Ensemble effects in the coupling of acetylene to benzene on a bimetallic surface: A study with Pd{111}/Au

Acetylene coupling to benzene on the Pd(lll) surface is greatly enhanced by the presence of catalytically inert Au atoms. LEED and Auger spectroscopy show that progressive annealing of Au overlayers on Pd(lll) leads to the formation of a series of random surface alloys with continuously varying composition. Cyclization activity is a strong function of surface composition-the most efficient catalyst corresponds to a surface of composition similar to 85% Pd. CO TPD and HREELS data show that acetylene cyclization activity is not correlated with the availability of singleton Pd atoms, nor just with the presence of 3-fold pure Pd sites-the preferred chemisorption site for C2H2 on Pd{111}. The data can be quantitatively rationalized in terms of a simple model in which catalytic activity is dominated by Pd6Au and Pd-7 surface ensembles, allowance being made for the known degree to which pure Pd{111} decomposes the reactant and product molecules.

The water-gas shift reaction over CeO/CuO:Operando SSITKA-DRIFTS-mass spectrometry study of low temperature mechanism

An inverse CeO2/CuO catalyst has been investigated by operando steady-state isotopic transient kinetic analysis (SSITKA) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under 3% CO +3% H2O reactant mixture at 473 K with the aim of determining intermediates involved in the water gas shift reaction at relatively low temperatures. Among the various species detected in the infrared spectra which may be involved in the reaction, i.e. formates, copper carbonyls and carbonates, a particular type of carbonate species is identified as a reaction intermediate on the basis of detailed analysis of the spectra during isotopic exchange in comparison with the change in the corresponding isotopically labelled CO2 product. 

Critical role of water in the direct oxidation of CO and hydrocarbons in diesel exhaust after treatment catalysis

CO and C3H6 oxidation have been carried out in the absence and presence of water over a Pd/Al2O3catalyst. It is clear that water promotes CO and, as a consequence, C3H6oxidation takes place at muchlower temperatures compared with the dry feed. The significant increase in the catalyst’s activity withrespect to CO oxidation is not simply associated with changes in surface concentration as a result ofcompetitive adsorption effects. Utilising18O2as the reactant allows the pathways whereby the oxidationdue to gaseous dioxygen and where the water activates the CO and C3H6to be distinguished. In thepresence of water, the predominant pathway is via water activation with C16O2and C16O18O being themajor species formed and oxidation with dioxygen plays a secondary role. The importance of wateractivation is further supported by the significant decrease in its effect when using D2O versus H2O.

Dye adsorption onto mesoporous materials: PH influence, kinetics and equilibrium in buffered and saline media

Mesoporous materials were used as adsorbents for dye removal in different media: non-ionic, buffered and saline. The mesoporous materials used were commercial (silica gel) as well as as-synthesised materials (SBA-15 and a novel mesoporous carbon). Dye adsorption onto all the materials was very fast and the equilibrium was reached before 1h. The pH has a significant influence on the adsorption capacity for the siliceous materials since the electrostatic interactions are the driving forces. However, the influence of the pH on the adsorption capacity of the carbonaceous material was lower, since the van der Waals interactions are the driving forces. The ionic strength has a great impact on the siliceous materials adsorption capacity, being their adsorption capacity in a buffered medium six times higher than the corresponding to a non-ionic medium. Nevertheless, ionic strength does not influence on the dye adsorption on the mesoporous carbon. Overall, the as-synthesised carbon material presents a clear potential to treat dye effluents, showing high adsorption capacity (q_e≈200mg/g) in all the pH range studied (from 3 to 11); even at low concentrations (C_e≈10mg/L) and at short contact times (t_e<30min).

Origin of extraordinarily high catalytic activity of Co3O4 and its morphological chemistry for CO oxidation at low temperature

Understanding and then designing efficient catalysts for CO oxidation at low temperature is one of the hottest topics in heterogeneous catalysis. Among the existing catalysts. Co3O4 is one of the most interesting systems: Morphology-controlled Co3O4 exhibits exceedingly high activity. In this study, by virtue of extensive density functional theory (OFT) calculations, the favored reaction mechanism in the system is identified. Through careful analyses on the energetics of elementary reactions on Co3O4(1 1 0)-A, Co3O4(1 1 0)-B, Co3O4(1 1 1) and Co3O4(1 0 0), which are the commonly exposed surfaces of Co3O4, we find the following regarding the relation between the activity and structure: (i) Co3+ is the active site rather than Co2+: and (ii) the three-coordinated surface oxygen bonded with three Co3+ may be slightly more reactive than the other two kinds of lattice oxygen, that is, the two-coordinated 0 bonded with one Co2+ and one Co3+ and the three-coordinated 0 bonded with one Co2+ and two Co3+. Following the results from Co3O4, we also extend the investigation to MnO2(1 1 0), Fe3O4(1 1 0), CuO(1 1 0) and CuO(1 1 1), which are the common metal oxide surfaces, aiming to understand the oxides in general. Three properties, such as the CO adsorption strength, the barrier of CO reacting with lattice 0 and the redox capacity, are identified to be the determining factors that can significantly affect the activity of oxides. Among these oxides, Co3O4 is found to be the most active one, stratifying all the three requirements. A new scheme to decompose barriers is introduced to understand the activity difference between lattice O-3c and O-2c on (1 1 0)-B surface. By utilizing the scheme, we demonstrate that the origin of activity variance lies in the geometric structures. (C) 2012 Elsevier Inc. All rights reserved.

