pukyong National University, 365 Sinseon-ro, Nam-gu, Busan 48513 (Korea, Republic of); Kim, Jinsoo [Department of Chemical Engineering, Kyung Hee University, 1732, Daogyong-daero, Giheung-gu, Yongin, Gyeonggi-do 17104 (Korea, Republic of); Kim, Seung-Soo, E-mail: sskim2008@kangwon.ac.kr [Department of Chemical Engineering, Kangwon National University, 346 Joongang-ro, Samcheok, Gangwon-do 25913 (Korea, Republic of); Choi, Bong Gill, E-mail: bgchoi@kangwon.ac.kr [Department of Chemical Engineering, Kangwon National University, 346 Joongang-ro, Samcheok, Gangwon-do 25913 (Korea, Republic of)

2017-06-15

Highlights: • The three-dimensional nanocomposites based on vertical MnO{sub 2} array on hemp-derived carbon (HDC) were prepared by hydrothermal method. • The 3D v-MnO{sub 2}/HDC nanocomposites showed well-defined porous nature with a high specific surface area of 382.3 m{sup 2} g{sup −1}. • PET glycolysis was performed using the 3D v-MnO{sub 2}/HDC nanocomposites as a catalyst, leading to efficient catalytic performance. - Abstract: Three-dimensional (3D) carbon materials derived from waste biomass have been attracted increasing attention in catalysis and materials science because of their great potential of catalyst supports with respect to multi-functionality, unique structures, high surface area, and low cost. Here, we present a facile and efficient way for preparing 3D heterogeneous catalysts based on vertical MnO{sub 2} wires deposited on hemp-derived 3D porous carbon. The 3D porous carbon materials are fabricated by carbonization and activation processes using hemp (Cannabis Sttiva L.). These 3D porous carbon materials are employed as catalyst supports for direct deposition of vertical MnO{sub 2} wires using a one-step hydrothermal method. The XRD and XPS results reveal the crystalline structure of α-MnO{sub 2} wires. The resultant composites are further employed as a catalyst for glycolysis of poly(ethylene terephthalate) (PET) with high conversion yield of 98%, which is expected to be expressly profitable for plastics recycling industry.

Reduction of light cycle oil in catalytic cracking of bitumen-derived crude HGOs through catalyst selection

Energy Technology Data Exchange (ETDEWEB)

Ding, Fuchen; Xu, Chunming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, 102200 (China); Ng, Siauw H. [National Centre for Upgrading Technology, 1 Oil Patch Drive, Suite A202, Devon, Alberta (Canada); Yui, Sok [Syncrude Research Centre, 9421-17 Avenue, Edmonton, Alberta (Canada)

2007-09-15

In an attempt to reduce the production of light cycle oil (LCO), a non-premium fluid catalytic cracking (FCC) product in North America, a large-pore catalyst containing rare-earth-exchanged Y (REY) zeolite, was used to crack two Canadian bitumen-derived crude heavy gas oils (HGOs) hydrotreated to different extents. For comparison, a regular equilibrium FCC catalyst with ultra-stable Y (USY) zeolite and a conventional western Canadian crude HGO were also included in the study. Cracking experiments were conducted in a fixed-bed microactivity test (MAT) reactor at 510 C, 30 s oil injection time, and varying catalyst-to-oil ratios for different conversions. The results show that pre-cracking of heavy molecules with wide-pore matrix, followed by zeolite cracking, enhanced conversion at the expense of light and heavy cycle oils at a constant catalyst-to-oil ratio, giving improved product selectivities (e.g., higher gasoline and lower dry gas, LCO, and coke yields, in general, at a given conversion). To systematically assess the benefits of employing the specialty catalyst over the regular catalyst in cracking Canadian HGOs, individual product yields were compared at common bases, including constant catalyst-to-oil ratios, conversions, and coke yields for three feeds, and at maximum gasoline yield for one feed. In most cases, the preferred choice of large-pore zeolite-rich catalyst over its counterpart was evident. The observed cracking phenomena were explained based on properties of catalysts and characterization data of feedstocks, including their hydrocarbon type analyses by gas chromatograph with a mass-selective detector (GC-MSD). (author)

Influência da temperatura e da natureza do catalisador na polimerização do glicerol Influence of temperature and nature of the catalyst on glycerol polymerization

Directory of Open Access Journals (Sweden)

Miguel de A. Medeiros

2010-09-01

Full Text Available Neste trabalho, a polimerização do glicerol na presença de catalisador ácido (H2SO4 ou H3PO4 e básico (NaOH, para produzir resinas termofixas foi investigada. Os resultados mostraram que as variáveis como a temperatura de reação, o tipo e a concentração do catalisador são críticas para a obtenção de bons rendimentos e seletividade para materiais poliméricos. Em condições otimizadas, i.e. H2SO4 como catalisador, 140 °C por 24 horas, foi possível obter polímeros com 98% de seletividade. Após polimerização, os materiais obtidos foram submetidos a extrações com diferentes solventes, i.e. água, THF e hexano. Os extratos foram caracterizados por ESI(+-MS e por espectroscopia na região do infravermelho, que permitiram verificar a presença de oligômeros de até seis unidades monoméricas. Para menores tempos de reação, e.g. 4 horas, foi possível obter elevada seletividade (100% para oligômeros, mas com baixa conversão de glicerol (25%. Além disso, verificou-se que os outros catalisadores (H3PO4 e NaOH apresentam baixa atividade para promover a polimerização do glicerol, e.g. rendimento de 25% após 24 horas.In this work, an investigation was made of the glycerol polymerization in the presence of acid (H2SO4 or H3PO4 and base (NaOH catalysts to produce thermosetting resins. The results showed that the reaction temperature and catalyst concentration are critical to obtain good yield and selectivity. Under optimum condition, i.e. H2SO4 catalyst, 140 °C for 24 hours it was possible to obtain polymers with 98% selectivity. After the polymerization the materials were submitted to extractions with different solvents, i.e. water, THF and hexane. The extracts were characterized by ESI(+-MS (Electro-Spray Ionization Mass Spectrometry and by FTIR, showing the presence of short-chain oligomers (up to six units. For shorter reaction times, e.g. 4 hours, it was possible to obtain high selectivity (100% for oligomers, but with low

Silica Sulfuric Acid: An Eco-Friendly and Reusable Catalyst for Synthesis of Benzimidazole Derivatives

Directory of Open Access Journals (Sweden)

Bahareh Sadeghi

2013-01-01

Full Text Available Silica sulfuric acid (SiO2-OSO3H as an eco-friendly, readily available, and reusable catalyst is applied to benzimidazole derivatives synthesis under reflux in ethanol. The procedure is very simple and the products are isolated with an easy workup in good-to-excellent yields.

FINAL TECHNICAL REPORT Synthetic, Structural and Mechanistic Investigations of Olefin Polymerization Catalyzed by Early Transition Metal Compounds

Energy Technology Data Exchange (ETDEWEB)

Bercaw, John E. [California Institute of Technology

2014-05-23

The goal of this project is to develop new catalysts and provide understanding of ligand effects on catalyst composition in order to guide development of superior catalyst systems for polymerization of olefins. Our group is designing and synthesizing new “LX2”,“pincer” type ligands and complexing early transition metals to afford precatalysts. In a collaboration with Hans Brintzinger from the University of Konstanz, we are also examining the structures of the components of catalyst systems obtained from reaction of zirconocene dichlorides with aluminum alkyls and aluminum hydrides. Such systems are currently used commercially to produce polyolefins, but the nature of the active and dormant species as well as the mechanisms of their interconversions are not understood. New information on catalyst design and performance may lead to new types of polymers and/or new chemical transformations between hydrocarbons and transition metal centers, ultimately contributing to the development of catalytic reactions for the production of fuels, commodity and polymeric materials.

Atom transfer radical polymerization of n-butyl acrylate catalyzed by atom transfer radical polymerization of n-butyl acrylate catalyzed by

NARCIS (Netherlands)

Zhang, H.; Linde, van der R.

2002-01-01

The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]0/[M]) versus the reaction time for the ATRP systems in different

Catalytic polymerization of olefins in supercritical carbon dioxide

NARCIS (Netherlands)

Kemmere, M.F.; Vries, de T.J.; Keurentjes, J.T.F.

2004-01-01

A novel process is being developed for the catalytic polymerization of olefins in supercritical carbon dioxide (sc CO2), for which potential applications will mainly be in the production of EPDM and other elastomers. For this purpose, the Brookhart catalyst has been tested for the homopolymerization

Novel catalysts for isotopic exchange between hydrogen and liquid water

International Nuclear Information System (INIS)

Butler, J.P.; Rolston, J.H.; Stevens, W.H.

1978-01-01

Catalytic isotopic exchange between hydrogen and liquid water offers many inherent potential advantages for the separation of hydrogen isotopes which is of great importance in the Canadian nuclear program. Active catalysts for isotopic exchange between hydrogen and water vapor have long been available, but these catalysts are essentially inactive in the presence of liquid water. New, water-repellent platinum catalysts have been prepared by: (1) treating supported catalysts with silicone, (2) depositing platinum on inherently hydrophobic polymeric supports, and (3) treating platinized carbon with Teflon and bonding to a carrier. The activity of these catalysts for isotopic exchange between countercurrent streams of liquid water and hydrogen saturated with water vapor has been measured in a packed trickle bed integral reactor. The performance of these hydrophobic catalysts is compared with nonwetproofed catalysts. The mechanism of the overall exchange reaction is briefly discussed. 6 figures

Surface Initiated Polymerizations via e-ATRP in Pure Water

Directory of Open Access Journals (Sweden)

Seyed Schwan Hosseiny

2013-10-01

Full Text Available Here we describe the combined process of surface modification with electrochemical atom transfer radical polymerization (e-ATRP initiated from the surface of a modified gold-electrode in a pure aqueous solution without any additional supporting electrolyte. This approach allows for a very controlled growth of the polymer chains leading towards a steady increase in film thickness. Electrochemical quartz crystal microbalance displayed a highly regular increase in surface confined mass only after the addition of the pre-copper catalyst which is reduced in situ and transformed into the catalyst. Even after isolation and washing of the modified electrode surface, reinitiation was achieved with retention of the controlled electrochemical ATRP reaction. This reinitiation after isolation proves the livingness of the polymerization. This approach has interesting potential for smart thin film materials and offers also the possibility of post-modification via additional electrochemical induced reactions.

A new magnetically recoverable catalyst promoting the synthesis of 1,4-dihydropyridine and polyhydroquinoline derivatives via the Hantzsch condensation under solvent-free conditions

Energy Technology Data Exchange (ETDEWEB)

Taheri, Narges; Heidarizadeh, Fariba; Kiasat, Alireza

2017-04-15

In the current study, 1,4-dihydropyridine and polyhydroquinoline derivatives were efficiently synthesized under solvent-less conditions with a magnetic catalyst containing novel acidic ionic liquid functionalized silica modified Fe{sub 3}O{sub 4} nanoparticles through a four component combination of β-ketoester, aldehydes and ammonium acetate (1, 2, 2). Several approaches have been reported for synthesizing these derivatives, while each of these approaches have some weaknesses including long time of reaction, excess of volatile organic solvent, low efficiency, costly reagents, complex operation, high temperatures, production of a number of side products, and difficult catalyst recovery. The simple operation, short time of reaction (5–30 min) and the high efficiency (80–94%) are the special advantages of this technique. The immobilized catalyst exhibited an appropriate thermal stability and excellent recyclability. Different methods such as FT-IR, SEM, EDX, TGA-DTA, and VSM were used to confirm and characterize the catalyst. - Highlights: • A new acidic ionic liquid were first synthesized and applied in both symmetric and asymmetric hantzsch reactions for preparing 1, 4-dihydropyridine and polyhydroquinoline derivatives with high efficiencies under solvent-less conditions. • The immobilized catalyst exhibited an appropriate thermal stability and excellent recyclability. • The nanomagnetic catalyst could be recovered from solution with an external magnet at once, allowing undemanding recovery and reuse. • The catalyst was reused for five times with no considerable decrease in catalytic activity.

Recent advances on polymeric membranes for membrane reactors

KAUST Repository

Buonomenna, M. G.

2012-06-24

Membrane reactors are generally applied in high temperature reactions (>400 °C). In the field of fine chemical synthesis, however, much milder conditions are generally applicable and polymeric membranes were applied without their damage. The successful use of membranes in membrane reactors is primary the result of two developments concerning: (i) membrane materials and (ii) membrane structures. The selection of a suited material and preparation technique depends on the application the membrane is to be used in. In this chapter a review of up to date literature about polymers and configuration catalyst/ membranes used in some recent polymeric membrane reactors is given. The new emerging concept of polymeric microcapsules as catalytic microreactors has been proposed. © 2012 Bentham Science Publishers. All rights reserved.

Site-selective metallization of polymeric substrates by the hyperbranched polymer templates

International Nuclear Information System (INIS)

Li, Peiyuan; Yang, Fang; Li, Xiangcheng; He, Chunling; Su, Wei; Chen, Jinhao; Huo, Lini; Chen, Rui; Lu, Chensheng; Liang, Lifang

2013-01-01

We demonstrate a simple, cost-effective and universal technique for the fabrication of copper circuit pattern on flexible polymeric substrate. This method relies on a ternary polyethylenimine-poly(acrylic acid)-substrate film incorporating palladium catalysts, which are used as adhesive interlayers for the copper metallization of flexible polymeric substrates. We demonstrated the fabrication of patterned copper films on a variety of flexible polymers with minimum feature sizes of 200 μm. And the resulting copper circuit showed strong adhesion with underlying flexible polymeric substrates. The films were characterized by ATR FT-IR, contact angle, XPS, XRD, TEM and SEM. The direct patterning of metallic circuit on flexible polymeric substrate indicates great potential for the use in electronics industry.

Site-selective metallization of polymeric substrates by the hyperbranched polymer templates

Energy Technology Data Exchange (ETDEWEB)

Li, Peiyuan, E-mail: lipearpear@163.com [College of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530001 (China); Yang, Fang [College of Chemistry and Life Science, Guangxi Teachers Education University, Nanning 530001 (China); Li, Xiangcheng [School of Computer, Electronics and Information, Guangxi University, Nanning 530001 (China); He, Chunling [College of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530001 (China); Su, Wei, E-mail: suwmail@163.com [College of Chemistry and Life Science, Guangxi Teachers Education University, Nanning 530001 (China); Chen, Jinhao [College of Chemistry and Life Science, Guangxi Teachers Education University, Nanning 530001 (China); Huo, Lini; Chen, Rui; Lu, Chensheng [College of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530001 (China); Liang, Lifang [College of Chemistry and Life Science, Guangxi Teachers Education University, Nanning 530001 (China)

2013-09-01

We demonstrate a simple, cost-effective and universal technique for the fabrication of copper circuit pattern on flexible polymeric substrate. This method relies on a ternary polyethylenimine-poly(acrylic acid)-substrate film incorporating palladium catalysts, which are used as adhesive interlayers for the copper metallization of flexible polymeric substrates. We demonstrated the fabrication of patterned copper films on a variety of flexible polymers with minimum feature sizes of 200 μm. And the resulting copper circuit showed strong adhesion with underlying flexible polymeric substrates. The films were characterized by ATR FT-IR, contact angle, XPS, XRD, TEM and SEM. The direct patterning of metallic circuit on flexible polymeric substrate indicates great potential for the use in electronics industry.

γ-Diimine palladium(II based complexes mediated polymerization of methyl methacrylate

Directory of Open Access Journals (Sweden)

Mahmoud Sunjuk

2017-02-01

Full Text Available The synthesis of new palladium(II complexes of the type [Pd(A–NC–ph–CN–ACl2] (4a–e (A = cyclohexyl (a, 2-isoprpropyl (b, pyrenyl (c, naphthyl (d, and 2,6-diisopropyl (e is described. The isolated γ-diimine ligands and their corresponding palladium(II complexes were characterized by their physical properties, elemental analysis, 1H NMR-, 13C NMR, and infrared spectroscopy. The palladium(II complexes (4a–e were employed successfully as catalysts for atom transfer radical polymerization (ATRP of methyl methacrylate (MMA in the presence of ethyl-2-bromoisobutyrate (EBIB as initiator at 90 °C. Polymerization with these catalyst systems afforded polymers with low molecular weight distribution (Mw/Mn and syndio-rich atactic poly (MMA with relatively higher [rr] diads.

Synthesis and butadiene polymerization behaviors of cationic cobalt-based catalyst

Directory of Open Access Journals (Sweden)

Li Liu

2017-01-01

Full Text Available A series of cationic cobalt-based compounds bearing different neutral N-bearing ligands (1,10-phenanthroline, bipyridine, benzimidazole, terpyridine and anionic ligands (trifluoromethanesulfonate, methanesulfonate were synthesized and the simple compound, Co(Phen2Cl2, was also prepared as a reference compound. All the compounds were characterized along with infrared spectra analysis and some of them were further confirmed by single crystal X-ray crystallographic analysis. Upon activation with ethylaluminum sesquichloride, these cationic cobalt(II compounds showed high catalytic activities for butadiene polymerization. The detailed investigations were carried out to disclose the influence of various polymerization conditions, sterical and electronic parameters of the ligands on their performing activities of the compounds.

Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

International Nuclear Information System (INIS)

Barkholtz, Heather M.; Liu, Di-Jia

2016-01-01

Over the past several years, metal-organic framework (MOF)-derived platinum group metal free (PGM-free) electrocatalysts have gained considerable attention due to their high efficiency and low cost as potential replacement for platinum in catalyzing oxygen reduction reaction (ORR). In this review, we summarize the recent advancements in design, synthesis and characterization of MOF-derived ORR catalysts and their performances in acidic and alkaline media. As a result, we also discuss the key challenges such as durability and activity enhancement critical in moving forward this emerging electrocatalyst science.

Ethylbenzene dehydrogenation over Mg3Fe0.5−xCoxAl0.5 catalysts derived from hydrotalcites: Comparison with Mg3Fe0.5−yNiyAl0.5 catalysts

KAUST Repository

Atanda, Luqman A.; Balasamy, Rabindran J.; Khurshid, Alam; Al-Ali, Ali A S; Sagata, Kunimasa; Asamoto, Makiko; Yahiro, Hidenori; Nomura, Kiyoshi; Sano, Tsuneji; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

2011-01-01

A series of Mg3Fe0.5-xCoxAl0.5 (x = 0-0.5) catalysts were prepared from hydrotalcite precursors and their activities in the dehydrogenation of ethylbenzene were compared with those of a series of Mg3Fe0.5-yNiyAl0.5 (y = 0-0.5) catalysts also derived

Palladium catalyst system comprising zwitterion and/or acid-functionalized ionic liquid

DEFF Research Database (Denmark)

2011-01-01

The present invention concerns a catalyst system in particular a catalyst system comprising Palladium (Pd), a zwitterion and/or an acid-functionalized ionic liquid, and one or more phosphine ligands, wherein the Pd catalyst can be provided by a complex precursor, such as Pd(CH3COO)2, PdCI2, Pd(CH3......COCHCOCH3), Pd (CF3COO)2, Pd(PPh3)4 or Pd2(dibenzylideneacetone)3. Such catalyst systems can be used for e.g. alkoxycarbonylation reactions, carboxylation reactions, and/or in a co-polymerization reaction, e.g. in the production of methyl propionate and/or propanoic acid, optionally in processes forming...... methyl methacrylate and/or methacrylic acid. Catalyst systems according to the invention are suitable for reactions forming separable product and catalyst phases and supported ionic liquid phase SILP applications....

Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

KAUST Repository

Falivene, Laura; Cavallo, Luigi; Talarico, Giovanni

2015-01-01

A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

Buried Volume Analysis for Propene Polymerization Catalysis Promoted by Group 4 Metals: a Tool for Molecular Mass Prediction

KAUST Repository

Falivene, Laura

2015-10-02

A comparison of the steric properties of homogeneous single site catalysts for propene polymerization using the percentage of buried volume (%VBur) as molecular descriptor is reported. The %VBur calculated on the neutral precursors of the active species seems to be a reliable tool to explain several experimental data related to the propene insertion and to the monomer chain transfer. Interestingly, a linear correlation between the buried volume calculated for a large set of neutral precursors and the energetic difference between propagation and termination steps calculated by DFT methods is found for Group 4 metal catalysts. The “master curves” derived for Ti, Zr and Hf confirm not only that the %VBur is an appropriate molecular descriptor for the systems considered but also that it could be used as tool for a large computational screening of new ligands.

A comparative study on synthesis of LLDPE/TiO2 nanocomposites using different TiO2 by in situ polymerization with zirconocene/dMMAO catalyst

International Nuclear Information System (INIS)

Owpradit, Wathanyoo; Jongsomjit, Bunjerd

2008-01-01

The present study revealed the effect of different TiO 2 nanoparticles employed on catalytic and characteristic properties of LLDPE/TiO 2 nanocomposites synthesized by the in situ polymerization with zirconocene/dMMAO catalyst. It was found that the presence of rutile phase in titania apparently resulted in decreased activities due to low intrinsic activity of active sites being present. Based on 13 C NMR results, all LLDPE/TiO 2 samples exhibited the random copolymer having different degree of 1-hexene insertion. The highly dispersion of titania can enhance the degree of 1-hexene insertion resulting in decreased crystallinity

Catalyst in Basic Oleochemicals

Directory of Open Access Journals (Sweden)

Eva Suyenty

2007-10-01

Full Text Available Currently Indonesia is the world largest palm oil producer with production volume reaching 16 million tones per annum. The high crude oil and ethylene prices in the last 3 – 4 years contribute to the healthy demand growth for basic oleochemicals: fatty acids and fatty alcohols. Oleochemicals are starting to replace crude oil derived products in various applications. As widely practiced in petrochemical industry, catalyst plays a very important role in the production of basic oleochemicals. Catalytic reactions are abound in the production of oleochemicals: Nickel based catalysts are used in the hydrogenation of unsaturated fatty acids; sodium methylate catalyst in the transesterification of triglycerides; sulfonic based polystyrene resin catalyst in esterification of fatty acids; and copper chromite/copper zinc catalyst in the high pressure hydrogenation of methyl esters or fatty acids to produce fatty alcohols. To maintain long catalyst life, it is crucial to ensure the absence of catalyst poisons and inhibitors in the feed. The preparation methods of nickel and copper chromite catalysts are as follows: precipitation, filtration, drying, and calcinations. Sodium methylate is derived from direct reaction of sodium metal and methanol under inert gas. The sulfonic based polystyrene resin is derived from sulfonation of polystyrene crosslinked with di-vinyl-benzene. © 2007 BCREC UNDIP. All rights reserved.[Presented at Symposium and Congress of MKICS 2007, 18-19 April 2007, Semarang, Indonesia][How to Cite: E. Suyenty, H. Sentosa, M. Agustine, S. Anwar, A. Lie, E. Sutanto. (2007. Catalyst in Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 22-31.  doi:10.9767/bcrec.2.2-3.6.22-31][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.2-3.6.22-31 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/6

Biomass processing over gold catalysts

CERN Document Server

Simakova, Olga A; Murzin, Dmitry Yu

2014-01-01

The book describes the valorization of biomass-derived compounds over gold catalysts. Since biomass is a rich renewable feedstock for diverse platform molecules, including those currently derived from petroleum, the interest in various transformation routes has become intense. Catalytic conversion of biomass is one of the main approaches to improving the economic viability of biorefineries.  In addition, Gold catalysts were found to have outstanding activity and selectivity in many key reactions. This book collects information about transformations of the most promising and important compounds derived from cellulose, hemicelluloses, and woody biomass extractives. Since gold catalysts possess high stability under oxidative conditions, selective oxidation reactions were discussed more thoroughly than other critical reactions such as partial hydrogenation, acetalization, and isomerization. The influence of reaction conditions, the role of the catalyst, and the advantages and disadvantages of using gold are pre...

Research and development of a technology to create original high-function materials in fiscal 1998 (development of precision structure controlling materials by improving petroleum refining). Report on achievements in research and development of precision catalytic polymerization; 1998 nendo dokusoteki kokino zairyo sosei gijutsu no kenkyu kaihatsu seika hokokusho. Sekiyu seisei kodoka seimitsu kozo seigyo zairyo kaihatsu (seimitsu shokubai jugo no kenkyu kaihatsu)

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

Research and development on precision catalytic polymerization aims at developing polymerizing catalysts that can control arbitrarily the molecular weight and three-dimensional regularity by which rapid enhancement can be expected in performance of additional polymerization type polymers, and the primary structure of terminal groups. Works are being done on two sub-themes of ultimate additional polymerization and orientation catalyst polymerization. The research and development of the ultimate additional polymerization included structural control in polymerization reaction in vinyl chloride, vinylester and acrylic monomers, radical polymerization with precision orientation control, anionic polymerization with precision structural control, and precision polymerization utilizing asymmetric metal porphyrin complexes. In the research and development of the orientation catalyst polymerization, the orientation catalyst polymerization was researched and developed, elementary reaction of metallocene was elucidated, high-performance carrier catalysts were developed, advanced function polymers were synthesized at high precision based on metathesis, and improvement of functions of polyolefin was researched and developed. Surveys and studies were carried out on fundamental technologies common to the above two themes re-commissioned to five universities. (NEDO)

Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

Institute of Scientific and Technical Information of China (English)

Dong Jinyong

2006-01-01

Functionalization of polyolefins is an industrially important yet scientifically challenging research subject.This paper summarizes our recent effort to access structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization.In one approach,polypropylenes containing side chain functional groups of controlled concentrations were obtained by Ziegler-Natta-catalyzed copolymerization of propylene in combination with either living anionic or controlled radical polymerization of polar monomers.The copolymerization of propylene with 1,4-divinylbenzene using an isospecific MgC12-supported TIC14 catalyst yielded potypropylenes containing pendant styrene moieties.Both metalation reaction with n-butyllithium and hydrochlorination reaction with dry hydrogen chloride selectively and quantitatively occurred at the pendant reactive sites,generating polymeric benzyllithium and 1-chloroethylbenzene species.These species initiated living anionic polymerization of styrene(S)and atom transfer radical polymerization(in the presence of CuC1 and pentamethyldiethylenetriamine) of methyl methacrylate(MMA),respectively,resulting in functional polypropylene graft copolymers(PP-g-PS and PP-g-PMMA)with controllable graft lengths.In another approach,chain end-functionalized polypropylenes containing a terminal OH-group with controlled molecular weights were directly prepared by propylene polymerization with a metaUocene catalyst through a selective aluminum chain transfer reaction.Both approaches proved to be desirable polyolefin functionalization routes in terms of efficiency and polymer structure controllability.

Polymerization of Polar Monomers from a Theoretical Perspective

KAUST Repository

Alghamdi, Miasser

2016-10-11

Density functional theory calculations have been used to investigate catalytic mechanism of polymer formation containing polar groups, from the synthesis of the monomer to the synthesis of the macromolecule. In the spirit of a sustainable and green chemistry, we initially focused attention on the coupling of CO2 as economically convenient and recyclable C1 source with C2H4 to form acrylate and/or butirro-lactone, two important polar monomers. In this process formation of a mettallolactone via oxidative coupling of CO2 and C2H4 is an important intermediate. Given this background, we explored in detail (chapter-3) several Ni based catalysts for CO2 coupling with C2H4 to form acrylate. In this thesis we report on the competitive reaction mechanisms (inner vs outer sphere) for the oxidative coupling of CO2 and ethylene for a set of 11 Ni-based complexes containing bisphosphine ligands. In another effort, considering incorporation of a C=C bond into a metal-oxygen-Functional-Group moiety is a challenging step in several polymerization reactions, we explored the details of this reaction (chapter4) using two different catalysts that are capable to perform this reaction in the synthesis of heterocycles. Specifically, the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-Bis-diphenylphosphino-propane), and the [Pd]/BPh3 intramolecular alkoxyfunctionalizations. Rest of the thesis we worked on understanding the details of the polymerization of polar monomers using organocatalysts based on N-heterocyclic carbenes (NHC) or N-heterocyclic olefins (NHO). In particular (chapter-5) we studied the polymerization of N-methyl N-carboxy- anhydrides, towards cyclic poly(N-substituted glycine)s, promoted by NHC catalysts. In good agreement with the experimental findings, we demonstrated that NHC promoted ring opening polymerization of N-Me N-Carboxyanhydrides may proceed via two different catalytic pathways. In a similar effort we studied polymerization of

A New Initiator Cholesteryl Chloroformate for Cupper-Based Atom Transfer Radical Polymerization of Methyl Methacrylate

Institute of Scientific and Technical Information of China (English)

曹健; 楚娟; 张可达

2004-01-01

The polymerization of metyl methacrylate (MMA) was studied in detail by use of CuCl/L as a catalyst and cholesteryl chloroformate (CC) as an initiator. It was found that the atom transfer radical polymerization of MMA could proceed when L equals to a multidentate aliphatic amine ligand, N,N,N',N",N"-penta(methyl acrylate)diethylenetriamine (MA5-DETA), and no polymerization was occurred while L=2,2'-bipyridine and 1,10-phenanthroline. The linear proportionality of the molecular weights to the conversions and straight lines observed in ln[M]0/[M] versus time plots indicated that the present polymerization system had the typical controlled polymerization characteristics.

Novel catalysts for upgrading coal-derived liquids. Final technical progress report

Energy Technology Data Exchange (ETDEWEB)

Thompson, L.T.; Savage, P.E.; Briggs, D.E.

1995-03-31

Research described in this report was aimed at synthesizing and evaluating supported Mo oxynitrides and oxycarbides for the selective removal of nitrogen, sulfur and oxygen from model and authentic coal-derived liquids. The Al{sub 2}O{sub 3}-supported oxynitrides and oxycarbides were synthesized via the temperature programmed reaction of supported molybdenum oxides or hydrogen bronzes with NH{sub 3} or an equimolar mixture of CH{sub 4} and H{sub 2}. Phase constituents and composition were determined by X-ray diffraction, CHN analysis, and neutron activation analysis. Oxygen chemisorption was used to probe the surface structure of the catalysts. The reaction rate data was collected using specially designed micro-batch reactors. The Al{sub 2}O{sub 3}-supported Mo oxynitrides and oxycarbides were competitively active for quinoline hydrodenitrogenation (HDN), benzothiophene hydrodesulfurization (HDS) and benzofuran hydrodeoxygenation (HDO). In fact, the HDN and HDO specific reaction rates for several of the oxynitrides and oxycarbides were higher than those of a commercial Ni-Mo/Al{sub 2}O{sub 3} hydrotreatment catalyst. Furthermore, the product distributions indicated that the oxynitrides and oxycarbides were more hydrogen efficient than the sulfide catalysts. For HDN and HDS the catalytic activity was a strong inverse function of the Mo loading. In contrast, the benzofuran hydrodeoxygenation (HDO) activities did not appear to be affected by the Mo loading but were affected by the heating rate employed during nitridation or carburization. This observation suggested that HDN and HDS occurred on the same active sites while HDO was catalyzed by a different type of site.

Oxidative regeneration of Ni-Mo-gamma-Al/sub 2/O/sub 3/ catalysts used for hydrotreatment of coal-derived oil

Energy Technology Data Exchange (ETDEWEB)

Yoshimura, Yuji; Furimsky, Edward; Sato, Toshio; Shimada, Hiromichi; Matsubayashi, Nobuyuki; Nishijima, Akio

1986-10-23

In order to easily find the oxidative reaction characteristics of carbonaceous materials and sulfur deposited on the catalysts used for hydrogenation, oxidative regeneration behavior as studied with a fixed bed reactor, and the surfaces of the spent catalysts were analyzed by XPS to find the changes in form of active metals and sulfur on the catalysts. Ni-Mo-gamma-Al/sub 2/O/sub 3/ catalysts were used for hydrotreatment of primary coal-derived oil from Morwell coal. The spent catalysts were extracted by THF, dried and crushed into 100-200 mesh powder. The relation between catalyst regeneration temperature and CO/sub 2/ or SO/sub 2/, the relation between generated gas compositions and temperature in regeneration, and the activation energy of carbon and sulfur in the catalysts for oxidative reaction were indicated with data. As a result, it was found that a part of the active metals turned to sulfates by hydrotreatment and the residual sulfur existed in form of sulfate. ( 6 figs, 2 tabs, 4 refs )

Factors influencing catalytic behavior of titanium complexes bearing bisphenolate ligands toward ring-opening polymerization of L-lactide and ε-caprolactone

Directory of Open Access Journals (Sweden)

M-T. Jiang

2018-02-01

Full Text Available A series of titanium complexes bearing substituted diphenolate ligands (RCH(phenolate2, where R = H, CH3, o-OTs-phenyl, o-F-phenyl, o-OMe-phenyl, 2,4-OMe-phenyl was synthesized and studied as catalysts for the ring opening polymerization of L-lactide and ε-caprolactone. Ligands were designed to probe the role of chelate effect and steric effect in the catalytic performance. From the structure of triphenolate (with one extra coordination site than diphenolate ligand Ti complex, TriOTiOiPr2, we found no additional chelation to influence the catalytic activity of Ti complexes. It was found that bulky aryl groups in the diphenolate ligands decreased the rate of polymerization most. We conclude that steric effect is the most controlling factor in these polymerization reactions by using Ti complexes bearing diphenolate ligands as catalysts since it is responsible for the exclusion of needed space for incoming monomer by the bulky substituents on the catalyst.

INFLUENCE OF CELLULOSE POLYMERIZATION DEGREE AND CRYSTALLINITY ON KINETICS OF CELLULOSE DEGRADATION

OpenAIRE

Edita Jasiukaitytė-Grojzdek,; Matjaž Kunaver,; Ida Poljanšek

2012-01-01

Cellulose was treated in ethylene glycol with p-toluene sulfonic acid monohydrate as a catalyst at different temperatures. At the highest treatment temperature (150 °C) liquefaction of wood pulp cellulose was achieved and was dependant on cellulose polymerization degree (DP). Furthermore, the rate of amorphous cellulose weight loss was found to increase with cellulose degree of polymerization, while the rate of crystalline cellulose weight loss was reciprocal to the size of the crystallites. ...

Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

Science.gov (United States)

Zelenay, Piotr; Wu, Gang

2014-04-29

A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

Amphiphilic phase-transforming catalysts for transesterification of triglycerides

Science.gov (United States)

Nawaratna, Gayan Ivantha

Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be

Organic and inorganic ion exchangers as catalysts for the heterogeneous alkylation of aromatics

Energy Technology Data Exchange (ETDEWEB)

Klein, J; Widdecke, H [Technische Univ. Braunschweig (Germany, F.R.). Inst. fuer Chemische Technologie

1979-06-01

Ion exchangers have advantages over low molecular for use in industrial alkylation reactions. The reactivity and selectivity behaviour of the polymeric catalysts was found to be markedly influenced by the structure of the polymeric matrix as well as the type and number of the functional groups. In this connection many similarities between inorganic ion exchangers (zeolites) and organic ion exchange resins were detected.

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

Science.gov (United States)

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impregnation of β-tricalcium phosphate robocast scaffolds by in situ polymerization.

Science.gov (United States)

Martínez-Vázquez, Francisco J; Perera, Fidel H; van der Meulen, Inge; Heise, Andreas; Pajares, Antonia; Miranda, Pedro

2013-11-01

Ring-opening polymerization of ε-caprolactone (ε-CL) and L-lactide (LLA) was performed to impregnate β-tricalcium phosphate (β-TCP) scaffolds fabricated by robocasting. Concentrated colloidal inks prepared from β-TCP commercial powders were used to fabricate porous structures consisting of a 3D mesh of interpenetrating rods. ε-CL and LLA were in situ polymerized within the ceramic structure by using a lipase and stannous octanoate, respectively, as catalysts. The results show that both the macropores inside the ceramic mesh and the micropores within the ceramic rods are full of polymer in either case. The mechanical properties of scaffolds impregnated by in situ polymerization (ISP) are significantly increased over those of the bare structures, exhibiting similar values than those obtained by other, more aggressive, impregnation methods such as melt-immersion (MI). ISP using enzymatic catalysts requires a reduced processing temperature which could facilitate the incorporation of growth factors and other drugs into the polymer composition, thus enhancing the bioactivity of the composite scaffold. The implications of these results for the optimization of the mechanical and biological performance of scaffolds for bone tissue engineering applications are discussed. Copyright © 2013 Wiley Periodicals, Inc.

