Selective hydrogenation of acetylene in ethylene rich feed streams at high pressure over ligand modified Pd/TiO2

The selective hydrogenation of acetylene from ethylene rich streams was conducted at high pressure and in the presence of CO over two 1 wt% loaded Pd/TiO2 catalysts with differing dispersions. Although, the more poorly dispersed sample did not result in high acetylene conversion only a small proportion of the total available ethylene was hydrogenated to ethane. The more highly dispersed sample was able to remove acetylene to a level below the detection limit but this was at the expense of significant proportion (ca. 30%) of the available ethylene. Modification of the catalysts by exposure to triphenyl phosphine or diphenyl sulfide and subsequent reduction at 393 K led to improved performance with increased conversion of acetylene and decreased propensity to hydrogenate ethylene resulting in an overall net gain in ethylene. The higher dispersed sample which had been ligand modified provided the best results overall and in particular for the diphenyl sulfide treated sample which was able to completely eliminate acetylene and still obtain a net gain in ethylene. The differences observed are thought to be due to the creation of appropriate active ensembles of Pd atoms which are able to accommodate acetylene but have limited ability to adsorb ethylene. Sub-surface hydrogen formation was suppressed, but not eliminated, by exposure to modifier.

Topochemical polymerization in self-assembled rodlike micelles of bisurea bolaamphiphiles

Rod-like micelles, formed from bolaamphiphiles with oligo(ethylene oxide) hydrophilic outer segments and a hydrophobic segment with diacetylene flanked by two urea moieties, were covalently fixated by topochemical photopolymerization to high degrees of polymerization by optimizing the hydrophobic core and the hydrophilic periphery of the bolaamphiphiles. Analysis of the polymerized product with dynamic light scattering in chloroform showed degrees of polymerization of approximately 250. Cryo-TEM of bolaamphiphiles before and after UV irradiation showed that the morphology of the rods was conserved upon topochemical polymerization. © 2014 The Royal Society of Chemistry.

Selective Hydrogenation of Acetylene over Pd-Boron Catalysts: A Density Functional Theory Study

Boron-modified Pd catalysts have shown excellent performance for the selective hydrogenation of alkynes experimentally. In the current work, we investigated the hydrogenation of acetylene on boron-modified Pd(111) and Pd(211) surfaces, utilizing density functional theory calculations. The activity of acetylene hydrogenation has been studied by estimating the effective barrier of the whole process. The selectivity of ethylene formation is investigated from a comparison between the desorption and the hydrogenation of ethylene as well as comparison between the ethylene and the 1,3-butadiene formation. Formation of subsurface carbon and hydrogen on both boron-modified Pd(111) and Pd(211) surfaces has also been evaluated, since these have been reported to affect both the activity and the selectivity of acetylene hydrogenation to produce ethylene on Pd surfaces. Our results provide some important insights into the Pd B catalysts for selective hydrogenation of acetylene and also for more complex hydrogenation systems, such as stereoselective hydrogenation of longer chain alkynes and selective hydrogenation of vegetable oil.

A DFT study of the transition metal promotion effect on ethylene chemisorption on Co(0001)

Transition metals are often introduced to a catalyst as promoters to improve catalytic performance. In this work, we study the promotion effect of transition metals on Co, the preferred catalytic metal for Fischer-Tropsch synthesis because of its good compromise of activity, selectivity and stability, for ethylene chemisorption using density functional theory (DFT) calculations, aiming to provide some insight into improving the alpha-olefin selectivity. In order to obtain the general trend of influence on ethylene chemisorption, twelve transition metals (Zr, Mn, Re, Ru, Rh, It, Ni, Pd, Pt, Cu, Ag and Au) are calculated. We find that the late transition metals (e.g. Pd and Cu) can decrease ethylene chemisorption energy. These results suggest that the addition of the late transition metals may improve alpha-olefin selectivity. Electronic structure analyses (both charge density distributions and density of states) are also performed and the understanding of calculated results is presented. (C) 2009 Elsevier B.V. All rights reserved.