Structure and Catalytic Activity of Gold in Low-Temperature CO Oxidation

Structures and catalytic activities of Au thin films supported at anatase TiO(2)(101)) and a Au substrate are studied by using density functional theory calculations. The results show that O(2) can hardly adsorb at flat and stepped Au thin films, even supported by fully reduced TiO(2)(101) that can highly disperse Au atoms and offer strong electronic promotion. Interestingly, in both oxide-supported and pure Au. systems, wire-structured Au can adsorb both CO and O(2) rather strongly, and kinetic analysis suggests its high catalytic activity for low-temperature CO oxidation. The d-band center of Au at the catalytic site is determined to account for the unusual activity of the wire-structured film. A generalized structural model based on the wire-structured film is proposed for active Au, and possible support effects are discussed: Selected oxide surfaces can disperse Au atoms and stabilize the formation of a filmlike structure; they may also serve as a template for the preferential arrangement of Au atoms in a wire structure under low Au coverage.

A density functional theory study of CO and atomic oxygen chemisorption on Pt(111)

Ab initio total energy calculations within a density functional theory framework have been performed for CO and atomic oxygen chemisorbed on the Pt(111) surface. Optimised geometries and chemisorption energies for CO and O on four high-symmetry sites, namely the top, bridge, fee hollow and hcp hollow sites, are presented, the coverage in all cases being 0.25 ML. The differences in CO adsorption energies between these sites are found to be small, suggesting that the potential energy surface for CO diffusion across Pt(111) is relatively flat. The 5 sigma and 2 pi molecular orbitals of CO are found to contribute to bonding with the metal. Some mixing of the 4 sigma and 1 pi molecular orbitals with metal states is also observed. For atomic oxygen, the most stable adsorption site is found to be the fee hollow site, followed in decreasing order of stability by the hcp hollow and bridge sites, with the top site being the least stable. The differences in chemisorption energies between sites for oxygen are larger than in the case of CO, suggesting a higher barrier to diffusion for atomic oxygen. The co-adsorption of CO and O has also been investigated. Calculated chemisorption energies for CO on an O/fcc-precovered surface show that of the available chemisorption sites, the top site at the oxygen atom's next-nearest neighbour surface metal atom is the most stable, with the other four sites calculated bring at least 0.29 eV less stable. The trend of CO site stability in the coadsorption system is explained in terms of a 'bonding competition' model. (C) 2000 Elsevier Science B.V. All rights reserved.

ORBITAL MIXING IN CO CHEMISORPTION ON TRANSITION-METAL SURFACES

The chemisorption of CO on metal surfaces is widely accepted as a model for understanding chemical bonding between molecules and solid surfaces, but is nevertheless still a controversial subject. Ab initio total energy calculations using density functional theory with gradient corrections for CO chemisorption on an extended Pd{110} slab yield good agreement with experimental adsorption energies. Examination of the spatial distribution of individual Bloch states demonstrates that the conventional model for CO chemisorption involving charge donation from CO 5 sigma states to metal states and back-donation from metal states into CO 2 pi states is too simplistic, but the computational results provide direct insight into the chemical bonding within the framework of orbital mixing (or hybridisation). The results provide a sound basis for understanding the bonding between molecules and metal surfaces.

Qutting and restarting smoking: cohort study of patients with angina in primary care

Objective To examine variations in self-reported smoking habit among a cohort of individuals with chronic coronary heart disease over a five year period. Design Cross-sectional cohort; interviews at baseline, 2 years and 5 years. Setting Primary care. Participants A cross-sectional sample of 688 patients previously diagnosed as having angina, identified from 18 general practices in the Greater Belfast Area; a cohort of 487 were followed for five years. Outcome measures Changes in self-reported smoking habits; breath carbon monoxide measurement. Results Initially 92 of the 487 participants (19%) reported smoking, 34 (27%) subsequently reported non-smoking. Of the 395 self-reported non-smokers at baseline, 21 (5%) subsequently reported smoking. The prevalence of self-reported smoking amongst the cohort was 19% and 15% at two and five years respectively. However, changes in reported smoking habits indicating periods of abstinence and resumption were reported by 55/487 (11%) participants. Of the 21 non-smokers who changed their report, 20 had smoked previously, five reported having stopped for less than one year but nine for more than five years. Of the initial sample twice as many smokers as non-smokers had died by 2 years (10% v 5%; p

DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.

Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.

The structural characterization and hydroformylation activity of the tri-rhodium complex [Rh-3(mu(2)-dppm)(2)(mu(2)-CO)(3)(K-1-CO)(3)]BF4

Rh-2(cod)(2)(mu(2)-dppm)(mu(2)-Cl)]BF4 (1) rearranges under carbon monoxide to give [Rh-3(mu(2)-dppm)(2)-(mu(2)-CO)(3)(K-1-CO)(3)]BF4 (2). Complex 2 has been structurally characterized by single crystal X-ray crystallography. The hydroformylation activities of 1 and 2 were compared for substrates styrene and 1-hexene and the activity of 2 found to be unexpectedly high.