Gas Phase Homo- and Co-polymerization of Ethylene over Mg(O Et){sub 2}/T HF/Si Cl{sub 4}/Ti Cl{sub 4}/ Catalysts

Energy Technology Data Exchange (ETDEWEB)

Min-Chul, Chung [Korea Advanced Institute of Science and Techology., Taejeon (Korea, Republic of); Il, Kim [Univ. of Ulsan., Ulsan (Korea, Republic of); Jae-Ha, Kim [Korea Petrochemial Ind., Kyungnam (Korea, Republic of); Hong-Ki Choi [Korea Advanced Institute of Science and Technology., Taejeon (Korea, Republic of); Seung-Ihl, Woo

1994-08-01

Homo- and co-polymerization of ethylene were carried out in both gas and slurry phases over Mg(O Et)2/T HF/Si Cl{sub 4}/Ti Cl{sub 4}-Al Et{sub 3} catalysts in the range of temperature 20-70{sup o} C and pressure 2-10 psig. In gas phase polymerization, maximum activity was measured at the Al/Ti mole ratio of 377, and reaction rate dependence on Al Et{sub 3} concentration could be explained with the Langmuir-Hinshelwood adsorption model. Even though maximum activities were obtained at the same temperature, 60{sup o} C in both gas and slurry phases, overall activation energy was higher for the slurry phase(13 kCal/mol) than for the gas phase(4.7 kCal/mol) polymerization. The molecular weight behavior has been examined by measuring intrinsic viscosity. The molecular weight was increased as the ethylene pressure increased, and as the temperature and the concentration of Al Et{sub 3} and hydrogen decreased. Using two different co monomers(propylene and butene-1), the copolymerization of ethylene was carried out. The intrinsic viscosity and the melt index were decreased as co monomer concentration increased, and the maximum activity was observed when the concentration of comonomer is about 20 mol%. (author). 28 refs. 6 tabs. 13 figs.

Montmorillonite Supported Titanium/Antimony Catalyst:Preparation, Characterization and Immobilization

Institute of Scientific and Technical Information of China (English)

CHEN Guiyong; WANG Xiaoqun; ZHAO Chuan; DU Shanyi

2014-01-01

Montmorillonite supported titanium (Ti-MMT) or antimony catalyst (Sb-MMT) has been a hot area of research on preparing polyethylene terephthalate/montmorillonite (PET/MMT) nanocomposites by in situ polymerization. So removal of Ti or Sb from Ti-MMT or Sb-MMT is not expected during in situ polymerization. Studies on immobilization of Ti or Sb on Ti-MMT or Sb-MMT are seldom reported. In this work, a series of montmorillonite supported catalysts of titanium (Ti-MMT) or antimony (Sb-MMT) and co-intercalated montmorillonite of titanium and antimony (Ti/Sb-MMT) were prepared by (1) the reaction of sodium bentonite suspension with intercalating solution containing titanium tetrachloride and/or antimony chloride, and (2) drying or calcinating the products at different temperature (100, 150, 240, 350 and 450℃). The physicochemical properties of these MMT supported catalysts were studied by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma optical emission spectrometer (ICPOES), N2 adsorption/desorption isotherms, UV-visible diffuse reflectance spectroscopy(UV-vis) and transmission electron microscopy (TEM). The immobile character of Ti or Sb on MMT supported catalysts was evaluated by a two-step method in deionized water or ethylene glycol. Several results were obtained, i e, (a) during the preparation, with an increase in drying or calcinating temperature, the amount of titanium and/or antimony species remained on these MMT supported catalysts decreased, (b) the experiments about immobile character of Ti or/and Sb showed that with an increase in drying or calcinating temperature, the immobilization of Ti and/or Sb species remained on these MMT supported catalysts increased gradually, (c) Ti-MMT calcinated at 450℃had the biggest pore volume, which means Ti-MMT had the best adsorption application prospect.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

Science.gov (United States)

Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

Science.gov (United States)

Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Hydrodeoxygenation of heavy oils derived from low-temperature coal gasification over NiW catalysts-effect of pore structure

Energy Technology Data Exchange (ETDEWEB)

Dieter Leckel [Sasol Technology Research and Development, Sasolburg (South Africa). Fischer-Tropsch Refinery Catalysis

2008-01-15

The effect of the pore structure on the hydroprocessing of heavy distillate oils derived from low-temperature coal gasification residues was studied using four NiW catalysts with different pore size distributions. The hydroprocessing was conducted at a pressure of 17.5 MPa, a temperature range of 370-410{sup o}C, and a 0.50 h{sup -1} space velocity. The degree of hydrodeoxygenation (HDO) in terms of phenolics removal was influenced by the catalyst pore structure, with the most preferable peak pore diameter for HDO ranging between 6.8 and 16 nm. The catalyst with the highest volume of pores in the 3.5-6 nm range showed the lowest HDO activity. The apparent activation energies for the HDO reaction varied between 59 and 87 kJ/mol, whereby the lowest values are obtained for the catalysts with a peak pore diameter of 11 and 16 nm. 30 refs., 5 figs., 6 tabs.

Esterification of oily-FFA and transesterification of high FFA waste oils using novel palm trunk and bagasse-derived catalysts

International Nuclear Information System (INIS)

Ezebor, Francis; Khairuddean, Melati; Abdullah, Ahmad Zuhairi; Boey, Peng Lim

2014-01-01

Highlights: • Novel palm trunk and bagasse derived catalysts have been prepared. • Reduction of FFAs from 42 to <1 wt.% in 15 min under pseudo-infinite methanol. • Transesterification of waste oil results in FAME yield of 80.6–83.2% in 4 h. • Pseudo-infinite methanol affords two-folds FAME yield of conventional methods. - Abstract: Waste cooking oil is increasingly becoming a significant component of biodiesel feedstock and its conversion to FAME requires coupling of esterification and transesterification processes. In this study, new environmentally benign catalysts were prepared from oil palm trunk and sugarcane bagasse, which are sustainable because of the superfluity of oil palm trunk and abundant supply of bagasse. Effect of preparation variable, surface acidity and textural properties, pre-esterification of FFA in oil matrices and transesterification of waste oil under pseudo-infinite methanol and conventional methods were investigated. The preparation variable, H 2 SO 4 impregnation time showed marginal effect on sulfonic acid density after 6 h, and the corresponding values for 6–10 h impregnations were 1.33 ± 0.01–1.41 ± 0.01mmol g −1 for OPT and 1.44 ± 0.01–1.48 ± 0.01mmol g −1 for SCB catalysts. In esterification of palmitic acid, activity of catalysts with different H 2 SO 4 impregnation time correlates with their sulfonic acid density. The catalysts demonstrated rapid esterification of FFA in oil matrices under pseudo infinite methanol, reducing its content from 42 wt.% to <1 wt.% in just 15 min. Similarly, the conversions of waste oil by OPT and SCB derived catalysts were 80.6% and 83.2%, respectively after 4 h under pseudo-infinite methanol, and 43.7% and 45%, respectively after 6 h under conventional method. These catalysts have shown remarkable properties that are suitable for biodiesel production from waste oil

Conductive cotton prepared by polyaniline in situ polymerization using laccase.

Science.gov (United States)

Zhang, Ya; Dong, Aixue; Wang, Qiang; Fan, Xuerong; Cavaco-Paulo, Artur; Zhang, Ying

2014-09-01

The high-redox-potential catalyst laccase, isolated from Aspergillus, was first used as a biocatalyst in the oxidative polymerization of water-soluble conductive polyaniline, and then conductive cotton was prepared by in situ polymerization under the same conditions. The polymerization of aniline was performed in a water dispersion of sodium dodecylbenzenesulfonate (SDBS) micellar solution with atmospheric oxygen serving as the oxidizing agent. This method is ecologically clean and permits a greater degree of control over the kinetics of the reaction. The conditions for polyaniline synthesis were optimized. Characterizations of the conducting polyaniline and cotton were carried out using Fourier transform infrared spectroscopy, UV-vis spectroscopy, cyclic voltammetry, the fabric induction electrostatic tester, and the far-field EMC shielding effectiveness test fixture.

Determination of polymerization particle morphology using synchrotron computed microtomography

International Nuclear Information System (INIS)

Jones, K.W.; Spanne, P.; Lindquist, W.B.; Conner, W.C.; Ferrero, M.

1991-10-01

Polymerization of monomers over heterogeneous catalysts results in the fragmentation of the catalysts and subsequent transport in the polymer particles that are produced. Characterization of the process using nondestructive synchrotron computed microtomography techniques makes possible measurement of the distribution of the catalyst fragments in an individual particle and, in addition, gives an estimate of the particle porosity and surface area. The present experiment was carried out using the x-ray microscopy facility at the Brookhaven National Synchrotron Light Source (NSLS) X26 beam line. The tomographic sections were analyzed using autocorrelation techniques to determine porosity and surface area values. The results are compared to values obtained using conventional methods. This procedure makes possible the extraction of quantitative information about porosity and specific area from the tomograms. 9 refs., 7 figs., 1 tab

Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities

Science.gov (United States)

McLeod, David Charles

Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular

Catalytic behaviors of Co{sup II} and Mn{sup II} compounds bearing α-Diimine ligands for oxidative polymerization or drying oils

Energy Technology Data Exchange (ETDEWEB)

Lima, Gilvan E.S.; Nunes, Everton V.; Dantas, Roberta C.; Meneghetti, Mario R.; Meneghetti, Simoni M.P., E-mail: simoni.plentz@gmail.com [Universidade Federal de Alagoas (UFAL), Maceió, AL (Brazil). Grupo de Catálise e Reatividade Química; Simone, Carlos A. de [Universidade de Sao Paulo (USP), São Carlos, USP, SP (Brazil). Instituto de Física

2018-05-01

The oxidative polymerization of linseed oil was investigated comparing the classical catalysts cobalt(II) 2-ethylhexanoate and manganese(II) 2-ethylhexanoate and their derivatives modified by the presence of chelating nitrogen ligands, i.e., 2,2’-bipyridyl, 2-(acetyl-2,6-diisopropylphenylimine)- pyridine and [N-(2,6-diisopropylphenyl)imine]acenaphthoquinone. The suitable stoichiometries between the two precursor complexes with the three ligands were determined by UV-visible spectroscopy. All complexes were characterized by infrared spectroscopy, and one complex was characterized also by X-ray diffraction. The apparent kinetic constants of oxidative polymerization of linseed oil was determined, for each catalytic system, via the periodic measurements of the oil viscosity during the oxidation reaction. The results indicated that the modifications of the classical two complexes with the chelating nitrogen ligands improved the catalytic efficiency at least to the manganese complex. (author)

Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate

International Nuclear Information System (INIS)

Cataldo, Franco; Strazzulla, Giovanni; Iglesias-Groth, Susana

2009-01-01

Phenylacetylene was polymerized as inclusion compound (clathrate) inside deoxycholic acid (DOCA) crystals. The polymerization was initiated by γ radiation and a total dose of 320 kGy was employed. The resulting polyphenylacetylene (PPA) was isolated by dissolution of deoxycholic acid in boiling ethanol. PPA high polymer was accompanied by a series of phenylacetylene oligomers, which were detected by liquid chromatographic analysis (HPLC). PPA was characterized by electronic absorption spectroscopy and by FT-IR spectroscopy in comparison to a reference PPA prepared by a stereospecific catalyst. The microstructure of PPA from inclusion polymerization was highly trans type, similar to that observed on PPA prepared by bulk radiolysis. No optical activity was detected by polarimetry on PPA prepared by inclusion polymerization. The host-guest complex PPA/DOCA was studied by differential thermal analysis (DTA) and by thermogravimetry (TGA). DTA provided evidences of the host-guest complex formation from the shift of the melting point of DOCA while the TGA confirmed the identity - in terms of thermal behaviour - of the PPA from inclusion polymerization with that from stereospecific polymerization

Tacticities study of high poly-α-olefins, from poly-1-hexene to poly-1-octadecene, obtained with metallocenes catalysts

International Nuclear Information System (INIS)

Silva, Luciano F. da; Galland, Griselda B.

2003-01-01

High poly-α-olefins such as poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, poly-1-tetradecene, poly-1-hexadecene and poly-1-octadecene were obtained with the homogeneous iso specific catalyst rac-Et[Ind]ZrCl 2 /MAO and with the homogeneous syndiospecific catalyst Me 2 C[Cp(9-Flu)]ZrCl 2 /MAO at the polymerization temperatures of 0 deg C, 30 deg C and 60 deg C. The polymers were analyzed by 13 C NMR to study the influence of the α - olefins sizes, the catalysts type and the polymerization temperatures in their tacticities. The stereospecific control of both catalytic systems decreased with the increase of the reaction temperature and with the α-olefin size. (author)

Metal nanoparticles/ionic liquid/cellulose: polymeric membrane for hydrogenation reactions

Directory of Open Access Journals (Sweden)

Marcos Alexandre Gelesky

2014-01-01

Full Text Available Rhodium and platinum nanoparticles were supported in polymeric membranes with 10, 20 and 40 µm thickness. The polymeric membranes were prepared combining cellulose acetate and the ionic liquid (IL 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonylimide (BMI.(NTf2. The presence of metal nanoparticles induced an increase in the polymeric membrane surface areas. The increase of the IL content resulted in an improvement of elasticity and decrease in tenacity and toughness, whereas the stress at break was not affected. The presence of IL probably causes an increase in the separation between the cellulose molecules that result in a higher flexibility and processability of the polymeric membrane. The CA/IL/M(0 combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The CA/IL/M(0 polymeric membrane displays higher catalytic activity (up to 7.353 h-1 for the 20 mm of CA/IL/Pt(0 and stability than the nanoparticles dispersed only in the IL.

Selective hydrodeoxygenation of biomass-derived oxygenates to unsaturated hydrocarbons using molybdenum carbide catalysts.

Science.gov (United States)

Ren, Hui; Yu, Weiting; Salciccioli, Michael; Chen, Ying; Huang, Yulin; Xiong, Ke; Vlachos, Dionisios G; Chen, Jingguang G

2013-05-01

Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando

2016-07-07

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

2016-01-01

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

NARCIS (Netherlands)

Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

2001-01-01

Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

N-Heterocyclic (4-Phenylpiperazin-1-yl)methanones Derived from Phenoxazine and Phenothiazine as Highly Potent Inhibitors of Tubulin Polymerization

DEFF Research Database (Denmark)

Prinz, Helge; Ridder, Ann-Kathrin; Vogel, Kirsten

2017-01-01

We report here a series of 27 10-(4-phenylpiperazin-1-yl)methanones derived from tricyclic heterocycles which were screened for effects on tumor cell growth, inhibition of tubulin polymerization, and induction of cell cycle arrest. Several analogues, among them the 10-(4-(3-methoxyphenyl)piperazi...

Luminescent Lanthanide Metal Organic Frameworks for cis-Selective Isoprene Polymerization Catalysis

Directory of Open Access Journals (Sweden)

Samantha Russell

2015-11-01

Full Text Available In this study, we are combining two areas of chemistry; solid-state coordination polymers (or Metal-Organic Framework—MOF and polymerization catalysis. MOF compounds combining two sets of different lanthanide elements (Nd3+, Eu3+/Tb3+ were used for that purpose: the use of neodymium was required due to its well-known catalytic properties in dienes polymerization. A second lanthanide, europium or terbium, was included in the MOF structure with the aim to provide luminescent properties. Several lanthanides-based MOF meeting these criteria were prepared according to different approaches, and they were further used as catalysts for the polymerization of isoprene. Stereoregular cis-polyisoprene was received, which in some cases exhibited luminescent properties in the UV-visible range.

Enzymatic polymerization of bio-based monomers for applications in hydrogels and coatings

DEFF Research Database (Denmark)

Hoffmann, Christian; Nguyen, Hiep Dinh; Storgaard, Thomas

of the enzymatic catalysts that can provide control over polymer structure in functional polymers. Lipase catalyzed polymerizations (specifically CALB) has been applied to prepare functional polyesters and to evaluate the possibilities of using less stable bio-based monomers such as itaconic acid or its...

Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1-Octene Polymerization and Chain Transfer Using Quench-Labeling Methods.

Science.gov (United States)

Cueny, Eric S; Johnson, Heather C; Anding, Bernie J; Landis, Clark R

2017-08-30

Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the "bulk" (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph 3 C][B(C 6 F 5 ) 4 ]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt 2 under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt 2 reveal that ZnEt 2 does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt 2 is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment.

Comparison of product selectivity during hydroprocessing of bitumen derived gas oil in the presence of NiMo/Al{sub 2}O{sub 3} catalyst containing boron and phosphorus

Energy Technology Data Exchange (ETDEWEB)

D. Ferdous; A.K. Dalai; J. Adjaye [University of Saskatchewan, SK (Canada). Catalysis and Chemical Reactor Engineering Laboratories, Department of Chemical Engineering

2006-06-15

A detailed experimental study was performed in a trickle-bed reactor using bitumen derived gas oil. The objective of this work was to compare the activity of NiMo/Al{sub 2}O{sub 3} catalyst containing boron or phosphorus for the hydrotreating and mild hydrocracking of bitumen derived gas oil. Experiments were performed at the temperature and LHSV of 340-420{sup o}C and 0.5-2 h{sup -1}, respectively, using NiMo/Al{sub 2}O{sub 3} catalysts containing 1.7 wt% boron or 2.7 wt% phosphorus. In the temperature range of 340-390{sup o}C, higher nitrogen conversion was observed from boron containing catalyst than that from phosphorus containing catalyst whereas in the same temperature range, phosphorus containing catalyst gave higher relative removal of sulfur than boron containing catalyst. Phosphorus containing catalyst showed excellent hydrocracking and mild hydrocracking activities at all operating conditions. Higher naphtha yield and selectivity were obtained using phosphorus containing catalyst at all operating conditions. Maximum gasoline selectivity of {approximately}45 wt% was obtained at the temperature, pressure, and LHSV of 400{sup o}C, 9.4 MPa and 0.5 h{sup -1}, respectively, using catalyst containing 2.7 wt% phosphorus. 40 refs., 13 figs., 1 tab.

Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

Science.gov (United States)

Shah, Pinakin M.

1990-01-01

An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

Hydrotreating of heavy gas oil derived from Athabasca bitumen using NiMo/Al2O3 catalyst containing boron and phosphorus : effects of process conditions on the product selectivity

Energy Technology Data Exchange (ETDEWEB)

Ferdous, D.; Dalai, A.K. [Saskatchewan Univ., Saskatoon, SK (Canada). Dept. of Chemistry and Chemical Engineering; Adjaye, J. [Syncrude Canada Ltd., Edmonton, AB (Canada). Edmonton Research Centre

2004-07-01

In response to concerns regarding the depletion of conventional oil reserves, there has been much interest in modifying the hydrotreating process for upgrading tar sands and shale oils for producing transportation fuels. Oil sand bitumens and their derived products have a high level of nitrogen which deactivates the catalysts used in fluid catalytic cracking and hydrocracking. A better catalyst is needed to efficiently remove nitrogen from oil sand-derived gas oils. In this study, a trickle-bed reactor containing NiMo/Al{sub 2}O{sub 3} catalysts with boron and phosphorous was used to remove the sulfur and nitrogen from heavy gas oils derived from Athabasca bitumen. The operating conditions of the reactor in terms of temperature and pressure were described. Sulfur and nitrogen conversion was found to increase substantially with the boron catalysts. Gasoline selectivity also increased with an increase in temperature. However, a change in operating conditions did not significantly affect the net content of the gas oil fraction. This study also compared the results of using either the boron or phosphorous catalyst.

Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha. 1. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

Energy Technology Data Exchange (ETDEWEB)

Raje, A.P.; Liaw, S.-J.; Srinivasan, R.; Davis, B.H. [University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

1997-03-13

Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha was evaluated over unsupported transition metal sulfide catalysts (Ru, Rh, Mo, Pd, Zr, Mb). The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enable the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha. 22 refs., 3 figs., 4 tabs.

Catalytic olefin polymerization with early transition metal compounds

OpenAIRE

Eshuis, Johan Jan Willem

1991-01-01

The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

Immobilization of isolated FI catalyst on polyhedral oligomeric silsesquioxane-functionalized silica for the synthesis of weakly entangled polyethylene.

Science.gov (United States)

Li, Wei; Yang, Huaqin; Zhang, Jingjing; Mu, Jingshan; Gong, Dirong; Wang, Xiaodong

2016-09-25

Polyhedral oligomeric silsesquioxanes (POSSs) were adsorbed on methylaluminoxane-activated silica for the immobilization of fluorinated bis(phenoxyimine)Ti complexes (FI catalyst). These POSSs have been characterized as horizontal spacers isolating the active sites and hindering the chain overlap in polymerization. The heterogeneous catalyst exhibits considerable activity in the synthesis of weakly entangled polyethylene.

Phosphasalen indium complexes showing high rates and isoselectivities in rac-lactide polymerizations

Energy Technology Data Exchange (ETDEWEB)

Myers, Dominic; White, Andrew J.P. [Department of Chemistry, Imperial College London (United Kingdom); Forsyth, Craig M. [School of Chemistry, Monash University, Clayton, VIC (Australia); Bown, Mark [CSIRO Manufacturing, Bayview Avenue, Clayton, VIC (Australia); Williams, Charlotte K. [Department of Chemistry, Oxford University (United Kingdom)

2017-05-02

Polylactide (PLA) is the leading bioderived polymer produced commercially by the metal-catalyzed ring-opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac-lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m{sup -1} min{sup -1}, THF, 298 K), high control, low loadings (0.2 mol %), and isoselectivity (P{sub i}=0.92, THF, 258 K). Furthermore, the phosphasalen indium catalysts do not require any chiral additives. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis of polypropylene/graphite nanocomposites by means of in situ polymerization

International Nuclear Information System (INIS)

Montagna, Larissa S.; Basso, Nara R.S.

2009-01-01

The nanotechnology presents a large field for research and development of new polymeric materials based in nanocomposites. This work is related to the synthesis of nanocomposites of polypropylene with graphite as filler. The sheets of graphite in nanometer dimensions were made by means of the chemical exfoliation and thermal treatment. The synthesis of the nanocomposites was carried through by means of the in situ polymerization using a metallocene catalyst and with different amounts of inorganic load (0,5; 1 and 2%). The synthesized nanocomposites were characterized by scanning electron microscopy (SEM) and X-Ray diffraction (XRD). (author)

Prepolymerization and morphology. Study on the factors determining powder morphology in propylene polymerization.

NARCIS (Netherlands)

Pater, J.T.M.

2001-01-01

Due to the developments in catalysis and the use of improved and dedicated catalysts in modern polymerization processes, the variety of different grades of polyolefins produced (and with that the variety of possible applications) has increased rapidly over the past decades. Combined with the low

Efficient hydrolysis of cellulose over a magnetic lignin-derived solid acid catalyst in 1-butyl-3-methylimidazolium chloride

International Nuclear Information System (INIS)

Hu, Lei; Wu, Zhen; Xu, Jiaxing; Zhou, Shouyong; Tang, Guodong

2016-01-01

A green and efficient strategy for the hydrolysis of cellulose was developed by using a magnetic lignin-derived solid acid catalyst (MLC-SO 3 H) in the presence of ionic liquid 1-butyl-3-methylimidazolium chloride ([BMIM]Cl). The results indicated that reaction temperature, reaction time, catalyst loading and water content have a big influence on the yield of total reducing sugars (TRS). By optimizing these reaction parameters, 69.3% TRS yield was observed at 140 .deg. C for 150 min with the addition of 40 wt% MLC-SO 3 H and 1 wt% water. More importantly, MLC-SO 3 H could be easily separated from the reaction mixture with an external magnet and could be repeatedly used five times without an obvious loss of catalytic activity, demonstrating that it possessed excellent recyclability. Furthermore, a plausible mechanism involving three consecutive processes of dissolution, adsorption and catalysis for the hydrolysis of cellulose in [BMIM]Cl over a catalyst of MLC-SO 3 H was also proposed.

Effect of the polymerization with formaldehyde on the thermal reactivity of a low-temperature coal tar pitch

Energy Technology Data Exchange (ETDEWEB)

Jose L. Crespo; Ana Arenillas; Jose A. Vin; Roberto Garcia; Colin E. Snape; Sabino R. Moinelo [Instituto Nacional del Carbon (CSIC), Oviedo (Spain)

2005-04-01

The influence of polymerization with formaldehyde on the thermal reactivity of a low-temperature coal tar pitch has been investigated. The mechanism and extent of the polymerization depends on the catalyst used, the greatest extent of polymerization being achieved under basic catalytic conditions. After the polymerization treatment, samples were carbonized at 420{sup o}C and the products were characterized by optical microscopy. According to the results, polymerization with formaldehyde increases the reactivity of the pitch, giving rise to increased carbonization yields and leading to the formation of the mesophase with milder conditions. The polymerization process also affects the morphology of the resultant anisotropic material, giving rise to the formation of irregularly shaped mesophase particles and reducing the optical texture size of the anisotropic domains, giving mosaic texture, especially when basic catalysis is used. 36 refs., 11 figs., 5 tabs.

Surface grafting via photo-induced copper-mediated radical polymerization at extremely low catalyst concentrations

Czech Academy of Sciences Publication Activity Database

Laun, J.; Vorobii, Mariia; de los Santos Pereira, Andres; Pop-Georgievski, Ognen; Trouillet, V.; Welle, A.; Barner-Kowollik, C.; Rodriguez-Emmenegger, Cesar; Junkers, T.

2015-01-01

Roč. 36, č. 18 (2015), s. 1681-1686 ISSN 1022-1336 R&D Projects: GA ČR(CZ) GJ15-09368Y; GA MŠk(CZ) ED1.1.00/02.0109 Grant - others:OPPK(XE) CZ.2.16/3.1.00/21545 Program:OPPK Institutional support: RVO:61389013 Keywords : copper-mediated polymerization * photo-induced polymerization * polymer brushes Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.638, year: 2015

Ziegler-Natta Catalyst Based on MgCl₂/Clay/ID/TiCl₄ for the Synthesis of Spherical Particles of Polypropylene Nanocomposites.

Science.gov (United States)

Cardoso, Renata da Silva; Oliveira, Jaqueline da Silva; Ramis, Luciana Bortolin; Marques, Maria de Fátima V

2018-07-01

In the present work, we have designed MgCl2/clay/internal donor (ID)/TiCl4 based bisupported Ziegler-Natta catalysts containing varying amounts of organoclay (montmorillonite) in order to synthesize spherical particles of polypropylene/clay nanocomposites (PCN). The organoclay was introduced into the catalyst support formulation and PCN was obtained using the in situ polymerization technique. Decreasing the reaction time, it was possible to obtain nanocomposites with high concentrations of clay (masterbatches). Micrographs of SEM confirmed the spherical morphology of the catalysts. In addition, XRD patterns show that the active sites for polymerization were inserted in the clay galleries. The catalytic performance was evaluated in slurry propylene polymerization using triethylaluminium as cocatalyst and silane as external electron donor at 70 °C, 4 bar, and different reaction times. The PCNs obtained containing different clay amounts were characterized by X-ray diffraction, thermal analyses, transmission electronic microscopy, and extractables in heptane. The results revealed that the synthesized PP/clay particles were also spherical showing that the morphological control is possible even using catalysts containing high amounts of clay. The PCN presented high degradation temperature (459 °C). The XRD peak related to the clay interlamellar distance has shifted to lower angles, and TEM images confirmed the formation of exfoliated/intercalated clay on the PP matrix and absence of microparticles of clay.

Improvement of the stability of basic mixed oxides used as catalysts for aldol condensation of bio-derived compounds by palladium addition

International Nuclear Information System (INIS)

Faba, Laura; Díaz, Eva; Ordóñez, Salvador

2013-01-01

Aqueous-phase aldol condensation of biomass-derived ketones and aldehydes is a key step in the preparation of fuels and chemicals from renewable resources. Furfural–acetone aldol condensation yielding C 8 and C 13 adducts was studied at 323 K and 1 MPa in a stirred batch reactor. We propose a new strategy for minimizing catalytic deactivation, consisting of modifying catalysts (MgO–ZrO 2 and MgO–Al 2 O 3 ) by Pd addition (2%). This modification slightly changes the morphology and surface chemistry of the supports, leading to changes on the catalysts performance but not reaction mechanism modifications. If condensation is performed in hydrogen atmosphere, the partial hydrogenation of the condensation adducts increases its water solubility, minimizing catalyst deactivation. In that way, the selectivity for C13 adduct decreases only 25% between two successive reaction cycles using Pd/MgO–ZrO 2 catalyst, whereas this decrease is of 90% for the un-doped mixed oxides. These effects are less marked for the MgO–Al 2 O 3 catalyst. Highlights: •Furfural and acetone aldolization on Pd/MgO–ZrO 2 and Pd/MgO–Al 2 O 3 . •Conversion and selectivity towards C8 and C13 low and unstable catalysts. •Aldolization in H 2 decreases coke formation: higher reusability of the catalysts

New fillers in the synthesis of polypropylene nano composites with Ziegler-Natta catalysts

International Nuclear Information System (INIS)

Rosa, Jeferson L.S.; Silva, Marcelo C.V.; Marques, Maria F.V.

2011-01-01

In this study, Ziegler-Natta catalysts bi-supported on MgCl 2 and natural clays were prepared in order to synthesize polypropylene nanocomposites. The employed clays were bentonite, as reference, as well as halloysite, vermiculite and mica. Propylene polymerizations were carried out using those catalysts and the properties of the obtained materials were analyzed using techniques of thermogravimetric analysis X-ray diffraction, dynamic mechanical thermal analysis e scanning electronic microscopy. Results showed the production of nanocomposites with higher thermal degradation temperature. (author)

Electroplating sludge derived zinc-ferrite catalyst for the efficient photo-Fenton degradation of dye.

Science.gov (United States)

Cao, Zhenbang; Zhang, Jia; Zhou, Jizhi; Ruan, Xiuxiu; Chen, Dan; Liu, Jianyong; Liu, Qiang; Qian, Guangren

2017-05-15

A zinc-dominant ferrite catalyst for efficient degradation of organic dye was prepared by the calcination of electroplating sludge (ES). Characterizations indicated that zinc ferrite (ZnFe 2 O 4 ) coexisted with Fe 2 O 3 structure was the predominant phase in the calcined electroplating sludge (CES). CES displayed a high decolorization ratio (88.3%) of methylene blue (MB) in the presence of H 2 O 2 combined with UV irradiation. The high efficiency could be ascribed to the photocatalytic process induced by ZnFe 2 O 4 and the photo-Fenton dye degradation by ferrous content, and a small amount of Al and Mg in the sludge might also contribute to the catalysis. Moreover, the degradation capability of dye by CES was supported by the synthetic ZnFe 2 O 4 with different Zn to Fe molar ratio (n(Zn): n(Fe)), as 84.81%-86.83% of dye was removed with n(Zn): n(Fe) ranged from 1:0.5 to 1:3. All synthetic ferrite samples in the simulation achieved adjacent equilibrium decolorization ratio, the flexible proportioning of divalent metal ions (M 2+ ) to trivalent metal ions (M 3+ ) applied in the synthesis indicated that the catalyst has a high availability. Therefore, an efficacious catalyst for the degradation of dye can potentially be derived from heavy metal-containing ES, it's a novel approach for the reutilization of ES. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polymerization of MMA catalyzed by different novel mixed ligand lanthanocene ｛ ( Cp ) ( Cl ) LnSchiff-base (THF) ｝, ( COT ) Ln(methoxyethylindenyl) (THF)/Al (i-Bu) 3 systems

Institute of Scientific and Technical Information of China (English)

YOUSAF, Muhammad; QIAN, Yan-Long; FENG, Zuo-Feng; HUANG, Ji-Ling; SUN, Jun-Quan; PAN, Zhi-Da

2000-01-01

This article deals that the rare earth metal complexes along with Al (i-Bu)3 can catalyze the polymerization of methyl methacrylate (MMA) into high molecular weight poly(MMA) along with narrow molecular weight distributions (MWD). A typical example wan mentioned in the case of ｛Cp(Cl)Sm Schiff-base(THF)｝ which expresses maximum (conv.%= 55.46 and Mn=354×103) efficiency along with narrow MWD(Mw/Mn＜2) at 60°C. The resulting polymer was partially syndiotactic (＞60%). The effect of the catalyst, temperature, catalyst/MMA molar ratio, catalyst/Al(i-Bu)3 molar ratio on the polymerization of MMA at 60°C were also investigated.

Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

Science.gov (United States)

Ghampson, Isaac Tyrone

The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the

FLUIDDYNAMIC ASPECTS OF GAS-PHASE ETHYLENE POLYMERIZATION REACTOR DESIGN

Directory of Open Access Journals (Sweden)

Guardani R.

1998-01-01

Full Text Available The relative importance of design variables affecting the fluiddynamic behavior of a fluidized bed reactor for the gas-phase ethylene polymerization is discussed, based on mathematical modeling. The three-phase bubbling fluidized bed model is based on axially distributed properties for the bubble, cloud and emulsion phases, combined with correlations for population balance and entrainment. Under the operating conditions adopted in most industrial processes, the reactor performance is affected mainly by the reaction rate and solids entrainment. Simulation results indicate that an adequate design of the freeboard and particle collecting equipment is of primary importance in order to produce polymeric particles with the desired size distribution, as well as to keep entrainment and catalyst feed rates at adequate levels.

Origin of Life and the Phosphate Transfer Catalyst

Science.gov (United States)

Piast, Radosław W.; Wieczorek, Rafał M.

2017-03-01

In this paper, we revisit several issues relevant to origin-of-life research and propose a Phosphate Transfer Catalyst hypothesis that furthers our understanding of some of the key events in prebiotic chemical evolution. In the Phosphate Transfer Catalyst hypothesis, we assume the existence of hypothetical metallopeptides with phosphate transfer activity that use abundant polyphosphates as both substrates and energy sources. Nonspecific catalysis by this phosphate transfer catalyst would provide a variety of different products such as phosphoryl amino acids, nucleosides, polyphosphate nucleotides, nucleic acids, and aminoacylated nucleic acids. Moreover, being an autocatalytic set and metabolic driver at the same time, it could possibly replicate itself and produce a collective system of two polymerases; a nucleic acid able to catalyze peptide bond formation and a peptide able to polymerize nucleic acids. The genetic code starts at first as a system that reduces the energy barrier by bringing substrates (2'/3' aminoacyl-nucleotides) together, an ancestral form of the catalysis performed by modern ribosomes.

Synthesis of cationic dibenzosemibullvalene-based phase-transfer catalysts by di-π-methane rearrangements of pyrrolinium-annelated dibenzobarrelene derivatives

Directory of Open Access Journals (Sweden)

Jia Luo

2011-01-01

Full Text Available Dibenzobarrelene derivatives, that are annelated with a pyrrolinium unit [N,N-dialkyl-3,4-(9',10'-dihydro-9',10'-anthraceno-3-pyrrolinium derivatives], undergo a photo-induced di-π-methane rearrangement upon triplet sensitization to give the corresponding cationic dibenzosemibullvalene derivatives [N,N-dialkyl-3,4-{8c,8e-(4b,8b-dihydrodibenzo[a,f]cyclopropa[cd]pentaleno}pyrrolidinium derivatives]. Whereas the covalent attachment of a benzophenone functionality to the pyrrolinium nitrogen atom did not result in an internal triplet sensitization, the introduction of a benzophenone unit as part of the counter ion enables the di-π-methane rearrangement of the dibenzobarrelene derivative in the solid-state. Preliminary experiments indicate that a cationic pyrrolidinium-annelated dibenzosemibullvalene may act as phase-transfer catalyst in alkylation reactions.