Poly(ethylene-co-acrylic acid) random copolymers : amphiphilic properties and self-assembly in aqueous medium

Les travaux de recherche présentés ici avaient pour objectif principal la synthèse de copolymères statistiques à base d’éthylène et d’acide acrylique (AA). Pour cela, la déprotection des groupements esters d’un copolymère statistique précurseur, le poly(éthylène-co-(tert-butyl)acrylate), a été effectuée par hydrolyse à l’aide d’iodure de triméthylsilyle. La synthèse de ce précurseur est réalisée par polymérisation catalytique en présence d’un système à base de Palladium (Pd). Le deuxième objectif a été d’étudier et de caractériser des polymères synthétisés à l’état solide et en suspension colloïdale. Plusieurs copolymères précurseurs comprenant différents pourcentages molaires en tert-butyl acrylate (4 à 12% molaires) ont été synthétisés avec succès, puis déprotégés par hydrolyse pour obtenir des poly(éthylène-coacide acrylique) (pE-co-AA) avec différentes compositions. Seuls les copolymères comprenant 10% molaire ou plus de AA sont solubles dans le Tétrahydrofurane (THF) et uniquement dans ce solvant. De telles solutions peuvent être dialysées dans l’eau, ce qui conduit à un échange lent entre cette dernière et le THF, et l’autoassemblage du copolymère dans l’eau peut ensuite être étudié. C’est ainsi qu’ont pu être observées des nanoparticules stables dans le temps dont le comportement est sensible au pH et à la température. Les polymères synthétisés ont été caractérisés par Résonance Magnétique Nucléaire (RMN) ainsi que par spectroscopie Infra-Rouge (IR), avant et après déprotection. Les pourcentages molaires d’AA ont été déterminés par combinaison des résultats de RMN et ii de titrages conductimètriques. A l’état solide, les échantillons ont été analysés par Calorimétrie différentielle à balayage (DSC) et par Diffraction des rayons X. Les solutions colloïdales des polymères pE-co-AA ont été caractérisées par Diffusion dynamique de la lumière et par la DSC-haute sensibilité. De la microscopie électronique à transmission (TEM) a permis de visualiser la forme et la taille des nanoparticules.

Polymer-supported nitroxyl catalysts for selective oxidation of alcohols

Novel non-toxic poly(ethylene glycol)-supported 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties are demonstrated to give an excellent interfacial catalysis for the selective oxidation of alcohols to the corresponding carbonyl species in biphasic media and investigation for the recovery of these new macromolecular catalysts via precipitation with diethyl ether after catalysis has also been briefly studied.

Catalytic oxidation of alcohols using molecular oxygen mediated by poly(ethylene glycol)-supported nitroxyl radicals

The selective catalytic oxidation of alcohols over a mixture of copper(l) chloride and a number of linear 'linker-less' or 'branched' poly(ethylene glycol)-supported nitroxyl radicals of the 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) family as a catalyst system has been investigated in the presence of molecular oxygen in a batch reactor. It is found that the activity profile of the polymer-supported nitroxyl radicals is in good agreement with that of low-molecular weight nitroxyl catalysts, for example, allylic and benzylic alcohols are oxidised faster than aliphatic alcohols. The oxidations can be tuned to be highly selective such that aldehydes are the only oxidation products observed in the oxidation of primary alcohols and the oxidations of secondary alcohols yield the corresponding ketones. A strong structural effect of the polymeric nitroxyl species on catalytic activity that is dependent upon their spatial orientation of the nitroxyl radicals is particularly noted. The new soluble macromolecular catalysts can be recovered readily from the reaction mixture by solvent precipitation and filtration. In addition, the recycled catalysts demonstrate a similar selectivity with only a small decrease in activity compared to the fresh catalyst even after five repetitive cycles. (c) 2005 Elsevier B.V. All rights reserved.

Design and theoretical study of nickel catalysts for syndiotactic polyolefins

A nickel catalyst was modeled with ligand L-2, [ NH = CH-CH = CH-O](-), which should have potential use as a syndiotactic polyolefin catalyst, and the reaction mechanism was studied by theoretical calculations using the density functional method at the B3LYP/ LANL2MB level. The mechanism involves the formation of the intermediate [(NiLMe)-Me-2](+), in which the metal occuples a T-shaped geometry. - This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L-2. The results show that both structures can lead to the desired product via similar reaction paths, A and B. Thus, the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-O or trans to the Ni-N bond in the catalyst. The polymerization process thus favors the catalysis of syndiotactic polyolefins. The syndiotactic synthesis effects could also be enhanced by variations in the ligand substituents. From energy considerations, we can conclude that it is more favorable for the methyl group to occupy the trans-O position to form a complex than to occupy the trans-N position. From bond length considerations, it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position.

