Polymer-supported l-prolinol-based catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines

l-Prolinol-based ligands anchored to Merrifield or Wang-type resins have been shown to form efficient catalysts for the enantioselective addition of dialkylzinc reagents to N-(diphenylphosphinyl)imines. The enantioselectivity achieved with the polymeric catalyst (ee up to 88%) is slightly lower than the one obtained with the homogeneous ligand N-benzyl-l-prolinol, but the polymer-supported ligand presents the advantage of its recyclability: it can be recovered and used in up to six consecutive catalytic cycles with only a slight decrease in the enantiomeric excess. The phosphinamides obtained as addition products can be transformed into the corresponding enantiomerically enriched α-branched primary amines under mild acidic conditions.

Catalytic role of pre-adsorbed CO in platinum-based catalysts : the reduction of SO 2 by CO on Pt l Au m (CO) n

Using density functional theory, we have investigated the catalytic properties of bimetallic complex catalysts PtlAum(CO)n (l + m = 2, n = 1–3) in the reduction of SO2 by CO. Due to the strong coupling between the C-2p and metal 5d orbitals, pre-adsorption of CO molecules on the PtlAum is found to be very effective in not only reducing the activation energy, but also preventing poisoning by sulfur. As result of the coupling, the metal 5d band is broadened and down-shifted, and charge is transferred from the CO molecules to the PtlAum. As SO2 is adsorbed on the catalyst, partial charge moves to the anti-σ bonding orbitals between S and O in SO2, weakening the S–O bond strength. This effect is enhanced by pre-adsorbing up to three CO molecules, therefore the S–O bonds become vulnerable. Our results revealed the mechanism of the excellent catalytic properties of the bimetallic complex catalysts.

Partial oxidation of ethane to syngas over nickel-based catalysts modified by alkali metal oxide and rare earth metal oxide

The catalytic activity, thermal stability and carbon deposition of various modified NiO/gamma-Al2O3 and unmodified NiO/gamma-Al2O3 catalysts were investigated with a flow reactor, XRD, TG and UVRRS analysis. The activity and selectivity of the NiO/gamma-Al2O3 catalyst showed little difference from those of the modified nickel-based catalysts. However, modification with alkali metal oxide (Li, Na, K) and rare earth metal oxide (La, Ce, Y, Sm) can improve the thermal stability of the NiO/gamma-Al2O3 and enhance its ability to suppress carbon deposition during the partial oxidation of ethane (POE). The carbon deposition contains graphite-like species that were detected by UVRRS. The nickel-based catalysts modified by alkali metal oxide and rare earth metal oxide have excellent catalytic activities (C2H6 conversion of similar to 100%, CO selectivity of similar to 94%, 7x 10(4) l/(kg h), 1123 K), good thermal stability and carbon-deposition resistance.

The formation of Co2C species in activated carbon supported cobalt-based catalysts and its impact on Fischer-Tropsch reaction

The cobalt carbide (Co2C) species was formed in some activated carbon supported cobalt-based (Co/AC) catalysts during the activation of catalysts. It was found that the activity of Fischer-Tropsch reaction over Co-based catalysts decreased due to the formation of cobalt carbide species. Some promoters and pretreatment of activated carbon with steam could restrain the formation of cobalt carbide.

The effect of SO2 on the activity of Pd-based catalysts in methane combustion

The effect of SO2 on Pd-based catalysts for the combustion of methane has been investigated. It is shown that while SO2 poisons Al2O3- and SiO2-supported catalysts. pre-treatment of Pd/ZrO2 by SO2 enhances the activity substantially.

Catalytic hydrogenation of tertiary amides at low temperatures and pressures using bimetallic Pt/Re-based catalysts

Hydrogenation of tertiary amides, in particular, N-methylpyrrolidin-2-one, can be efficiently facilitated by a TiO(2)-supported bimetallic Pt/Re catalyst at low temperatures and pressures. Characterisation of the catalysts and kinetic tests have shown that the close interaction between the Re and Pt is crucial to the high activity observed. DFT calculations were used to examine a range of metal combinations and show that the role of the uncoordinated Re is to activate the C=O and that of the Pt is as a hydrogenation catalyst, removing intermediates from the catalyst surface. The rate enhancement observed on the TiO(2) support is thought to be due to the presence of oxygen vacancies allowing adsorption and weakening of the C=O bond. (C) 2011 Elsevier Inc. All rights reserved.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO2-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, Cu-63 nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO2 catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO2 at 120 degrees C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO2 at 140 degrees C, corresponding to an initial reaction rate of 104 mmol g(cat)(-1) s(-1). The activation energy on the Cu/mesoporous TiO2 catalyst was found to be (144 +/- 5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123 +/- 3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO2 support (75 +/- 2 kJ mol(-1)).

Effect of solvent on the hydrogenation of 4-phenyl-2-butanone over Pt based catalysts

The hydrogenation of 4-phenyl-2-butanone over Pt/TiO2 and Pt/SiO2 catalysts has been performed in a range of solvents and it has been observed that the solvent impacted on the selectivity of ketone and aromatic ring hydrogenation as well as the overall TOF of the titania catalyst with no solvent effect on selectivity observed using the silica supported catalyst where ring hydrogenation was favored. For the titania catalyst, alkanes were found to favor ring hydrogenation whereas aromatics and alcohols led to carbonyl hydrogenation. A two-site catalyst model is proposed whereby the aromatic ring hydrogenation occurs over the metal sites while carbonyl hydrogenation is thought to occur predominantly at interfacial sites, with oxygen vacancies in the titania support activating the carbonyl. The effect of the solvent on the hydrogenation reaction over the titania catalyst was related to competition for the active sites between solvent and 4-phenyl-2-butanone.

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.

Stability of clay-based catalysts in contact with water vapour

The search for cleaner processes is one of the major challenges in modern chemical industries. In this context clay derived materials are environmentally friendly catalysts that can be easily tailored to optimize their catalytic activity for a precise reaction of interest. Furthermore, clay-based catalysts can be easily separated, recovered and reused and their versatility, low cost, high catalytic activity and/or selectivity render them very attractive materials. Considering that the stability towards water vapour is a crucial aspect for catalytic performance and reuse of the catalysts, we present a study of the pore structure stability, in the presence of water vapour, of clay catalysts prepared by acid activation with HCl solutions and ion-exchange with sodium, aluminium and iron, from a natural clay collected at Serra de Dentro (Porto Santo Island, Portugal) [1]. For elucidating the influence of water vapour on the pore structure stability, water vapour adsorption- -desorption isotherm, at 298 K, was determined on each sample by gravimetric method as well as n-pentane adsorption−desorption isotherms, at 298 K, which were determined before and after the corresponding water adsorption-desorption isotherms. Prior to the measurements, the samples were outgassed during 5 h at 473 K and the adsorptives were outgassed by repeated freeze–thaw cycles. The results to be reported in the communication allow us to state that, upon contact with water vapour, the less acid activated catalysts suffered some reduction in pore volume reflecting changes in the pore structure, while the more acid activated catalysts and those prepared by ion-exchange presented excellent stability upon one cycle of water vapour adsorption-desorption. The results are corroborated by nitrogen adsorption-desorption isotherms determined, at 77 K, before and after the water and n-pentane adsorption-desorption measurements.