Extensive optical and near-infrared observations of the nearby, narrow-lined type Ic SN 2007gr: days 5 to 415

We present photometric and spectroscopic observations at optical and near-infrared wavelengths of the nearby type Ic supernova 2007gr. These represent the most extensive data-set to date of any supernova of this sub-type, with frequent coverage from shortly after discovery to more than one year post-explosion. We deduce a rise time to B-band maximum of 11.5 +/- 2.7 d. We find a peak B-band magnitude of M-B = -16.8, and light curves which are remarkably similar to the so-called "hypernova" SN 2002ap. In contrast, the spectra of SNe 2007gr and 2002ap show marked differences, not least in their respective expansion velocities. We attribute these differences primarily to the density profiles of their progenitor stars at the time of explosion i.e. a more compact star for SN 2007gr compared to SN 2002ap. From the quasi-bolometric light curve of SN 2007gr, we estimate that 0.076 +/- 0.010 M-circle dot of Ni-56 was produced in the explosion. Our near-infrared (IR) spectra clearly show the onset and disappearance of the first overtone of carbon monoxide (CO) between similar to 70 to 175 d relative to B-band maximum. The detection of the CO molecule implies that ionised He was not microscopically mixed within the carbon/oxygen layers. From the optical spectra, near-IR light curves, and colour evolution, we find no evidence for dust condensation in the ejecta out to about +400 d. Given the combination of unprecedented temporal coverage, and high signal-to-noise data, we suggest that SN 2007gr could be used as a template object for supernovae of this sub-class.

Antitumour prodrug development using cytochrome P450 (CYP) mediated activation

An ideal cancer chemotherapeutic prodrug is completely inactive until metabolized by a tumour-specific enzyme, or by an enzyme that is only metabolically competent towards the prodrug under physiological conditions unique to the tumour. Human cancers, including colon, breast, lung, liver, kidney and prostate, are known to express cytochrome P450 (CYP) isoforms including 3A and 1A subfamily members. This raises the possibility that tumour CYP isoforms could be a focus for tumour-specific prodrug activation. Several approaches are reviewed, including identification of prodrugs activated by tumour-specific polymorphic CYPs, use of CYP-gene directed enzyme prodrug therapy and CYPs acting as reductases in hypoxic tumour regions. The last approach is best exemplified by AQ4N, a chemotherapeutic prodrug that is bioreductively activated by CYP3A. This study shows that freshly isolated murine T50/80 mammary carcinoma and RIF-1 fibrosarcoma 4-electron reduces AQ4N to its cytotoxic metabolite, AQ4 (T50/80 K-m = 26.7 mu M, V-max = 0.43 mu M/mg protein/min; RIF-1 K-m = 33.5 mu M, V-max = 0.42 mu M/mg protein/min) via AQM, a mono-N-oxide intermediate (T50/80 K-m = 37.5 mu M; V-max = 1.4 mu M/mg protein/min; RIF-1 K-m = 37.5 mu M; V-max = 1.2 mu M/mg protein/min). The prodrug conversion was dependent on NADPH and inhibited by air or carbon monoxide. Cyp3A mRNA and protein were both present in T50/80 carcinoma grown in vivo (RIF-1 not measured). Exposure of isolated tumour cells to anoxia (2 h) immediately after tumour excision increased cyp3A protein 2-3-fold over a 12 h period, after which time the cyp protein levels returned to the level found under aerobic conditions. Conversely, cyp3A mRNA expression showed an initial 3-fold decrease under both oxic and anoxic conditions; this returned to near basal levels after 8-24 h. These results suggest that cyp3A protein is stabilized in the absence of air, despite a decrease in cyp3A mRNA. Such a 'stabilization factor' may decrease cyp3A protein turnover without affecting the translation efficiency of cyp3A mRNA. Confirmation of the CYP activation of AQ4N bioreduction was shown with human lymphoblastoid cell microsomes transfected with CYP3A4, but not those transfected with CYP2B6 or cytochrome P450 reductase. AQ4N is also reduced to AQ4 in NADPH-fortified human renal cell carcinoma (K-m = 4 mu M, V-max = 3.5 pmol/mg protein/min) and normal kidney (K-m = 4 mu M, V-max = 4.0 pmol/mg protein/min), both previously shown to express CYP3A. Germane to the clinical potential of AQ4N is that although both normal and tumour cells are capable of reducing AQ4N to its cytotoxic species, the process requires low oxygen conditions. Hence, AQ4N metabolism should be restricted to hypoxic tumour cells. The isoform selectivity of AQ4N reduction, in addition to its air sensitivity, indicates that AQ4N haem coordination and subsequent oxygen atom transfer from the active-site-bound AQ4N is the likely mechanism of N-oxide reduction. The apparent increase in CYP3A expression under hypoxia makes this a particularly interesting application of CYPs for tumour-specific prodrug activation.