High molecular weight chitosan derivative polymeric micelles encapsulating superparamagnetic iron oxide for tumor-targeted magnetic resonance imaging

Directory of Open Access Journals (Sweden)

Xiao Y

2015-02-01

Full Text Available Yunbin Xiao,1,* Zuan Tao Lin,2,* Yanmei Chen,1 He Wang,1 Ya Li Deng,2 D Elizabeth Le,3 Jianguo Bin,1 Meiyu Li,1 Yulin Liao,1 Yili Liu,1 Gangbiao Jiang,2 Jianping Bin1 1State Key Laboratory of Organ Failure Research, Division of Cardiology, Nanfang Hospital, Southern Medical University, Guangzhou, People’s Republic of China; 2Department of Pharmaceutical Engineering, South China Agricultural University, Guangzhou, People’s Republic of China; 3Cardiovascular Division, Oregon Health and Science University, Portland, OR, USA *These authors contributed equally to this work Abstract: Magnetic resonance imaging (MRI contrast agents based on chitosan derivatives have great potential for diagnosing diseases. However, stable tumor-targeted MRI contrast agents using micelles prepared from high molecular weight chitosan derivatives are seldom reported. In this study, we developed a novel tumor-targeted MRI vehicle via superparamagnetic iron oxide nanoparticles (SPIONs encapsulated in self-aggregating polymeric folate-conjugated N-palmitoyl chitosan (FAPLCS micelles. The tumor-targeting ability of FAPLCS/SPIONs was demonstrated in vitro and in vivo. The results of dynamic light scattering experiments showed that the micelles had a relatively narrow size distribution (136.60±3.90 nm and excellent stability. FAPLCS/SPIONs showed low cytotoxicity and excellent biocompatibility in cellular toxicity tests. Both in vitro and in vivo studies demonstrated that FAPLCS/SPIONs bound specifically to folate receptor-positive HeLa cells, and that FAPLCS/SPIONs accumulated predominantly in established HeLa-derived tumors in mice. The signal intensities of T2-weighted images in established HeLa-derived tumors were reduced dramatically after intravenous micelle administration. Our study indicates that FAPLCS/SPION micelles can potentially serve as safe and effective MRI contrast agents for detecting tumors that overexpress folate receptors. Keywords: superparamagnetic

Preparation of Biocolorant and Eco-Dyeing Derived from Polyphenols Based on Laccase-Catalyzed Oxidative Polymerization

Directory of Open Access Journals (Sweden)

Fubang Wang

2018-02-01

Full Text Available Natural products have been believed to be a promising source to obtain ecological dyes and pigments. Plant polyphenol is a kind of significant natural compound, and tea provides a rich source of polyphenols. In this study, biocolorant derived from phenolic compounds was generated based on laccase-catalyzed oxidative polymerization, and eco-dyeing of silk and wool fabrics with pigments derived from tea was investigated under the influence of pH variation. This work demonstrated that the dyeing property was better under acidic conditions compared to alkalinity, and fixation rate was the best when pH value was 3. Furthermore, breaking strength of dyed fabrics sharply reduced under the condition of pH 11. Eventually, the dyeing method was an eco-friendly process, which was based on bioconversion, and no mordant was added during the process of dyeing.

Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

KAUST Repository

Isimjan, Tayirjan T.

2013-04-01

The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application in green catalysis, and they are shown to be effective in the hydrolysisreduction sequence of tandem catalytic reactions required for conversion of 2-phenyl-1,3-dioxolane to toluene or of phenol to cyclohexane. The two distinct components in the catalyst, Pd nanoparticles and acidic PSSH, are capable of catalyzing sequential reactions in one pot under mild conditions. This work has demonstrated a powerful approach toward designing highperformance, multifunctional, scalable, and environmentally friendly nanostructured tandem catalysts. © 2013 American Chemical Society.

Tannic Acid an Efficient Catalyst for the Synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one Derivatives

Directory of Open Access Journals (Sweden)

Deepak S. Kawade

2015-06-01

Full Text Available Tannic acid explore a highly efficient catalytic activity for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-one derivatives in excellent yields via cyclocondensation of aromatic aldehyde, β-naphthol and dimedone. Catalyst having advantages such as it is cheap and biodegradable and the protocol avoids the use of expensive catalyst and toxic solvent. We believe that this methodology is an efficient, simple, highly yielding, time saving and environmentally friendly. DOI: http://dx.doi.org/10.17807/orbital.v7i2.683

A Facile Strategy for Catalyst Separation and Recycling Suitable for ATRP of Hydrophilic Monomers Using a Macroligand.

Science.gov (United States)

Jiang, Xiaowu; Wu, Jian; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2016-01-01

How to simply and efficiently separate and recycle catalyst has still been a constraint for the wide application of atom transfer radical polymerization (ATRP), especially for the polymerization systems with hydrophilic monomers because the polar functional groups may coordinate with transition metal salts, resulting in abundant catalyst residual in the resultant water-soluble polymers. In order to overcome this problem, a latent-biphasic system is developed, which can be successfully used for ATRP catalyst separation and recycling in situ for various kinds of hydrophilic monomers for the first time, such as poly(ethylene glycol) monomethyl ether methacrylate (PEGMA), 2-hydroxyethyl methacrylate (HEMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), N,N-dimethyl acrylamide (DMA), and N-isopropylacrylamide (NIPAM). Herein, random copolymer of octadecyl acrylate (OA), MA-Ln (2-(bis(pyridin-2-ylmethyl)amino)ethyl acrylate), and POA-ran-P(MA-Ln) is designed as the macroligand, and heptane/ethanol is selected as the biphasic solvent. Copper(II) bromide (CuBr2 ) is employed as the catalyst, PEG-bound 2-bromo-2-methylpropanoate (PEG350 -Br) as the water-soluble ATRP initiator and 2,2'-azobis(isobutyronitrile) (AIBN) as the azo-initiator to establish an ICAR (initiators for continuous activator regeneration) ATRP system. Importantly, well-defined water-soluble polymers are obtained even though the recyclable catalyst is used for sixth times. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Plasma-Polymerized Fused Polycyclic Compounds for Binding Conducting Polymers

DEFF Research Database (Denmark)

Winther-Jensen, Bjørn; Norrman, Kion; Kingshott, Peter

2005-01-01

with hydrogen in the position which is able to co-polymerize with thiophene derivatives polymerized by conventional oxidative polymerization, thereby forming a conducting thiophene polymer bonded to the substrate. The durability of the surface modification procedure is demonstrated by micropatterning of PEDT...

ROMP-Derived cyclooctene-based monolithic polymeric materials reinforced with inorganic nanoparticles for applications in tissue engineering

Directory of Open Access Journals (Sweden)

Franziska Weichelt

2010-12-01

Full Text Available Porous monolithic inorganic/polymeric hybrid materials have been prepared via ring-opening metathesis copolymerization starting from a highly polar monomer, i.e., cis-5-cyclooctene-trans-1,2-diol and a 7-oxanorborn-2-ene-derived cross-linker in the presence of porogenic solvents and two types of inorganic nanoparticles (i.e., CaCO3 and calcium hydroxyapatite, respectively using the third-generation Grubbs initiator RuCl2(Py2(IMesH2(CHPh. The physico-chemical properties of the monolithic materials, such as pore size distribution and microhardness were studied with regard to the nanoparticle type and content. Moreover, the reinforced monoliths were tested for the possible use as scaffold materials in tissue engineering, by carrying out cell cultivation experiments with human adipose tissue-derived stromal cells.

Graphene-derived Fe/Co-N-C catalyst in direct methanol fuel cells: Effects of the methanol concentration and ionomer content on cell performance

Science.gov (United States)

Park, Jong Cheol; Choi, Chang Hyuck

2017-08-01

Non-precious metal catalysts (typically Fe(Co)-N-C catalysts) have been widely investigated for use as cost-effective cathode materials in low temperature fuel cells. Despite the high oxygen reduction activity and methanol-tolerance of graphene-based Fe(Co)-N-C catalysts in an acidic medium, their use in direct methanol fuel cells (DMFCs) has not yet been successfully implemented, and only a few studies have investigated this topic. Herein, we synthesized a nano-sized graphene-derived Fe/Co-N-C catalyst by physical ball-milling and a subsequent chemical modification of the graphene oxide. Twelve membrane-electrode-assemblies are fabricated with various cathode compositions to determine the effects of the methanol concentration, ionomer (i.e. Nafion) content, and catalyst loading on the DMFC performance. The results show that a graphene-based catalyst is capable of tolerating a highly-concentrated methanol feed up to 10.0 M. The optimized electrode composition has an ionomer content and catalyst loading of 66.7 wt% and 5.0 mg cm-2, respectively. The highest maximum power density is ca. 32 mW cm-2 with a relatively low PtRu content (2 mgPtRu cm-2). This study overcomes the drawbacks of conventional graphene-based electrodes using a nano-sized graphene-based catalyst and further shows the feasibility of their potential applications in DMFC systems.

Lignin-Based Materials Through Thiol-Maleimide "Click" Polymerization.

Science.gov (United States)

Buono, Pietro; Duval, Antoine; Averous, Luc; Habibi, Youssef

2017-03-09

In the present report an environmentally friendly approach to transforming renewable feedstocks into value-added materials is proposed. This transformation pathway was conducted under green conditions, without the use of solvents or catalyst. First, controlled modification of lignin, a major biopolymer present in wood and plants, was achieved by esterification with 11-maleimidoundecylenic acid (11-MUA), a derivative from castor oil that contains maleimide groups, following its transformation into 11-maleimidoundecanoyl chloride (11-MUC). Different degrees of substitution were achieved by using various amounts of the 11-MUC, leading to an efficient conversion of lignin hydroxy groups, as demonstrated by 1 H and 31 P NMR analyses. These fully biobased maleimide-lignin derivatives were subjected to an extremely fast (ca. 1 min) thiol-ene "click" polymerization with thiol-containing linkers. Aliphatic and aromatic thiol linkers bearing two to four thiol groups were used to tune the reactivity and crosslink density. The properties of the resulting materials were evaluated by swelling tests and thermal and mechanical analyses, which showed that varying the degree of functionality of the linker and the linker structure allowed accurate tailoring of the thermal and mechanical properties of the final materials, thus providing interesting perspectives for lignin in functional aromatic polymers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymerization of 3-ethynylthiophene with homogeneous and heterogeneous Rh catalysts

Czech Academy of Sciences Publication Activity Database

Svoboda, J.; Sedláček, J.; Zedník, J.; Dvořáková, G.; Trhlíková, O.; Rédrová, D.; Balcar, Hynek; Vohlídal, J.

2008-01-01

Roč. 46, č. 8 (2008), s. 2776-2787 ISSN 0887-624X R&D Projects: GA AV ČR KAN100500652; GA ČR GA203/05/2194; GA ČR GD203/03/H140; GA ČR(CZ) GD203/08/H032 Institutional research plan: CEZ:AV0Z40400503 Keywords : catalysis * conjugated polymers * organometallic catalysts * polyacetylenes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.821, year: 2008

Nanocomposite catalyst with palladium nanoparticles encapsulated in a polymeric acid: A model for tandem environmental catalysis

KAUST Repository

Isimjan, Tayirjan T.; He, Quan; Liu, Yong; Zhu, Jesse; Puddephatt, Richard J.; Anderson, Darren Jason

2013-01-01

The synthesis and characterization of a novel hybrid nanocomposite catalyst comprised of palladium nanoparticles embedded in polystyrene sulfonic acid (PSSH) and supported on metal oxides is reported. The catalysts are intended for application

Methyleneation of peptides by N,N,N,N-tetramethylethylenediamine (TEMED) under conditions used for free radical polymerization: a mechanistic study.

Science.gov (United States)

Shirangi, Mehrnoosh; Sastre Toraño, Javier; Sellergren, Börje; Hennink, Wim E; Somsen, Govert W; van Nostrum, Cornelus F

2015-01-21

Free radical polymerization is often used to prepare protein and peptide-loaded hydrogels for the design of controlled release systems and molecular imprinting materials. Peroxodisulfates (ammonium peroxodisulfates (APS) or potassium peroxodisulfates (KPS)) with N,N,N,N-tetramethylethylenediamine (TEMED) are frequently used as initiator and catalyst. However, exposure to these free radical polymerization reagents may lead to modification of the protein and peptide. In this work, we show the modification of lysine residues by ammonium peroxodisulfate (APS)/TEMED of the immunostimulant thymopentin (TP5). Parallel studies on a decapeptide and a library of 15 dipeptides were performed to reveal the mechanism of modification. LC-MS of APS/TEMED-exposed TP5 revealed a major reaction product with an increased mass (+12 Da) with respect to TP5. LC-MS(2) and LC-MS(3) were performed to obtain structural information on the modified peptide and localize the actual modification site. Interpretation of the obtained data demonstrates the formation of a methylene bridge between the lysine and arginine residue in the presence of TEMED, while replacing TEMED with a sodium bisulfite catalyst did not show this modification. Studies with the other peptides showed that the TEMED radical can induce methyleneation on peptides when lysine is next to arginine, proline, cysteine, aspargine, glutamine, histidine, tyrosine, tryptophan, and aspartic acid residues. Stability of peptides and protein needs to be considered when using APS/TEMED in in situ polymerization systems. The use of an alternative catalyst such as sodium bisulfite may preserve the chemical integrity of peptides during in situ polymerization.

Surface modification of nanodiamond through metal free atom transfer radical polymerization

Science.gov (United States)

Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2016-12-01

Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

A green synthetic approach toward the synthesis of structurally diverse spirooxindole derivative libraries under catalyst-free conditions.

Science.gov (United States)

Kausar, Nazia; Masum, Abdulla Al; Islam, Md Maidul; Das, Asish R

2017-05-01

A catalyst-free green methodology for the synthesis of pharmacologically important spirooxindole derivatives has been developed by a three-component domino reaction between isatin, various amino compounds, and 1,3-dicarbonyl or 3-phenylisoxazolone compounds in ethyl L-lactate medium at room temperature. This new efficient synthetic method facilitated the formation of a wide range of biologically significant spirooxindole derivatives (including 17 new spirooxindoles) under very mild conditions. The cytotoxic activity of one of the isoxazole-fused spirooxindoles was evaluated in MDA-MB 468 breast cancer cell line. It was found that cell survivability decreases with increasing concentration of the selected compound in MDA-MB 468 breast cancer cells.

Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

KAUST Repository

Ladelta, Viko

2016-12-12

A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

Ring-opening polymerization of ω-pentadecalactone catalyzed by phosphazene superbases

KAUST Repository

Ladelta, Viko; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikolaos

2016-01-01

A fast and living ring-opening polymerization (ROP) of ω-pentadecalactone (PDL), a representative monomer of macrolactones, was achieved using a primary alcohol as the initiator and t-BuP or t-octP as the catalyst. The use of t-BuP instead of the t-BuP superbase slows down the polymerization rate. The ROP of PDL proceeds to high conversion not only at 80 °C in bulk but also at room temperature and in dilute solution. The synthesized PDL homopolymers and block copolymers with poly(ethylene glycol) were characterized by high-temperature GPC (HT-GPC), H NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Melting temperatures, determined by differential scanning calorimetry, are also reported.

Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

KAUST Repository

Zhao, Junpeng

2015-02-04

Organocatalytic ring-opening polymerization (ROP) reactions of three renewable 5-alkyl δ-lactones, namely δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) were investigated. Room temperature, together with a relatively high monomer concentration (≥3 M), was demonstrated to be suitable for achieving a living ROP behavior, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, containing a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the compounds with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP4-promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers. Therefore, this reinforces the previously developed "catalyst switch" strategy, making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers from a large variety of epoxide and lactone monomers. © The Royal Society of Chemistry 2015.

Polymer Catalysts Imprinted with Metal Ions as Biomimics of Metalloenzymes

Directory of Open Access Journals (Sweden)

Joanna Czulak

2013-01-01

Full Text Available This work presents the preparation and properties of molecularly imprinted polymers (MIPs with catalytic centers that mimic the active sites of metalloenzymes. The MIP synthesis was based on suspension polymerization of functional monomers (4-vinylpyridine and acrylonitrile with trimethylolpropane trimethacrylate as a crosslinker in the presence of transition metal ions and 4-methoxybenzyl alcohol as a template. Four metal ions have been chosen for imprinting from among the microelements that are the most essential in the native enzymes: Cu2+, Co2+, Mn2+, and Zn2+. To prepare catalysts, the required loading of metal ions was obtained during sorption process. The catalysts imprinted with Cu2+, Co2+, and Zn2+ were successfully used for hydroquinone oxidation in the presence of hydrogen peroxide. The Mn2+-imprinted catalyst showed no activity due to the insufficient metal loading. Cu2+ MIP showed the highest efficiency. In case of Cu- and Co-MIP catalysts, their activity was additionally increased by the use of surface imprinting technique.

Modelagem do Processo de Fragmentação de Catalisadores Suportados Durante a Pré-polimerização de Olefinas Modeling of Catalyst Fragmentation During Olefin Pre-polymerizations

Directory of Open Access Journals (Sweden)

Douglas M. Merquior

2002-01-01

Full Text Available Uma metodologia é proposta para descrever a morfologia das partículas de polímero que são obtidas durante os momentos iniciais da polimerização de olefinas via catálise heterogênea. O método é baseado na análise matemática da capacidade da partícula em liberar a energia mecânica acumulada no seu interior devido à rápida produção de polímero. O balanço entre as quantidades de energia acumulada e liberada é calculado com o auxílio de um modelo dinâmico da reação de pré-polimerização. A combinação da metodologia proposta com o modelo dinâmico permitiu a análise dos mecanismos de fragmentação, indicando a morfologia da partícula de polímero produzida em função do tamanho da partícula e da temperatura do reator.A model-based methodology is proposed for describing the morphology of the polymer particles that are obtained during the very early stages of the olefin polymerization. The method is based on the analysis of the particle capacity to release the amount of energy that is accumulated in its interior during the polymerization, due to the fast polymer production. The balance between the accumulated and released amounts of energy is calculated with the help of a dynamic pre-polymerization reaction model. The combination of the fragmentation criteria and of the polymerization model allows the analysis of the prepolymerization step, indicating the morphology of the final polymer particles as a function of the catalyst particle diameter and reactor temperature.

The competing effects of microbially derived polymeric and low molecular-weight substances on the dispersibility of CeO2 nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Nakano, Yuriko; Ochiai, Asumi; Kawamoto, Keisuke; Takeda, Ayaka; Ichiyoshi, Kenta; Ohnuki, Toshihiko; Hochella, Michael F.; Utsunomiya, Satoshi

2018-02-26

To understand the competing effects of the components in extracellular substances (ES), polymeric substances (PS) and low-molecular-weight small substances (SS) <1 kDa derived from microorganisms, on the colloidal stability of cerium dioxide nanoparticles (CeNPs), we investigated their adsorption to sparingly soluble CeNPs at room temperature at pH 6.0. The ES was extracted from the fungus S. cerevisiae. The polypeptides and phosphates in all components preferentially adsorbed onto the CeNPs. The zeta potentials of ES + CeNPs, PS + CeNPs, and SS + CeNPs overlapped on the plot of PS itself, indicating the surface charge of the polymeric substances controls the zeta potentials. The sizes of the CeNP aggregates, 100–1300 nm, were constrained by the zeta potentials. The steric barrier derived from the polymers, even in SS, enhanced the CeNP dispersibility at pH 1.5–10. Consequently, the PS and SS had similar effects on modifying the CeNP surfaces. The adsorption of ES, which contains PS + SS, can suppress the aggregation of CeNPs over a wider pH range than that for PS only. The present study addresses the non-negligible effects of small-sized molecules derived from microbial activity on the migration of CeNP in aquatic environments, especially where bacterial consortia prevail.

Antileishmanial activity and tubulin polymerization inhibition of podophyllotoxin derivatives on Leishmania infantum

Directory of Open Access Journals (Sweden)

José Miguel Escudero-Martínez

2017-12-01

Full Text Available Leishmania microtubules play an important role not only in cell division, but also in keeping the shape of the parasite and motility of its free-living stages. Microtubules result from the self-assembly of alpha and beta tubulins, two phylogenetically conserved and very abundant eukaryotic proteins in kinetoplastids. The colchicine binding domain has inspired the discovery and development of several drugs currently in clinical use against parasites. However, this domain is less conserved in kinetoplastids and may be selectively targeted by new compounds. This report shows the antileishmanial effect of several series of compounds (53, derived from podophyllotoxin (a natural cyclolignan isolated from rhizomes of Podophyllum spp. and podophyllic aldehyde, on a transgenic, fluorescence-emitting strain of Leishmania infantum. These compounds were tested on both promastigotes and amastigote-infected mouse splenocytes, and in mammalian – mouse non-infected splenocytes and liver HepG2 cells – in order to determine selective indexes of the drugs. Results obtained with podophyllotoxin derivatives showed that the hydroxyl group at position C-7α was a structural requisite to kill the parasites. On regards podophyllic aldehyde, derivatives with C9-aldehyde group integrated into a bicyclic heterostructure displayed more potent antileishmanial effects and were relatively safe for host cells. Docking studies of podophyllotoxin and podophyllic aldehyde derivatives showed that these compounds share a similar pattern of interaction at the colchicine site of Leishmania tubulin, thus pointing to a common mechanism of action. However, the results obtained suggested that despite tubulin is a remarkable target against leishmaniasis, there is a poor correlation between inhibition of tubulin polymerization and antileishmanial effect of many of the compounds tested, fact that points to alternative pathways to kill the parasites. Keywords: Leishmania, Tubulin, DNA

Selective Conversion of Lignin-Derivable 4-Alkylguaiacols to 4-Alkylcyclohexanols over Noble and Non-Noble-Metal Catalysts

Energy Technology Data Exchange (ETDEWEB)

Schutyser, Wouter; Van den Bossche, Gil; Raaffels, Anton; Van den Bosch, Sander; Koelewijn, Steven-Friso; Renders, Tom; Sels, Bert F.

2016-10-03

Recent lignin-first catalytic lignocellulosic biorefineries produce large quantities of two potential platform chemicals, 4-n-propylguaiacol (PG) and 4-n-propylsyringol. Because conversion into 4-n-propylcyclohexanol (PCol), a precursor for novel polymer building blocks, presents a promising valorization route, reductive demethoxylation of PG was examined here in the liquid-phase over three commercial hydrogenation catalysts, viz. 5 wt % Ru/C, 5 wt % Pd/C and 65 wt % Ni/SiO2-Al2O3, at elevated temperatures ranging from 200 to 300 degrees C under hydrogen atmosphere. Kinetic profiles suggest two parallel conversion pathways: Pathway I involves PG hydrogenation to 4-n-propyl-2-methoxycyclohexanol (PMCol), followed by its demethoxylation to PCol, whereas Pathway II constitutes PG hydrodemethoxylation to 4-n-propylphenol (PPh), followed by its hydrogenation into PCol. The slowest step in the catalytic formation of PCol is the reductive methoxy removal from PMCol. Moreover, under the applied reaction conditions, PCol may react further into hydrocarbons. The following criteria are therefore essential to reach a high PCol yield: (i) catalytic pathway II is preferred as this route does not involve stable intermediates; (ii) reactivity of PMCol should be higher than that of PCol, and (iii) the overall carbon balance should be high. Both the catalyst type and the reaction conditions have a substantial impact on the PCol yield. Only the commercial Ni catalyst meets the three criteria, provided the reaction is performed at 250 degrees C in hexadecane. Additional advantages of this solvent choice are a high boiling point (low operational pressure in closed reactor systems), high solubility of PG and derived products, high thermal, reductive stability, and easy derivability from fatty biomass feedstock. This Ni catalyst also showed an excellent stability in recycling runs and is capable of converting highly concentrated (up to 20 wt %) PG in hexadecane. Ru and Pd on carbon

Further studies on hydration of alkynes by the PtCl4-CO catalyst

Energy Technology Data Exchange (ETDEWEB)

Israelsohn, Osnat; Vollhardt, K. Peter C.; Blum, Jochanan

2002-01-18

Under CO atmosphere, between 80 and 120 C, a glyme solution of PtCl{sub 4} forms a carbonyl compound that promotes hydration of internal as well as terminal alkynes to give aldehyde-free ketones. The catalytic process depends strongly on the electronic and steric nature of the substrates. Part of the carbonyl functions of the catalyst can be replaced by phosphine ligands. Chiral DIOP reacts with the PtCl{sub 4}-CO compound to give a catalyst that promotes partial kinetic resolution of a racemic alkyne. Replacement of part of the CO by polystyrene-bound diphenylphosphine enables to attach the catalyst to the polymeric support. Upon entrapment of the platinum compound in a silica sol-gel matrix, it reacts as a partially recyclable catalyst. A reformulated mechanism for the PdCl{sub 4}-CO catalyzed hydration is suggested on the basis of the present study.

ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

Science.gov (United States)

Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

2018-04-01

Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

In-Situ Immobilization of Ni Complex on Amine-Grafted SiO₂ for Ethylene Polymerization.

Science.gov (United States)

Lee, Sang Yun; Ko, Young Soo

2018-02-01

The results on the In-Situ synthesis of Ni complex on amine-grafted SiO2 and its ethylene polymerization were explained. SiO2/2NS/(DME)NiBr2 and SiO2/3NS/(DME)NiBr2(Ni(II) bromide ethylene glycol dimethyl ether) catalysts were active for ethylene polymerization. The highest activity was shown at the polymerization temperature of 25 °C, and SiO2/2NS/(DME)NiBr2 exhibited higher activity than SiO2/3NS/(DME)NiBr2. The PDI values of SiO2/2NS/(DME)NiBr2 were in the range of 8~18. The aminosilane compounds and Ni were evenly grafted and distributed in the silica. It was proposed that DME ligand was mostly removed during the supporting process, and only NiBr2 was complexed with the amine group of 2NS based on the results of FT-IR and ethylene polymerization.

Hydrotreating and hydrocracking of Athabasca bitumen derived heavy gas oils using NiMo catalyst supported on titania modified alumina

Energy Technology Data Exchange (ETDEWEB)

Ferdous, D.; Bakhshi, N.N.; Dalai, A.K.; Adjaye, J. [Saskatchewan Univ., Saskatoon, SK (Canada). Dept. of Chemical Engineering, Catalysis and Chemical Reaction Engineering Laboratories]|[Syncrude Canada Ltd., Edmonton, AB (Canada)

2006-07-01

Different NiMo catalysts supported on titania modified Al{sub 2}O{sub 3} were synthesized and characterized in an effort to study the hydrodenitrigenation (HDN) and hydrodesulfurization (HDS) of different gas oils derived from Athabasca bitumen. The Al{sub x}O{sub 3} supports were modified by incorporating up to 9 wt per cent titanium (Ti). All modified supports as well as fresh and spent catalysts were characterized by BET surface area, pore volume and pore diameter, XRD, TPR, TPD and SEM. A trickle-bed reactor using 3 different gas oils from the Athabasca bitumen was used to test the initial activity of these catalysts. The 3 oils were light gas oil (LGO), heavy gas oil (HGO) and blended gas oil having 50 per cent LGO and 50 per cent HGO. The study showed that nitrogen conversion increased for all the gas oils when Ti was incorporated into the alumina. With an increase in Ti concentrations from 0 to 6 wt per cent, nitrogen conversion increased from 57-69.5 wt per cent, 75-80.2 wt per cent, 83-91.5 wt per cent and for LGO, HGO and blended, respectively. Nearly 86 wt per cent sulphur conversion was obtained for all Ti concentrations for LGO, while HGO and blended sulphur conversions were in the range of 96-97 wt per cent. Detailed hydrotreating and hydrocracking of HGO was then performed using the 6 wt per cent Ti modified catalyst because it achieved the maximum nitrogen conversion. This paper also presented the temperature, pressure and liquid hourly space velocity for this catalyst along with the maximum nitrogen and sulphur conversions. Results were compared with those of commercial catalysts. tabs., figs.

Emulsion Polymerization of Tung Oil-Based Latexes with Asolectin as a Biorenewable Surfactant

Directory of Open Access Journals (Sweden)

Ashley Johns

2016-11-01

Full Text Available Bio-based vesicles, with potential application in drug delivery and/or catalyst encapsulation, have been prepared by the free radical emulsion co-polymerization of tung oil, divinylbenzene (DVB, n-butyl methacrylate (BMA, and asolectin in a xylene/water mixture. The free radical polymerization was initiated by di-tert-butyl peroxide (DTBP at 100 °C in a convection oven. Molecular weights of approximately 11,000 Da were measured by Matrix-assisted Laser Desorption/Ionization-Time of Flight (Maldi-TOF for tung oil-asolectin copolymers, verifying that significant polymerization occurs under the cure conditions employed. The cure of the co-monomer mixture employed in this work was monitored by Dielectric Analysis (DEA, while changes in the Raman spectrum of all co-monomers before and after the cure, along with differential scanning calorimetry (DSC analysis, have been used to verify the need of a post-cure step and completion of the polymerization reaction. Scanning Transmission Electron Microscopy (STEM images of the emulsion after polymerization indicate that vesicles were formed, and vesicle size distribution of samples prepared with different amounts of tung oil were determined using a Zetasizer.

Poly(Ionic Liquid: A New Phase in a Thermoregulated Phase Separated Catalysis and Catalyst Recycling System of Transition Metal-Mediated ATRP

Directory of Open Access Journals (Sweden)

Lan Yao

2018-03-01

Full Text Available Poly(ionic liquids (PILs have become the frontier domains in separation science because of the special properties of ionic liquids as well as their corresponding polymers. Considering their function in separation, we designed and synthesized a thermoregulated PIL. That is, this kind of PIL could separate with an organic phase which dissolves the monomers at ambient temperature. When heated to the reaction temperature, they become a homogeneous phase, and they separate again when the temperature falls to the ambient temperature after polymerization. Based on this, a thermoregulated phase separated catalysis (TPSC system for Cu-based atom transfer radical polymerization (ATRP was constructed. The copper catalyst (CuBr2 used here is easily separated and recycled in situ just by changing the temperature in this system. Moreover, even when the catalyst had been recycled five times, the controllability over resultant polymers is still satisfying. Finally, only 1~2 ppm metal catalyst was left in the polymer solution phase, which indicates the really high recycling efficiency.

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei

2011-11-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

Electrocatalytic Activity and Stability of M-Fe Catalysts Synthesized by Polymer Complex Method for PEFC Cathode

KAUST Repository

Ou, Yiwei; Kumagai, Hiromu; Yin, Fengxiang; Okada, Saori; Hatasawa, Haruna; Morioka, Hiroyuki; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

2011-01-01

The polymerized complex (PC) method was used to synthesize highly dispersed iron-based catalysts for the oxygen reduction reaction (ORR). The catalysts were prepared with an addition of 1,10-phenanthroline (Phen) and transition metals (M), such as Ta, Ti, and W, in an attempt to enhance the ORR activity and durability of the catalysts. The composition and properties of the catalysts were characterized by thermogravimetric analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst components, after extensive dissolution in a strong acid solution, were characterized by inductively coupled plasma mass spectroscopy and ultraviolet-visible spectroscopy. It was found that the Ti-Fe catalyst showed improved ORR performance, and the Ta-Fe catalyst showed enhanced stability towards ORR in acidic solution. The catalytic activity and stability for ORR was observed by adding Ti or Ta into the catalyst formulation, suggesting that the interaction between added hetero-ions (Ti and Ta) and ionic Fe active sites was beneficial for the ORR. A single-cell test with the synthesized catalyst in the cathode initially generated a high power density, but the low stability remains an issue to be solved.

Polymeric media for tritium fixation. Supplement I

International Nuclear Information System (INIS)

Franz, J.A.; Burger, L.L.

1976-01-01

Procedures for the fixation of tritium as TH or THO in two different polymeric media are described. The complete procedure for THO fixation in a polyureylene-polyurethane polumer, including polymer molding procedures and leach tests is presented. The catalytic tritiation of polystyrene under very mild conditions using a rhodium catalyst is also described. Thermal stabilities and cost estimates for the polymers examined under this program are discussed. Organic polymers were found to have attractive features for the fixation and storage of concentrated tritium wastes due to the convenience of fixation procedures and favorable properties of the resulting media

Microwave plasma enhanced chemical vapor deposition growth of few-walled carbon nanotubes using catalyst derived from an iron-containing block copolymer precursor

International Nuclear Information System (INIS)

Wang Peng; Lu, Jennifer; Zhou, Otto

2008-01-01

The microwave plasma enhanced chemical vapor deposition (MPECVD) method is now commonly used for directional and conformal growth of carbon nanotubes (CNTs) on supporting substrates. One of the shortcomings of the current process is the lack of control of the diameter and diameter distribution of the CNTs due to difficulties in synthesizing well-dispersed catalysts. Recently, block copolymer derived catalysts have been developed which offer the potential of fine control of both the size of and the spacing between the metal clusters. In this paper we report the successful growth of CNTs with narrow diameter distribution using polystyrene-block-polyferrocenylethylmethylsilane (PS-b-PFEMS) as the catalyst precursor. The study shows that higher growth pressure leads to better CNT growth. Besides the pressure, the effects on the growth of CNTs of the growth parameters, such as temperature and precursor gas ratio, are also studied

KF/Al2O3 as a Recyclable Basic Catalyst for 1,3-Dipolar Cycloaddition Reaction: Synthesis of Indolizine-1-Carbonitrile Derivatives

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Abaszadeh Mehdi

2017-07-01

Full Text Available KF/Al2O3 as a green and efficient catalyst has been used for synthesis of indolizine-1-carbonitrile derivatives. It can be proceeded by using 1,3-dipolar cycloaddition reaction of 1-alkyl-2-chloropyridinium bromides, malononitrile and benzaldehyde in ethanol, at reflux. The great advantage of this catalyst is the ease of handling. KF/Al2O3 can be used and removed by filtration, avoiding cumbersome aqueous workups and decreasing solvent waste handling issues. High conversions, short reaction times and a cleaner reaction profiles are some of the outstanding advantages of this method.

Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

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Véronique Pitchon

2012-02-01

Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

Cooperative catalysis designing efficient catalysts for synthesis

CERN Document Server

Peters, René

2015-01-01

Written by experts in the field, this is a much-needed overview of the rapidly emerging field of cooperative catalysis. The authors focus on the design and development of novel high-performance catalysts for applications in organic synthesis (particularly asymmetric synthesis), covering a broad range of topics, from the latest progress in Lewis acid / Br?nsted base catalysis to e.g. metal-assisted organocatalysis, cooperative metal/enzyme catalysis, and cooperative catalysis in polymerization reactions and on solid surfaces. The chapters are classified according to the type of cooperating acti

Thermal polymerization of Moringa oleifera oil

International Nuclear Information System (INIS)

Melo, Tania M.S.; Novack, Katia M.; Leandro, Cristiano

2011-01-01

It is increasingly clear both for society and the scientific community, that is necessary to find alternatives to reduce the use of polymeric materials because of their damage to the environment. One way to minimize the environmental problems related to the use of polymers is try to make them quickly degradable. In this study it was obtained a material with polymeric appearance derived from heating of the vegetable oil extracted from seeds of Moringa oleifera. The resulting product is an interesting alternative to obtain polymeric materials that may have biodegradable characteristics, coming from a renewable source and low cost. Moringa oil can be used since it has a high content of unsaturated fatty acids, and its main constituent oleic acid. All samples were characterized by FTIR, NMR and GPC. It was obtained a polymeric material, malleable, high viscosity, with some elasticity, low crystallinity and no unpleasant odor. (author)

Porous nitrogen-enriched carbonaceous material from marine waste: chitosan-derived layered CNX catalyst for aerial oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid

Data.gov (United States)

U.S. Environmental Protection Agency — Chitosan-derived, porous and layered nitrogen-enriched carbonaceous CNx catalyst (PLCNx) has been synthesized from marine waste and its use demonstrated in a...

