Investigation of the effect of the preparation method on the activity and stability of Au/CeZrO4 catalysts for the low temperature water gas shift reaction

The impact of the preparation method on the activity and stability of gold supported on ceria-zirconia low temperature water-gas shift (WGS) catalysts have been investigated. The influence of the gold deposition method, nature of the gold precursor, nature of the washing solution, drying method, Ce: Zr ratio of the support and sulfation of the support have been evaluated. The highest activity catalysts were obtained using a support with a Ce: Zr mole ratio 1: 1, HAuCl4 as the gold precursor deposited via deposition precipitation using sodium carbonate as the precipitation agent and the catalyst washed with water or 0.1 M NH4OH solution. In addition, the drying used was found to be critical with drying under vacuum at room temperature found to be most effective.

Label-free detection of nanomolar unmodified single- and double-stranded dna by using surface-enhanced raman spectroscopy on Ag and Au colloids

Unlabelled single- and double-stranded DNA (ssDNA and dsDNA, respectively) has been detected at concentrations =10-9?M by surface-enhanced Raman spectroscopy. Under appropriate conditions the sequences spontaneously adsorbed to the surface of both Ag and Au colloids through their nucleobases; this allowed highly reproducible spectra with good signal-to-noise ratios to be recorded on completely unmodified samples. This eliminated the need to promote absorption by introducing external linkers, such as thiols. The spectra of model ssDNA sequences contained bands of all the bases present and showed systematic changes when the overall base composition was altered. Initial tests also showed that small but reproducible changes could be detected between oligonucleotides with the same bases arranged in a different order. The spectra of five ssDNA sequences that correspond to different strains of the Escherichia coli bacterium were found to be sufficiently composition-dependent so that they could be differentiated without the need for any advanced multivariate data analysis techniques.

Enhancing the Activity and Tuning the Mechanism of Formic acid Oxidation at Tetrahexahedral Pt Nanocrystals by Au Decoration

Tetrahexahedral Pt nanocrystals (THH Pt NCs), bound by high index facets, belong to an emerging class of nanomaterials that promise to bridge the gap between model and practical electrocatalysts. The atomically stepped surfaces of THH Pt NCs are extremely active for the electrooxidation of small organic molecules but they also readily accommodate the dissociative chemisorption of such species, resulting in poisoning by strongly adsorbed CO. Formic acid oxidation is an ideal reaction for studying the balance between these competing catalyst characteristics, since it can proceed by either a direct or a CO mediated pathway. Herein, we describe electrochemical and in situ FTIR spectroscopic investigations of formic acid electrooxidation at both clean and Au adatom modified THH Pt NC surfaces. The Au decoration leads to higher catalytic currents and enhanced CO2 production in the low potential range. As the CO oxidation behaviour of the catalyst is not changed by the presence of the Au, it is likely that the role of the Au is to promote the direct pathway. Beyond their fundamental importance, these results are significant in the development of stable, poison resistant anodic electrocatalysts for direct formic acid fuel cells.

La justice sociale dans la jurisprudence au Royaume-Uni

This chapter surveys the extent to which UK courts have developed the concept of social justice. It focuses on decisions reached in the areas of equality, welfare law, education, and health care, and concludes with a consideration of the extent to which UK judges consider that individuals should take personal responsibility for their own well-being.

Origin of the Increase of Activity and Selectivity of Nickel Doped by Au, Ag, and Cu for Acetylene Hydrogenation

Activity and selectivity are both important issues in heterogeneous catalysis and recent experimental results have shown that Ni catalysts doped by gold exhibit high activity for the hydrogenation of acetylene with good selectivity of ethylene formation. To unravel the underlying mechanism for this observation, the general trend of activity and selectivity of Ni surfaces doped by Au, Ag, and Cu has been investigated using density functional theory calculations. Complete energy profiles from C2H2 to C2H4 on Ni(111), Au/Ni(111), Ag/Ni(111) and Cu/Ni(111) are obtained and their turnover frequencies (TOFs) are computed. The results show that acetylene adsorption on Ni catalyst is strong which leads to the low activity while the doping of Au, Ag, and Cu on the Ni catalyst weakens the acetylene adsorption, giving rise to the increase of activity. The selectivity of ethylene formation is also quantified by using the energy difference between the hydrogenation barriers and the absolute value of the adsorption energies of ethylene. It is found that the selectivity of ethylene formation increases by doping Au and Ag, while those of Cu/Ni and Ni are similar.