Thermal Fractionation and isothermal crystallization of polyethylene nanocomposites prepared by in situ polymerization

Nanocomposites of high-density polyethylene (HDPE) and carbon nanotubes (CNT) of different geometries (single wall, double wall, and multiwall; SWNT, DWNT, and MWNT) were prepared by in situ polymerization of ethylene on CNT whose surface had been previously treated with a metallocene catalytic system. In this work, we have studied the effects of applying the successive self-nucleation and annealing thermal fractionation technique (SSA) to the nanocomposites and have also determined the influence of composition and type of CNT on the isothermal crystallization behavior of the HDPE. SSA results indicate that all types of CNT induce the formation of a population of thicker lamellar crystals that melt at higher temperatures as compared to the crystals formed in neat HDPE prepared under the same catalytic and polymerization conditions and subjected to the same SSA treatment. Furthermore, the peculiar morphology induced by the CNT on the HDPE matrix allows the resolution of thermal fractionation to be much better. The isothermal crystallization results indicated that the strong nucleation effect caused by CNT reduced the supercooling needed for crystallization. The interaction between the HDPE chains and the surface of the CNT is probably very strong as judged by the results obtained, even though it is only physical in nature. When the total crystallinity achieved during isothermal crystallization is considered as a function of CNT content, it was found that a competition between nucleation and topological confinement could account for the results. At low CNT content the crystallinity increases (because of the nucleating effect of CNT on HDPE), however, at higher CNT content there is a dramatic reduction in crystallinity reflecting the increased confinement experienced by the HDPE chains at the interfaces which are extremely large in these nanocomposites. Another consequence of these strong interactions is the remarkable decrease in Avrami index as CNT content increases. When the Avrami index reduces to I or lower, nucleation dominates the overall kinetics as a consequence of confinement effects. Wide-angle X-ray experiments were performed at a high-energy synchrotron source and demonstrated that no change in the orthorhombic unit cell of HDPE occurred during crystallization with or without CNT.

Synthesis of NiO-MgO-ZrO(2) catalysts and their performance in reforming of model biogas

Catalysts containing NiO/MgO/ZrO(2) mixtures were synthesized by the polymerization method in a single step. They were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR) and physisorption of N(2) (BET) and then tested in the reforming of a model biogas (1.5CH4:1CO(2)) in the presence of air (1.5CH(4) + 1CO(2) + 0.25O(2)) at 750 degrees C for 6h. It was observed that the catalyst Ni20MZ performed better in catalytic processes than the well known catalysts, Ni/ZrO(2) and Ni/MgO, synthesized under the same conditions. The formation of solid solutions, MgO-ZrO(2) and NiO-MgO, increased the rate of conversion of reactants (CH(4) and CO(2)) into synthesis gas (H(2) + CO). The formation of oxygen vacancies (in samples containing ZrO(2) and MgO) seems to promote removal of the coke deposited on the nickel surface. The values of the H(2)/CO ratio were generally found to be slightly lower than stoichiometric, owing to the reverse water gas shift reaction occurring in parallel. (C) 2011 Elsevier B.V. All rights reserved.

Carbon dioxide reforming of ethanol over Ni/Y(2)O(3)-ZrO(2) catalysts

Supported nickel catalysts of composition Ni/Y(2)O(3)-ZrO(2) were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y(2)O(3)-ZrO(2) in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO(2) conversion of 61% on the 5NiYZ catalyst at 800 degrees C, representing a better response than for the catalyst of the same composition prepared by wet impregnation. (C) 2009 Published by Elsevier B.V.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

The influence of perhydroazepine and piperidine as further ancillary ligands on Ru-PPh(3)-based catalysts for ROMP of norbornene and norbornadiene

