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.

Origin of Low CO2 Selectivity on Platinum in the Direct Ethanol Fuel Cell

Calculated answer: First-principles calculations have been applied to calculate the energy barrier for the key step in CO formation on a Pt surface (see picture; Pt blue, Pt atoms on step edge yellow) to understand the low CO2 selectivity in the direct ethanol fuel cell. The presence of surface oxidant species such as O (brown bar) and OH (red bar) led to an increase of the energy barrier and thus an inhibition of the key step. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Bridging the Gap between CO Adsorption Studies on Gold Model Surfaces and Supported Nanoparticles

A happy medium: Volumetric adsorption of carbon monoxide at 308 K and UHR-HAADF-STEM, HREM, and computer modeling techniques were compared. Experimental CO/Au ratios at saturation coverage for two supported gold catalysts were shown to fit very well the predictions of a nanostructural model that considers CO adsorption on gold sites with coordination numbers of less than eight.

PROTONATED HCN IN MOLECULAR CLOUDS

Observations of protonated HCN (HCNH+) in a selection of galactic molecular clouds are reported. This species plays a key role in understanding the chemistry of the important high density tracer HCN. HCNH+ has been detected in the nearby cold dust cloud TMC-1 with an ratio relative to HCN of [HCNH+]/[HCN] between 0.015 and 0.26 (preferred value 0.03) and tentatively in DR21(OH) with a ratio of approximately 0.01. This is about 100 times higher than the ratio of protonated carbon monoxide to CO [HCO+]/[CO], but comparable to the [HCS+]/[CS] ratio. Possible explanations of these high abundance ratios are discussed in the light of model calculations.

Performance and characteristics of platinum, palladium/rhodium and palladium automotive catalysts when subjected to ethanol, acetaldehyde and a synthetic E85 exhaust gas mixture

The performance optimisation of automotive catalysts has been the focus of a great deal of research for many years as the automotive industry has endeavored to reduce the emission of toxic and pollutant gases generated from internal combustion engines. Just as the emissions from diesel and gasoline combustion vary so do the emissions from combustion of alternative fuels such as ethanol; the variation is in both quantity and chemical composition. In particular, when ethanol is contained in the fuel, ethanol and acetaldehyde are present in the exhaust gas stream and these are two compounds which the catalytic converter has not traditionally been designed to manage. The aim of the study outlined in this paper was to assess the performance of various catalyst formulations when subjected to a representative ethanol exhaust gas mixture. Three automotive catalytic converter formulations were tested including a fully Pt sample, a PdRh three-way catalyst sample and a fully Pd sample. Initially the samples were tested using single component hydrocarbon light-off tests followed by a set of tests with carbon monoxide included as an inlet gas to observe its effect on each individual hydrocarbon oxidation. Finally, each formulation was tested using a full E85 exhaust gas mixture. The study was carried out using a synthetic gas reactor along with FTIR and FID exhaust gas analysers. All formulations showed selectivity toward acetaldehyde formation from ethanol dehydrogenation which resulted in negative acetaldehyde conversion across each of the samples during the mixture tests. The fully Pt sample was the most detrimentally affected by the introduction of carbon monoxide into the gas feed. The Pd and PdRh samples exhibited a tendency toward acetaldehyde decomposition resulting in methane and carbon monoxide formation. The Pt sample did not form methane but did form ethylene as a result of ethanol dehydration.

Low-pressure solubilities and thermodynamics of solvation of eight gases in 1-butyl-3-methylimidazolium hexafluorophosphate

Experimental values for the solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon and carbon monoxide in 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6] - a room temperature ionic liquid - are reported as a function of temperature between 283 and 343 K and at pressures close to atmospheric. Carbon dioxide is the most soluble and hydrogen is the least soluble of the gases studied with mole fraction solubilities of the order of 10-2 and 10-4, respectively. All the mole fraction solubilities decrease with temperature except for hydrogen for which a maximum is observed at temperatures close to 310 K. From the variation of solubility, expressed as Henry's law constants, with temperature, the partial molar thermodynamic functions of solvation such as the standard Gibbs energy, the enthalpy, and the entropy are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is better than ±1%. © 2005 Elsevier B.V. All rights reserved.