Reactivity of Aryl Halides for Reductive Dehalogenation in (Seawater Using Polymer-Supported Terpyridine Palladium Catalyst

Directory of Open Access Journals (Sweden)

Toshimasa Suzuka

2015-05-01

Full Text Available A polymer-supported terpyridine palladium complex was prepared. The complex was found to promote hydrodechlorination of aryl chlorides with potassium formate in seawater. Generally, reductive cleavage of aryl chlorides using transition metal catalysts is more difficult than that of aryl bromides and iodides (reactivity: I > Br > Cl; however, the results obtained did not follow the general trend. Therefore, we investigated the reaction inhibition agents and found a method to remove these inhibitors. The polymeric catalysts showed high catalytic activity and high reusability for transfer reduction in seawater.

Complex Macromolecular Architectures by Living Cationic Polymerization

KAUST Repository

Alghamdi, Reem D.

2015-05-01

Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or �

Correlation between ECM guidance and actin polymerization on osteogenic differentiation of human adipose-derived stem cells

Energy Technology Data Exchange (ETDEWEB)

Keller, Vivian; Deiwick, Andrea [Laser Zentrum Hannover e.V., Department of Nanotechnology, Hollerithallee 8, D-30419 Hannover (Germany); Pflaum, Michael [Leibniz Research Laboratories for Biotechnology and Artificial Organs (LEBAO), Hannover Medical School, Carl-Neuberg-Str. 1, D-30625 Hannover (Germany); Schlie-Wolter, Sabrina, E-mail: s.schlie@lzh.de [Laser Zentrum Hannover e.V., Department of Nanotechnology, Hollerithallee 8, D-30419 Hannover (Germany); Institute of Quantum Optics, Leibniz University of Hannover, Welfengarten 1, D-30617 Hannover (Germany)

2016-10-01

The correlation between extracellular matrix (ECM) components, cell shape, and stem cell guidance can shed light in understanding and mimicking the functionality of stem cell niches for various applications. This interplay on osteogenic guidance of human adipose-derived stem cells (hASCs) was focus of this study. Proliferation and osteogenic markers like alkaline phosphatase activity and calcium mineralization were slightly increased by the ECM components laminin (LA), collagen I (COL), and fibronectin (FIB); with control medium no differentiation occurred. ECM guided differentiation was rather dependent on osterix than on Runx2 pathway. FIB significantly enhanced cell elongation even in presence of actin polymerization blockers cytochalasin D (CytoD) and ROCK inhibitor Y-27632, which generally caused more rounded cells. Except for the COL surface, both inhibitors increased the extent of osterix, while the Runx2 pathway was more sensitive to the culture condition. Both inhibitors did not affect hASC proliferation. CytoD enabled osteogenic differentiation independently from the ECM, while it was rather blocked via Y-27632 treatment; on FIB the general highest extent of differentiation occurred. Taken together, the ECM effect on hASCs occurs indirectly and selectively via a dominant role of FIB: it sustains osteogenic differentiation in case of a tension-dependent control of actin polymerization. - Highlights: • Interplay of ECM and cell shape guides osteogenic differentiation of hASCs. • ECM components only present a promotive but not stimulative effect. • No direct correlation between ECM-enhanced cell elongation and differentiation. • Suppression of differentiation depends on a specific actin polymerization blocking. • Fibronectin sustains cell elongation and differentiation in case of blocking actin.

Fluid Effects in Polymers and Polymeric Composites

CERN Document Server

Weitsman, Y Jack

2012-01-01

Fluid Effects in Polymers and Polymeric Composites, written by the late Dr. Y. Jack Weitsman, addresses the wide range of parameters that affect the interaction of fluids with polymers and polymeric composites. The book aims at broadening the scope of available data, mostly limited up to this time to weight-gain recordings of fluid ingress into polymers and composites, to the practical circumstances of fluctuating exposure. Various forms of experimental data are given, in conjunction with theoretical models derived from basic scientific principles, and correlated with severity of exposure conditions and interpreted by means of rationally based theoretical models. The practical implications of the effects of fluids are discussed. The issue of fluid effects on polymers and polymeric composites is of concern to engineers and scientists active in aerospace and naval structures, as an increasing portion of these structures are made of polymeric composites and employ polymeric adhesives as a joining device. While...

ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

Energy Technology Data Exchange (ETDEWEB)

Wang, Hao; Yin, Feng-Xiang; Chen, Biao-Hua; He, Xiao-Bo; Lv, Peng-Liang; Ye, Cai-Yun; Liu, Di-Jia

2017-05-01

Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wa Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.

Chain-growth cycloaddition polymerization via a catalytic alkyne [2 + 2 + 2] cyclotrimerization reaction and its application to one-shot spontaneous block copolymerization.

Science.gov (United States)

Sugiyama, Yu-ki; Kato, Rei; Sakurada, Tetsuya; Okamoto, Sentaro

2011-06-29

A cobalt-catalyzed alkyne [2 + 2 + 2] cycloaddition reaction has been applied to polymerizations yielding linear polymers via selective cross-cyclotrimerization of yne-diyne monomers, which occurs in a chain-growth manner. Additionally, through control of the alkyne reactivity of the two monomers, this method was efficiently applied to the spontaneous block copolymerization of their mixture. Here we present the proposed mechanism of the catalyst transfer process of this cycloaddition polymerization.

Tuning the redox potential of vitamin K3 derivatives by oxidative functionalization using a Ag(i)/GO catalyst.

Science.gov (United States)

El-Hout, S I; Suzuki, H; El-Sheikh, S M; Hassan, H M A; Harraz, F A; Ibrahim, I A; El-Sharkawy, E A; Tsujimura, S; Holzinger, M; Nishina, Y

2017-08-03

We propose herein initial results to develop optimum redox mediators by the combination of computational simulation and catalytic functionalization of the core structure of vitamin K 3 . We aim to correlate the calculated energy value of the LUMO of different vitamin K 3 derivatives with their actual redox potential. For this, we optimized the catalytic alkylation of 1,4-naphthoquinones with a designed Ag(i)/GO catalyst and synthesized a series of molecules.

Sonolytic and Silent Polymerization of Methacrlyic Acid Butyl Ester Catalyzed by a New Onium Salt with bis-Active Sites in a Biphasic System — A Comparative Investigation

Directory of Open Access Journals (Sweden)

Perumberkandgai A. Vivekanand

2013-02-01

Full Text Available Currently, ingenious new analytical and process experimental techniques which are environmentally benign techniques, viz., ultrasound irradiation, have become immensely popular in promoting various reactions. In this work, a novel soluble multi-site phase transfer catalyst (PTC viz., 1,4-bis-(propylmethyleneammounium chloridebenzene (BPMACB was synthesized and its catalytic efficiency was assessed by observing the kinetics of sonolytic polymerization of methacrylic acid butyl ester (MABE using potassium persulphate (PPS as an initiator. The ultrasound–multi-site phase transfer catalysis (US-MPTC-assisted polymerization reaction was compared with the silent (non-ultrasonic polymerization reaction. The effects of the catalyst and various reaction parameters on the catalytic performance were in detail investigated by following the kinetics of polymerization of MABE in an ethyl acetate-water biphasic system. From the detailed kinetic investigation we propose a plausible mechanism. Further the kinetic results demonstrate clearly that ultrasound-assisted phase-transfer catalysis significantly increased the reaction rate when compared to silent reactions. Notably, this environmentally benign and cost-effective process has great potential to be applied in various polymer industries.

Colloidal polymer particles as catalyst carriers and phase transfer agents in multiphasic hydroformylation reactions.

Science.gov (United States)

Peral, D; Stehl, D; Bibouche, B; Yu, H; Mardoukh, J; Schomäcker, R; Klitzing, R von; Vogt, D

2018-03-01

Colloidal particles have been used to covalently bind ligands for the heterogenization of homogeneous catalysts. The replacement of the covalent bonds by electrostatic interactions between particles and the catalyst could preserve the selectivity of a truly homogeneous catalytic process. Functionalized polymer particles with trimethylammonium moieties, dispersed in water, with a hydrophobic core and a hydrophilic shell have been synthesized by emulsion polymerization and have been thoroughly characterized. The ability of the particles with different monomer compositions to act as catalyst carriers has been studied. Finally, the colloidal dispersions have been applied as phase transfer agents in the multiphasic rhodium-catalyzed hydroformylation of 1-octene. The hydrodynamic radius of the particles has been shown to be around 100 nm, and a core-shell structure could be observed by atomic force microscopy. The polymer particles were proven to act as carriers for the water-soluble hydroformylation catalyst, due to electrostatic interaction between the functionalized particles bearing ammonium groups and the sulfonated ligands of the catalyst. The particles were stable under the hydroformylation conditions and the aqueous catalyst phase could be recycled three times. Copyright © 2017 Elsevier Inc. All rights reserved.

Evaluation of alumina-aluminium phosphate catalyst supports for hydrodenitrogenation of pyridine and coal-derived liquids

Energy Technology Data Exchange (ETDEWEB)

Menon, R.; Joo, H.S.; Guin, J.A.; Reucroft, P.J.; Kim, J.Y. [Auburn University, Auburn, AL (United States). Dept. of Chemical Engineering

1996-05-01

Several alumina-aluminum phosphate (AAP) catalyst supports were prepared by a coprecipitation method. Effect of variations in Al/P atomic ratios on support textural properties were examined. Finished NiMo/AAP catalysts containing nominally 3 wt% Ni and 13 wt% Mo were prepared by incipient wetness and characterized by several methods including elemental, BET, and XPS surface analysis. Initial hydrodenitrogenation (HDN) activities of the catalysts were examined in both pyridine model compound and coal liquid reactions. The AAP supports showed the opportunity to tailor the catalyst pore size by variation of the Al/P ratio. On a per unit surface areas basis, the AAP-supported catalysts had initial HDN activities comparable to those of a commercial P-promoted NiMo/Al{sub 2}O{sub 3} catalyst. Because of their unique textural properties, i.e. variable pore sizes, the AAP catalysts may offer advantages when dealing with macromolecular feedstocks where hindered diffusion may slow reaction rates. 37 refs., 8 figs., 6 tabs.

Magnetic porous Fe3O4/carbon octahedra derived from iron-based metal-organic framework as heterogeneous Fenton-like catalyst

Science.gov (United States)

Li, Wenhui; Wu, Xiaofeng; Li, Shuangde; Tang, Wenxiang; Chen, Yunfa

2018-04-01

The synthesis of effective and recyclable Fenton-like catalyst is still a key factor for advanced oxidation processes. Herein, magnetic porous Fe3O4/carbon octahedra were constructed by a two-step controlled calcination of iron-based metal organic framework. The porous octahedra were assembled by interpenetrated Fe3O4 nanoparticles coated with graphitic carbon layer, offering abundant mesoporous channels for the solid-liquid contact. Moreover, the oxygen-containing functional groups on the surface of graphitic carbon endow the catalysts with hydrophilic nature and well-dispersion into water. The porous Fe3O4/carbon octahedra show efficiently heterogeneous Fenton-like reactions for decomposing the organic dye methylene blue (MB) with the help of H2O2, and nearly 100% removal efficiency within 60 min. Furthermore, the magnetic catalyst retains the activity after ten cycles and can be easily separated by external magnetic field, indicating the long-term catalytic durability and recyclability. The good Fenton-like catalytic performance of the as-synthesized Fe3O4/carbon octahedra is ascribed to the unique mesoporous structure derived from MOF-framework, as well as the sacrificial role and stabilizing effect of graphitic carbon layer. This work provides a facile strategy for the controllable synthesis of integrated porous octahedral structure with graphitic carbon layer, and thereby the catalyst holds significant potential for wastewater treatment.

Graphene–poly(5-aminoindole) composite film as Pt catalyst support for methanol electrooxidation in alkaline medium

International Nuclear Information System (INIS)

Yue, Ruirui; Zhang, Qiang; Wang, Caiqin; Du, Yukou; Yang, Ping; Xu, Jingkun

2013-01-01

Highlights: • Electropolymerization of 5-aminoindole (AIn) in the presence of graphene (GE). • Significant catalytic effect of GE on the polymerization of AIn. • PAIn/GE/GC used as Pt catalyst support. • The enhanced catalytic activity of Pt/PAIn/GE/GC for methanol electrooxidation. -- Abstract: 5-Aminoindole (AIn) was electropolymerized on graphene (GE) modified glass carbon (GC) electrode in 0.5 M H 2 SO 4 aqueous solution containing 0.01 M AIn. Because of the catalytic effect of GE, the polymerization efficiency of AIn and the electrochemical activity of as-formed poly(5-aminoindole) (PAIn) were significantly improved on GE/GC electrode as compared to that on the bare GC electrode. The prepared PAIn/GE/GC electrode was used as substrate for Pt particle electrodeposition. SEM, EDX and Raman spectral were used to characterize the prepared electrodes. Electrocatalytic experiments demonstrate that the Pt/PAIn/GE/GC electrode possesses high catalytic activity toward methanol electrooxidation in alkaline medium, due to the good dispersion of Pt particles on PAIn/GE/GC and the electronic interactions between the metal particles and the polymer matrixes. Thus, PAIn can be a promising alternative for polymeric catalyst support in direct alcohol fuel cells

Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

KAUST Repository

Zhang, Yuetao

2013-11-27

This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (ItBu), 1,3- dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4- triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by ItBu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, ItBu is the most active catalyst of the series and converts quantitatively 1000-3000 equiv of MMBL in 1 min or 10 000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of Mn = 70-85 kg/mol, regardless of the [MMBL]/[ItBu] ratio employed. The ItBu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s -1 and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine

Organocatalytic conjugate-addition polymerization of linear and cyclic acrylic monomers by N-heterocyclic carbenes: Mechanisms of chain initiation, propagation, and termination

KAUST Repository

Zhang, Yuetao; Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2013-01-01

This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (ItBu), 1,3- dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4- triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by ItBu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, ItBu is the most active catalyst of the series and converts quantitatively 1000-3000 equiv of MMBL in 1 min or 10 000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of Mn = 70-85 kg/mol, regardless of the [MMBL]/[ItBu] ratio employed. The ItBu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s -1 and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine

One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

KAUST Repository

Alamri, Haleema

2016-04-20

A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

One-pot synthesis of well-defined polyether/polyester block copolymers and terpolymers by a highly efficient catalyst switch approach

KAUST Repository

Alamri, Haleema; Hadjichristidis, Nikolaos

2016-01-01

A highly efficient methodology, based on a novel catalyst switch approach with rapid crossover characteristics, was developed for the one-pot synthesis of block co/terpolymers of cyclic ethers and esters. This new approach, which takes advantage of one of the best catalysts for epoxide (t-BuP4) and cyclic ester (t-BuP2) polymerization, opens new horizons toward the synthesis of cyclic ether/ester complex macromolecular architectures. © The Royal Society of Chemistry 2016.

TiO2-Containing Carbon Derived from a Metal-Organic Framework Composite: A Highly Active Catalyst for Oxidative Desulfurization.

Science.gov (United States)

Bhadra, Biswa Nath; Song, Ji Yoon; Khan, Nazmul Abedin; Jhung, Sung Hwa

2017-09-13

A new metal-organic framework (MOF) composite consisting of Ti- and Zn-based MOFs (ZIF-8(x)@H 2 N-MIL-125; in brief, ZIF(x)@MOF) was designed and synthesized. The pristine MOF [H 2 N-MIL-125 (MOF)]- and an MOF-composite [ZIF(30)@MOF]-derived mesoporous carbons consisting of TiO 2 nanoparticles were prepared by pyrolysis (named MDC-P and MDC-C, respectively). MDC-C showed a higher surface area, larger pore sizes, and larger mesopore volumes than MDC-P. In addition, the TiO 2 nanoparticles on MDC-C have more uniform shapes and sizes and are smaller than those of MDC-P. The obtained MDC-C and MDC-P [together with MOF, ZIF(30)@MOF, pure/nanocrystalline TiO 2 , and activated carbon] were applied in the oxidative desulfurization reaction of dibenzothiophene in a model fuel. The MDC-C, even with a lower TiO 2 content than that of MDC-P, showed an outstanding catalytic performance, especially with a very low catalyst dose (i.e., a very high quantity of dibenzothiophene was converted per unit weight of the catalyst), fast kinetics (∼3 times faster than that for MDC-P), and a low activation energy (lower than that for any reported catalyst) for the oxidation of dibenzothiophene. The large mesopores of MDC-C and the well-dispersed/small TiO 2 might be the dominant factors for the superior catalytic conversions. The oxidative desulfurization of other sulfur-containing organic compounds with various electron densities was also studied with MDC-C to understand the mechanism of catalysis. Moreover, the MDC-C catalyst can be reused many times in the oxidative desulfurization reaction after a simple washing with acetone. Finally, composing MOFs and subsequent pyrolysis is suggested as an effective way to prepare a catalyst with well-dispersed active sites, large pores, and high mesoporosity.

Schlenk Techniques for Anionic Polymerization

KAUST Repository

Ratkanthwar, Kedar

2015-09-01

Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

Regeneration of cello-oligomers via selective depolymerization of cellulose fibers derived from printed paper wastes.

Science.gov (United States)

Voon, Lee Ken; Pang, Suh Cem; Chin, Suk Fun

2016-05-20

Cellulose extracted from printed paper wastes were selectively depolymerized under controlled conditions into cello-oligomers of controllable chain lengths via dissolution in an ionic liquid, 1-allyl-3-methylimidazolium chloride (AMIMCl), and in the presence of an acid catalyst, Amberlyst 15DRY. The depolymerization process was optimized against reaction temperature, concentration of acid catalyst, and reaction time. Despite rapid initial depolymerization process, the rate of cellulose depolymerization slowed down gradually upon prolonged reaction time, with 75.0 wt% yield of regenerated cello-oligomers (mean Viscosimetric Degree of Polymerization value of 81) obtained after 40 min. The depolymerization of cellulose fibers at 80 °C appeared to proceed via a second-order kinetic reaction with respect to the catalyst concentration of 0.23 mmol H3O(+). As such, the cellulose depolymerization process could afford some degree of control on the degree of polymerization or chain lengths of cello-oligomers formed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cobalt-embedded carbon nanofiber derived from a coordination polymer as a highly efficient heterogeneous catalyst for activating oxone in water.

Science.gov (United States)

Lin, Kun-Yi Andrew; Tong, Wai-Chi; Du, Yunchen

2018-03-01

Carbon fiber (CF) supported cobalt nanoparticles (NPs) are promising catalysts for activating Oxone because carbon is non-metal and earth-abundant, and CF-based catalysts exhibit a high aspect ratio, which affords more accessible and dense catalytic sites. Nevertheless, most of CF-supported catalysts are fabricated by post-synthetic methods, which involve complicated preparations. More importantly, metallic NPs are attached to the outer surface of CF rather than embedded within CF. However, there is still a great demand for developing Co-bearing carbon fibers for Oxone activation via simple and effective methods. Thus, this study proposes to develop a cobalt NP-embedded carbon nanofiber (CCNF) by a simple hydrothermal reaction of Co and nitrilotriacetic acid (NA), followed by one-step carbonization. Owing to the coordinative structure of CoNA, the derivative CCNF exhibits a fibrous carbon matrix embedded with evenly distributed and densely packed Co 3 O 4 and magnetic Co 0 nanoparticles. The fibrous structure, magnetism and embedded Co NPs enable CCNF to be a promising catalyst for Oxone activation. As degradation of Rhodamine B (RhB) is selected as a model reaction, CCNF not only rapidly activates Oxone to fully degrade RhB but also shows a much higher catalytic activity than the most common Oxone activator, Co 3 O 4 . CCNF also exhibits the lowest activation energy than any reported catalysts for Oxone activation to degrade RhB. In addition, CCNF could be re-used to activate Oxone for RhB degradation. These results indicate that CCNF is a conveniently prepared and highly effective fibrous Co/C hybrid material for activating Oxone to oxidize contaminants in water. Copyright © 2017. Published by Elsevier Ltd.

Volumetric polymerization shrinkage of contemporary composite resins

Directory of Open Access Journals (Sweden)

Halim Nagem Filho

2007-10-01

Full Text Available The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill Magic, Alert, and Solitaire to determine whether there are differences among these materials. The tests were conducted with precision of 0.1 mg. The volumetric shrinkage was measured by hydrostatic weighing before and after polymerization and calculated by known mathematical equations. One-way ANOVA (a or = 0.05 was used to determine statistically significant differences in volumetric shrinkage among the tested composite resins. Suprafill (1.87±0.01 and Definite (1.89±0.01 shrank significantly less than the other composite resins. SureFil (2.01±0.06, Filtek Z250 (1.99±0.03, and Fill Magic (2.02±0.02 presented intermediate levels of polymerization shrinkage. Alert and Solitaire presented the highest degree of polymerization shrinkage. Knowing the polymerization shrinkage rates of the commercially available composite resins, the dentist would be able to choose between using composite resins with lower polymerization shrinkage rates or adopting technical or operational procedures to minimize the adverse effects deriving from resin contraction during light-activation.

Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

KAUST Repository

Altaher, Maryam

2015-01-01

Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

KAUST Repository

Altaher, Maryam

2015-05-01

Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

Science.gov (United States)

Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

2017-08-01

In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.

Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

Science.gov (United States)

Gogoi, Satyabrat; Karak, Niranjan

2017-10-01

Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

Process for the exchange of hydrogen isotopes using a catalyst packed bed assembly

International Nuclear Information System (INIS)

Butler, J.P.; den Hartog, J.; Molson, F.W.R.

1978-01-01

A process for the exchange of hydrogen isotopes between streams of gaseous hydrogen and liquid water is described, wherein the streams of liquid water and gaseous hydrogen are simultaneously brought into contact with one another and a catalyst packed bed assembly while at a temperature in the range 273 0 to 573 0 K. The catalyst packed bed assembly may be composed of discrete carrier bodies of e.g. ceramics, metals, fibrous materials or synthetic plastics with catalytically active metal crystallites selected from Group VIII of the Periodic Table, partially enclosed in and bonded to the carrier bodies by a water repellent, water vapor and hydrogen gas permeable, porous, polymeric material, and discrete packing bodies having an exterior surface which is substantially hydrophilic and relatively noncatalytically active with regard to hydrogen isotope exchange between hydrogen gas and water vapor to that of the catalyst bodies

Efficient Air Desulfurization Catalysts Derived from Pig Manure Liquefaction Char

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Rajiv Wallace

2017-11-01

Full Text Available Biochar from the liquefaction of pig manure was used as a precursor of H2S desulfurization adsorbents. In its inorganic matter, it contains marked quantities of calcium, magnesium and iron, which are known as hydrogen sulfide oxidation catalysts. The char was used either as-received or mixed with 10% nanographite. The latter was added to increase both the content of the carbon phase and conductivity. ZnCl2 in two different ratios of char to an activation agent (1:1 and 1:2 was used to create the porosity in the carbon phase. The content of the later was between 18–45%. The activated samples adsorbed 144 mg/g H2S. Sulfur was the predominant product of reactive adsorption. Its deposition in the pore system and blockage of the most active pores ceased the materials’ activity. The presence of the catalytic phase was necessary but not sufficient to guarantee good performance. The developed porosity, which can store oxidation products in the resulting composite, is essential for the good performance of the desulfurization process. The surface of the composite with nanographite showed the highest catalytic activity, similar to that of the commercial Midas® carbon catalyst. The results obtained indicate that a high quality reactive adsorbent/catalyst for H2S removal can be obtained from pig manure liquefaction wastes.

An Undergraduate Chemistry Laboratory: Synthesis of Well-Defined Polymers by Low-Catalyst-Concentration ATRP and Postpolymerization Modification to Fluorescent Materials

Science.gov (United States)

Tsarevsky, Nicolay V.; Woodruf, Shannon R.; Wisian-Neilson, Patty J.

2016-01-01

A two-session experiment is designed to introduce undergraduate students to concepts in catalysis, transition metal complexes, polymer synthesis, and postpolymerization modifications. In the first session, students synthesize poly(glycidyl methacrylate) via low-catalyst-concentration atom transfer radical polymerization (ATRP). The…

Inhibition of Microbial Growth by Fatty Amine Catalysts from Polyurethane Foam Test Tube Plugs

Science.gov (United States)

Bach, John A.; Wnuk, Richard J.; Martin, Delano G.

1975-01-01

When polyurethane foam test tube plugs are autoclaved, they release volatile fatty amines that inhibit the growth of some microorganisms. The chemical structures of these amines were determined by the use of a gas chromatographmass spectrometer. They are catalysts used to produce the foam. The problem of contaminating growth media with toxic substances released from polymeric materials is discussed. PMID:1096816

Synthesis, characterization and performance of NiMo catalysts supported on titania modified alumina for the hydroprocessing of different gas oils derived from Athabasca bitumen

Energy Technology Data Exchange (ETDEWEB)

Ferdous, D.; Bakhshi, N.N.; Dalai, A.K. [Catalysis and Chemical Reactor Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, Sask. (Canada); Adjaye, J. [Syncrude Canada Ltd., Edmonton Research Center, No. 9421, 17th Avenue, Edmonton, Alta. (Canada)

2007-03-08

In this work, a series of NiMo/Al{sub 2}O{sub 3} catalyst was prepared using different Al{sub 2}O{sub 3} supports modified by titania (0-9 wt%). All modified supports and fresh catalysts were characterized by BET surface area, pore volume and pore diameter measurement, TPR, TPD, XRD, FTIR and Raman spectroscopy analyses. The initial activity of these catalysts were tested in a trickle-bed reactor using three different gas oils such as light gas oil (LGO), blended gas oil (blended: 50% LGO and 50% HGO) and heavy gas oil (HGO), all derived from Athabasca bitumen. Little structural change in alumina was observed with the incorporation of titania. XRD analysis showed the well dispersion of Ni and Mo on the support. Titania in alumina increased the formation of polymolybdenum oxide on the catalyst as evident from TPR and Raman analyses. Weak-intermediate-strong acid sites on the catalyst were observed at all titania concentrations. The Lewis and Bronsted acidity on the catalyst surface increased with the increase in titania concentration from 0 to 9 wt%. Nitrogen conversion increased from 57 to 71 wt%, from 83 to 93 wt% and from 75 to 80 wt% for LGO, blended and HGO, respectively and also sulfur conversion of LGO increased from 86 to 92 wt% when titania concentration was increased from 0 to 9 wt%. For blended and HGO, sulfur conversion was in the range 96-99 wt% at all titania concentrations. (author)

The Use of Electron Donors to Increase Stereospecificity in Ziegler-Natta Propylene Polymerization

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Farshid Nouri-Ahangarani

2016-05-01

Full Text Available Different chemical components in traditional Ziegler–Natta catalytic system include: (1 titanium and vanadium containing compounds, mostly TiCl4, as an active centre, (2 trialkylaluminium-based Lewis acid compounds, especially triethylaluminium, as precatalyst and alkylating agent, and (3 inorganic compounds, specifically MgCl2 and silica, as catalyst supports. Besides these compounds, shortly after the first discovery of Ziegler-Natta catalysts, electron donors have been considered as the key components for MgCl2-supported Ziegler-Natta catalysts, as they improve the stereospecificity and activity of these types of catalysts. Most electron donor compounds have oxygen atom and only a few contain nitrogen atom in their structure. Starting from benzoate for third-generation Ziegler–Natta catalysts, the discovery of new donors has always updated the performance of Ziegler–Natta catalysts. Since the first discovery of these compounds numerous efforts have been devoted in both industry and academic laboratories, not only to discover new electron donors but also to understand their roles in Ziegler–Natta olefin polymerization and suitable MgCl2-alcohol adducts formation. This article reviews the history of such research and development efforts. The first part of the article describes the historical developments of catalyst, with a special focus on donors of industrial importance, followed by an account given on recent trends in the latest donors developed. The next part of the article covers the historical progress toward mechanistic understanding of how donors improve the performance of Ziegler–Natta catalysts and how they undergo decomposition by interaction with Lewis acidic species such as the AlEt3 and TiCl.

Comparison of Ethylene/1-Hexene Copolymers Microstructures Synthesized by Homogeneous and Heterogeneous Metallocene Catalysts

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Saeid Ahmadjo

2013-05-01

Full Text Available The substituted (bis-2-PhIndZrCl2 and non-substituted (bis-IndZrCl2 indenylbased metallocene catalysts were synthesized and used in homogenous and heterogeneous forms for copolymerization of ethylene and 1-hexene. The MCM-41 nano silica was used as support in heterogenization of the catalysts. The substituted (bis-2-PhIndZrCl2 metallocene catalyst in homogenous and heterogeneous forms showed lower activities in comparison to non-substituted (bis-IndZrCl2 metallocene catalyst. The microstructures of the obtained copolymers were investigated by techniques such as DSC, CNMR and TRRF. The kinetic study showed that the decay index (DI was decreased for both homogeneous catalysts due to unstable kinetic behaviors. However, the decay index contents approached one, using heterogeneous forms of catalyst which was an indication of stable kinetic behaviors. The kinetic results also displayed negative effect on the catalysts activities both in the homogeneous and heterogeneous forms by addition of comonomer on the polymerization. The triad distributions of obtained polymer by NMR technique exhibited the higher ratio of EEH, EHE, EEE triads than the other triads. The comonomer incorporationacceptability of substituted metallocene catalyst (bis-2-PhIndZrCl2 was higher than non-substituted catalyst (bis-IndZrCl2 as its comonomer acceptability increased from 1.3% to 5.4% by substitution mechanism. Microstructures of copolymers obtained by supported metallocene catalyst showed more non-uniform comonomer distribution in comparison with unsupported catalyst. The lamella thickness distributions for polymer obtained by supported substituted metallocene catalyst (bis-2-PhIndZrCl2 were in the ranges (3-8 . However, for supported metallocene non-substituted catalysts (bis-IndZrCl2 the lamella thickness were in the ranges (3-16 .

Radical-Scavenging Activity of Thiols, Thiobarbituric Acid Derivatives and Phenolic Antioxidants Determined Using the Induction Period Method for Radical Polymerization of Methyl Methacrylate

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Seiichiro Fujisawa

2012-04-01

Full Text Available The radical-scavenging activities of two thiols, eight (thiobarbituric acid derivatives and six chain-breaking phenolic antioxidants were investigated using the induction period method for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2’-azobisisobutyronitrile (AIBN and monitored by differential scanning calorimetry (DSC. The induction period (IP for the thiols 2-mercaptoethanol (ME and 2-mercapto-1-methylimidazole (MMI was about half that for phenolic antioxidants. Except for the potent inhibitor 5,5-dimethyl-2-thiobarbituric acid (3, the IP for thiobarbituric acid derivatives was about one tenth of that for phenolic antioxidants. The IP for 1,3,5-trimethyl-2-thiobarbituric acid (1 and 5-allyl-1, 3-dimethyl-2-thiobarbituric acid (7 was less than that of the control, possibly due to inhibition by a small amount of atmospheric oxygen in the DSC container. The ratio of the chain inhibition to that of chain propagation (CI/CP for the thiols and thiobarbituric acid compounds except for 1, 3 and 7 was about 10 times greater or greater than that for phenolic compounds. A kinetic chain length (KCL about 10% greater than that of the control was observed for 1, suggesting that 1 had chain transfer reactivity in the polymerization of MMA. The average molecular weight of polymers formed from thiobarbituric acid derivatives is discussed.

Porous nitrogen-enriched carbonaceous material from marine waste: chitosan-derived layered CNX catalyst for aerial oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid

Science.gov (United States)

Chitosan derived porous layered nitrogen-enriched carbonaceous CNx catalyst (PLCNx) has been synthesized from marine waste and its use demonstrated in a metal-free heterogeneous selective oxidation of 5-hydroxymethyl-furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) using aeria...

Direct catalytic conversion of brown seaweed-derived alginic acid to furfural using 12-tungstophosphoric acid catalyst in tetrahydrofuran/water co-solvent

International Nuclear Information System (INIS)

Park, Geonu; Jeon, Wonjin; Ban, Chunghyeon; Woo, Hee Chul; Kim, Do Heui

2016-01-01

Highlights: • Furfural was produced by catalytic conversion of macroalgae-derived alginic acid. • 12-Tungstophosphoric acid (H_3PW_1_2O_4_0) showed remarkable catalytic performance. • Tetrahydrofuran (THF) as a reaction medium significantly enhanced production of furfural. - Abstract: Furfural, a biomass-derived platform chemical, was produced by acid-catalyzed reaction of alginic acid extracted from brown seaweed. Three acid catalysts, H_2SO_4, Amberlyst15 and 12-tungstophosphoric acid (H_3PW_1_2O_4_0), were compared to evaluate their catalytic performance for the alginic acid conversion. The H_3PW_1_2O_4_0 catalyst showed the highest catalytic activity, yielding the maximum furfural yield (33.8%) at 180 °C for 30 min in tetrahydrofuran/water co-solvent. Higher reaction temperature promoted the conversion of alginic acid to furfural, but the transformation of furfural to humin was also accelerated. To our knowledge, this is the highest furfural yield among studies about the direct catalytic conversion of alginic acid. Furthermore, products distribution with time-on-stream was investigated in detail, which led us to propose a reaction pathway.

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Design, synthesis and molecular modeling of new 4-phenylcoumarin derivatives as tubulin polymerization inhibitors targeting MCF-7 breast cancer cells.

Science.gov (United States)

Batran, Rasha Z; Kassem, Asmaa F; Abbas, Eman M H; Elseginy, Samia A; Mounier, Marwa M

2018-07-23

A new set of 4-phenylcoumarin derivatives was designed and synthesized aiming to introduce new tubulin polymerization inhibitors as anti-breast cancer candidates. All the target compounds were evaluated for their cytotoxic effects against MCF-7 cell line, where compounds 2f, 3a, 3b, 3f, 7a and 7b, showed higher cytotoxic effect (IC 50  = 4.3-21.2 μg/mL) than the reference drug doxorubicin (IC 50  = 26.1 μg/mL), additionally, compounds 1 and 6b exhibited the same potency as doxorubicin (IC 50  = 25.2 and 28.0 μg/mL, respectively). The thiazolidinone derivatives 3a, 3b and 3f with potent and selective anticancer effects towards MCF-7 cells (IC 50  = 11.1, 16.7 and 21.2 μg/mL) were further assessed for tubulin polymerization inhibition effects which showed that the three compounds were potent tubulin polymerization suppressors with IC 50 values of 9.37, 2.89 and 6.13 μM, respectively, compared to the reference drug colchicine (IC 50  = 6.93 μM). The mechanistic effects on cell cycle progression and induction of apoptosis in MCF-7 cells were determined for compound 3a due to its potent and selective cytotoxic effects in addition to its promising tubulin polymerization inhibition potency. The results revealed that compound 3a induced cell cycle cessation at G2/M phase and accumulation of cells in pre-G1 phase and prevented its mitotic cycle, in addition to its activation of caspase-7 mediating apoptosis of MCF-7 cells. Molecular modeling studies for compounds 3a, 3b and 3f were carried out on tubulin crystallography, the results indicated that the compounds showed binding mode similar to the co-crystalized ligand; colchicine. Moreover, pharmacophore constructed models and docking studies revealed that thiazolidinone, acetamide and coumarin moieties are crucial for the activity. Molecular dynamics (MD) studies were carried out for the three compounds over 100 ps. MD results of compound 3a showed that it reached the stable state

Carbons and carbon supported catalysts in hydroprocessing

Energy Technology Data Exchange (ETDEWEB)

Furimsky, Edward

2009-07-01

This book is a comprehensive summary of recent research in the field and covers all areas of carbons and carbon materials. The potential application of carbon supports, particularly those of carbon black (CB) and activated carbon (AC) in hydroprocessing catalysis are covered. Novel carbon materials such as carbon fibers and carbon nano tubes (CNT) are also covered, including the more recent developments in the use of fullerenes in hydroprocessing applications. Although the primary focus of this book is on carbons and carbon supported catalysts, it also identifies the difference in the effect of carbon supports compared with the oxidic supports, particularly that of the Al{sub 2}O{sub 3}. The difference in catalyst activity and stability was estimated using both model compounds and real feeds under variable conditions. The conditions applied during the preparation of carbon supported catalysts are also comprehensively covered and include various methods of pretreatment of carbon supports to enhance catalyst performance. The model compounds results consistently show higher hydrodesulfurization and hydrodeoxygenation activities of carbon supported catalysts than that of the Al{sub 2}O{sub 3} supported catalysts. Also, the deactivation of the former catalysts by coke deposition was much less evident. Chapter 6.3.1.3 is on carbon-supported catalysts: coal-derived liquids.

