Pretreatment Effect on Pt/CeO2 Catalyst in the Selective Hydrodechlorination of Trichloroethylene

Pt-ceria catalysts present different surface chemistries depending on the preparation method and the pretreatment. The catalytic behavior of Pt/CeO2 catalysts in the hydrodechlorination of trichloroethylene (TCE) to ethylene was examined as a function of the pretreatment conditions and the noble metal precursor salts. Using FTIR and X-ray photoelectron spectroscopy, significant differences were observed in the surface properties of Pt/CeO2 prepared from the H2PtCl6 precursor after different pretreatment procedures (i.e.. reduction or oxidation-reduction). These surface changes are related to chloride residues from the synthesis. Strong changes were observed in the selectivity of the catalysts to ethylene depending on the pretreatment conditions. The 0.5%Pt/CeO2 catalyst showed a 13% selectivity toward ethylene after reduction, whereas alter oxidation, followed by reduction, the selectivity increased up to 85% at the same conversion level. This effect was only observed when a chloride-containing precursor was used in the preparation. In this way, it is demonstrated that the use of a Cl-containing Pt precursor and an air treatment prior to reduction strongly improves the ethylene selectivity of Pt-CeO2 dechlorination catalysts. This can be explained by formation or a CeOCl phase during the synthesis that decomposes upon air tempering, producing oxygen vacancies on the ceria support. We propose that these oxygen vacancies are active for cleaving off Cl from the TCE. Pt then supplies II to clean-off Cl as HCl. Reaction of TCE on Pt produces rather ethane, so Pt may be partly Cl-poisoned for the hydrodechlorination reaction but not for II, dissociation or CO adsorption.

Dinitrogen formation over low-exchanged Cu-ZSM-5 in the selective reduction of NO by propane

The role of gaseous NO and C3H8 has been studied over low-exchanged Cu-ZSM-5 zeolite employing TPD, FTIR and pulse technique with the alternate introduction of NO or C3H8 onto the catalyst surface. The rate of the N-2 formation is directly proportional to the content of gaseous NO and the surface coverage with 2-nitrosopropane. There was no formation of N-2 during interaction of gaseous C3H8 with NO adsorbates. However, 2-nitrosopropane and its isomer acetone oxime were also formed in this reaction.

Catalytic performance of sheet-like Fe/ZSM-5 zeolites for the selective oxidation of benzene with nitrous oxide

Hierarchical Fe/ZSM-5 zeolites were synthesized with a diquaternary ammonium surfactant containing a hydrophobic tail and extensively characterized by XRD, Ar porosimetry, TEM, DRUV-Vis, and UV-Raman spectroscopy. Their catalytic activities in catalytic decomposition of NO and the oxidation of benzene to phenol with NO as the oxidant were also determined. The hierarchical zeolites consist of thin sheets limited in growth in the b-direction (along the straight channels of the MFI network) and exhibit similar high hydrothermal stability as a reference Fe/ZSM-5 zeolite. Spectroscopic and catalytic investigations point to subtle differences in the extent of Fe agglomeration with the sheet-like zeolites having a higher proportion of isolated Fe centers than the reference zeolite. As a consequence, these zeolites have a somewhat lower activity in catalytic NO decomposition (catalyzed by oligomeric Fe), but display higher activity in benzene oxidation (catalyzed by monomeric Fe). The sheet-like zeolites deactivate much slower than bulk Fe/ZSM-5, which is attributed to the much lower probability of secondary reactions of phenol in the short straight channels of the sheets. The deactivation rate decreases with decreasing Fe content of the Fe/ZSM-5 nanosheets. It is found that carbonaceous materials are mainly deposited in the mesopores between the nanosheets and much less so in the micropores. This contrasts the strong decrease in the micropore volume of bulk Fe/ZSM-5 due to rapid clogging of the continuous micropore network. The formation of coke deposits is limited in the nanosheet zeolites because of the short molecular trafficking distances. It is argued that at high Si/Fe content, coke deposits mainly form on the external surface of the nanosheets. © 2012 Elsevier Inc. All rights reserved.