Regulation of erythropoietin gene expression depends on two different oxygen-sensing mechanisms

Erythropoietin (Epo), a glycoprotein hormone produced principally in the fetal kidney and in the adult liver in response to hypoxia, is the prime regulator of growth and differentiation in erythroid progenitor cells. The regulation of Epo gene expression is not fully understood, but two mechanisms have been proposed. One involves the participation of a heme protein capable of reversible oxygenation and the other depends on the intracellular concentration of reactive oxygen species (ROS), assumed to be a function of pO2. We have investigated the production of Epo in response to three stimuli, hypoxia, cobalt chloride, and the iron chelator desferrioxamine, in Hep3B cells. As expected, hypoxia caused a marked rise in Epo production. When the cells were exposed to the paired stimuli of hypoxia and cobalt no further increase was found. In contrast, chelation of iron under hypoxic conditions markedly enhanced Epo production, suggesting that the two stimuli act by separate pathways. The addition of carbon monoxide inhibited hypoxia-induced Epo production, independent of desferrioxamine concentration. Taken together these data support the concept that pO2 and ROS are sensed independently.

Combined studies of DFT atomistic modelling and in situ FTIR spectroscopy on surface oxidants and CO oxidation at Ru electrodes

We report the combined studies of density functional theory (DFT) calculations and electrochemical in situ FTIR spectroscopy on surface oxidants and mechanisms of CO oxidation at the Ru(0001) electrodes. It is shown that CO can co-adsorb with both O and OH species at lower potential region where a low coverage of the (2 x 2)-O/OH adlayer formed; the oxidation of CO adsorbates takes place at higher potentials where a high coverage of the (1 x 1)-O/OH adlayer formed. Surface O species are not the active oxidants under all coverages studied, due to the high reaction barriers between CO and O (>1 eV). However, surface OH species with higher coverage are identified as the active oxidants, and CO oxidation takes place via a two-steps' mechanism of CO + 3OH -> COOH + 2OH -> CO2 + H2O + OH, in which three nearby OH species are involved in the CO2 formation: CO reacts with OH, forming COOH; COOH then transfers the H to a nearby OH to form H2O and CO2, at the same time, another H in the H2O transfers to a nearby OH to form a weak adsorbed H2O and a new OH. The reaction barrier of these processes is reduced significantly to around 0.50 eV. These new results not only provide an insight into surface active oxidants on Ru, which is directly relevant to fuel cell catalysis, but also reveals the extra complexity of catalytic reactions taking place at solid/liquid electrochemical interface in comparison to the relatively simpler ones at solid/gas phase. 

Time-Resolved DRIFTS, MS, and Resistance Study of SnO2 Materials: The Role of Surface Hydroxyl Groups in Formation of Donor States

Time-resolved DRIFTS, MS, and resistance measurements were used to study the interaction of undoped and Pd-doped SnO2 with H-2 in air and argon at 300 degrees C. Using first-order kinetics, we compare the time constants for the resistance drop and its partial recovery with those of the surface hydroxyl evolution and water formation in the gas phase upon exposure to hydrogen. In the case of the undoped oxide, resistance and bridging hydroxyls (BOHs) evolve similarly, manifesting a fast main drop followed by recovery at a similar rate. The rate of water formation for this material was found to be much slower than that of the main drop in both the resistance and BOHs. In contrast, the resistance change for SnO2-Pd appeared to be similar to that of water formation, and no correlation was found between the evolution of resistance and surface OHs. Isotopic exchange on both materials revealed that water formation occurs via fast and slow hydrogen transfer to surface oxygen species. While the former originates from just-adsorbed hydrogen, the latter appears to proceed from the preadsorbed OHs. Both surfaces exhibit close interaction between chemisorbed oxygen and existing bridging OH groups, indicating that the latter is an intermediate in the hydrogen oxidation and generation of donor states on the surface.

A spectroscopic study of the chemistry and reactivity of SO2 on Pt{111}: Reactions with O-2, CO and C3H6

The chemisorption and reactivity of SO2 on Pt{111} have been studied by HREELS, XPS, NEXAFS and temperature-programmed desorption. At 160 K SO2 adsorbs intact at high coverages, with eta(2) S-O coordination to the surface. On annealing to 270 K, NEXAFS indicates the SO2 molecular plane essentially perpendicular to the surface. Preadsorbed O-a reacts with SO2 to yield adsorbed SO4, identified as the key surface species responsible for SO2-promoted catalytic alkane oxidation. Coadsorbed CO or propene efficiently reduce SO2 overlayers to deposit S-a, and the implications of this for catalytic systems are discussed.

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.