A Thermally Re-mendable Cross-Linked Polymeric Material

Science.gov (United States)

Chen, Xiangxu; Dam, Matheus A.; Ono, Kanji; Mal, Ajit; Shen, Hongbin; Nutt, Steven R.; Sheran, Kevin; Wudl, Fred

2002-03-01

We have developed a transparent organic polymeric material that can repeatedly mend or ``re-mend'' itself under mild conditions. The material is a tough solid at room temperature and below with mechanical properties equaling those of commercial epoxy resins. At temperatures above 120°C, approximately 30% (as determined by solid-state nuclear magnetic resonance spectroscopy) of ``intermonomer'' linkages disconnect but then reconnect upon cooling, This process is fully reversible and can be used to restore a fractured part of the polymer multiple times, and it does not require additional ingredients such as a catalyst, additional monomer, or special surface treatment of the fractured interface.

Molecular heterogeneous catalysts derived from bipyridine-based organosilica nanotubes for C-H bond activation.

Science.gov (United States)

Zhang, Shengbo; Wang, Hua; Li, Mei; Han, Jinyu; Liu, Xiao; Gong, Jinlong

2017-06-01

Heterogeneous metal complex catalysts for direct C-H activation with high activity and durability have always been desired for transforming raw materials into feedstock chemicals. This study described the design and synthesis of one-dimensional organosilica nanotubes containing 2,2'-bipyridine (bpy) ligands in the framework (BPy-NT) and their post-synthetic metalation to provide highly active and robust molecular heterogeneous catalysts. By adjusting the ratios of organosilane precursors, very short BPy-NT with ∼50 nm length could be controllably obtained. The post-synthetic metalation of bipyridine-functionalized nanotubes with [IrCp*Cl(μ-Cl)] 2 (Cp* = η 5 -pentamethylcyclopentadienyl) and [Ir(cod)(OMe)] 2 (cod = 1,5-cyclooctadiene) afforded solid catalysts, IrCp*-BPy-NT and Ir(cod)-BPy-NT, which were utilized for C-H oxidation of heterocycles and cycloalkanes as well as C-H borylation of arenes. The cut-short nanotube catalysts displayed enhanced activities and durability as compared to the analogous homogeneous catalysts and other conventional heterogeneous catalysts, benefiting from the isolated active sites as well as the fast transport of substrates and products. After the reactions, a detailed characterization of Ir-immobilized BPy-NT via TEM, SEM, nitrogen adsorption, UV/vis, XPS, and 13 C CP MAS NMR indicated the molecular nature of the active species as well as stable structures of nanotube scaffolds. This study demonstrates the potential of BPy-NT with a short length as an integration platform for the construction of efficient heterogeneous catalytic systems for organic transformations.

Influence of clay type on the performance of Ziegler-Natta catalyst for the synthesis of nanocomposites of PE and PP

International Nuclear Information System (INIS)

Almeida, Lidiane A.; Marques, Maria F.V.; Oliveira, Jaqueline S.

2011-01-01

Polymer nanocomposites present highly improved general properties in comparison with original polymer and their conventional composites. The mayor disadvantage in preparing these materials is the difficulty in the dispersion of the nanofillers in the polymer matrix. In the present work, the synthesis of bisupported (MgCl 2 /clay) catalyst was performed for obtaining polyethylene and polypropylene nanocomposites by in situ polymerization with the aim to achieve higher dispersion of the nanofillers in the polyolefin matrix. Moreover, the influence of ammonium salt (employed in the organophilization of the clay) on the fixation of the catalyst components and therefore, on the catalyst activity was evaluated. The catalysts were characterized by TGA, SEM, EDX, and XRD. Polymers were characterized by DSC, isotactic index through heptane extractables (HS), TGA, EDX, XRD, and optical microscopy (OM). The results showed that the type of clay modifier has a great influence on the catalyst performance. (author)

Computational fluid dynamic modeling of fluidized-bed polymerization reactors

Energy Technology Data Exchange (ETDEWEB)

Rokkam, Ram [Iowa State Univ., Ames, IA (United States)

2012-01-01

Polyethylene is one of the most widely used plastics, and over 60 million tons are produced worldwide every year. Polyethylene is obtained by the catalytic polymerization of ethylene in gas and liquid phase reactors. The gas phase processes are more advantageous, and use fluidized-bed reactors for production of polyethylene. Since they operate so close to the melting point of the polymer, agglomeration is an operational concern in all slurry and gas polymerization processes. Electrostatics and hot spot formation are the main factors that contribute to agglomeration in gas-phase processes. Electrostatic charges in gas phase polymerization fluidized bed reactors are known to influence the bed hydrodynamics, particle elutriation, bubble size, bubble shape etc. Accumulation of electrostatic charges in the fluidized-bed can lead to operational issues. In this work a first-principles electrostatic model is developed and coupled with a multi-fluid computational fluid dynamic (CFD) model to understand the effect of electrostatics on the dynamics of a fluidized-bed. The multi-fluid CFD model for gas-particle flow is based on the kinetic theory of granular flows closures. The electrostatic model is developed based on a fixed, size-dependent charge for each type of particle (catalyst, polymer, polymer fines) phase. The combined CFD model is first verified using simple test cases, validated with experiments and applied to a pilot-scale polymerization fluidized-bed reactor. The CFD model reproduced qualitative trends in particle segregation and entrainment due to electrostatic charges observed in experiments. For the scale up of fluidized bed reactor, filtered models are developed and implemented on pilot scale reactor.

Polymeric carbon nitride/mesoporous silica composites as catalyst support for Au and Pt nanoparticles.

Science.gov (United States)

Xiao, Ping; Zhao, Yanxi; Wang, Tao; Zhan, Yingying; Wang, Huihu; Li, Jinlin; Thomas, Arne; Zhu, Junjiang

2014-03-03

Small and homogeneously dispersed Au and Pt nanoparticles (NPs) were prepared on polymeric carbon nitride (CNx )/mesoporous silica (SBA-15) composites, which were synthesized by thermal polycondensation of dicyandiamide-impregnated preformed SBA-15. By changing the condensation temperature, the degree of condensation and the loading of CNx can be controlled to give adjustable particle sizes of the Pt and Au NPs subsequently formed on the composites. In contrast to the pure SBA-15 support, coating of SBA-15 with polymeric CNx resulted in much smaller and better-dispersed metal NPs. Furthermore, under catalytic conditions the CNx coating helps to stabilize the metal NPs. However, metal NPs on CNx /SBA-15 can show very different catalytic behaviors in, for example, the CO oxidation reaction. Whereas the Pt NPs already show full CO conversion at 160 °C, the catalytic activity of Au NPs seems to be inhibited by the CNx support. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiolytic Synthesis of Pt-Ru Catalysts Based on Functional Polymer-Grafted MWNT and Their Catalytic Efficiency for CO and MeOH

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Dae-Soo Yang

2011-01-01

Full Text Available Pt-Ru catalysts based on functional polymer-grafted MWNT (Pt-Ru@FP-MWNT were prepared by radiolytic deposition of Pt-Ru nanoparticles on functional polymer-grafted multiwalled carbon nanotube (FP-MWNT. Three different types of functional polymers, poly(acrylic acid (PAAc, poly(methacrylic acid (PMAc, and poly(vinylphenyl boronic acid (PVPBAc, were grafted on the MWNT surface by radiation-induced graft polymerization (RIGP. Then, Pt-Ru nanoparticles were deposited onto the FP-MWNT supports by the reduction of metal ions using γ-irradiation to obtain Pt-Ru@FP-MWNT catalysts. The Pt-Ru@FP-MWNT catalysts were then characterized by XRD, XPS, TEM ,and elemental analysis. The catalytic efficiency of Pt-Ru@FP-MWNT catalyst was examined for CO stripping and MeOH oxidation for use in a direct methanol fuel cell (DMFC. The Pt-Ru@PVPBAc-MWNT catalyst shows enhanced activity for electro-oxidation of CO and MeOH oxidation over that of the commercial E-TEK catalyst.

High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

Energy Technology Data Exchange (ETDEWEB)

Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

2016-12-01

High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

Facile synthesis of porous graphene-like carbon nitride nanosheets with high surface area and enhanced photocatalytic activity via one-step catalyst-free solution self-polymerization

Science.gov (United States)

Wu, Shikai; Wen, Shengwu; Xu, Xinmei; Huang, Guozhi; Cui, Yifan; Li, Jinyu; Qu, Ailan

2018-04-01

Porous graphite carbon nitride nanosheets (g-C3N4) are achieved via one-step catalyst-free solution self-polymerization from a single melamine precursor. The resultant porous g-C3N4 nanosheets with the best photodegradation capacity provided the surface area of 669.15 m2/g, which is superior to the surface area of any other porous g-C3N4 reported. Results showed enhanced adsorption and degradation capacity of methyl orange (MO) under UV-visible light irradiation (λ > 350 nm) compared to bulk g-C3N4. The MO oxidation of the porous g-C3N4 nanosheets is driven mostly by the participation of holes, and secondly by rad O2- and rad OH radicals. This approach shed lights on porous g-C3N4 production simply by self-polycondensation of single functional monomer. It also provided a low-cost and eco-friendly method to facilely mass-produce g-C3N4 nanosheets with high surface area for many potential applications.

Non-Covalent Supported of l-Proline on Graphene Oxide/Fe3O4 Nanocomposite: A Novel, Highly Efficient and Superparamagnetically Separable Catalyst for the Synthesis of Bis-Pyrazole Derivatives

Directory of Open Access Journals (Sweden)

Mosadegh Keshavarz

2018-02-01

Full Text Available A superparamagnetic graphene oxide/Fe3O4/l-proline nano hybrid that was obtained from the non-covalent immobilization of l-proline on graphene oxide/Fe3O4 nanocomposite was used as a new magnetically separable catalyst for the efficient synthesis of 4,4′-(arylmethylenebis(1H-pyrazol-5-ol derivatives. The prepared heterogeneous catalyst was characterized using FTIR, TGA, DTG, XRD, TEM, SEM, and elemental analysis techniques. Short reaction times (5–15 min, excellent yields (87–98%, and simple experimental procedure with an easy work-up are some of the advantages of the introduced catalyst.

Development of high-speed reactive processing system for carbon fiber-reinforced polyamide-6 composite: In-situ anionic ring-opening polymerization

International Nuclear Information System (INIS)

Kim, Sang-Woo; Seong, Dong Gi; Yi, Jin-Woo; Um, Moon-Kwang

2016-01-01

In order to manufacture carbon fiber-reinforced polyamide-6 (PA-6) composite, we optimized the reactive processing system. The in-situ anionic ring-opening polymerization of ε-caprolactam was utilized with proper catalyst and initiator for PA-6 matrix. The mechanical properties such as tensile strength, inter-laminar shear strength and compressive strength of the produced carbon fiber-reinforced PA-6 composite were measured, which were compared with the corresponding scanning electron microscope (SEM) images to investigate the polymer properties as well as the interfacial interaction between fiber and polymer matrix. Furthermore, kinetics of in-situ anionic ring-opening polymerization of ε-caprolactam will be discussed in the viewpoint of increasing manufacturing speed and interfacial bonding between PA-6 matrix and carbon fiber during polymerization.

Development of high-speed reactive processing system for carbon fiber-reinforced polyamide-6 composite: In-situ anionic ring-opening polymerization

Energy Technology Data Exchange (ETDEWEB)

Kim, Sang-Woo; Seong, Dong Gi; Yi, Jin-Woo; Um, Moon-Kwang [Composites Research Division, Korea Institute of Materials Science (KIMS), Changwon, Gyeongnam, 642–831 (Korea, Republic of)

2016-05-18

In order to manufacture carbon fiber-reinforced polyamide-6 (PA-6) composite, we optimized the reactive processing system. The in-situ anionic ring-opening polymerization of ε-caprolactam was utilized with proper catalyst and initiator for PA-6 matrix. The mechanical properties such as tensile strength, inter-laminar shear strength and compressive strength of the produced carbon fiber-reinforced PA-6 composite were measured, which were compared with the corresponding scanning electron microscope (SEM) images to investigate the polymer properties as well as the interfacial interaction between fiber and polymer matrix. Furthermore, kinetics of in-situ anionic ring-opening polymerization of ε-caprolactam will be discussed in the viewpoint of increasing manufacturing speed and interfacial bonding between PA-6 matrix and carbon fiber during polymerization.

Surface modification of nanodiamond through metal free atom transfer radical polymerization

Energy Technology Data Exchange (ETDEWEB)

Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

2016-12-30

Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by {sup 1}H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

Surface modification of nanodiamond through metal free atom transfer radical polymerization

International Nuclear Information System (INIS)

Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2016-01-01

Highlights: • Surface modification of ND with water soluble and biocompatible polymers. • Functionalized ND through metal free surface initiated ATRP. • The metal free surface initiated ATRP is rather simple and effective. • The ND-poly(MPC) showed high dispersibility and desirable biocompatibility. - Abstract: Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1 H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

Heterogenization of Homogeneous Catalysts: the Effect of the Support

Energy Technology Data Exchange (ETDEWEB)

Earl, W.L.; Ott, K.C.; Hall, K.A.; de Rege, F.M.; Morita, D.K.; Tumas, W.; Brown, G.H.; Broene, R.D.

1999-06-29

We have studied the influence of placing a soluble, homogeneous catalyst onto a solid support. We determined that such a 'heterogenized' homogeneous catalyst can have improved activity and selectivity for the asymmetric hydrogenation of enamides to amino acid derivatives. The route of heterogenization of RhDuPhos(COD){sup +} cations occurs via electrostatic interactions with anions that are capable of strong hydrogen bonding to silica surfaces. This is a novel approach to supported catalysis. Supported RhDuPhos(COD){sup +} is a recyclable, non-leaching catalyst in non-polar media. This is one of the few heterogenized catalysts that exhibits improved catalytic performance as compared to its homogeneous analog.

Reactions of synthesis gas on silica supported transition metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Niemelae, M. [VTT Chemical Technology, Espoo (Finland). Lab. of Industrial Chemistry

1997-12-31

The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO{sub 2} catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO{sub 2} considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO{sub 2} appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO{sub 2} ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO{sub 2} catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh{sub 4}(CO){sub 12}/SiO{sub 2} from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes. (orig.) 69 refs.

Ethylbenzene dehydrogenation over Mg3Fe0.5−xCoxAl0.5 catalysts derived from hydrotalcites: Comparison with Mg3Fe0.5−yNiyAl0.5 catalysts

KAUST Repository

Atanda, Luqman A.

2011-04-01

A series of Mg3Fe0.5-xCoxAl0.5 (x = 0-0.5) catalysts were prepared from hydrotalcite precursors and their activities in the dehydrogenation of ethylbenzene were compared with those of a series of Mg3Fe0.5-yNiyAl0.5 (y = 0-0.5) catalysts also derived from hydrotalcite. The hydrotalcites prepared by co-precipitation were calcined at 550 °C to the mixed oxides with a high surface area of 150-240m2gcat-1; they were composed of Mg(Fe,Me,Al)O periclase and Mg(Me)(Fe,Al)2O4 spinel (Me = Co or Ni). Bimetallic Fe3+-Co2+ system showed a synergy, i.e., an increase in the activity, whereas Fe3+-Ni2+ bimetallic system showed no synergy. The high styrene yield was obtained on Mg 3Fe0.1Co0.4Al0.5; however, a large substitution of Fe3+ with Co2+ caused a decrease in styrene selectivity along with coking on the catalysts, due to an isolation of CoOx on the catalyst surface. The highest yield as well as the highest selectivity for styrene production was obtained at x = 0.25 at time on stream of 30 min. The coprecipitation at pH = 10.0 and the composition of Mg3Fe0.25Co0.25Al0.5 were the best for preparing the active catalyst. This is partly due to the formation of a good hydrotalcite structure. On this catalyst, the active Fe3+ species was reduced at a low temperature by the Fe3+-Co2+ bimetal formation, leading to a high activity. Simultaneously, the amount of reducible Fe3+ was the smallest, resulting in a high stability of the active Fe3+ species. It is likely that the dehydrogenation was catalyzed by the reduction-oxidation between Fe3+ and Fe2+ and that Co2+ assisted the reduction-oxidation by forming Fe 3+-Co2+ (1/1) bimetallic active species. © 2011 Elsevier B.V. All rights reserved.

Click polymerization for the synthesis of reduction-responsive polymeric prodrug

Science.gov (United States)

Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

2018-05-01

Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

Pulsed-laser polymerization in compartmentalized liquids. 1. Polymerization in vesicles

NARCIS (Netherlands)

Jung, M.; Casteren, van I.A.; Monteiro, M.J.; Herk, van A.M.; German, A.L.

2000-01-01

Polymerization in vesicles is a novel type of polymerization in heterogeneous media, leading to parachute-like vesicle-polymer hybrid morphologies. To explore the kinetics of vesicle polymerizations and to learn more about the actual locus of polymerization we applied the pulsed-laser polymerization

Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

KAUST Repository

Ramos-Gonzá lez, R.; Garcí a-Cerda, L. A.; Alshareef, Husam N.; Gnade, Bruce E.; Quevedo-Ló pez, Manuel Angel Quevedo

2010-01-01

This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

Study of hafnium (IV) oxide nanoparticles synthesized by polymerized complex and polymer precursor derived sol-gel methods

KAUST Repository

Ramos-González, R.

2010-03-01

This work reports the preparation and characterization of hafnium (IV) oxide (HfO2) nanoparticles grown by derived sol-gel routes that involves the formation of an organic polymeric network. A comparison between polymerized complex (PC) and polymer precursor (PP) methods is presented. For the PC method, citric acid (CA) and ethylene glycol (EG) are used as the chelating and polymerizable reagents, respectively. In the case of PP method, poly(acrylic acid) (PAA) is used as the chelating reagent. In both cases, different precursor gels were prepared and the hafnium (IV) chloride (HfCl4) molar ratio was varied from 0.1 to 1.0 for the PC method and from 0.05 to 0.5 for the PP method. In order to obtain the nanoparticles, the precursors were heat treated at 500 and 800 °C. The thermal characterization of the precursor gels was carried out by thermogravimetric analysis (TGA) and the structural and morphological characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the samples obtained by both methods shows the formation of HfO2 at 500 °C with monoclinic crystalline phase. The PC method exhibited also the cubic phase. Finally, the HfO2 nanoparticles size (4 to 11 nm) was determined by TEM and XRD patterns. © (2010) Trans Tech Publications.

Reactivity of Amine/E(C6F53 (E = B, Al Lewis Pairs toward Linear and Cyclic Acrylic Monomers: Hydrogenation vs. Polymerization

Directory of Open Access Journals (Sweden)

Jiawei Chen

2015-05-01

Full Text Available This work reveals the contrasting reactivity of amine/E(C6F53 (E = B, Al Lewis pairs toward linear and cyclic acrylic monomers, methyl methacrylate (MMA and biorenewable γ-methyl-α-methylene-γ-butyrolactone (γMMBL. While mixing of 2,2,6,6-tetramethylpiperidine (TMP and B(C6F53 leads to a frustrated Lewis pair (FLP, Et3N reacts with B(C6F53 to form disproportionation products, ammonium hydridoborate ionic pair and iminium zwitterion. On the other hand, the stoichiometric reaction of either TMP or Et3N with Al(C6F53 leads to clean formation of a classic Lewis adduct (CLA. Neither TMP nor Et3N, when paired with E(C6F53, polymerizes MMA, but the Et3N/2B(C6F53 pair promotes transfer hydrogenation of MMA to form methyl isobutyrate. In contrast, the amine/E(C6F53 pairs promote rapid polymerization of γMMBL carrying the more reactive exocyclic methylene moiety, achieving full conversion in less than 3 min even at a low catalyst loading of 0.0625 mol %. TMP is more effective than Et3N for the polymerization when paired with either the borane or the alane, while the alane exhibits higher polymerization activity than the borane when paired with Et3N. Overall, the TMP/Al(C6F53 system exhibits the highest polymerization activity, achieving a maximum turn-over frequency of 96,000 h−1 at 0.125 mol % of catalyst loading, producing high molecular weight PγMMBL with Mn = 1.29 × 105 g∙mol−1.

A series of NiMo/Al{sub 2}O{sub 3} catalysts containing boron and phosphorus. Part 2. Hydrodenitrogenation and hydrodesulfurization using heavy gas oil derived from Athabasca bitumen

Energy Technology Data Exchange (ETDEWEB)

Ferdous, D.; Dalai, A.K. [Catalysis and Chemical Reactor Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon (Canada) SK S7N 5C9; Adjaye, J. [Syncrude Canada Ltd., Edmonton Research Center (Canada)

2004-04-08

The hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activity of a series of NiMo/Al{sub 2}O{sub 3} catalyst containing boron (B) and phosphorus (P) were tested in a trickle bed reactor using heavy gas oil derived from Athabasca bitumen. Detailed characterization of these catalysts is given in Part I of this paper. Addition of B and P caused the formation of extremely strong acid sites on the catalyst and enhanced its HDN activity. The total (TN), basic (BN) and non-basic nitrogen (NBN) conversions increased from 61.9 to 78.0wt.%, from 78.9 to 93.0wt.% and from 52.8 to 70.0wt.%, respectively, with the increase in B concentration from 0 to 1.7wt.% to NiMo/Al{sub 2}O{sub 3} catalyst. Similarly, TN, BN and NBN conversions increased from 61.9 to 78.4wt.%, from 78.9 to 91.0wt.%, and from 52.8 to 71.6wt.% with the addition of 2.7wt.% P. Though the addition of B and P to NiMo/Al{sub 2}O{sub 3} catalyst did not show any significant effect on S conversion, the HDN and HDS activities of the catalyst containing 1.7wt.% B and the one containing 2.7wt.% P are comparable to those of a commercial catalyst. The activity over extended period indicated that catalysts L and K were more stable (lower deactivation rate) in terms of nitrogen removal activity than catalyst B (reference catalyst). On the other hand, the stability for sulfur removal was comparable with catalyst B. Selected catalysts after use were characterized using BET surface area, TPR, TPD and SEM techniques which were correlated further with their activities.

Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO2 and Glucoside

KAUST Repository

Pati, Debasis; Feng, Xiaoshuang; Hadjichristidis, Nikolaos; Gnanou, Yves

2017-01-01

Two bicyclic glycocarbonates were synthesized in five steps from α-methyl-d-glucoside without resorting to phosgene or to its derivatives for the first time. The 4- and 6-positions of glucose were modified to introduce a six-membered carbonate ring, using CO as the carbonylating reagent; the 2- and 3-positions of the same glucoside substrate were first transformed into either methyl or triethylene glycol monomethyl ether groups to protect these positions from undesirable reactions and also to impart hydrophobicity in the first case and hydrophilicity in the second. The polymerization behavior of these bicyclic glycocarbonates was then investigated under different conditions. On the one hand, through ring-opening polymerization of the above monomers, linear polyglycocarbonate homopolymers and diblock copolymers were obtained initiated by p-methylbenzyl alcohol using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst; on the other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates in water was investigated and characterized by cryo-TEM.

Hydrophobic, Hydrophilic, and Amphiphilic Polyglycocarbonates with Linear and Macrocyclic Architectures from Bicyclic Glycocarbonates Derived from CO2 and Glucoside

KAUST Repository

Pati, Debasis

2017-02-09

Two bicyclic glycocarbonates were synthesized in five steps from α-methyl-d-glucoside without resorting to phosgene or to its derivatives for the first time. The 4- and 6-positions of glucose were modified to introduce a six-membered carbonate ring, using CO as the carbonylating reagent; the 2- and 3-positions of the same glucoside substrate were first transformed into either methyl or triethylene glycol monomethyl ether groups to protect these positions from undesirable reactions and also to impart hydrophobicity in the first case and hydrophilicity in the second. The polymerization behavior of these bicyclic glycocarbonates was then investigated under different conditions. On the one hand, through ring-opening polymerization of the above monomers, linear polyglycocarbonate homopolymers and diblock copolymers were obtained initiated by p-methylbenzyl alcohol using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst; on the other hand, macrocyclic polyglycocarbonate homopolymers and diblock copolymers were grown using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) which served as zwitterionic initiator. The various architectures derived were all thoroughly characterized by NMR, GPC, and MALDI-tof and shown to exhibit the expected structure. Finally, the self-assembly of linear and macrocyclic amphiphilic copolyglycocarbonates in water was investigated and characterized by cryo-TEM.

Continuous-Flow O-Alkylation of Biobased Derivatives with Dialkyl Carbonates in the Presence of Magnesium-Aluminium Hydrotalcites as Catalyst Precursors.

Science.gov (United States)

Cattelan, Lisa; Perosa, Alvise; Riello, Piero; Maschmeyer, Thomas; Selva, Maurizio

2017-04-10

The base-catalysed reactions of OH-bearing biobased derivatives (BBDs) including glycerol formal, solketal, glycerol carbonate, furfuryl alcohol and tetrahydrofurfuryl alcohol with non-toxic dialkyl carbonates (dimethyl and diethyl carbonate) were explored under continuous-flow (CF) conditions in the presence of three Na-exchanged Y- and X-faujasites (FAUs) and four Mg-Al hydrotalcites (HTs). Compared to previous etherification protocols mediated by dialkyl carbonates, the reported procedure offers substantial improvements not only in terms of (chemo)selectivity but also for the recyclability of the catalysts, workup, ease of product purification and, importantly, process intensification. Characterisation studies proved that both HT30 and KW2000 hydrotalcites acted as catalyst precursors: during the thermal activation pre-treatments, the typical lamellar structure of the hydrotalcite was broken down gradually into a MgO-like phase (periclase) or rather a magnesia-alumina solid solution, which was the genuine catalytic phase. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap

Directory of Open Access Journals (Sweden)

Ramesh Karunagaran

2018-01-01

Full Text Available Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF and carbon microspheres (N-CMS synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism.

Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap.

Science.gov (United States)

Karunagaran, Ramesh; Coghlan, Campbell; Shearer, Cameron; Tran, Diana; Gulati, Karan; Tung, Tran Thanh; Doonan, Christian; Losic, Dusan

2018-01-28

Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas) into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR) in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF) and carbon microspheres (N-CMS) synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism.

Catalytic Hydrodeoxygenation of Biomass Pyrolysis Vapor Model Compounds over Molybdenum Sulfide Catalysts: Influence of Support, H₂S and Water

DEFF Research Database (Denmark)

Arndal, Trine Marie Hartmann; Høj, Martin; Pintos, Delfina Garcia

value, acidity and stability [1,2]. Upgrading ofcondensed pyrolysis oil is challenged by severe polymerization and coking upon heating. Instead, it is proposed toperform pyrolysis in the presence of hydrogen and an HDO catalyst for immediate stabilization and upgrading ofreactive pyrolysis products...

Micelle-derived catalysts for extended Schulz-Flory. Technical progress report, July 1, 1986--September 30, 1986

Energy Technology Data Exchange (ETDEWEB)

Abrevaya, H.

1986-12-31

The objective of this program is to develop a synthesis gas conversion catalyst with higher selectivity to liquid fuels, while maintaining catalytic activity and stability at least equivalent relative to state-of-the-art precipitated iron catalysts. During this quarter, the emphasis in the program has been the investigation of the hydrocarbon cutoff hypothesis with supported ruthenium catalysts. An alumina-supported catalyst with smaller than 20{Angstrom} ruthenium particles was tested under conditions of maximal water gas shift activity. During this test more than 90% of the water made in the Fischer-Tropsch synthesis reaction was converted to H{sub 2}. However, the extent of ruthenium metal agglomeration was not reduced. Accordingly, it was not possible to conclude whether hydrocarbon cutoff occurs with smaller than 20{Angstrom} ruthenium particles on {gamma}-alumina. A ruthenium catalyst prepared on Y-type zeolite had 20{Angstrom} or smaller ruthenium particles according to STEM examination and a 15{Angstrom} average ruthenium metal particle size according to EXAFS examination. The ruthenium metal particle size was stable during the test with this catalyst. The hydrocarbon product distribution was Anderson-Schulz-Flory with no cutoff up to a carbon number of 160. A well-dispersed titania-supported ruthenium catalyst is going to be evaluated during the next quarter in order to determine whether hydrocarbon cutoff occurs.

Catalysis Science Initiative: Catalyst Design by Discovery Informatics

Energy Technology Data Exchange (ETDEWEB)

Delgass, William Nicholas [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States) Department of Chemistry; Caruthers, James [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Ribeiro, Fabio [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Thomson, Kendall [Purdue Univ., West Lafayette, IN (United States). Chemical Engineering; Schneider, William [Univ. of Notre Dame, IN (United States)

2016-07-08

atoms in the interfacial region. Some of the first theoretical descriptions of this important chemistry and potential new source of control of catalyst properties are be in preparation for submission. On the homogeneous catalysis side, we have used single site olefin polymerization as the testbed. This system is important because changes in a single ligand bonded to the catalytically active metal site can alter the rates of individual steps in the polymerization sequence and thereby change the properties of the resulting polymer, potentially improving its value in a hundred million pound per year industry. We have made a major advance in understanding such systems by developing a population balance kinetic model that allows us to predict the molecular weight distribution (MWD) of the product. That, in turn, allows use of MWD data to fit kinetic parameters. By combining monomer loss data, MWD, measurement of the number of working active sites, and polymer end group analysis, we have a rich data set that is highly discriminating of kinetic mechanism. Thus, we have a robust tool for producing high quality, detailed kinetic parameters, which we have used to refine mechanisms presented in the literature and discover relationships between steric and electronic properties of group IV catalysts and individual rate constants in a number of systems. Our recent work on six-coordinate Zr, Ti, and Hf amine bis(phenolate) systems, we have shown that: • The sterics (bulkiness) of the ligands specifically affect the chain termination reaction • The electron density on the metal controls misinsertion (flipped orientation) of the olefin into the growing polymer • Steric effects related to the size of the ortho ligand on the catalyst have been shown to strongly affect its the degree of dormancy, i.e. tendency to stop reacting • Changes in the size of the amine pendent group on the catalyst can have such a strong effect on chain termination as to change the catalyst from one that

Tunable regioselectivity in 1,3-butadiene polymerization by using 2,6-bis(dimethyl-2-oxazolin-2-yl)pyridine incorporated transition metal (Cr, Fe and Co) catalysts

KAUST Repository

Gong, Dirong; Liu, Wen; Pan, Weijing; Chen, Tao; Jia, Xiaoyu; Huang, Kuo-Wei; Zhang, Xuequan

2015-01-01

Tridentate complexes Cr(III)Cl3L, [L = 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine], Fe(III)Cl3L, Fe(II)Cl2L and Co(II)Cl2L have been prepared and fully characterized. The solid structures of Cr(III)Cl3L, Fe(III)Cl3L and Co(II)Cl2L have been revealed by single crystal X-ray diffraction, and the Cr(III)Cl3L and Fe(III)Cl3L complexes both exhibit a distorted octahedral geometry, while the Co(II)Cl2L complex has a trigonal bipyramidal conformation. Four complexes have been examined in regioselective polymerization of butadiene in combination with MAO in toluene at room temperature. The trans-1,4, cis-1,4 enchainment of resultant polybutadiene are controlled by the metal center. Activated by MAO, complex Cr(III)Cl3L produces high level of trans-1,4 selectivity (trans-1,4 up to 93.3%) with moderate polymer yield, complexes Fe(III)Cl3L and Fe(II)Cl2L both show equal cis-1,4 and trans-1,4 with minor 1,2 selectivity (<10%), and Co(II)Cl2L catalyst displays predominated cis-1,4 selectivity, which can be shifted to 1,2 selectivity by adding PPh3 as an additive. Thus, tuning of the cis-1,4, trans-1,4 and 1,2 selectivity in full range via central metal and additive chosen by these 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine supported catalysts has been achieved. © 2015 Elsevier B.V. All rights reserved.

Tunable regioselectivity in 1,3-butadiene polymerization by using 2,6-bis(dimethyl-2-oxazolin-2-yl)pyridine incorporated transition metal (Cr, Fe and Co) catalysts

KAUST Repository

Gong, Dirong

2015-05-21

Tridentate complexes Cr(III)Cl3L, [L = 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine], Fe(III)Cl3L, Fe(II)Cl2L and Co(II)Cl2L have been prepared and fully characterized. The solid structures of Cr(III)Cl3L, Fe(III)Cl3L and Co(II)Cl2L have been revealed by single crystal X-ray diffraction, and the Cr(III)Cl3L and Fe(III)Cl3L complexes both exhibit a distorted octahedral geometry, while the Co(II)Cl2L complex has a trigonal bipyramidal conformation. Four complexes have been examined in regioselective polymerization of butadiene in combination with MAO in toluene at room temperature. The trans-1,4, cis-1,4 enchainment of resultant polybutadiene are controlled by the metal center. Activated by MAO, complex Cr(III)Cl3L produces high level of trans-1,4 selectivity (trans-1,4 up to 93.3%) with moderate polymer yield, complexes Fe(III)Cl3L and Fe(II)Cl2L both show equal cis-1,4 and trans-1,4 with minor 1,2 selectivity (<10%), and Co(II)Cl2L catalyst displays predominated cis-1,4 selectivity, which can be shifted to 1,2 selectivity by adding PPh3 as an additive. Thus, tuning of the cis-1,4, trans-1,4 and 1,2 selectivity in full range via central metal and additive chosen by these 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine supported catalysts has been achieved. © 2015 Elsevier B.V. All rights reserved.

Polystyrene-supported aluminum chloride as an efficient and reusable catalyst for condensation of indole with various carbonyl compounds

Directory of Open Access Journals (Sweden)

BAHMAN TAMAMI

2010-04-01

Full Text Available Crosslinked polystyrene-supported aluminum chloride (PS–AlCl3 is a stable, recyclable and environmental friendly heterogeneous catalyst for the condensation of indole with aldehydes and ketones to afford diindolylmethanes. In addition, PS–AlCl3 shows satisfactory selectivity in the reaction of mixtures of an aldehyde and a ketone with indole. Although AlCl3 is water sensitive, corrosive and environmentally harmful compound, PS–AlCl3 is a stable and water-tolerant species. The mild reaction conditions, short reaction times, easy work-up, high to excellent yields, chemoselectivity, reuse of the catalyst for at least ten times without significant change in its catalytic activity, low cost, and easy preparation and handling of the polymeric catalyst are obvious advan-tages of the present method.

Plasma and catalyst for the oxidation of NOx

DEFF Research Database (Denmark)

Jõgi, Indrek; Erme, Kalev; Levoll, Erik

2018-01-01

. In the case of indirect oxidation, only ozone could reach the catalyst surface and improve the oxidation of NO2 to N2O5. The effect of catalyst at different experimental conditions was quantitatively described with the aid of simple global chemical kinetic models derived for the NO x oxidation either...... by plasma or ozone. The models allowed to compare the effect of different catalysts and to analyze the limitations for the efficiency improvement by catalyst....... to NO mediated by O radicals in plasma. Indirect NO oxidation by plasma produced ozone allows to circumvent the back-reaction and further oxidize NO2 to N2O5 but the slow reaction rate for the latter process limits the efficiency of this process. Present paper gives an overview of the role of metal...

Hybrid Carbon Fibers/Carbon Nanotubes Structures for Next Generation Polymeric Composites

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M. Al-Haik

2010-01-01

Full Text Available Pitch-based carbon fibers are commonly used to produce polymeric carbon fiber structural composites. Several investigations have reported different methods for dispersing and subsequently aligning carbon nanotubes (CNTs as a filler to reinforce polymer matrix. The significant difficulty in dispersing CNTs suggested the controlled-growth of CNTs on surfaces where they are needed. Here we compare between two techniques for depositing the catalyst iron used toward growing CNTs on pitch-based carbon fiber surfaces. Electrochemical deposition of iron using pulse voltametry is compared to DC magnetron iron sputtering. Carbon nanostructures growth was performed using a thermal CVD system. Characterization for comparison between both techniques was compared via SEM, TEM, and Raman spectroscopy analysis. It is shown that while both techniques were successful to grow CNTs on the carbon fiber surfaces, iron sputtering technique was capable of producing more uniform distribution of iron catalyst and thus multiwall carbon nanotubes (MWCNTs compared to MWCNTs grown using the electrochemical deposition of iron.