Facet-Dependent Catalytic Activity of Platinum Nanocrystals for Triiodide Reduction in Dye-Sensitized Solar Cells

Platinum (Pt) nanocrystals have demonstrated to be an effective catalyst in many heterogeneous catalytic processes. However, pioneer facets with highest activity have been reported differently for various reaction systems. Although Pt has been the most important counter electrode material for dye-sensitized solar cells (DSCs), suitable atomic arrangement on the exposed crystal facet of Pt for triiodide reduction is still inexplicable. Using density functional theory, we have investigated the catalytic reaction processes of triiodide reduction over {100}, {111} and {411} facets, indicating that the activity follows the order of Pt(111) > Pt(411) > Pt(100). Further, Pt nanocrystals mainly bounded by {100}, {111} and {411} facets were synthesized and used as counter electrode materials for DSCs. The highest photovoltaic conversion efficiency of Pt(111) in DSCs confirms the predictions of the theoretical study. These findings have deepened the understanding of the mechanism of triiodide reduction at Pt surfaces and further screened the best facet for DSCs successfully.

Theoretical Study of Heteroatom Doping in Tuning the Catalytic Activity of Graphene for Triiodide Reduction

Graphene with heteroatom doping has found increasing applications in a broad range of catalytic reactions. However, the doping effects accounting for the enhanced catalytic activity still remain elusive. In this work, taking the triiodide electroreduction reaction as an example, we study systematically the intrinsic activity of graphene and explore the origin of doping-induced activity variation using first-principles calculations, in which two typical N and S dopants are tested. The most common graphene structures, basal plane, armchair edge, and zigzag edge, are considered, and it is found that the former two structures show a weak adsorption ability for the iodine atom (the key intermediate in the triiodide electroreduction reaction), corresponding to a low catalytic activity. Doping either N or S can strengthen the adsorption and thus increase the activity, and the codoping of N and S (NS-G) exhibits a synergistic effect. A detailed investigation into the whole process of the triiodide electroreduction reaction at the CH3CN/NS-G interface is also carried out to verify these activity trends. It is found that the zigzag edges which contain spin electrons show a relatively stronger adsorption strength compared with the basal plane and armchair edge, and initial doping would result in the spin disappearance that evidently weakens the adsorption; with the disappearance of spin, however, further doping can increase the adsorption again, suggesting that the spin electrons may play a preliminary role in affecting the intrinsic activity of graphene. We also analyzed extensively the origin of doping-induced adsorption enhancement of graphene in the absence of spin; it can be rationalized from the electronic and geometric factors. Specifically, N doping can result in a more delocalized “electron-donating area” to enhance I adsorption, while S doping provides a localized structural distortion, which activates the nearest sp2-C into coordinatively unsaturated sp3-C. These results explain well the improved activity of the doping and the synergistic effect of the codoping. The understandings are generalized to provide insight into the enhanced activity of the oxygen reduction reaction on heteroatom doped graphene. This work may be of importance toward the design of high-activity graphene based material.

Heterogeneously catalysed selective hydrogenation reactions in ionic liquids

The selective hydrogenation of , unsaturated aldehydes has been performed in a range of room temperature ionic liquids. The reaction data reported show that it is possible to enhance the selectivity of supported palladium catalysts for the reduction of the conjugated CC bond by using ionic liquids as solvents compared with conventional molecular organic solvents. The catalyst system is easily recycled without the need to isolate or filter the catalyst and may be used without further treatment.

Differential expression of components of the cardiomyocyte adrenomedullin/intermedin receptor system following blood pressure reduction in nitric oxide-deficient hypertension.