Nana, Prostitution and the Textual Foundations of Zola’s 'Au Bonheur des Dames'

This article considers the textual forces operating in Au Bonheur des Dames, Zola's 1883 novel on modern commerce. It proposes that, with its echoes of the disorderly impulses that governed the infamous prostitute Nana earlier in the Rougon-Macquart cycle, coupled with its appreciation of the benefits of regulation, the dynamics of controlled and contained prostitution constitute the energy which fuels an efficient and successful business model in Au Bonheur des Dames. By closely analyzing both texts as well as Zola's preparatory documents, and borrowing from Genette's theories of intertextuality, this study reads Nana as a pre-historic hypotext, buried in the textual chantier from which the structure of Au Bonheur des Dames emerges.

Actively Tuned Plasmons on Elastomerically Driven Au Nanoparticle Dimers

We demonstrate a novel way to actively tune surface plasmons by fabricating plasmonic nanostructures on stretchable elastomeric films. This allows reversible modification of the metal geometry on the nanometer scale. Using 100 nm scale Au nanoparticle dimers whose spacing is stretch-tuned reveals radically different spectral tuning than previously reported for sub-10-nm nanoparticles, but which can be explained by a revised interpretation of existing models. Tuning plasmons in this way offers a much more robust way than lithography to interrogate the physics of localized plasmons and has applications in optimized surface-enhanced luminescence and Raman scattering.

Le survivant de la Shoah face au texte de fiction: un écran protecteur ou un écran projecteur? L’exemple d’Anna Langfus

La terminologie ‘écriture écran’ est souvent utilisée dans un sens proche de celui que lui donne Annie Ernaux lorsqu’elle écrit que ‘la fiction protège’ en permettant à un auteur de dire tout en gardant le lecteur à distance. Pourtant, de Blanchot à Genette, de nombreux critiques ont souligné que le texte est par essence un espace qui n’existe que dans et par cet échange, le lecteur – surtout dans le cas des textes de fiction – devant s’investir, se projeter dans le texte lu. Le texte de fiction serait-il donc un écran protecteur pour celui qui tient la plume et un écran projecteur pour celui qui tient le livre ? En nous basant principalement sur des textes de la psychanalyste Rachel Rosenblum et de l’auteure et survivante de la Shoah Anna Langfus, nous suggèrerons que, pour l’auteur comme pour le lecteur, le texte de fiction est à la fois un écran protecteur et un écran projecteur, ces deux fonctions étant étroitement liées et nullement contradictoires. Nous montrerons en effet qu’aucun genre n’est a priori protecteur puisque c’est l’acte de lecture ou d’écriture qui peut se transformer en morbide compulsion de répétition quand la mémoire d’un lecteur ou d’un auteur est devenue pathologique.

Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction

On-stream deactivation during a water gas shift (WGS) reaction over gold supported on a ceria-zirconia catalyst was examined. Although the fresh catalyst has very high low temperature (<200 degrees C) for WGS activity, a significant loss of CO conversion is found under steady-state operations over hours. This has been shown to be directly related to the concentration of water in the gas phase. The same catalyst also undergoes thermal deactivation above 250 degrees C, and using a combined experimental and theoretical approach, a common deactivation mechanism is proposed. In both cases, the gold nanoparticles, which are found under reaction conditions, are thought to detach from the oxide support either through hydrolysis, <200 degrees C, or thermally, > 200 degrees C. This process reduces the metal-support interaction, which is considered to be critical in determining the high activity of the catalyst.

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.

Resonant Rayleigh light scattering response of individual Au nanoparticles to antigen--antibody interaction

A proof-of-concept study was reported on analysis of antigen–antibody recognition based on resonant Rayleigh scattering response of single Au nanoparticles in an imaging chamber. As benefited by a traditional dark-field microscope and a spectrograph, individual Au nanoparticles (30 nm) were observed with high signal-to-noise ratio and they were effectively utilized to monitor changes in refractive index induced by specific binding of the adsorbates. Using PSA antigen as a model, a LSPR ?max shift of about 2.85 nm was recorded for a molecular binding corresponding to 0.1 pg ml-1 of the protein biomarker. This result successfully demonstrates a non-labeling detection system for proteins as well as thousands of different chemical or biological species, and it possesses a great potential as a sensitive, on-chip and multiplexing detection.