Lipase-catalyzed ring-opening polymerization of lactones to polyesters and its mechanistic aspects.

Science.gov (United States)

Namekawa, S; Suda, S; Uyama, H; Kobayashi, S

1999-01-01

Lipase catalysis induced a ring-opening polymerization of lactones with different ring-sizes. Small-size (four-membered) and medium-size lactones (six- and seven-membered) as well as macrolides (12-, 13-, 16-, and 17-membered) were subjected to lipase-catalyzed polymerization. The polymerization behaviors depended primarily on the lipase origin and the monomer structure. The macrolides showing much lower anionic polymerizability were enzymatically polymerized faster than epsilon-caprolactone. The granular immobilized lipase derived from Candida antartica showed extremely efficient catalysis in the polymerization of epsilon-caprolactone. Single-step terminal functionalization of the polyester was achieved by initiator and terminator methods. The enzymatic polymerizability of lactones was quantitatively evaluated by Michaelis-Menten kinetics.

Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

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Shouyun Cheng

2016-12-01

Full Text Available The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction, and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.

Living Polycondensation: Synthesis of Well-Defined Aromatic Polyamide-Based Polymeric Materials

KAUST Repository

Alyami, Mram Z.

2016-11-01

Chain growth condensation polymerization is a powerful tool towards the synthesis of well-defined polyamides. This thesis focuses on one hand, on the synthesis of well-defined aromatic polyamides with different aminoalkyl pendant groups with low polydispersity and controlled molecular weights, and on the other hand, on studying their thermal properties. In the first project, well-defined poly (N-octyl-p-aminobenzoate) and poly (N-butyl-p-aminobenzoate) were synthesized, and for the first time, their thermal properties were studied. In the second project, ethyl4-aminobenzoate, ethyl 4-octyl aminobenzoate and 4-(hydroxymethyl) benzoic acid were used as novel efficient initiators of ε-caprolactone with t-BuP2 as a catalyst. Macroinitiator and Macromonomer of poly (ε-caprolactone) were synthesized with ethyl 4-octyl aminobenzoate and ethyl 4-aminobenzoate as initiators to afford polyamide-block-poly (ε-caprolactone) and polyamide-graft-poly (ε-caprolactone) by chain growth condensation polymerization (CGCP). In the third project, a new study has been done on chain growth condensation polymerization to discover the probability to synthesize new polymers and studied their thermal properties. For this purpose, poly (N-cyclohexyl-p-aminobenzoate) and poly (N-hexyl-p-aminobenzoate) were synthesized with low polydispersity and controlled molecular weights.

Exploring electronic and steric effects on the insertion and polymerization reactivity of phosphinesulfonato pdii catalysts

KAUST Repository

Neuwald, Boris; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Mecking, Stefan

2013-01-01

incorporation at low MA concentrations in the copolymerization; and 3) steric shielding leads to a pronounced increase in polymer molecular weight in the copolymerization. The catalyst properties induced by a given P-aryl (alkyl) moiety were combined effectively

Superhydrophobic Surfaces with Very Low Hysteresis Prepared by Aggregation of Silica Nanoparticles During In Situ Urea-Formaldehyde Polymerization.

Science.gov (United States)

Diwan, Anubhav; Jensen, David S; Gupta, Vipul; Johnson, Brian I; Evans, Delwyn; Telford, Clive; Linford, Matthew R

2015-12-01

We present a new method for the preparation of superhydrophobic materials by in situ aggregation of silica nanoparticles on a surface during a urea-formaldehyde (UF) polymerization. This is a one-step process in which a two-tier topography is obtained. The polymerization is carried out for 30, 60, 120, 180, and 240 min on silicon shards. Silicon surfaces are sintered to remove the polymer. SEM and AFM show both an increase in the area covered by the nanoparticles and their aggregation with increasing polymerization time. Chemical vapor deposition of a fluorinated silane in the presence of a basic catalyst gives these surfaces hydrophobicity. Deposition of this low surface energy silane is confirmed by the F 1s signal in XPS. The surfaces show advancing water contact angles in excess of 160 degrees with very low hysteresis (polymerization times for 7 nm and 14 nm silica, respectively. Depositions are successfully demonstrated on glass substrates after they are primed with a UF polymer layer. Superhydrophobic surfaces can also be prepared on unsintered substrates.

Noble metal catalysts in the production of biofuels

Energy Technology Data Exchange (ETDEWEB)

Gutierrez, A.

2013-11-01

The energy demand is increasing in the world together with the need to ensure energy security and the desire to decrease greenhouse gas emissions. While several renewable alternatives are available for the production of electricity, e.g. solar energy, wind power, and hydrogen, biomass is the only renewable source that can meet the demand for carbon-based liquid fuels and chemicals. The technology applied in the conversion of biomass depends on the type and complexity of the biomass, and the desired fuel. Hydrogen and hydrogen-rich mixtures (synthesis gas) are promising energy sources as they are more efficient and cleaner than existing fuels, especially when they are used in fuel cells. Hydrotreatment is a catalytic process that can be used in the conversion of biomass or biomass-derived liquids into fuels. In autothermal reforming (ATR), catalysts are used in the production of hydrogen-rich mixtures from conventional fuels or bio-fuels. The different nature of biomass and biomass-derived liquids and mineral oil makes the use of catalysts developed for the petroleum industry challenging. This requires the improvement of available catalysts and the development of new ones. To overcome the limitations of conventional hydrotreatment and ATR catalysts, zirconia-supported mono- and bimetallic rhodium, palladium, and platinum catalysts were developed and tested in the upgrading of model compounds for wood-based pyrolysis oil and in the production of hydrogen, using model compounds for gasoline and diesel. Catalysts were also tested in the ATR of ethanol. For comparative purposes commercial catalysts were tested and the results obtained with model compounds were compared with those obtained with real feedstocks (hydrotreatmet tests with wood-based pyrolysis oil and ATR tests with NExBTL renewable diesel). Noble metal catalysts were active and selective in the hydrotreatment of guaiacol used as the model compound for the lignin fraction of wood-based pyrolysis oil and wood

Modification of Clays by Sol-Gel Reaction and Their Use in the Ethylene In Situ Polymerization for Obtaining Nanocomposites

Directory of Open Access Journals (Sweden)

E. Moncada

2012-01-01

Full Text Available The nanocomposites formation by in situ polymerization used a metallocene catalyst (butyl-2-cyclopentadienyl zirconium 2-chlorines and a hectorite synthetic clay type which is discussed. This research was carried out in two phases. The first phase consisted of mixing the components of the metallocenic polymerization reaction (metallocene-methylaluminoxane-ethylene with clay in a reactor. In the second phase, the metallocenic catalytic system was supported by clay particles and then a polymerization reaction was made. In this second phase, the clay particles were modified using a sol-gel reaction with different pH values: pH = 3, pH = 8, and pH = 12. The results were compared in terms of the catalytic activity in the different systems (phase 1 and phase 2 and the nanoparticle morphology of nanocomposites generated in this study.

New Titanium-Based Catalysts for the Synthesis of Poly(ethylene terephthalate)

International Nuclear Information System (INIS)

Yang, Youngkeun; Yoon, Seungwoong; Hwang, Yongtaek; Song, Bogeun

2012-01-01

Poly(ethylene terephthalate) (PET) is a polymer with relatively low cost and high performance, which is widely used in various applications such as bottles, textile fibers, films and engineering plastics for automobiles and electric industries. Commercial catalysts used for synthesis of PET are in general antimony (Sb) compounds. Antimony(III) oxide, antimony(III) acetate and antimony(III) glycolate are used as a catalyst in 95% of PET manufacturing industries worldwide. The few organoantimony compounds that have been identified in environmental and biological samples are all in the form of methylated Sb-species. The Sb trace element is extremely toxic to mammals, and interferes with embryonic and fetal development, also, carcinogenic to humans. In addition to being found in drinking water, food packaging and soft-drink bottles. According to the World Health Organization (WHO), Sb species concentration lower than 20 ppb are acceptable for drinking water. According to a recent study, in 14 brands of bottled water from Canada, Sb concentrations increased on average 19% during 6 months storage at room temperature, but 48 brands of water from 11 European countries increased on average 90% under identical conditions. Therefore, a very important challenge for polyester catalysis is to come-up with a new Sb-free catalysts with low environmental impact. Intensive efforts have been made to find other stable and more environmental friendly non-antimony catalysts, such as those based on titanium. Titanium-based catalysts have been known for many years and actually are used for polybutylene terephthalate (PBT) and polypropylene terephthalate (PPT) production, however, polycondensation (PC) of PET manufacture is not well studied in literature. To date, only few esterification processes have been applied for the synthesis of PET by titanium catalysts. Herein, we report an efficient synthesis characterization and polymerization of PET for a series of new nontoxic organotitanium

Catalytic pyrolysis of LDPE using modified vermiculite as a catalyst

International Nuclear Information System (INIS)

Bezerra, Franciel Aureliano; Figueiredo, Aneliese Lunguinho; Araujo, Antonio Souza de; Guedes, Ana Paula de Melo Alves

2016-01-01

Low density polyethylene (LDPE) is one of the most commonly-used polymers currently, and the great quantity of this polymer produced results in tons of waste that must be treated. We studied the thermocatalytic pyrolysis of LDPE with a modified clay vermiculite catalyst as an alternative for treatment of waste. The clay was treated with a solution of nitric acid at different concentrations and calcined at 400 °C. The materials were characterized by X-ray diffraction, thermogravimetry, nitrogen adsorption, and energy dispersive spectroscopy. Thermal and thermocatalytic pyrolysis were carried out in a microreactor coupled with GC/MS at 500 °C. The aim of the polymeric waste pyrolysis is the obtainment of light hydrocarbons (C<16), which can be used in the chemical and petrochemical industry, through breaks in the polymer chain. The results were satisfactory, with an increase in yield for light hydrocarbons by using catalysts reaching up to 71.4% of products with C<16, whereas thermal pyrolysis resulted in only 25.8%. (author)

Synthesis and essay of an Ionomer like catalyst of olefins epoxidation

International Nuclear Information System (INIS)

Boyaca Mendivelso, Alejandro; Tempesti, Ezio

1995-01-01

The purpose of the present work is the preparation of an ionomer with base in Molybdenum and to evaluate its activity like catalyst of olefins epoxidation like alternative of synthesis of catalysts of the Hawk process. A polymer is synthesized with available functional groups to stabilize the metal starting from sodium molybdate; the characterization is made by atomic absorption, spectroscopy to GO, and X.P.S. The characterization indicates that indeed it is possible to stabilize the Mo in the main polymeric. The evaluation in reaction in liquid phase allows similar conversions to those of a homogeneous catalyst. The selective epoxidation of olefins for alkyl hydroperoxides, it has acquired great importance inside the industrial processes obtaining of propylene oxide due to the recent use of the terbutilic alcohol (co-produced together with the epoxide), as preservative in gasoline free of lead. In the environment of these processes, and in particular in the Hawk process possibilities of technological innovation, in the concerning to the heterogenization of conventional catalysts, at the moment used in homogeneous phase. The present work collaborate to some tentative that look for to generate alternative of preparation of catalysts for the process Hawk, synthesizing and testing the activity of an ionomer like epoxidation catalyst, which tries to reproduce the chemical structure of the complexes organ-metallic pear to suppress the separation stages and necessary recovery facilitating its recurrent reutilization with eventual economic repercussions in the industrial process. It is described the procedure of synthesis of the ionomer, the characterization and the evaluation of the activity in reaction under diverse conditions. Of the made characterization it comes off that the heterogenization of catalysts for olefins epoxidation, according to the Hawk process, is possible by means of the preparation of polymers modified appropriately. Likewise the evaluation in

Change in activity of catalysts for the oxidation of tritium during a fire event

International Nuclear Information System (INIS)

Iwai, Yasunori; Sato, Katsumi; Yamanishi, Toshihiko

2012-01-01

Highlights: ► We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalysts for tritium oxidation. ► At 423 K, no considerable decrease in catalytic activity was observed. ► At 293 K, considerable increase in catalytic activity was initially observed due to the effect of produced hydrogen. Then the temporary decrease was observed due mainly to the effect of produced moisture, however the activity was gradually recovered. - Abstract: The catalytic performance should be maintained in any off normal events. Fire accident is the typical off normal event. In the fusion plant, typical combustibles are evaluated to be polymeric low-halogen cables. Produced gases from burned low-halogen cable may affect the activity of catalysts for the oxidation of tritium. We experimentally demonstrated the influence of produced gases from burned low-halogen cable on the activity of catalyst using tritium gas. Our evaluation showed that ethylene, methane and benzene were major produced gases. The activity of catalysts for the oxidation of tritium during a fire event was evaluated using a commercial hydrophilic Pt/Al 2 O 3 catalyst and a commercial hydrophobic Pt-catalyst. The temperature of catalytic reactor was selected to be 423 and 293 K. At 423 K, no considerable decrease in catalytic activity was observed for both catalysts even in the presence of produced gases from burned low-halogen cable. At 293 K, considerable increase in catalytic activity was initially observed for both catalysts due to the effect of produced hydrogen. Then the temporary decrease was observed, however the catalytic activity was gradually recovered to be the original activity. Consequently, the irreversible decrease in activity of the catalysts during a fire event was not observed.

Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane.

Science.gov (United States)

Zhang, Sheng; Kang, Peng; Bakir, Mohammed; Lapides, Alexander M; Dares, Christopher J; Meyer, Thomas J

2015-12-29

Developing sustainable energy strategies based on CO2 reduction is an increasingly important issue given the world's continued reliance on hydrocarbon fuels and the rise in CO2 concentrations in the atmosphere. An important option is electrochemical or photoelectrochemical CO2 reduction to carbon fuels. We describe here an electrodeposition strategy for preparing highly dispersed, ultrafine metal nanoparticle catalysts on an electroactive polymeric film including nanoalloys of Cu and Pd. Compared with nanoCu catalysts, which are state-of-the-art catalysts for CO2 reduction to hydrocarbons, the bimetallic CuPd nanoalloy catalyst exhibits a greater than twofold enhancement in Faradaic efficiency for CO2 reduction to methane. The origin of the enhancement is suggested to arise from a synergistic reactivity interplay between Pd-H sites and Cu-CO sites during electrochemical CO2 reduction. The polymer substrate also appears to provide a basis for the local concentration of CO2 resulting in the enhancement of catalytic current densities by threefold. The procedure for preparation of the nanoalloy catalyst is straightforward and appears to be generally applicable to the preparation of catalytic electrodes for incorporation into electrolysis devices.

Biocatalytic synthesis and polymerization via ROMP of new biobased phenolic monomers: a greener process towards sustainable antioxidant polymers

Science.gov (United States)

Diot-Néant, Florian; Migeot, Loïs; Hollande, Louis; Reano, Felix A.; Domenek, Sandra; Allais, Florent

2017-12-01

Antioxidant norbornene-based monomers bearing biobased sterically hindered phenols (SHP) - NDF (norbornene dihydroferulate) and NDS (norbornene dihydrosinapate) - have been successfully prepared through biocatalysis from naturally occurring ferulic and sinapic acids, respectively, in presence of Candida antarctica Lipase B (Cal-B). The ring opening metathesis polymerization (ROMP) of these monomers was investigated according to ruthenium catalyst type (GI) vs. (HGII) and monomer to catalyst molar ratio ([M]/[C]). The co-polymerization of antioxidant functionalized monomer (NDF or NDS) and non-active norbornene (N) has also been performed in order to adjust the number of SHP groups present per weight unit and tune the antioxidant activity of the copolymers. The polydispersity of the resulting copolymers was readily improved by a simple acetone wash to provide antioxidant polymers with well-defined structures. After hydrogenation with p-toluenesulfonylhydrazine (p-TSH), the radical scavenging ability of the resulting saturated polymers was evaluated using α,α-diphenyl-β-picrylhydrazyl (DPPH) analysis. Results demonstrated that polymers bearing sinapic acid SHP exhibited higher antiradical activity than the polymer bearing ferulic acid SHP. In addition it was also shown that only a small SHP content was needed in the copolymers to exhibit a potent antioxidant activity.

Oxidation catalyst

Science.gov (United States)

Ceyer, Sylvia T.; Lahr, David L.

2010-11-09

The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

Synthesis and Application of Polymeric Fluorescent Compounds Based on Coumarin

Directory of Open Access Journals (Sweden)

Guojun Liu

2015-06-01

Full Text Available In this work, a multifunctional yellowing inhibitor was synthesized by the Pechmann method. In order to obtain the target compound, 7-hydroxy-4-methyl coumarin was prepared by using the raw materials of resorcinol and ethyl acetoacetate, with toluene-p-sulfonic acid as the catalyst. New polymeric fluorescent compounds were synthesized by connecting the 7-hydroxy-4-methyl coumarin, the hindered amine light stabilizer 4-amion-2,2,6,6-tetramentylniperidine, and a series of polyethylene glycol segments into the same molecule with cyanuric chloride as a bridge. The structures of the synthesized molecules were confirmed by FT-IR, 1H NMR, and elemental analysis. The luminescent properties of the fluorescent compounds were studied by UV-vis spectroscopy and fluorescence spectroscopy. The integration effect between the fluorescent compounds and paper was tested by a scanning electron microscope. The light stability effect on the paper sheet was tested using an ultraviolet aging apparatus. The results indicate that the polymeric fluorescent compounds had a positive effect on the light stability of the high-yield pulp.

Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

KAUST Repository

Balasamy, Rabindran J.; Tope, Balkrishna B.; Khurshid, Alam; Al-Ali, Ali A S; Atanda, Luqman A.; Sagata, Kunimasa; Asamoto, Makiko; Yahiro, Hidenori; Nomura, Kiyoshi; Sano, Tsuneji; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

2011-01-01

A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

KAUST Repository

Balasamy, Rabindran J.

2011-05-01

A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

Upgrading Lignocellulosic Biomasses: Hydrogenolysis of Platform Derived Molecules Promoted by Heterogeneous Pd-Fe Catalysts

Directory of Open Access Journals (Sweden)

Claudia Espro

2017-03-01

Full Text Available This review provides an overview of heterogeneous bimetallic Pd-Fe catalysts in the C–C and C–O cleavage of platform molecules such as C2–C6 polyols, furfural, phenol derivatives and aromatic ethers that are all easily obtainable from renewable cellulose, hemicellulose and lignin (the major components of lignocellulosic biomasses. The interaction between palladium and iron affords bimetallic Pd-Fe sites (ensemble or alloy that were found to be very active in several sustainable reactions including hydrogenolysis, catalytic transfer hydrogenolysis (CTH and aqueous phase reforming (APR that will be highlighted. This contribution concentrates also on the different synthetic strategies (incipient wetness impregnation, deposition-precipitaion, co-precipitaion adopted for the preparation of heterogeneous Pd-Fe systems as well as on the main characterization techniques used (XRD, TEM, H2-TPR, XPS and EXAFS in order to elucidate the key factors that influence the unique catalytic performances observed.

Catalytic decomposition of tar derived from wood waste pyrolysis using Indonesian low grade iron ore as catalyst

Energy Technology Data Exchange (ETDEWEB)

Wicakso, Doni Rahmat [Chemical Engineering Department, Faculty of Engineering, Lambung Mangkurat University, Jalan A. Yani KM. 36 Banjarbaru, 70714, South Kalimantan (Indonesia); Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281 (Indonesia); Sutijan; Rochmadi [Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281 (Indonesia); Budiman, Arief, E-mail: abudiman@ugm.ac.id [Chemical Engineering Department, Faculty of Engineering, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur, Yogyakarta, 55281 (Indonesia); Center for Energy Studies, Gadjah Mada University, Sekip K1A, Yogyakarta, 55281 (Indonesia)

2016-06-03

Low grade iron ore can be used as an alternative catalyst for bio-tar decomposition. Compared to other catalysts, such as Ni, Rd, Ru, Pd and Pt, iron ore is cheaper. The objective of this research was to investigate the effect of using low grade iron ore as catalyst for tar catalytic decomposition in fixed bed reactor. Tar used in this experiment was pyrolysis product of wood waste while the catalyst was Indonesian low grade iron ore. The variables studied were temperatures between 500 – 600 °C and catalyst weight between 0 – 40 gram. The first step, tar was evaporated at 450 °C to produce tar vapor. Then, tar vapor was flowed to fixed bed reactor filled low grade iron ore. Gas and tar vapor from reactor was cooled, then the liquid and uncondensable gas were analyzed by GC/MS. The catalyst, after experiment, was weighed to calculate total carbon deposited into catalyst pores. The results showed that the tar components that were heavy and light hydrocarbon were decomposed and cracked within the iron ore pores to from gases, light hydrocarbon (bio-oil) and carbon, thus decreasing content tar in bio-oil and increasing the total gas product. In conclusion, the more low grade iron ore used as catalyst, the tar content in the liquid decrease, the H{sup 2} productivity increased and calorimetric value of bio-oil increased.

MgAl-Layered Double Hydroxide Solid Base Catalysts for Henry Reaction: A Green Protocol

Directory of Open Access Journals (Sweden)

Magda H. Abdellattif

2018-03-01

Full Text Available A series of MgAl-layered double hydroxide (MgAl-HT, the calcined form at 500 °C (MgAlOx, and the rehydrated one at 25 °C (MgAl-HT-RH were synthesized. Physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Surface area of the as-synthesized, calcined, and rehydrated catalysts was determined by N2 physisorption at −196 °C. CO2 temperature-programmed desorption (CO2-TPD was applied to determine the basic sites of catalysts. The catalytic test reaction was carried out using benzaldehyde and their derivatives with nitromethane and their derivatives. The Henry products (1–15 were obtained in a very good yield using MgAl-HT-RH catalyst either by conventional method at 90 °C in liquid phase or under microwave irradiation method. The mesoporous structure and basic nature of the rehydrated solid catalyst were responsible for its superior catalytic efficiency. The robust nature was determined by using the same catalyst five times, where the product % yield was almost unchanged significantly.

Effects of polymeric carbohydrates on growth and development

DEFF Research Database (Denmark)

Knudsen, Knud Erik Bach

, metabolized and net energy); available energy relative to protein is crucial for performance and carcass quality; second, the proportion of starch to NSP will influence rate and type of metabolites (glucose vs. SCFA) deriving from carbohydrate assimilation, and finally, type of starch (types A, B, and C......The main objective of the presentation is to provide insight into the role of polymeric carbohydrates in growth and development of pigs. Polymeric carbohydrates—starch and non-starch polysaccharides (NSP)—quantitatively represent the largest portion of the diets for pigs and are therefore...... at a slower and more constant rate and with SCFA being absorbed by passive diffusion. Type and levels of polymeric carbohydrates influence growth and development through different mechanisms; first, the proportion of starch to NSP plays an important role for the content of available energy (digestible...

Preparation and spectrometric identification of amide derivatives with antimalaric

International Nuclear Information System (INIS)

Ferreira, E.J.

1987-01-01

The structures of polymeric compounds using spectrometric analysis of infrared, ultraviolet and protonic magnetic resonance and 13 C nuclear magnetic resonance are studied. Some structural models are used such as antimalaric-sulfones and pyrimidinic derivatives, and non-polymeric derivatives of active compounds. A comparative analysis on structures less complexes is shown. (M.J.C.). Spectrums 186 p [pt

Biomass gasification bottom ash as a source of CaO catalyst for biodiesel production via transesterification of palm oil

International Nuclear Information System (INIS)

Maneerung, Thawatchai; Kawi, Sibudjing; Wang, Chi-Hwa

2015-01-01

Highlights: • CaO catalyst was successfully developed from wood gasification bottom ash. • CaCO 3 in bottom ash can be converted to CaO catalyst by calcination. • CaO catalysts derived from bottom ash exhibited high activity towards transesterification. • CaO catalysts derived from bottom ash can be reutilized up to four times. - Abstract: The main aim of this research is to develop environmentally and economically benign heterogeneous catalysts for biodiesel production via transesterification of palm oil. For this propose, calcium oxide (CaO) catalyst has been developed from bottom ash waste arising from woody biomass gasification. Calcium carbonate was found to be the main component in bottom ash and can be transformed into the active CaO catalyst by simple calcination at 800 °C without any chemical treatment. The obtained CaO catalysts exhibit high biodiesel production activity, over 90% yield of methyl ester can be achieved at the optimized reaction condition. Experimental kinetic data fit well the pseudo-first order kinetic model. The activation energy (E a ) of the transesterification reaction was calculated to be 83.9 kJ mol −1 . Moreover, the CaO catalysts derived from woody biomass gasification bottom ash can be reutilized up to four times, offering the efficient and low-cost CaO catalysts which could make biodiesel production process more economic and environmental friendly

Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

KAUST Repository

Balasamy, Rabindran J.; Khurshid, Alam; Al-Ali, Ali A S; Atanda, Luqman A.; Sagata, Kunimasa; Asamoto, Makiko; Yahiro, Hidenori; Nomura, Kiyoshi; Sano, Tsuneji; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

2010-01-01

A series of FeOx-MeOy/Mg(Al)O catalysts were prepared from hydrotalcite-like compounds as precursors and were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The hydrotalcite-like precursors of the metal compositions of Mg3Fe 0.25Me0.25Al0.5 (Me = Cu, Zn, Cr, Mn, Fe, Co and Ni) were coprecipitated from the nitrates of metal components and calcined to mixed oxides at 550 °C. After the calcination, the mixed oxides showed high surface area of 150-200 m2 gcat -1, and were mainly composed of (MgMe)(Fe3+Al)O periclase in the bulk, whereas the surface was enriched by (MgMe)(Fe3+Al)2O 4 pinel. Among the Me species tested, Co2+ was the most effective, followed by Ni2+. Co2+ addition increased the activity of original FeOx/Mg(Al)O catalyst, whereas Ni2+ increased the activity at the beginning of reaction, but deactivated the catalyst during the reaction. The other metals formed isolated MeOx species in the catalyst, resulting in a decrease in the activity compared to the original FeOx/Mg(Al)O catalyst. The active Fe species exists as metastable Fe3+ on the FeOx/Mg(Al)O catalyst. By the addition of Co2+, the reduction-oxidation between Fe3+ and Fe2+ was facilitated and, moreover, the active Fe3+ species was stabilized. It is likely that the dehydrogenation proceeds on the active Fe3+ species via its reduction-oxidation assisted by Co 2+. © 2010 Elsevier B.V.

Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

KAUST Repository

Balasamy, Rabindran J.

2010-12-20

A series of FeOx-MeOy/Mg(Al)O catalysts were prepared from hydrotalcite-like compounds as precursors and were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The hydrotalcite-like precursors of the metal compositions of Mg3Fe 0.25Me0.25Al0.5 (Me = Cu, Zn, Cr, Mn, Fe, Co and Ni) were coprecipitated from the nitrates of metal components and calcined to mixed oxides at 550 °C. After the calcination, the mixed oxides showed high surface area of 150-200 m2 gcat -1, and were mainly composed of (MgMe)(Fe3+Al)O periclase in the bulk, whereas the surface was enriched by (MgMe)(Fe3+Al)2O 4 pinel. Among the Me species tested, Co2+ was the most effective, followed by Ni2+. Co2+ addition increased the activity of original FeOx/Mg(Al)O catalyst, whereas Ni2+ increased the activity at the beginning of reaction, but deactivated the catalyst during the reaction. The other metals formed isolated MeOx species in the catalyst, resulting in a decrease in the activity compared to the original FeOx/Mg(Al)O catalyst. The active Fe species exists as metastable Fe3+ on the FeOx/Mg(Al)O catalyst. By the addition of Co2+, the reduction-oxidation between Fe3+ and Fe2+ was facilitated and, moreover, the active Fe3+ species was stabilized. It is likely that the dehydrogenation proceeds on the active Fe3+ species via its reduction-oxidation assisted by Co 2+. © 2010 Elsevier B.V.

Catalytic hydrolysis of ammonia borane for hydrogen generation using cobalt nanocluster catalyst supported on polydopamine functionalized multiwalled carbon nanotube

International Nuclear Information System (INIS)

Arthur, Ernest Evans; Li, Fang; Momade, Francis W.Y.; Kim, Hern

2014-01-01

Hydrogen was generated from ammonia borane complex by hydrolysis using cobalt nanocluster catalyst supported on polydopamine functionalized MWCNTs (multi-walled carbon nanotubes). The impregnation-chemical reduction method was used for the preparation of the supported catalyst. The nanocluster catalyst support was formed by in-situ oxidative polymerization of dopamine on the MWCNTs in alkaline solution at room temperature. The structural and physical–chemical properties of the nanocluster catalyst were characterized by FT-IR (Fourier transform infrared spectroscopy), EDX (energy-dispersive X-ray spectroscopy), SEM (scanning electron microscope), XRD (X-ray diffraction) and TEM (transmission electron microscopy). The nanocluster catalyst showed good catalytic activity for the hydrogen generation from aqueous ammonia borane complex. A reusability test to determine the practical usage of the catalyst was also investigated. The result revealed that the catalyst maintained an appreciable catalytic performance and stability in terms of its reusability after three cycle of reuse for the hydrolysis reaction. Also, the activation energy for the hydrolysis of ammonia borane complex was estimated to be 50.41 kJmol −1 , which is lower than the values of some of the reported catalyst. The catalyst can be considered as a promising candidate in developing highly efficient portable hydrogen generation systems such as PEMFC (proton exchange membrane fuel cells). - Highlights: • Co/Pdop-o-MWCNT (Pdop functionalized MWCNT supported cobalt nanocluster) catalyst was synthesized for hydrogen generation. • It is an active catalyst for hydrogen generation via hydrolysis of ammonia borane. • It showed good stability in terms of reusability for the hydrogen generation

New fillers in the synthesis of polypropylene nano composites with Ziegler-Natta catalysts; Novas cargas na sintese de nanocompositos de polipropileno com catalisadores Ziegler-Natta

Energy Technology Data Exchange (ETDEWEB)

NONE

2011-07-01

In this study, Ziegler-Natta catalysts bi-supported on MgCl{sub 2} and natural clays were prepared in order to synthesize polypropylene nanocomposites. The employed clays were bentonite, as reference, as well as halloysite, vermiculite and mica. Propylene polymerizations were carried out using those catalysts and the properties of the obtained materials were analyzed using techniques of thermogravimetric analysis X-ray diffraction, dynamic mechanical thermal analysis e scanning electronic microscopy. Results showed the production of nanocomposites with higher thermal degradation temperature. (author)

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

Energy Technology Data Exchange (ETDEWEB)

Alptekin, Gokhan [TDA Research, Inc., Wheat Ridge, CO (United States)

2013-02-15

Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies. We therefore investigated the impact of potential contaminants (H₂S, NH₃, HCN, AsH₃, PH₃, HCl, NaCl, KCl, AS₃, NH₄NO₃, NH₄OH, KNO₃, HBr, HF, and HNO₃) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts.

Conversion of Sugars to Lactic Acid Derivatives Using Heterogeneous Zeotype Catalysts

DEFF Research Database (Denmark)

Holm, Martin Spangsberg; Shunmugavel, Saravanamurugan; Taarning, Esben

2010-01-01

of mono-and disaccharides that are dissolved in methanol to methyl lactate at 160 C. With sucrose as the substrate, methyl lactate yield reaches 68%, and the heterogeneous catalyst can be easily recovered by filtration and reused multiple times after calcination without any substantial change...

Emprego de catalisadores à base de níquel para homo- e copolimerização de estireno The use of nickel-based catalysts for homo-and copolymerization of styrene

Directory of Open Access Journals (Sweden)

Luis Carlos Ferreira Jr.

2004-12-01

Full Text Available This review deals with the homo- and copolymerization of styrene with nickel catalysts. The catalytic activity, polymer stereoregularity, polymer molecular weight and polydispersity are dependent upon nickel ligands and reaction parameters. Catalysts supported on silica, treated with methylaluminoxane (MAO, have shown higher stereospecificity and activity compared to homogeneous ones. The influence of these parameters is discussed focusing on the elucidation of some aspects of the polymerization mechanism.

Conversion of Syngas-Derived C2+ Mixed Oxygenates to C3-C5 Olefins over ZnxZryOz Mixed Oxides Catalysts

Energy Technology Data Exchange (ETDEWEB)

Smith, Colin D.; Lebarbier, Vanessa M.; Flake, Matthew D.; Ramasamy, Karthikeyan K.; Kovarik, Libor; Bowden, Mark E.; Onfroy, Thomas; Dagle, Robert A.

2016-04-01

In this study we report on a ZnxZryOz mixed oxide type catalyst capable of converting a syngas-derived C2+ mixed oxygenate feedstock to isobutene-rich olefins. Aqueous model feed comprising of ethanol, acetaldehyde, acetic acid, ethyl acetate, methanol, and propanol was used as representative liquid product derived from a Rh-based mixed oxygenate synthesis catalyst. Greater than 50% carbon yield to C3-C5 mixed olefins was demonstrated when operating at 400-450oC and 1 atm. In order to rationalize formation of the products observed feed components were individually evaluated. Major constituents of the feed mixture (ethanol, acetaldehyde, acetic acid, and ethyl acetate) were found to produce isobutene-rich olefins. C-C coupling was also demonstrated for propanol feedstock - a minor constituent of the mixed oxygenate feed - producing branched C6 olefins, revealing scalability to alcohols higher than ethanol following an analogous reaction pathway. Using ethanol and propanol feed mixtures, cross-coupling reactions produced mixtures of C4, C5, and C6 branched olefins. The presence of H2 in the feed was found to facilitate hydrogenation of the ketone intermediates, thus producing straight chain olefins as byproducts. While activity loss from coking is observed complete catalyst regeneration is achieved by employing mild oxidation. For conversion of the mixed oxygenate feed a Zr/Zn ratio of 2.5 and a reaction temperature of 450oC provides the best balance of stability, activity, and selectivity. X-ray diffraction and scanning transmission electron microscopy analysis reveals the presence of primarily cubic phase ZrO2 and a minor amount of the monoclinic phase, with ZnO being highly dispersed in the lattice. The presence of ZnO appears to stabilize the cubic phase resulting in less monoclinic phase as the ZnO concentration increases. Infrared spectroscopy shows the mixed oxide acid sites are characterized as primarily Lewis type acidity. The direct relationship between

Kinetics of Waterborne Alkyd/Acrylic Hybrid Resin Free Radical Polymerization by Two Systems of Redox and Thermal Initiators

Directory of Open Access Journals (Sweden)

shirin Madadi

2012-12-01

Full Text Available Kinetics of radical polymerizations of waterborne alkyd/acrylic hybrid resin via batch mini-emulsion technique was studied using redox initiators (TBHP/Fe2+/EDTA/AsAc  and  TBHP/Fe2+/EDTA/SFS at relatively low temperatures and thermal initiators (BPO, KPS and AIBN at higher temperatures to seek the most suitable initiator system. At the end of all reactions the unreacted monomer content was reduced using post-polymerization technique; consequently, leading to increased monomer conversion and flm formation with improved properties. The kinetics of mini-emulsion polymerization showed that in all redox initiator systems (Fe2+ catalyst + EDTA chelating agent, the radials are produced at relatively low temperature with more effcient control of the reactor temperature. It was found that at 45°C TBHP/Fe2+/EDTA/SFS redox initiator system leads to 98% monomer conversion, a much higher rate than that of systems involved thermal initiators.

Low oxygen biomass-derived pyrolysis oils and methods for producing the same

Science.gov (United States)

Marinangeli, Richard; Brandvold, Timothy A; Kocal, Joseph A

2013-08-27

Low oxygen biomass-derived pyrolysis oils and methods for producing them from carbonaceous biomass feedstock are provided. The carbonaceous biomass feedstock is pyrolyzed in the presence of a catalyst comprising base metal-based catalysts, noble metal-based catalysts, treated zeolitic catalysts, or combinations thereof to produce pyrolysis gases. During pyrolysis, the catalyst catalyzes a deoxygenation reaction whereby at least a portion of the oxygenated hydrocarbons in the pyrolysis gases are converted into hydrocarbons. The oxygen is removed as carbon oxides and water. A condensable portion (the vapors) of the pyrolysis gases is condensed to low oxygen biomass-derived pyrolysis oil.