Adrenomedullin (AM) and intermedin (IMD; adrenomedulln-2) are vasodilator peptides related to calcitonin gene-related peptide (CGRP). The actions of these peptides are mediated by the calcitonin receptor-like receptor (CLR) in association with one of three receptor activity-modifying proteins. CGRP is selective for CLR/receptor activity modifying protein (RAMP)1, AM for CLR/RAMP2 and -3, and IMD acts at both CGRP and AM receptors. In a model of pressure overload induced by inhibition of nitric-oxide synthase, up-regulation of AM was observed previously in cardiomyocytes demonstrating a hypertrophic phenotype. The current objective was to examine the effects of blood pressure reduction on cardiomyocyte expression of AM and IMD and their receptor components. Nomega-nitro-L-arginine methyl ester (L-NAME) (35 mg/kg/day) was administered to rats for 8 weeks, with or without concurrent administration of hydralazine (50 mg/kg/day) and hydrochlorothiazide (7.5 mg/kg/day). In left ventricular cardiomyocytes from L-NAME-treated rats, increases (-fold) in mRNA expression were 1.6 (preproAM), 8.4 (preproIMD), 3.4 (CLR), 4.1 (RAMP1), 2.8 (RAMP2), and 4.4 (RAMP3). Hydralazine/hydrochlorothiazide normalized systolic blood pressure (BP) and abolished mRNA up-regulation of hypertrophic markers sk-alpha-actin and BNP and of preproAM, CLR, RAMP2, and RAMP3 but did not normalize cardiomyocyte width nor preproIMD or RAMP1 mRNA expression. The robust increase in IMD expression indicates an important role for this peptide in the cardiac pathology of this model but, unlike AM, IMD is not associated with pressure overload upon the myocardium. The concordance of IMD and RAMP1 up-regulation indicates a CGRP-type receptor action; considering also a lack of response to BP reduction, IMD may, like CGRP, have an anti-ischemic function.

LPCVD of tungsten by selective deposition on silicon

Beta-phase W, selectively grown at 440C had resistivity 20 micro-ohm cm and maximum layer thickness 100nm. Hydrogen passivation proved essential in this process. Higher deposition temperatures resulted in increased layer thickness but incorporated WSi2 and alpha- phase W. Self limiting W grown on polycrystalline and heavily doped silicon yielded reduced thickness. Boron is involved in the WF6 reduction reaction but phosphorus is not and becomes incorporated in the W layer. The paper establishes an optimised and novel CVD process suited to IC contact technology. A funded technology transfer contract with National Semiconductor Greenock (M Fallon) resulted from this work.

CO oxidation and NO reduction on metal surfaces: density functional theory investigations

This article reviews the accumulated theoretical results, in particular density functional theory calculations, on two catalytic processes, CO oxidation and NO reduction on metal surfaces. Owing to their importance in automotive emission control, these two reactions have generated a lot of interest in the last 20 years. Here the pathways and energetics of the involved elementary reactions under different catalytic conditions are described in detail and the understanding of the reactions is generalized. It is concluded that density functional theory calculations can be applied to catalysis to elucidate mechanisms of complex surface reactions and to understand the electronic structure of chemical processes in general. The achieved molecular knowledge of chemical reactions is certainly beneficial to new catalyst design.

The catalytic role of water in CO oxidation

Water, one of the most popular species in our planet, can play a catalytic role in many reactions, including reactions in heterogeneous catalysis. In a recent experimental work, Bergeld, Kasemo, and Chakarov demonstrated that water is able to promote CO oxidation under low temperatures (similar to200 K). In this study, we choose CO oxidation on Pt(111) in the presence of water as a model system to address the catalytic role of water for surface reactions in general using density functional theory. Many elementary steps possibly involved in the CO oxidation on Pt(111) at low temperatures have been investigated. We find the following. First, in the presence of water, the CO oxidation barrier is reduced to 0.33 eV (without water the barrier is 0.80 eV). This barrier reduction is mainly due to the H-bonding between the H in the H2O and the O at the transition state (TS), which stabilizes the TS. Second, CO can readily react with OH with a barrier of 0.44 eV, while COOH dissociation to produce CO2 is not easy (the barrier is 1.02 eV). Third, in the H2O+OH mixed phase, CO can be easily converted into CO2. It occurs through two steps: CO reacts with OH, forming COOH; and COOH transfers the H to a nearby H2O and, at the same time, an H in the H2O transfers to a OH, leading to CO2 formation. The reaction barrier of this process is 0.60 eV under CO coverage of 1/6 ML and 0.33 eV under CO coverage of 1/3 ML. The mechanism of CO oxidation at low temperatures is discussed. On the basis of our calculations, we propose that the water promotion effect can in general be divided into two classes: (i) By H-bonding between the H of H2O and an electron negative species such as the O in the reaction of CO+O+H2O-->CO2+H2O, H2O can stabilize the TS of the reaction and hence reduce the barrier. (ii) H2O first dissociates into H and OH and then OH or H participates directly in the reaction to induce new reaction mechanism with more favorable routes, in which OH or H can act as an intermediate. (C) 2003 American Institute of Physics.