Polynorbornadiene and polynorbornene were synthesized via ring opening metathesis polymerization (ROMP) with [RuCl(2)(PPh(3))(2)(amine)] as catalyst precursors, amine = piperidine (1) or perhydroazepine (2) in the presence of 5 mu L of ethyl diazoacetate (EDA) ([monomer]/[Ru] = 5000; 40 degrees C with 1; 25 degrees C with 2). The effects of the solvent volume (2-8 mL of CHCl(3)) reaction time (5-120 min) and atmosphere type (argon and air) on the yields were investigated to observe the behavior of the two different precursors. Quantitative yields were obtained for 60 or 120 min regardless of the starting volumes, either in argon or air, with both Ru species. However, low yields were obtained for short times (5-30 min) when the reactions are performed with large volumes (6-8 mL). In argon, the yields were larger with 2, associated to a faster propagation reaction controlled by the Ru active species. In air, the yields were larger with 1, associated to a higher resistance to O(2) of the starting and propagating Ru species. The different activities between 1 and 2 are discussed considering the steric hindrance and electronic characteristics of the amines such as ancillary ligands and their arrangements with PPh(3) and Cl(-) ions in the metal centers. (c) 2009 Elsevier B.V. All rights reserved.

Copolimeros de propileno-etileno com baixos teores de etileno : estrutura, morfologia e propriedades

A estrutura básica predomínante encontrada em todos os copolímeros foi a de longos blocos de polipropileno cristalizáveis, separados por unidades isoladas de etileno, que atuaram como defeitos cristalínos, reduzindo o grau de cristalínidade, além da perfeição e da espessura dos cristais. O gradual aumento do teor de etileno nas amostras origínais, até aproximadamente5 moI % provocou redução progressiva no comprimento dos blocos de propileno em ambas as frações cristalizável e elastomérica. Acima daquela concentração, o etileno mostrou por principal efeito a elevação do teor de borracha de etileno-propileno(EPR), refletíndo-seem pronunciado aumento da resistência ao impacto dos copolímeros, com pouca alteração do comprimento das seqüências propiJênicas nas frações cristaJizáveJe elastomérica. A estrutura e a morfologia da borracha EPR gerada foram analisadas, observando-se sua excepcional dispersão na fase contínua cristalína. Análise das curvas de fusão por DSC, utilizando-se conceitos cínéticos, demonstrou a existência de uma energia de ativação aparente de fusão, associada à introdução de unidades etilênicas nas cadeias, e relacionada ao processo de fusão dos cristais poliméricos. A redução de cristalínidade das amostras e o aumento de mobilidade de cadeia da fase amorfa para teores crescentes de etileno resultaram em redução da rigidez dos copolímeros. Propriedades ópticas, como "haze" e brilho mostraram-se dependentesdo balanço entre o teor de cristais e o teor de borracha. Um balanço global das propriedades analisadas sugere uma composição ótima para aplicações típicas de copolímeros de propileno-etileno aquela com teores de etileno entre 4 e 6 moI % (aproximadamente 3 -4 % em massa).

DNA Psi-condensation and reentrant decondensation: Effect of the PEG degree of polymerization

psi-Condensation of DNA fragments of about 4 kbp was induced by poly(ethylene glycol) (PEG), with degrees of polymerization ranging from 45 to 182, and univalent salt (NaCl). Using circular dichroism spectroscopy, we were able to accurately determine the critical amount of PEG needed to induce condensation, as a function of the NaCl concentration. A significant dependence on the PEG degree of polymerization was found. Phase boundaries determined for the multimolecular condensation were very similar to those observed previously for the monomolecular collapse, with two asymptotic regimes at low and high salt concentrations. We analyze our data using a theoretical model that properly takes into account both the polyelectrolyte nature of the DNA and the liquid crystallinity of the condensed phase. The model assumes that all PEG is excluded from the condensates and shows reentrant decondensation only at low salt. We also systematically study reentrant decondensation and find a very strong dependence on PEG molecular weight. At low PEG molecular weight, decondensation occurs at relatively low concentrations of PEG, and over a wide range of salt concentrations. This suggests that in the reentrant decondensation the flexible polymers used are not completely excluded from the condensed phase.