Synthesis of new annulated pyrano[2,3-d]pyrimidine derivatives using organo catalyst (DABCO in aqueous media

Directory of Open Access Journals (Sweden)

Ajmal R. Bhat

2017-01-01

Full Text Available A selective method for the synthesis of annulated pyrano[2,3-d]pyrimidines has been developed. It was shown that base catalysis is more efficient in this reaction, rather than acid catalysis as it is believed that 1,4-diazabicyclo[2.2.2]octane (DABCO is N-type base catalyst used for the synthesis of pyrano[2,3-d]pyramidine derivatives via one-pot three component condensation reactions of various aromatic aldehydes, active methylene compounds and barbituric acid in aqueous ethanol carried at normal temperature. The potential application of DABCO in organic synthesis increasing rapidly because of its reaction simplicity, less pollution, and minimum reaction time, high yields of the biological active products, uses less toxic solvents and low cost chemicals.

Engineering of RuMb: Toward a Green Catalyst for Carbene Insertion Reactions.

Science.gov (United States)

Wolf, Matthew W; Vargas, David A; Lehnert, Nicolai

2017-05-15

The small, stable heme protein myoglobin (Mb) was modified through cofactor substitution and mutagenesis to develop a new catalyst for carbene transfer reactions. The native heme was removed from wild-type Mb and several Mb His64 mutants (H64D, H64A, H64V), and the resulting apoproteins were reconstituted with ruthenium mesoporphyrin IX (RuMpIX). The reconstituted proteins (RuMb) were characterized by UV-vis and circular dichroism spectroscopy and were used as catalysts for the N-H insertion of aniline derivatives and the cyclopropanation of styrene derivatives. The best catalysts for each reaction were able to achieve turnover numbers (TON) up to 520 for the N-H insertion of aniline, and 350 TON for the cyclopropanation of vinyl anisole. Our results show that RuMb is an effective catalyst for N-H insertion, with the potential to further increase the activity and stereoselectivity of the catalyst in future studies. Compared to native Mb ("FeMb"), RuMb is a more active catalyst for carbene transfer reactions, which leads to both heme and protein modification and degradation and, hence, to an overall much-reduced lifetime of the catalyst. This leads to lower TONs for RuMb compared to the iron-containing analogues. Strategies to overcome this limitation are discussed. Finally, comparison is also made to FeH64DMb and FeH64AMb, which have not been previously investigated for carbene transfer reactions.

Conversion of furan derivatives for preparation of biofuels over Ni-Cu/C catalyst

DEFF Research Database (Denmark)

Fu, Zhaolin; Wang, Z.; Lin, Weigang

2017-01-01

Conversions of furfural and 5-hydroxymethylfurfural as model components in bio-oil were investigated over Ni-Cu/C catalyst with formic acid as hydrogen donor in isopropanol solvent to produce biofuels. The effects of reaction temperature, feed ratio, and reaction time were studied. A high yield...... of 2-methylfuran up to 91 mol% was obtained from furfural in 8 h at 200°C, and under same conditions 80 mol% yield of 2,5-dimethylfuran could also be obtained from 5-hydroxymethylfurfural in 6 h. The results verified the catalyst performance and the availability of the reaction conditions for producing...

Physical chemistry research for engineering and applied sciences, v.2 polymeric materials and processing

CERN Document Server

Pearce, Eli M; Pethrick, Richard A

2015-01-01

PrefaceInvestigation on the Influence of a Strong Electric Field on the Electrical, Transport and Diffusion Properties of Carbon Nanostructures; S. A. Sudorgin and N. G. LebedevA Study Thermal Stability of Polyurethane Elastomers; I. A. Novakov, M. A. Vaniev, D. V. Medvedev, N. V. Sidorenko, G. V. Medvedev, and D. O. GusevTrends in Aromatic Polyesters; Z. S. Khasbulatova and G. E. ZaikovMicroheterogeneous Titanium Ziegler-Natta Catalysts: 1,3-Diene Polymerization Under Ultrasound Irradiations; V. P. Zakharov, V. Z. Mingaleev, I. D. Zakirov

The utilization of hydroxyapatite-supported CaO-CeO_2 catalyst for biodiesel production

International Nuclear Information System (INIS)

Yan, Beibei; Zhang, Ying; Chen, Guanyi; Shan, Rui; Ma, Wenchao; Liu, Changye

2016-01-01

Highlights: • Hydroxyapatite derived from waste animal bones was served as the support for bimetallic CaO-CeO_2 catalyst. • The 30%CaO-CeO_2/HAP-650 catalyst exhibited excellent performance on biodiesel production. • The yield of FAME was 84.4 % after eight cycles. • Minor leaching concentrations of cerium and calcium species were detected in the product. - Abstract: The study investigated the effect of a bimetallic supported catalyst in biodiesel production. Calcined waste bone derived hydroxyapatite (HAP), a solid waste from animal, was served as the support for CaO-CeO_2 catalyst. Various characterization techniques such as FT-IR, BET, SEM-EDS, CO_2-TPD and XRD analysis were used to analyse the activity of this heterogeneous catalyst. The effect of main parameters in preparation process such as calcination temperature and active component loading on catalyst performance were discussed to obtain the optimal preparation conditions. Under the optimal reaction conditions (11 wt.% dosage of 30%CaO-CeO_2/HAP-650 catalyst and 9:1 methanol to oil molar ratio at 65 °C for 3 h) the highest biodiesel yield of 91.84% was obtained. Stability test indicated that the yield (84.4%) of fatty acid methyl ester was produced after 8 re-used cycles due to the low leaching of catalyst components. The experimental results showed that biodiesel production cost might be lowered while producing relatively high yield at the present of long life-span catalyst.

Construction of Hierarchical Polymer Brushes on Upconversion Nanoparticles via NIR-Light-Initiated RAFT Polymerization.

Science.gov (United States)

Xie, Zhongxi; Deng, Xiaoran; Liu, Bei; Huang, Shanshan; Ma, Pingan; Hou, Zhiyao; Cheng, Ziyong; Lin, Jun; Luan, Shifang

2017-09-13

Photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization generally adopts high-energy ultraviolet (UV) or blue light. In combination with photoredox catalyst, the excitation light wavelength was extended to the visible and even near-infrared (NIR) region for photoinduced electron transfer RAFT polymerization. In this report, we introduce for the first time a surface NIR-light-initiated RAFT polymerization on upconversion nanoparticles (UCNPs) without adding any photocatalyst and construct a functional inorganic core/polymer shell nanohybrid for application in cancer theranostics. The multilayer core-shell UCNPs (NaYF 4 :Yb/Tm@NaYbF 4 :Gd@NaNdF 4 :Yb@NaYF 4 ), with surface anchorings of chain transfer agents, can serve as efficient NIR-to-UV light transducers for initiating the RAFT polymerization. A hierarchical double block copolymer brush, consisting of poly(acrylic acid) (PAA) and poly(oligo(ethylene oxide)methacrylate-co-2-(2-methoxy-ethoxy)ethyl methacrylate) (PEG for short), was grafted from the surface in sequence. The targeting arginine-glycine-aspartic (RGD) peptide was modified at the end of the copolymer through the trithiolcarbonate end group. After loading of doxorubicin, the UCNPs@PAA-b-PEG-RGD exhibited an enhanced U87MG cancer cell uptake efficiency and cytotoxicity. Besides, the unique upconversion luminescence of the nanohybrids was used for the autofluoresence-free cell imaging and labeling. Therefore, our strategy verified that UCNPs could efficiently activate RAFT polymerization by NIR photoirradiation and construct the complex nanohybrids, exhibiting prospective biomedical applications due to the low phototoxicity and deep penetration of NIR light.

NATO Advanced Research Workshop on Frontiers in Polymerization Catalysis and Polymer Synthesis

CERN Document Server

Guyot, A

1987-01-01

Due to their specific properties, polymers with well-defined structures have been receiving increasing attention over the last several years. Owing to the wide variability of their properties, these specialty polymers have been used in various areas from biomedical engineering to electronics or energy applications. The synthesis of such polymers necessi­ tates the use of new methods of polymerization which derived from an insight into the mechanism of polymerization reactions. A NATO Advanced Research Workshop on "Frontiers in Polymerization Catalysis and Polymer Synthesis" was held in BANDOl (FRANCE) in February 1987. Its aim was to assess the new polymerization methods, as well as the latest advances in the mechanisms of conventional polymerization reactions together with their applications to the synthesis of new macromolecular structures. The financial support from the NATO Scientific Affairs Division which covered the "lecturers' accomodation and travel expenses as well as the organization charges of th...

Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins.

Science.gov (United States)

Falkenhagen, Jan P; Maisonneuve, Lise; Paalanen, Pasi P; Coste, Nathalie; Malicki, Nicolas; Weckhuysen, Bert M

2018-03-26

Co-Fe-Mn/γ-Al 2 O 3 Fischer-Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C 2 -C 4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al 2 O 3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 catalyst the selectivity towards the fractions of C 5+ and CH 4 could be reduced, whereas the selectivity towards the fraction of C 4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al 2 O 3 ) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radical-Mediated Enzymatic Polymerizations

Science.gov (United States)

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

Catalytic biomass conversion methods, catalysts, and methods of making the same

Science.gov (United States)

Delgass, William Nicholas; Agrawal, Rakesh; Ribeiro, Fabio Henrique; Saha, Basudeb; Yohe, Sara Lynn; Abu-Omar, Mahdi M; Parsell, Trenton; Dietrich, Paul James; Klein, Ian Michael

2017-10-10

Described herein are processes for one-step delignification and hydrodeoxygenation of lignin fraction a biomass feedstock. The lignin feedstock is derived from by-products of paper production and biorefineries. Additionally described is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function. Finally, also described herein is a process for converting biomass-derived oxygenates to lower oxygen-content compounds and/or hydrocarbons in the liquid or vapor phase in a reactor system containing hydrogen and a catalyst comprised of a hydrogenation function and/or an oxophilic function and/or an acid function.

Polymeric molecular sieve membranes for gas separation

Science.gov (United States)

Dai, Sheng; Qiao, Zhenan; Chai, Songhai

2017-08-15

A porous polymer membrane useful in gas separation, the porous polymer membrane comprising a polymeric structure having crosslinked aromatic groups and a hierarchical porosity in which micropores having a pore size less than 2 nm are present at least in an outer layer of the porous polymer membrane, and macropores having a pore size of over 50 nm are present at least in an inner layer of the porous polymer membrane. Also described are methods for producing the porous polymer membrane in which a non-porous polymer membrane containing aromatic rings is subjected to a Friedel-Crafts crosslinking reaction in which a crosslinking molecule crosslinks the aromatic rings in the presence of a Friedel-Crafts catalyst and organic solvent under sufficiently elevated temperature, as well as methods for using the porous polymer membranes for gas or liquid separation, filtration, or purification.

Upgrading including heteroatom removal from Victorian brown coal-derived liquids

Energy Technology Data Exchange (ETDEWEB)

Larkins, F.P.; Youings, J.C.; Jackson, W.R.; Park, D. (University of Tasmania, Hobart, Tasmania (Australia))

1989-10-01

It has been shown using model compounds that the hydrodeoxygenation performance of a catalyst is severely inhibited by the presence of nitrogen-containing compounds under conditions of moderate reaction severity. For a low molecular weight coal-derived liquid commercial catalysts were effective for HDO and HDN at 400{degree}C, 10 MPa H{sub 2} for 30 min reaction time. For a coal-derived liquid high in asphaltene commercial catalysts and others prepared and tested in this study were ineffective. Alternative catalysts and hydrotreating conditions of greater severity will be required for such materials to effect acceptable heteroatom removal. 3 refs., 2 figs., 2 tabs.

Synthesis and Characterization of the Most Active Copper ATRP Catalyst Based on Tris[(4-dimethylaminopyridyl)methyl]amine.

Science.gov (United States)

Ribelli, Thomas G; Fantin, Marco; Daran, Jean-Claude; Augustine, Kyle F; Poli, Rinaldo; Matyjaszewski, Krzysztof

2018-01-31

The tris[(4-dimethylaminopyridyl)methyl]amine (TPMA NMe2 ) as a ligand for copper-catalyzed atom transfer radical polymerization (ATRP) is reported. In solution, the [Cu I (TPMA NMe2 )Br] complex shows fluxionality by variable-temperature NMR, indicating rapid ligand exchange. In the solid state, the [Cu II (TPMA NMe2 )Br][Br] complex exhibits a slightly distorted trigonal bipyramidal geometry (τ = 0.89). The UV-vis spectrum of [Cu II (TPMA NMe2 )Br] + salts is similar to those of other pyridine-based ATRP catalysts. Electrochemical studies of [Cu(TPMA NMe2 )] 2+ and [Cu(TPMA NMe2 )Br] + showed highly negative redox potentials (E 1/2 = -302 and -554 mV vs SCE, respectively), suggesting unprecedented ATRP catalytic activity. Cyclic voltammetry (CV) in the presence of methyl 2-bromopropionate (MBrP; acrylate mimic) was used to determine activation rate constant k a = 1.1 × 10 6 M -1 s -1 , confirming the extremely high catalyst reactivity. In the presence of the more active ethyl α-bromoisobutyrate (EBiB; methacrylate mimic), total catalysis was observed and an activation rate constant k a = 7.2 × 10 6 M -1 s -1 was calculated with values of K ATRP ≈ 1. ATRP of methyl acrylate showed a well-controlled polymerization using as little as 10 ppm of catalyst relative to monomer, while side reactions such as Cu I -catalyzed radical termination (CRT) could be suppressed due to the low concentration of L/Cu I at a steady state.

Selective and eco-friendly procedures for the synthesis of benzimidazole derivatives. The role of the Er(OTf3 catalyst in the reaction selectivity

Directory of Open Access Journals (Sweden)

Natividad Herrera Cano

2016-11-01

Full Text Available An improved and greener protocol for the synthesis of benzimidazole derivatives, starting from o-phenylenediamine, with different aldehydes is reported. Double-condensation products were selectively obtained when Er(OTf3 was used as the catalyst in the presence of electron-rich aldehydes. Conversely, the formation of mono-condensation products was the preferred path in absence of this catalyst. One of the major advantages of these reactions was the formation of a single product, avoiding extensive isolation and purification of products, which is frequently associated with these reactions.Theoretical calculations helped to understand the different reactivity established for these reactions. Thus, we found that the charge density on the oxygen of the carbonyl group has a significant impact on the reaction pathway. For instance, electron-rich aldehydes better coordinate to the catalyst, which favours the addition of the amine group to the carbonyl group, therefore facilitating the formation of double-condensation products.Reactions with aliphatic or aromatic aldehydes were possible, without using organic solvents and in a one-pot procedure with short reaction time (2–5 min, affording single products in excellent yields (75–99%. This convenient and eco-friendly methodology offers numerous benefits with respect to other protocols reported for similar compounds.

Selective and eco-friendly procedures for the synthesis of benzimidazole derivatives. The role of the Er(OTf)3 catalyst in the reaction selectivity.

Science.gov (United States)

Herrera Cano, Natividad; Uranga, Jorge G; Nardi, Mónica; Procopio, Antonio; Wunderlin, Daniel A; Santiago, Ana N

2016-01-01

An improved and greener protocol for the synthesis of benzimidazole derivatives, starting from o -phenylenediamine, with different aldehydes is reported. Double-condensation products were selectively obtained when Er(OTf) 3 was used as the catalyst in the presence of electron-rich aldehydes. Conversely, the formation of mono-condensation products was the preferred path in absence of this catalyst. One of the major advantages of these reactions was the formation of a single product, avoiding extensive isolation and purification of products, which is frequently associated with these reactions. Theoretical calculations helped to understand the different reactivity established for these reactions. Thus, we found that the charge density on the oxygen of the carbonyl group has a significant impact on the reaction pathway. For instance, electron-rich aldehydes better coordinate to the catalyst, which favours the addition of the amine group to the carbonyl group, therefore facilitating the formation of double-condensation products. Reactions with aliphatic or aromatic aldehydes were possible, without using organic solvents and in a one-pot procedure with short reaction time (2-5 min), affording single products in excellent yields (75-99%). This convenient and eco-friendly methodology offers numerous benefits with respect to other protocols reported for similar compounds.

Synthesis, anticancer activity, and inhibition of tubulin polymerization by conformationally restricted analogues of lavendustin A.

Science.gov (United States)

Mu, Fanrong; Hamel, Ernest; Lee, Debbie J; Pryor, Donald E; Cushman, Mark

2003-04-24

Compounds in the lavendustin A series have been shown to inhibit both protein-tyrosine kinases (PTKs) and tubulin polymerization. Since certain lavendustin A derivatives can exist in conformations that resemble both the trans-stilbene structure of the PTK inhibitor piceatannol and the cis-stilbene structure of the tubulin polymerization inhibitor combretastatin A-4, the possibility exists that the ratio of the two types of activities of the lavendustins could be influenced through the synthesis of conformationally restricted analogues. Accordingly, the benzylaniline structure of a series of pharmacologically active lavendustin A fragments was replaced by either their cis- or their trans-stilbene relatives, and effects on both inhibition of tubulin polymerization and cytotoxicity in cancer cell cultures were monitored. Both dihydrostilbene and 1,2-diphenylalkyne congeners were also prepared and evaluated biologically. Surprisingly, conformational restriction of the bridge between the two aromatic rings of the lavendustins had no significant effect on biological activity. On the other hand, conversion of the three phenolic hydroxyl groups of the lavendustin A derivatives to their corresponding methyl ethers consistently abolished their ability to inhibit tubulin polymerization and usually decreased cytotoxicity in cancer cell cultures as well, indicating the importance of at least one of the phenolic hydroxyl groups. Further investigation suggested that the phenolic hydroxyl group in the salicylamide ring was required for activity, while the two phenol moieties in the hydroquinone ring could be methylated with retention of activity. Two of the lavendustin A derivatives displayed IC(50) values of 1.4 microM for inhibition of tubulin polymerization, which ranks them among the most potent of the known tubulin polymerization inhibitors.

21 CFR 175.300 - Resinous and polymeric coatings.

Science.gov (United States)

2010-04-01

... descriptions: (1) Coatings cured by oxidation. (2) Coatings cured by polymerization, condensation, and/or cross... condensation product formed by the reaction of hydrogenated castor oil with polyamide derived from...-oil emulsion, high- or low-fat. B. Oil-in-water emulsion, high- or low-fat. V. Low moisture fats and...

Accessibility enhancement of TS-1-based catalysts for improving the epoxidation of plant oil-derived substrates

Czech Academy of Sciences Publication Activity Database

Wilde, N.; Přech, Jan; Pelz, M.; Kubů, Martin; Čejka, Jiří; Gläser, R.

2016-01-01

Roč. 6, č. 19 (2016), s. 7280-7288 ISSN 2044-4753 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Catalyst selectivity * Catalysts * Efficiency Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.773, year: 2016

Biochemical indicators of nephrotoxicity in blood serum of rats treated with novel 4-thiazolidinone derivatives or their complexes with polyethylene glycol-containing nanoscale polymeric carrier

Directory of Open Access Journals (Sweden)

L. I. Kоbylinska

2016-02-01

Full Text Available The aim of this study was to compare the effect of new synthetic 4-thiazolidinone derivatives (potential anticancer compounds denoted as 3882, 3288 and 3833 and doxorubicin (positive control in free form and in their complexes with synthetic polyethylene glycol-containing nanoscale polymeric carrier on the biochemical indicators of nephrotoxicity in blood serum of rats. The concentration of total protein, urea, creatinine, glucose, ions of sodium, potassium, calcium, iron and chloride was measured. It was found that after injection of the investigated compounds, the concentration of sodium cations and chloride anions in blood serum was increased compared with control (untreated animals. Doxorubicin’s injection was accompanied by a decrease in the concentration of iron cations. The concentration of total protein, urea and creatinine decreased under the influence of the studied compounds. Complexation of these аntineoplastic substances with a synthetic polymeric nanocarrier lowered the concentration of the investigated metabolites substantially compared to the effect of these compounds in free form. The normalization of concentration of total protein, urea and creatinine in blood serum of rats treated with complexes of the studied compounds with the polymeric carrier comparing with increased concentration of these indicators at the introduction of such compounds in free form was found.

Electrochemical behaviour of PES ionomer and Pt-free catalyst for PEMFCs

Directory of Open Access Journals (Sweden)

STEFANIA GIORDANO

2013-06-01

Full Text Available Proton Exchange Membrane Fuel Cells (PEMFCs represent promising technologies to the world economy, with many applications and low environmental impact. A most important aspect concerning their widespread implementation is the cost of polymeric membranes, typically perfluorinated membranes and platinum-based catalytic electrode materials, all of which are necessary to promote electrode reactions, thus increasing fuel cell energy efficiency. In this work, we present some data about non-fluorinated polyetheresulphone (PES membranes and Pt-free catalysts, as possible substitutes of the above materials. Their electrochemical behaviour in oxygen reduction reaction in acidic media are investigated and compared with available reference materials.

A tailored catalyst for the sustainable conversion of glycerol to acrolein: mechanistic aspect of sequential dehydration.

Science.gov (United States)

Yun, Danim; Kim, Tae Yong; Park, Dae Sung; Yun, Yang Sik; Han, Jeong Woo; Yi, Jongheop

2014-08-01

Developing a catalyst to resolve deactivation caused from coke is a primary challenge in the dehydration of glycerol to acrolein. An open-macropore-structured and Brønsted-acidic catalyst (Marigold-like silica functionalized with sulfonic acid groups, MS-FS) was synthesized for the stable and selective production of acrolein from glycerol. A high acrolein yield of 73% was achieved and maintained for 50 h in the presence of the MS-FS catalyst. The hierarchical structure of the catalyst with macropores was found to have an important effect on the stability of the catalyst because coke polymerization and pore blocking caused by coke deposition were inhibited. In addition, the behavior of 3-hydroxypropionaldehyde (3-HPA) during the sequential dehydration was studied using density functional theory (DFT) calculations because 3-HPA conversion is one of the main causes for coke formation. We found that the easily reproducible Brønsted acid sites in MS-FS permit the selective and stable production of acrolein. This is because the reactive intermediate (3-HPA) is readily adsorbed on the regenerated acid sites, which is essential for the selective production of acrolein during the sequential dehydration. The regeneration ability of the acid sites is related not only to the selective production of acrolein but also to the retardation of catalyst deactivation by suppressing the formation of coke precursors originating from 3-HPA degradation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of free fatty acid in Palm Fatty Acid Distillate using sulfonated carbon catalyst derived from biomass wastefor biodiesel production

Science.gov (United States)

Hidayat, Arif; Rochmadi; Wijaya, Karna; Budiman, Arief

2016-01-01

In this research, the esterification of PFAD using the sulfonatedcoconut shell biochar catalyst was studied. Carbon solid catalysts were prepared by a sulfonation of carbonized coconut shells. The performances of the catalysts were evaluated in terms of the reaction temperatures, the molar ratios of methanol to PFAD, the catalyst loading and the reaction times. The reusability of the solid acid carbon catalysts was also studied in this work. The results indicated that the FFA conversion was significantly increased with increasing catalyst loading and reaction times. It can be concluded that the optimal conditions were an PFAD to methanol molar ratio of 1:12, the amount of catalyst of 10%w, and reaction temperature of 60oC.At this optimum condition, the conversion to biodieselreached 88%.

Conversion of glycerol to polyglycerol over waste duck-bones as a catalyst in solvent free etherification process

Science.gov (United States)

Ayoub, Muhammad; Sufian, Suriati; Mekuria Hailegiorgis, Sintayehu; Ullah, Sami; Uemura, Yoshimitsu

2017-08-01

The alkaline catalyst derived from the duck-bones was used for conversion of glycerol to polyglycerol via solvent free etherification process. The physicochemical properties of prepared materials were duck-bones were systematically investigated as a catalyst by latest techniques of Thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface properties. TGA showed different trends of duck-bones decomposition from room temperature to 1000C. XRD pattern showed a clear and sharp peaks of a crystalline phase of CaO. The activity of the catalysts was in line with the basic amount of the strong base sites, surface area, and crystalline phase in the catalysts. The prepared catalyst derived from duck-bones provided high activity (99 %) for glycerol conversion and around 68 % yield for polyglycerol production. These ample wastes of duck-bones have good potential to be used as polyglycerol production catalysts due to have high quantity of Ca compare to other types of bones like cow, chicken and fish bones.

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

International Nuclear Information System (INIS)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang

2011-01-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al 2 O 3 , Ni-W/Al 2 O 3 , and Ni-W/SiO 2 catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H 2 -TPR and NH 3 -TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al 2 O 3 supported catalysts were found to have higher catalytic activities than on SiO 2 supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

Studies in reactive extrusion processing of biodegradable polymeric materials

Science.gov (United States)

Balakrishnan, Sunder

Various reaction chemistries such as Polymerization, Polymer cross-linking and Reactive grafting were investigated in twin-screw extruders. Poly (1,4-dioxan-2-one) (PPDX) was manufactured in melt by the continuous polymerization of 1,4-dioxan-2-one (PDX) monomer in a twin-screw extruder using Aluminum tri-sec butoxide (ATSB) initiator. Good and accurate control over molecular weight was obtained by controlling the ratio of monomer to initiator. A screw configuration consisting of only conveying elements was used for the polymerization. The polymerization reaction was characterized by a monomer-polymer dynamic equilibrium, above the melting temperature of the polymer, limiting the equilibrium conversion to 78-percent. Near complete (˜100-percent) conversion was obtained on co-polymerizing PDX monomer with a few mol-percent (around 8-percent) Caprolactone (CL) monomer in a twin-screw extruder using ATSB initiator. The co-polymers exhibited improved thermal stability with reduction in glass transition temperature. The extruder was modeled as an Axial Dispersed Plug Flow Reactor for the polymerization of CL monomer using Residence Time Distribution (RTD) Analysis. The model provided a good fit to the experimental RTD and conversion data. Aliphatic and aliphatic-aromatic co-polyesters, namely Polycaprolactone (PCL) and Poly butylenes (adipate-co-terephthalate) (Ecoflex) were cross-linked in a twin-screw extruder using radical initiator to form micro-gel reinforced biodegradable polyesters. Cross-linked Ecoflex was further extrusion blended with talc to form blends suitable to be blown into films. A screw configuration consisting of conveying and kneading elements was found to be effective in dispersion of the talc particles (5--10 microns) in the polyester matrix. While the rates of crystallization increased for the talc filled polyester blends, overall crystallinity reduced. Mechanical, tear and puncture properties of films made using the talc filled polyester blends

Effect of organoelemental compounds of group 3 elements on radical polymerization of vinyl monomers

International Nuclear Information System (INIS)

Grishin, D.F.; Mojkin, A.A.

1996-01-01

When alkyl, alkyl alkoxy, and alkyl halide derivatives of boron and aluminium are introduced into the system in amounts that are comparable to the concentration of initiator, they coordinate to the growing macroradicals, thus changing their reactivity, and exert regulating effect on the rate of polymerization of vinyl monomers and the molecular mass of the resulting polymers. The said organoelemental compounds accelerate the polymerization of butyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and vinylidene chloride, reduce the molecular mass of acrylic polymers, and virtually do not affect the polymerization of styrene. The specific features of vinyl polymerization are associated with participation of organoelemental additives at the stages of chain growth and chain termination and can be explained within the framework of the mechanism of radical-coordination polymerization. 32 refs., 3 tabs

A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis.

Science.gov (United States)

Bu, Quan; Lei, Hanwu; Zacher, Alan H; Wang, Lu; Ren, Shoujie; Liang, Jing; Wei, Yi; Liu, Yupeng; Tang, Juming; Zhang, Qin; Ruan, Roger

2012-11-01

Catalytic hydrodeoxygenation (HDO) of lignin-derived phenols which are the lowest reactive chemical compounds in biomass pyrolysis oils has been reviewed. The hydrodeoxygenation (HDO) catalysts have been discussed including traditional HDO catalysts such as CoMo/Al(2)O(3) and NiMo/Al(2)O(3) catalysts and transition metal catalysts (noble metals). The mechanism of HDO of lignin-derived phenols was analyzed on the basis of different model compounds. The kinetics of HDO of different lignin-derived model compounds has been investigated. The diversity of bio-oils leads to the complexities of HDO kinetics. The techno-economic analysis indicates that a series of major technical and economical efforts still have to be investigated in details before scaling up the HDO of lignin-derived phenols in existed refinery infrastructure. Examples of future investigation of HDO include significant challenges of improving catalysts and optimum operation conditions, further understanding of kinetics of complex bio-oils, and the availability of sustainable and cost-effective hydrogen source. Copyright © 2012 Elsevier Ltd. All rights reserved.

Elektroaktive polymerer

DEFF Research Database (Denmark)

West, K.

Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

Transesterification of Nannochloropsis oculata microalga's oil to biodiesel using calcium methoxide catalyst

International Nuclear Information System (INIS)

Teo, Siow Hwa; Islam, Aminul; Yusaf, Talal; Taufiq-Yap, Yun Hin

2014-01-01

Biodiesel is an environmental friendly liquid fuel similar to conventional diesel in combustion properties. It has received international attention in recent times, as that biodiesel is renewable, non-toxic and safe to store. In this study, high grade biodiesel was produced from microalgae (Nannochloropsis oculata) derived lipids via transesterification reaction with methanol in the presence of heterogeneous Ca(OCH 3 ) 2 (calcium methoxide) catalyst. The biodiesel was produced with high yield; (92%) at 60 °C compared to the highest yield reported as 22% with the use of a Mg–Zr catalyst. The product exhibited excellent performances. The catalyst was characterized by TG/DTA (thermogravimetric-differential thermal analyses), XRD (X-ray diffraction), BET (Brunauer – Emmett – Teller), FTIR (Fourier transform infrared), SEM-EDX (scanning electron microscopy-energy dispersive spectrometer) and TEM (transmission electron microscopy) analysis. The effect of different reaction parameters including reaction time, methanol/oil molar ratio and catalyst dosage on the yield of FAME (fatty acid methyl ester) was studied. Interestingly, the catalyst can be reused five times successively without affecting the biodiesel yield. Biodiesel produced from microalgae oil consists of high levels of polyunsaturated fatty acids, making it highly suitable as winter grade biodiesel. - Highlights: • Biodiesel synthesis from microalgae derived oil by Ca(OCH 3 ) 2 solid catalyst. • Studied effects of methanol/oil ratio, catalyst concentration and reaction time. • Biodiesel yields >90% in 3 h using 12 wt.% catalyst, 30:1 methanol/oil at 60 °C. • Catalyst could be reused up to five times without significant lost of activity

UV-Raman spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption studies of model and bulk heterogeneous catalysts

Energy Technology Data Exchange (ETDEWEB)

Tewell, Craig Richmond [Univ. of California, Berkeley, CA (United States)

2002-01-01

X-ray photoelectron spectroscopy (XPS) and Temperature Programmed Desorption (TPD) have been used to investigate the surface structure of model heterogeneous catalysts in ultra-high vacuum (UHV). UV-Raman spectroscopy has been used to probe the structure of bulk model catalysts in ambient and reaction conditions. The structural information obtained through UV-Raman spectroscopy has been correlated with both the UHV surface analysis and reaction results. The present day propylene and ethylene polymerization catalysts (Ziegler-Natta catalysts) are prepared by deposition of TiCl₄ and a Al(Et)₃ co-catalyst on a microporous Mg-ethoxide support that is prepared from MgCl₂ and ethanol. A model thin film catalyst is prepared by depositing metallic Mg on a Au foil in a UHV chamber in a background of TiCl₄ in the gas phase. XPS results indicate that the Mg is completely oxidized to MgCl₂ by TiCl₄ resulting in a thin film of MgCl₂/TiCl_x, where x = 2, 3, and 4. To prepare an active catalyst, the thin film of MgCl₂/TiCl_x on Au foil is enclosed in a high pressure cell contained within the UHV chamber and exposed to ~1 Torr of Al(Et)₃.

Efficient hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-polyoxometalate catalyst.

Science.gov (United States)

Alotaibi, Mshari A; Kozhevnikova, Elena F; Kozhevnikov, Ivan V

2012-07-21

Acidic heteropoly salt Cs(2.5)H(0.5)PW(12)O(40) doped with Pt nanoparticles is a highly active and selective catalyst for one-step hydrogenation of methyl isobutyl and diisobutyl ketones to the corresponding alkanes in the gas phase at 100 °C with 97-99% yield via metal-acid bifunctional catalysis.

Synthesis of highly efficient Mn2O3 catalysts for CO oxidation derived from Mn-MIL-100

Science.gov (United States)

Zhang, Xiaodong; Li, Hongxin; Hou, Fulin; Yang, Yang; Dong, Han; Liu, Ning; Wang, Yuxin; Cui, Lifeng

2017-07-01

In this work, metal-organic frameworks (MOFs) Mn-MIL-100 were first prepared, which were next used as templates to obtain the irregular porous Mn2O3 cubes through calcination with air at different temperature. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), H2-temperature program reduction (H2-TPR) and X-ray photoelectron spectroscopic (XPS). The catalytic activity for CO oxidation over Mn2O3 catalysts was investigated. It was found that calcination temperature had a strong effect on the structure and catalytic activity of Mn2O3 catalyst. Mn2O3 catalyst obtained by calcined at 700 °C (Mn2O3-700) showed a smaller specific surface area, but displayed a high catalytic activity and excellent stability with a complete CO conversion temperature (T98) of 240 °C, which was attributed to the unique structure, a high quantity of surface active oxygen species, smaller particle size, oxygen vacancies and good low temperature reduction behavior. The effect of water vapor on catalytic activity was also examined. The introduction of water vapor to the feedstock induced a positive effect on CO oxidation over Mn2O3-700 catalyst. Furthermore, no obvious drop is observed in activity over catalysts even in the presence of water vapor during 48 h.

Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst

KAUST Repository

Mazoyer, Etienne; Merle, Nicolas; Mallmann, Aimery De; Basset, Jean-Marie; Berrier, Elise; Delevoye, Laurent; Paul, Jean Franois; Nicholas, Christopher P.; Gauvin, Ré gis M.; Taoufik, Mostafa

2010-01-01

A well-defined, silica-supported tungsten oxo alkyl species prepared by the surface organometallic chemistry approach displays high and sustained activity in propene metathesis. Remarkably, its catalytic performances outpace those of the parent imido derivative, underlining the importance of the oxo ligand in the design of robust catalysts. © 2010 The Royal Society of Chemistry.

ADMET Polymerization Activities of Electrochemically Reduced W-Based Active Species for Ge- and Sn-Containing Dienes

Science.gov (United States)

Imamoglu, Yavuz; Aydogdu, Cemil; Karabulut, Solmaz; Düz, Bülent

In the last 20 years metal atom-containing polymers have become important classes of polymers [1]. Properties like high thermic stability, electric, and photo conductometry make them very interesting for producing films, fibers, and coating [2]. Many of these compounds can be synthesized by conventional methods [3]. For producing metal-containing polymers anionic, cationic, and radicalic polymerizations were used [4-6]. Metal-containing polymers were also synthesized via acyclic diene metathesis (ADMET) polymerization that is facilitated by Schrock’s molybdenum alkylidene, or Grubbs’ ruthenium carbene catalyst [7-9]. In 1979, Gilet and coworkers succeeded in synthesizing metathetically active species from electrochemical reduction of WCl6 and MoCl5 [10,11]. In the light of these works, we have showed that electrochemically generated tungsten-based active species (WCl6-e--Al-CH2Cl2) catalyzes various metathesis-related reactions [12-16].