Steric effects in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol using an Ir/C catalyst

The liquid phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol has been carried out over a graphite-supported iridium catalyst. The effect of reaction parameters such as temperature, pressure, concentration of reactant, the effect of addition of product to the feed and pre-reduction of the catalyst were studied. In situ pre-reduction of the catalyst with hydrogen had a very significant enhancing effect on the conversion of cinnamaldehyde and selectivity of the catalyst to cinnamyl alcohol. Kinetic analysis of the pre-reduced catalyst showed that the reaction is zero order with respect to cinnamaldehyde and first order with respect to hydrogen. The reaction follows an Arrhenius behaviour with an activation energy of 37 kJ mol(-1). Detailed analysis of the reaction showed that hydrogenation of the C=C double bond to give hydrocinnamaldehyde predominantly occurred at low conversions of cinnamaldehyde (

On the Sphere Decoder for Frequency-Selective MIMO channels

This paper compares the complexity of the sphere decoder (SD) and a previously proposed detection scheme, denoted here as block SD (BSD), when they are applied to the detection of multiple-input multiple-output (MIMO) systems in frequency-selective channels. The complexity of both algorithms depends on their preprocessing and tree search stages. Although the BSD was proposed as a means of greatly reducing the complexity of the preprocessing stage of the SD, no study was done on how the complexity of the tree search stage could be affected by that reduced preprocessing stage. This paper shows, both analytically and through simulation, that the reduction in preprocessing complexity provided by the BSD has the side effect of increasing the complexity of its tree search stage compared to that of the SD, independent of the signal-to-noise ratio (SNR). In addition, this paper shows how sorting the columns of the frequency-selective channel matrix in the SD does not reduce the complexity of the tree search stage, contrary to what occurs in frequency-flat channels.

A modified Tat peptide for selective intracellular delivery of macromolecules

Objectives The Tat peptide has been widely used for the intracellular delivery of macromolecules. The aim of this study was to modify the peptide to enable regulation of cellular uptake through a dependency on activation by proteases present in the local environment.

Methods The native Tat peptide sequence was altered to inhibit the initial interaction of the peptide with the cell membrane through the addition of the consensus sequence for urokinase plasminogen activator (uPA). uPA expression was characterised and semi-quantitatively rated in three cell lines (U251mg, MDA-MB-231 and HeLa). The modified peptide was incubated with both recombinant enzyme and with cells varying in uPA activity. Cellular uptake of the modified Tat peptide line was compared with that of the native peptide and rated according to uPA activity measured in each cell line.

Key findings uPA activity was observed to be high in U251mg and MDA-MB-231 and low in HeLa. In MDA-MB-231 and HeLa, uptake of the modified peptide correlated with the level of uPA expression detected (93 and 52%, respectively). In U251mg, however, the uptake of the modified peptide was much less (19% observed reduction) than the native peptide despite a high level of uPA activity detected.

Conclusions Proteolytic activation represents an interesting strategy for the targeted delivery of macromolecules using peptide-based carriers and holds significant potential for further exploitation.

ZnO based nanowires grown by chemical vapour deposition for selective hydrogenation of acetylene alcohols

Vertically aligned ZnO nanowires (NWs) with a length of 1.5-10 mu m and a mean diameter of ca. 150 nm were grown by chemical vapour deposition onto a c-oriented ZnO seed layer which was deposited by atomic layer deposition on Si substrates. The substrates were then spin-coated with an ethanol solution containing Pd nanoparticles with an average size of 2.7 and 4.5 nm. A homogeneous distribution of the Pd nanoparticles on ZnO NWs has been obtained using both Pd particle series. The catalytic activity of the ZnO NWs and Pd/ZnO NWs catalysts was measured in the semihydrogenation of 2-methyl-3-butyn-2-ol at 303-343 K and a pressure of 2-10 bar. The effect of the solvent used on the catalytic performance of the Pd/ZnO NWs catalyst was studied. The Pd/ZnO catalysts showed alkene selectivity of up to 95% at an alkyne conversion of 99%. A kinetic model is proposed to explain the activity and selectivity of the ZnO support and Pd/ZnO catalysts.