Investigation into the Catalytic Activity of Microporous and Mesoporous Catalysts in the Pyrolysis of Waste Polyethylene and Polypropylene Mixture

Directory of Open Access Journals (Sweden)

Kaixin Li

2016-06-01

Full Text Available Catalytic pyrolysis behavior of synthesized microporous catalysts (conventional Zeolite Socony Mobil–5 (C-ZSM-5, highly uniform nanocrystalline ZSM-5 (HUN-ZSM-5 and β-zeolite, Mesoporous catalysts (highly hydrothermally stable Al-MCM-41 with accessible void defects (Al-MCM-41(hhs, Kanemite-derived folded silica (KFS-16B and well-ordered Al-SBA-15 (Al-SBA-15(wo were studied with waste polyethylene (PE and polypropylene (PP mixture which are the main constituents in municipal solid waste. All the catalysts were characterized by Brunauer-Emmett-Teller (BET, X-ray powder diffraction (XRD, and NH3-temperature programmed desorption (TPD. The results demonstrated that microporous catalysts exhibited high yields of gas products and high selectivity for aromatics and alkene, whereas the mesoporous catalysts showed high yields of liquid products with considerable amounts of aliphatic compounds. The differences between the microporous and mesoporous catalysts could be attributed to their characteristic acidic and textural properties. A significant amount of C2–C4 gases were produced from both types of catalysts. The composition of the liquid and gas products from catalytic pyrolysis is similar to petroleum-derived fuels. In other words, products of catalytic pyrolysis of plastic waste can be potential alternatives to the petroleum-derived fuels.

Allene or alkyne treatment of olefin conversion catalysts

International Nuclear Information System (INIS)

Banks, R.L.

1986-01-01

This patent describes a disproportionation process which comprises contacting at least one olefin from the group consisting of: acyclic mono- and polyenes having at least 3 up to 10 carbon atoms per molecule, and cycloalkyl and aryl derivatives thereof; cyclic mono- and polyenes having at least 4 to 10 carbon atoms per molecule, and alkyl and aryl derivatives thereof; mixtures of two or more of the above olefins; and mixtures of ethylene with one or more of the above olefins capable of undergoing disproportionation with a tungsten oxide on silica disproportionation catalyst system under disproportionation conditions, the improvement comprising contacting the catalyst with an activating amount of at least one alkyne conforming to the formula: R-C=C-R wherein each R is independently H or a C/sub 1/-C/sub 6/ carbon radical per mole of tungsten oxide

Polymerization of Phenylacetylene-Based Monodendrons with Alkoxy Peripheral Groups and Oxygen/Nitrogen Permeation Behavior of Their Membranes

Directory of Open Access Journals (Sweden)

Takashi Kaneko

2012-01-01

Full Text Available Monodendron monomers with alkoxy peripheral groups were synthesized, and the focal point of monodendrons, terminal acetylene, was polymerized with rhodium catalyst to yield corresponding polydendrons with a high molecular weight. The polydendrons were soluble in common organic solvents and readily formed membranes. Oxygen permselectivity was improved in the polydendrons with a space-persistent dendritic crowd. It was found that the well-defined dendritic and rod-like structure of the polydendrons was useful for permselective membrane.

Polycyclopentene-Crystal-Decorated Carbon Nanotubes by Convenient Large-Scale In Situ Polymerization and their Lotus-Leaf-Like Superhydrophobic Films.

Science.gov (United States)

Xu, Lixin; Huang, Lingqi; Ye, Zhibin; Meng, Nan; Shu, Yang; Gu, Zhiyong

2017-02-01

In situ Pd-catalyzed cyclopentene polymerization in the presence of multi-walled carbon nanotubes (MWCNTs) is demonstrated to effectively render, on a large scale, polycyclopentene-crystal-decorated MWCNTs. Controlling the catalyst loading and/or time in the polymerization offers a convenient tuning of the polymer content and the morphology of the decorated MWCNTs. Appealingly, films made of the decorated carbon nanotubes through simple vacuum filtration show the characteristic lotus-leaf-like superhydrophobicity with high water contact angle (>150°), low contact angle hysteresis (<10°), and low water adhesion, while being electrically conductive. This is the first demonstration of the direct fabrication of lotus-leaf-like superhydrophobic films with solution-grown polymer-crystal-decorated carbon nanotubes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Combined Synthetic and DFT Study on the Catalyst-Free and Solvent-Assisted Synthesis of 1,3,4-Oxadiazole-2-thiol Derivatives

Directory of Open Access Journals (Sweden)

Mohammad Soleiman-Beigi

2013-01-01

Full Text Available A novel practical and efficient catalyst-free method for the synthesis of 5-substituted 1,3,4-oxadiazole-2-thiols has been developed, which is assisted by reaction solvent (DMF. The solvent effects on product selectivity were studied based on Onsager’s reaction field theory of electrostatic solvation. The ab initio theoretical studies on the effect of solvents on the process also supported the suitability of DMF as the reaction medium for the preparation of 1,3,4-oxadiazole-2-thiol derivatives.

Catalysts in petroleum refining and petrochemical industries 1995

Energy Technology Data Exchange (ETDEWEB)

Absi-Halabi, M.; Beshara, J.; Qabazard, H.; Stanislaus, A. [eds.] [Petroleum, Petrochemicals and Materials Division, Kuwait Institute of Scientific Research, Kuwait (Kuwait)

1996-07-01

Catalysis plays an increasingly critical role in modern petroleum refining and basic petrochemical industries. The market demands for and specifications of petroleum and petrochemical products are continuously changing. They have impacted the industry significantly over the past twenty years. Numerous new refining processes have been developed and significant improvements were made on existing technologies. Catalysts have been instrumental in enabling the industry to meet the continuous challenges posed by the market. As we enter the 21st century, new challenges for catalysis science and technology are anticipated in almost every field. Particularly, better utilization of petroleum resources and demands for cleaner transportation fuels are major items on the agenda. It is against this background that the 2nd International Conference on Catalysts in Petroleum Refining and Petrochemical Industries was organized. The papers from the conference were carefully selected from around 100 submissions. They were a mix of reviews providing an overview of selected areas, original fundamental research results, and industrial experiences. The papers in the proceedings were grouped in the following sections for quick reference: Plenary Papers; Hydroprocessing of Petroleum Residues and Distillates; Fluid Catalytic Cracking; Oxidation Catalysis; Aromatization and Polymerization Catalysis; Catalyst Characterization and Performance. The plenary papers were mostly reviews covering important topics related to the objectives of the conference. The remaining sections cover various topics of major impact on modern petroleum refining and petrochemical industries. A large number of papers dealt with hydroprocessing of petroleum distillates and residues which reflects the concern over meeting future sulfur-level specifications for diesel and fuel oils

Performance characterization of hydrogen isotope exchange and recombination catalysts for tritium processing

International Nuclear Information System (INIS)

Suppiah, S.; Ryland, D.; Marcinkowska, K.; Boniface, H.; Everatt, A.

2010-01-01

AECL's hydrogen isotope exchange catalyst and recombination catalysts have been successfully applied to a wide range of industrial tritium-removal applications. The catalysts are used for Liquid Phase Catalytic Exchange (LPCE) and for gas-phase and trickle-bed recombination of hydrogen isotopes and have led to process simplification, improved safety and operational advantages. Catalyst performance design equations derived from laboratory testing of these catalysts have been validated against performance under industrial conditions. In a Combined Electrolysis and Catalytic Exchange (CECE) demonstration plant analyses of LPCE and recombiner efficiency were carried out as a function of catalyst activity over a wide range of operation. A steady-state process simulation used to model and design the hydrogen-water isotopic exchange processes, such as the CECE detritiation plant, was validated using the results of this demonstration. Catalyst development for isotope-exchange and recombination applications has continued over the last decade. As a result, significant improvements in catalyst performance have been achieved for these applications. This paper outlines the uniqueness of AECL's specialized catalysts and process designs for these applications with examples from laboratory and industrial case studies.

Cell-derived matrix coatings for polymeric scaffolds.

Science.gov (United States)

Decaris, Martin L; Binder, Bernard Y; Soicher, Matthew A; Bhat, Archana; Leach, J Kent

2012-10-01

Cells in culture deposit a complex extracellular matrix that remains intact following decellularization and possesses the capacity to modulate cell phenotype. The direct application of such decellularized matrices (DMs) to 3D substrates is problematic, as transport issues influence the homogeneous deposition, decellularization, and modification of DM surface coatings. In an attempt to address this shortcoming, we hypothesized that DMs deposited by human mesenchymal stem cells (MSCs) could be transferred to the surface of polymeric scaffolds while maintaining their capacity to direct cell fate. The ability of the transferred DM (tDM)-coated scaffolds to enhance the osteogenic differentiation of undifferentiated and osteogenically induced MSCs under osteogenic conditions in vitro was confirmed. tDM-coated scaffolds increased MSC expression of osteogenic marker genes (BGLAP, IBSP) and intracellular alkaline phosphatase production. In addition, undifferentiated MSCs deposited significantly more calcium when seeded onto tDM-coated scaffolds compared with control scaffolds. MSC-seeded tDM-coated scaffolds subcutaneously implanted in nude rats displayed significantly higher blood vessel density after 2 weeks compared with cells on uncoated scaffolds, but we did not observe significant differences in mineral deposition after 8 weeks. These data demonstrate that DM-coatings produced in 2D culture can be successfully transferred to 3D substrates and retain their capacity to modulate cell phenotype.

Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst.

Science.gov (United States)

Duan, Haohong; Dong, Juncai; Gu, Xianrui; Peng, Yung-Kang; Chen, Wenxing; Issariyakul, Titipong; Myers, William K; Li, Meng-Jung; Yi, Ni; Kilpatrick, Alexander F R; Wang, Yu; Zheng, Xusheng; Ji, Shufang; Wang, Qian; Feng, Junting; Chen, Dongliang; Li, Yadong; Buffet, Jean-Charles; Liu, Haichao; Tsang, Shik Chi Edman; O'Hare, Dermot

2017-09-19

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.

Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

Science.gov (United States)

Franco, Ana; De, Sudipta; Balu, Alina M; Garcia, Araceli; Luque, Rafael

2017-01-01

Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc.) have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H 2 O 2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

Pressure-Induced Polymerization of Acetylene: Structure-Directed Stereoselectivity and a Possible Route to Graphane.

Science.gov (United States)

Sun, Jiangman; Dong, Xiao; Wang, Yajie; Li, Kuo; Zheng, Haiyan; Wang, Lijuan; Cody, George D; Tulk, Christopher A; Molaison, Jamie J; Lin, Xiaohuan; Meng, Yufei; Jin, Changqing; Mao, Ho-Kwang

2017-06-01

Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies on recycling and utilization of spent catalysts. Preparation of active hydrodemetallization catalyst compositions from spent residue hydroprocessing catalysts

Energy Technology Data Exchange (ETDEWEB)

Marafi, Meena; Stanislaus, Antony [Petroleum Refining Department, Petroleum Research and Studies Center, Kuwait Institute for Scientific Research, P.O. Box 24885, Safat (Kuwait)

2007-02-15

Spent catalysts form a major source of solid wastes in the petroleum refining industries. Due to environmental concerns, increasing emphasis has been placed on the development of recycling processes for the waste catalyst materials as much as possible. In the present study the potential reuse of spent catalysts in the preparation of active new catalysts for residual oil hydrotreating was examined. A series of catalysts were prepared by mixing and extruding spent residue hydroprocessing catalysts that contained C, V, Mo, Ni and Al{sub 2}O{sub 3} with boehmite in different proportions. All prepared catalysts were characterized by chemical analysis and by surface area, pore volume, pore size and crushing strength measurements. The hydrodesulfurization (HDS) and hydrodemetallization (HDM) activities of the catalysts were evaluated by testing in a high pressure fixed-bed microreactor unit using Kuwait atmospheric residue as feed. A commercial HDM catalyst was also tested under similar operating conditions and their HDS and HDM activities were compared with that of the prepared catalysts. The results revealed that catalyst prepared with addition of up to 40 wt% spent catalyst to boehmite had fairly high surface area and pore volume together with large pores. The catalyst prepared by mixing and extruding about 40 wt% spent catalyst with boehmite was relatively more active for promoting HDM and HDS reactions than a reference commercial HDM catalyst. The formation of some kind of new active sites from the metals (V, Mo and Ni) present in the spent catalyst is suggested to be responsible for the high HDM activity of the prepared catalyst. (author)

The red, purple and blue modifications of polymeric unsymmetrical hydroxyalkadiynyl-N-arylcarbamate derivatives in Langmuir-Schaefer films

Energy Technology Data Exchange (ETDEWEB)

Alekseev, Alexander, E-mail: alexanderalekseev@yandex.ru [A. M. Prokhorov General Physics Institute, Russian Academy of Sciences, Moscow 119991 (Russian Federation); Ihalainen, Petri, E-mail: petri.ihalainen@abo.fi [Laboratory of Physical Chemistry, Center for Functional Materials, Åbo Akademi University, Turku FI-20500 (Finland); Ivanov, Artem [A. M. Prokhorov General Physics Institute, Russian Academy of Sciences, Moscow 119991 (Russian Federation); Domnin, Ivan [Department of Chemistry, St. Petersburg State University, Peterhof, St. Petersburg 198904 (Russian Federation); Klechkovskaya, Vera; Orekhov, Anton [Shubnikov Institute of Crystallography, Russian Academy of Science, Moscow 119333 (Russian Federation); NRC Kurchatov Institute, Moscow 123182 (Russian Federation); Lemmetyinen, Helge; Vuorimaa-Laukkanen, Elina [Department of Chemistry and Bioengineering, Tampere University of Technology, Tampere FI-33101 (Finland); Peltonen, Jouko [Laboratory of Physical Chemistry, Center for Functional Materials, Åbo Akademi University, Turku FI-20500 (Finland); Vyaz' min, Sergey [Laboratory of Nanobiotechnologies, St. Petersburg Academic University-Nanotechnology Research and Education Centre, Russian Academy of Science, St. Petersburg 194021 (Russian Federation)

2016-08-01

Solid topochemical photopolymerization (STP) of Langmuir-Schaefer films of a new class of unsymmetrical diynes, containing N-arylcarbamate groups in the hydrophobic part and hydroxymethylene groups in the hydrophilic part of the molecules was examined. In addition, the monomeric Langmuir monolayer formation was studied by Brewster angle microscopy and the surface morphology of monomer and polymer films on solid substrates were studied by scanning electron microscopy and atomic force microscopy. Three phases of polydiacetylene (PDA) (red, purple and blue) were observed after UV-light polymerization of above-mentioned films of alcohol diacetylene (DA) derivatives. The substitution of MeO group in the aryl ring substituent by hydrogen atom and the variation of the methylene group number in the hydrophobic part from 5 to 6 changed significantly the result of STP: instead of blue phase PDA observed for diynes with MeO group, the red phase PDA was observed for DA with H-atom from the very beginning of diyne film UV irradiation. For two other diynilic N-arylcarbamates of identical chemical structures except of the substituents in the aryl ring of hydrophobic parts of the molecules, no changes in the efficiency of polymerization or the position and shape of absorption bands were observed. This indicated the formation of the purple phase PDA. For these molecules, the number of methylene groups in hydrophobic and hydrophilic parts of the molecules was 9 and 2, respectively. - Highlights: • STP reaction of diacetylenes in LS films depends on number and ratio of CH{sub 2} groups. • Three phases of polydiacetylene (red, purple and blue) were observed in LS films. • Structural organization of the monomer film determines the type of polymer phase.

Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

Science.gov (United States)

Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

2016-02-01

High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

Hydrodeoxygenation of bio-derived phenols to hydrocarbons using RANEY Ni and Nafion/SiO2 catalysts.

Science.gov (United States)

Zhao, Chen; Kou, Yuan; Lemonidou, Angeliki A; Li, Xuebing; Lercher, Johannes A

2010-01-21

A simple, green, cost- and energy-efficient route for converting phenolic components in bio-oil to hydrocarbons and methanol has been developed, with nearly 100% yields. In the heterogeneous catalysts, RANEY Ni acts as the hydrogenation catalyst and Nafion/SiO(2) acts as the Brønsted solid acid for hydrolysis and dehydration.

Catalysts, methods of making catalysts, and methods of use

KAUST Repository

Renard, Laetitia; El Eter, Mohamad; Caps, Valerie; Basset, Jean-Marie

2014-01-01

Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

Catalysts, methods of making catalysts, and methods of use

KAUST Repository

Renard, Laetitia

2014-03-06

Embodiments of the present disclosure provide for catalysts, methods of making catalysts, methods of using catalysts, and the like. In an embodiment, the method of making the catalysts can be performed in a single step with a metal nanoparticle precursor and a metal oxide precursor, where a separate stabilizing agent is not needed.

Influence of HAp on the polymerization processes of a possible radioactive bone cement

Energy Technology Data Exchange (ETDEWEB)

Montaño, Carlos J.; Campos, Tarcísio P.R., E-mail: carlmont@ucm.es, E-mail: tprcampos@yahoo.com.br [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte (Brazil). Dept. de Engenharia Nuclear. Lab. de Radiações Ionizantes; Silva, Adolfo H.M.; Araujo, Maria H., E-mail: adolfohmoraes@ufmg.br, E-mail: mharaujo1993@gmail.com [Universidade Federal de Minas Gerais (RMN/UFMG), Belo Horizonte (Brazil). Dept. de Ressonância Magnética Nuclear

2017-07-01

Polymethylmethacrylate PMMA is an acrylic that has been already proposed as a composite to adhere together the fractured bone structures. Subsequently, augmentation bone cements have incorporated Calcium Biophosphonates as vital part of its components to increase the biocompatibility with osseous tissues. Minimally invasive percutaneous techniques such as Vertebroplasty and Kyphoplasty have been developed to reduce surgical impact on patients, but in turn have been reported undesirable effects as extravasation of the cement outside of the planning target volume due to the compression of the internal bone fluids or other tissues. An in situ variable that helps favoring of the PMMA polymerization process is the temperature; however, it may bring deleterious effects. On the methodology, an assay was addressed varying the Hydroxyapatite HAp concentration. Also the cement processing was modified by setting water as a vehicle for particle dispersion. The ratios of HAp/PMMA concentrations were: 0.00000, 0.02167, 0.09062, 0.16619 and 0.50000 mixed in PMMA and liquid catalyst and monomer. The thermal profiles were measured during polymerization and analyzed. Nuclear magnetic resonance NMR analysis was carried out on the polymerization process in an aqueous state to monitor the H-H{sub 2}O proton signal. As results, an increasing in the cement hardness time was found in the proportion of the HAp concentration. The highest τ polymerization time was found for the x{sub 5} concentration and the signal from the water trapped in the HAp amorphous lattice was determined around ∼5 ppm in the {sup 1}H NMR spectra. (author)

Influence of HAp on the polymerization processes of a possible radioactive bone cement

International Nuclear Information System (INIS)

Montaño, Carlos J.; Campos, Tarcísio P.R.; Silva, Adolfo H.M.; Araujo, Maria H.

2017-01-01

Polymethylmethacrylate PMMA is an acrylic that has been already proposed as a composite to adhere together the fractured bone structures. Subsequently, augmentation bone cements have incorporated Calcium Biophosphonates as vital part of its components to increase the biocompatibility with osseous tissues. Minimally invasive percutaneous techniques such as Vertebroplasty and Kyphoplasty have been developed to reduce surgical impact on patients, but in turn have been reported undesirable effects as extravasation of the cement outside of the planning target volume due to the compression of the internal bone fluids or other tissues. An in situ variable that helps favoring of the PMMA polymerization process is the temperature; however, it may bring deleterious effects. On the methodology, an assay was addressed varying the Hydroxyapatite HAp concentration. Also the cement processing was modified by setting water as a vehicle for particle dispersion. The ratios of HAp/PMMA concentrations were: 0.00000, 0.02167, 0.09062, 0.16619 and 0.50000 mixed in PMMA and liquid catalyst and monomer. The thermal profiles were measured during polymerization and analyzed. Nuclear magnetic resonance NMR analysis was carried out on the polymerization process in an aqueous state to monitor the H-H 2 O proton signal. As results, an increasing in the cement hardness time was found in the proportion of the HAp concentration. The highest τ polymerization time was found for the x 5 concentration and the signal from the water trapped in the HAp amorphous lattice was determined around ∼5 ppm in the 1 H NMR spectra. (author)

Vegetable oil-derived epoxy monomers and polymer blends: A comparative study with review

Directory of Open Access Journals (Sweden)

T. P. Schuman

2013-03-01

Full Text Available Glycidyl esters of epoxidized fatty acids derived from soybean oil (EGS and linseed oil (EGL have been synthesized to have higher oxirane content, more reactivity and lower viscosity than epoxidized soybean oil (ESO or epoxidized linseed oil (ELO. The EGS and ESO, for comparison, were used neat and in blends with diglycidyl ether of bisphenol A (DGEBA. Thermosetting resins were fabricated with the epoxy monomers and either BF3 catalyst or anhydride. The curing behaviors, glass transition temperatures, crosslink densities and mechanical properties were tested. The results indicated that polymer glass transition temperatures were mostly a function of oxirane content with additional influence of glycidyl versus internal oxirane reactivity, pendant chain content, and chemical structure and presence of saturated components. EGS provided better compatibility with DGEBA, improved intermolecular crosslinking and glass transition temperature, and yielded mechanically stronger polymerized materials than materials obtained using ESO. Other benefits of the EGS resin blend systems were significantly reduced viscosities compared to either DGEBA or ESO-blended DGEBA counterparts. Therefore, EGS that is derived from renewable sources has improved potential for fabrication of structural and structurally complex epoxy composites, e.g., by vacuum-assisted resin transfer molding.

Rational design of Mg-Al mixed oxide-supported bimetallic catalysts for dry reforming of methane

Energy Technology Data Exchange (ETDEWEB)

Tsyganok, Andrey I. [Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, D' Iorio Hall, 10 Marie Curie Street, Ottawa, Ont. (Canada); Inaba, Mieko [Natural Gas Technology Development Team, Teikoku Oil Co., 9-23-30 Kitakarasuyama, Setagaya-ku, Tokyo 157-0061 (Japan); Tsunoda, Tatsuo; Uchida, Kunio; Suzuki, Kunio; Hayakawa, Takashi [Institute for Materials and Chemical Process, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Takehira, Katsuomi [Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527 (Japan)

2005-09-18

A novel synthetic strategy for preparing bimetallic Ru-M (M=Cr, Fe, Co, Ni and Cu) catalysts, supported on Mg-Al mixed oxide, has been introduced. It was based on a 'memory effect', i.e. on the ability of Mg-Al mixed oxide to reconstruct a layered structure upon rehydration with an aqueous solution. By repeated calcinations-rehydration cycles, layered double hydroxide (LDH) precursors of catalysts containing two different metals were synthesized. Bimetallic catalysts were then generated (1) in situ from LDH under methane reforming reaction conditions and (2) from mixed metal oxides obtained by preliminary LDH calcination. Among all the LDH-derived catalysts, a Ru{sup 0.1%}-Ni{sup 5.0%}/MgAlO{sub x} sample revealed the highest activity and selectivity to syngas, a suitable durability and a low coking capacity. A promoting effect of ruthenium on catalytic function of supported nickel was demonstrated. Preliminary LDH calcination was shown to markedly affect the catalytic activity of the derived catalysts and especially their coking properties.

Poly (p-phenylendiamine/TiO2) nanocomposite promoted Pt/C catalyst for methanol and ethanol electrooxidation in alkaline medium

International Nuclear Information System (INIS)

Rostami, Hussein; Rostami, Abbas Ali; Omrani, Abdollah

2016-01-01

In the present study, poly (p-phenylendiamine/titanium dioxide) (PpPDA/TiO 2 ) nanocomposites (NCs) were prepared by in situ polymerization of p-phenylenediamine monomer with of different TiO 2 loading. A facile method was developed to promote the electrocatalytic activity of commercial Pt/C catalyst by ultrasonically mixing Pt/C catalyst and PpPDA/TiO 2 NCs. The PpPDA/TiO 2 NC, Pt/C catalyst and composite catalyst of Pt/C + PpPDA/TiO 2 were characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. The surface morphology of Pt/C is significantly influenced by the presence of PpPDA/TiO 2 NC as confirmed by SEM observations. Cyclic voltammetry (CV) measurements showed that the PpPDA/TiO 2 NC leads to a significant improvement in the activity and stability of Pt/C for alcohol oxidation especially for ethanol oxidation in alkaline medium. For Pt/C + PpPDA/TiO 2 , the onset potentials shift to negative values by 30 and 160 mV compared to the onset potentials of Pt/C for methanol and ethanol oxidation, respectively. Chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) results also confirmed that this composite catalyst has superior catalytic performance towards ethanol oxidation compared to the pure Pt/C catalyst.

Sustainable utilization of waste palm oil and sulfonated carbon catalyst derived from coconut meal residue for biodiesel production.

Science.gov (United States)

Thushari, Indika; Babel, Sandhya

2018-01-01

In this study, an inexpensive, environmental benign acid catalyst is prepared using coconut meal residue (CMR) and employed for biodiesel production from waste palm oil (WPO). The total acid density of the catalyst is found to be 3.8mmolg -1 . The catalyst shows a unique amorphous structure with 1.33m 2 g -1 of surface area and 0.31cm 3 g -1 of mean pore volume. Successful activation is confirmed by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The highest biodiesel yield of 92.7% was obtained from WPO in an open reflux system using the catalyst. Results show that biodiesel yield increases with increasing methanol:oil (molar ratio) and reaction time up to an optimum value. It is found that the catalyst can be reused for at least four cycles for >80% biodiesel yield. Fuel properties of the produced biodiesel meet international biodiesel standards. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of P-containing {gamma}-Al{sub 2}O{sub 3} supported Ni-Mo bimetallic carbide, nitride and sulfide catalysts for HDN and HDS of gas oils derived from Athabasca bitumen

Energy Technology Data Exchange (ETDEWEB)

Sundaramurthy, V.; Dalai, A.K. [Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, SK (Canada); Adjaye, J. [Syncrude Edmonton Research Centre, Edmonton, AB (Canada)

2006-09-01

Phosphorus containing {gamma}-Al{sub 2}O{sub 3} supported bimetallic Ni-Mo carbide, nitride and sulfide catalysts have been synthesized from an oxide precursor containing 12.73wt.% Mo, 2.54wt.% Ni and 2.38wt.% P and characterized by elemental analysis, pulsed CO chemisorption, surface area measurements, X-ray diffraction, temperature-programmed reduction and DRIFT spectroscopy of CO adsorption. DRIFT spectroscopy of adsorbed CO on activated catalysts showed that carbide and nitride catalysts have surface exposed sites of Mo{sup o+} (0catalysts were compared against commercial Ni-Mo/Al{sub 2}O{sub 3} catalyst in a trickle bed reactor using light gas oil and heavy gas oil derived from Athabasca bitumen in the temperature range 340-370 and 375-400{sup o}C respectively at 8.8MPa. The gradual transformation of Ni-Mo carbide and nitride phases into Ni-Mo sulfide phases was observed during precoking period, and the formed Ni-Mo sulfide phases enhanced the HDN and HDS activities of carbide and nitride catalysts. The {gamma}-Al{sub 2}O{sub 3} supported Ni-Mo bimetallic sulfide catalyst was found to be more active for HDN and HDS of light gas oil and heavy gas oil than the corresponding carbide and nitride catalysts on the basis of unit weight. (author)

Revealing the Cytotoxicity of Residues of Phosphazene Catalysts Used for Synthesis of Poly(ethylene oxide)

KAUST Repository

Xia, Yening

2017-08-24

We herein report a case study on the toxicity of residual catalyst in metal-free polymer. Eight-arm star-like poly(ethylene oxide)s were successfully synthesized via phosphazene-catalyzed ring-opening polymerization of ethylene oxide using sucrose as an octahydroxy initiator. The products were subjected to MTT assay using human cancer cell lines (MDA-MB-231 and A2780). Comparison between the crude and purified products clearly revealed that the residual phosphazenium salts were considerably cytotoxic regardless of the anionic species, and that the cytotoxicity of more bulky t-BuP4 salt was higher than that of t-BuP2 salt. Such results have therefore put forward the necessity for removal of the catalyst residues from PEO-based polymers synthesized through phosphazene catalysis for bio-related applications, and for the development of less or non-toxic organocatalysts for such polymers.

Revealing the Cytotoxicity of Residues of Phosphazene Catalysts Used for Synthesis of Poly(ethylene oxide)

KAUST Repository

Xia, Yening; Shen, Jizhou; Alamri, Haleema; Hadjichristidis, Nikolaos; Zhao, Junpeng; Wang, Yucai; Zhang, Guangzhao

2017-01-01

We herein report a case study on the toxicity of residual catalyst in metal-free polymer. Eight-arm star-like poly(ethylene oxide)s were successfully synthesized via phosphazene-catalyzed ring-opening polymerization of ethylene oxide using sucrose as an octahydroxy initiator. The products were subjected to MTT assay using human cancer cell lines (MDA-MB-231 and A2780). Comparison between the crude and purified products clearly revealed that the residual phosphazenium salts were considerably cytotoxic regardless of the anionic species, and that the cytotoxicity of more bulky t-BuP4 salt was higher than that of t-BuP2 salt. Such results have therefore put forward the necessity for removal of the catalyst residues from PEO-based polymers synthesized through phosphazene catalysis for bio-related applications, and for the development of less or non-toxic organocatalysts for such polymers.

A facile approach towards increasing the nitrogen-content in nitrogen-doped carbon nanotubes via halogenated catalysts

International Nuclear Information System (INIS)

Ombaka, L.M.; Ndungu, P.G.; Omondi, B.; McGettrick, J.D.; Davies, M.L.; Nyamori, V.O.

2016-01-01

Nitrogen-doped carbon nanotubes (N-CNTs) have been synthesized at 850 °C via a CVD deposition technique by use of three ferrocenyl derivative catalysts, i.e. para-CN, -CF_3 and -Cl substituted-phenyl rings. The synthesized catalysts have been characterized by NMR, IR, HR-MS and XRD. The XRD analysis of the para-CF_3 catalyst indicates that steric factors influence the X-ray structure of 1,1′-ferrocenylphenyldiacrylonitriles. Acetonitrile or pyridine was used as carbon and nitrogen sources to yield mixtures of N-CNTs and carbon spheres (CS). The N-CNTs obtained from the para-CF_3 catalysts, in pyridine, have the highest nitrogen-doping level, show a helical morphology and are less thermally stable compared with those synthesized by use of the para-CN and -Cl as catalyst. This suggests that fluorine heteroatoms enhance nitrogen-doping in N-CNTs and formation of helical-N-CNTs (H-N-CNTs). The para-CF_3 and para-Cl catalysts in acetonitrile yielded iron-filled N-CNTs, indicating that halogens promote encapsulation of iron into the cavity of N-CNT. The use of acetonitrile, as carbon and nitrogen source, with the para-CN and -Cl as catalysts also yielded a mixture of N-CNTs and carbon nanofibres (CNFs), with less abundance of CNFs in the products obtained using para-Cl catalysts. However, para-CF_3 catalyst in acetonitrile gave N-CNTs as the only shaped carbon nanomaterials. - Graphical abstract: Graphical abstract showing the synthesis of N-CNTs using halogenated-ferrocenyl derivatives as catalyst with pyridine or acetonitrile as nitrogen and carbon sources via the chemical vapour deposition technique. - Highlights: • N-CNTs were synthesized from halogenated ferrocenyl catalysts. • Halogenated catalysts promote nitrogen-doping and pyridinic nitrogen in N-CNTs. • Halogenated catalysts facilitate iron filling of N-CNTs.

Ethylene homo- and copolymerization chain-transfers: A perspective from supported (n BuCp) 2 ZrCl 2 catalyst active centre distribution

KAUST Repository

Atiqullah, Muhammad

2015-04-01

Polymerization chain termination reactions and unsaturation of the polymer backbone end are related. Therefore, in this study, the parameters resulting from the modelling of the active centre distribution of the supported catalyst - silica/MAO/(nBuCp)2ZrCl2 - were applied to evaluate the active-centre-dependent ethylene homo- and copolymerization rates, as well as the corresponding chain termination rates. This approach, from a microkinetic mechanistic viewpoint, elucidates better the 1-hexene-induced positive comonomer effect and chain transfer phenomenon. The kinetic expressions, developed on the basis of the proposed polymerization mechanisms, illustrate how the active site type-dependent chain transfer phenomenon is influenced by the different apparent termination rate constants and momoner concentrations. The active centre-specific molecular weight M ni (for the above homo- and copolymer), as a function of chain transfer probability, p CTi, varied as follows: log (p C Ti) = log (mwru) - log (Mn i), where mw ru is the molecular weight of the repeat unit. The physical significance of this finding has been explained. The homo- and copolymer backbones showed all the three chain end unsaturations (vinyl, vinylidene, and trans-vinylene). The postulated polymerization mechanisms reveal the underlying polymer chemistry. The results of the present study will contribute to develop in future supported metallocene catalysts that will be useful to synthesize polyethylene precursors having varying chain end unsaturations, which can be eventually used to prepare functional polyethylenes. [Figure not available: see fulltext.] © 2015 Indian Academy of Sciences.

Novel Carbazole Skeleton-Based Photoinitiators for LED Polymerization and LED Projector 3D Printing

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Assi Al Mousawi

2017-12-01

Full Text Available Radical chemistry is a very convenient way to produce polymer materials. Here, an application of a particular photoinduced radical chemistry is illustrated. Seven new carbazole derivatives Cd1–Cd7 are incorporated and proposed as high performance near-UV photoinitiators for both the free radical polymerization (FRP of (methacrylates and the cationic polymerization (CP of epoxides utilizing Light Emitting Diodes LEDs @405 nm. Excellent polymerization-initiating abilities are found and high final reactive function conversions are obtained. Interestingly, these new derivatives display much better near-UV polymerization-initiating abilities compared to a reference UV absorbing carbazole (CARET 9H-carbazole-9-ethanol demonstrating that the new substituents have good ability to red shift the absorption of the proposed photoinitiators. All the more strikingly, in combination with iodonium salt, Cd1–Cd7 are likewise preferred as cationic photoinitiators over the notable photoinitiator bis(2,4,6-trimethylbenzoylphenylphosphine oxide (BAPO for mild irradiation conditions featuring their remarkable reactivity. In particular their utilization in the preparation of new cationic resins for LED projector 3D printing is envisioned. A full picture of the included photochemical mechanisms is given.

Hydrotreatment of heavy oil from coal liquefaction on Sulfide Ni - W Catalysts

Energy Technology Data Exchange (ETDEWEB)

Zhi-ping Lei; Li-juan Gao; Heng-fu Shui; Shi-biao, Ren; Zhi-cai Wang; Kang-shi Gang, E-mail: shhf@ahut.edu.c [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering. Anhui Key Lab. of Coal Clean Conversion and Utilization

2011-07-01

Heavy oil (distillation temperature: 320-340 deg C) derived from the direct coal liquefaction process using Shengli coal were hydrotreated using sulfided Ni-Mo/Al{sub 2}O{sub 3}, Ni-W/Al{sub 2}O{sub 3}, and Ni-W/SiO{sub 2} catalysts respectively. The sulfided catalysts were characterized by BET, XRD, H{sub 2}-TPR and NH{sub 3}-TPD respectively. The evaluations of the hydrodenitrogenation (HDN) and hydrodearomatization (HDA) properties of heavy oil on the three catalysts were carried out at 400 deg C and 5.0 MPa initial H2 pressure. The W-based catalysts displayed better performances than Mo-based catalysts for the HDN and HDA reactions. Al{sub 2}O{sub 3} supported catalysts were found to have higher catalytic activities than on SiO{sub 2} supported ones. The activities of sulfided catalysts were associated mainly with the nature of active sites, acidity, metal sulfide crystallite size and the amount of the reducible sulfur species of metal sulfide. (author)

Catalyst activity maintenance study for the liquid phase dimethyl ether process

Energy Technology Data Exchange (ETDEWEB)

Peng, X.D.; Toseland, B.A.; Underwood, R.P. [Air Products and Chemicals, Inc., Allentown, PA (United States)

1995-12-31

The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.