Reactions of ethanol over CeO2 and Ru/CeO2 catalysts

The reaction of ethanol has been investigated on Ru/CeO2 in steady state conditions as well as with temperature programmed desorption (TPD). High resolution transmission electron microscopy (HRTEM) images indicated that the used catalyst contained Ru particles with a mean size of ca. 1.5 nm well dispersed on CeO2 (of about 12–15 nm in size). Surface uptake of ethanol was measured by changing exposure to ethanol followed by TPD. Saturation coverage is found to be between 0.25 and 0.33 of a monolayer for CeO2 that has been prior heated with O2 at 773 K. The main reactions of ethanol on CeO2 during TPD are: re-combinative desorption of ethanol; dehydrogenation to acetaldehyde; and dehydration to ethylene. The dehydration to ethylene occurs mainly in a small temperature window at about 700 K and it is attributed to ethoxides adsorbed on surface-oxygen defects. The presence of Ru considerably modified the reaction of ceria towards ethanol. It has switched the desorption products to CO, CO2, CH4 and H2. These latter products are typical reforming products. Ethanol steam reforming (ESR) conducted on Ru/CeO2 indicated that optimal reaction activity is at about 673 K above which CO2 production declines (together with that of H2) due to reverse water gas shift. This trend was well captured during ethanol TPD where CO2 desorbed about 50 K below than CO on both oxidized and reduced Ru/CeO2 catalysts.Peer ReviewedPostprint (author's final draft

Highly acid-durable carbon coated Co3O4 nanoarrays as efficient oxygen evolution electrocatalysts

Most oxygen evolution reaction (OER) electrocatalysts are not stable in corrosive acids. Even the expensive RuO2 or IrO2, the most acid-resistant oxides, can be dissolved at an oxidative potential. Herein, we realize that the failures of OER catalysts are mostly caused by the weak interface between catalysts and the substrates. Hence, the study of the interface structure between catalysts and substrates is critical. In this work, we observe that the cheap OER catalysts Co3O4 can be more durable than the state-of-the-art RuO2 if the interface quality is good enough. The Co3O4 nanosheets deposited on carbon paper (Co3O4/CP) is prepared by electroplating of Co-species and followed by a two-step calcination process. The 1st step occurs in vacuum in order to maintain the surface integrity of the carbon paper and converts Co-species to Co(II)O. The 2nd step is a calcination in ambient conditions which enables the complete transformation of Co(II)O to Co3O4 without degrading the mechanical strength of the Co3O4-CP interface. Equally important, an in situ formation of a layer of amorphous carbon on top of Co3O4 further enhances the OER catalyst stability. Therefore, these key advances make the Co3O4 catalyst highly active toward the OER in 0.5 M H2SO4 with a small overpotential (370 mV), to reach 10 mA/cm2. The observed long lifetime for 86.8 h at a constant current density of 100 mA/cm2, is among the best of the reported in literature so far, even longer than the state-of-art RuO2 on CP. Overall, our study provides a new insight and methodology for the construction of a high-performance and high stability OER electrocatalysts in corrosive acidic environments

Comparing the Reaction Rates of Plasmonic (Gold) and Non-Plasmonic (Palladium) Metal Particles in Photocatalytic Hydrogen Production

Both Pd and Au metal particles are used in photocatalytic hydrogen generation. Yet while both act as electron sink only gold is poised to respond to visible light due to its plasmonic response. In order to quantitatively gauge their relative contribution into the reaction, the photocatalytic H2 production, from Au/TiO2 and Pd/TiO2 catalysts was studied under UV and UV–Vis light. While under UV light excitation, a weak dependence on the work function of the metal is observed, under UV–Vis light, Au is found to be twice more active than Pd. Under identical UV–Vis light irradiation, the turn over frequency calculated from XPS at.% is found to be 2.8 and 1.8 s−1 for Au and Pd, respectively. The effect is far more pronounced when the rates are normalized to the number of particles of each metal. Both the semiconductor TiO2 (UV light) and the plasmonic metal (visible light) need to be excited for the enhancement to occur; visible light alone causes a negligible reaction rate. Photocurrent measurements further confirmed the difference in the photocatalytic activity under UV and UV–Vis light excitation. Moreover, because of the presence of Au particles responding to visible light the reaction rate is enhanced due to “light penetration depth” effect

Etude du satut phylogénétique du bovin Kouri du lac Tchad à l'aide de marqueurs moléculaires

Le polymorphisme de 25 systèmes de marqueurs génétiques autosomaux(11 systèmes de groupes sanguins, 5 locus de lactoprotéines et 9 microsatellites) a été analysé dans un échantillon de la population de bovins Kouri du lac Tchad provenant de la zone en bordure du lac et d'iles localisées dans la préfecture de Bol. Les résultats obtenus, ainsi que les données déjà acquises sur différentes populations de taurins et de zébus africains et sur les races françaises, ont été traités par analyse factorielle des correspondances et par des méthodes de classification pour tenter de préciser le statut phylogénétique du Kouri. Selon cette étude, basée sur des marqueurs autosomaux, le Kouri se rapproche plus des zébus que des taurins africains alors que, dépourvu de bosse et possédant le chromosome Y submétacentrique de Bos taurus, il est classé normalement parmi les taurins. Il reste à évaluer la validité de diverses hypothèses explicatives, d'ailleurs non exclusives, différant par l'ancienneté postulée de l'apport de gènes de zébus : parenté du Kouri avec le Sanga du Sud de l'Afrique, introgression du zébu lors de son expansion sur le continent à partir du VIIIe siècle après J.-C., ou métissages, à l'époque moderne, avec les zébus entourant le bassin du lac Tchad. (Résumé d'auteur

High-RI resist polymers for 193 nm immersion lithography

A critical aim within the field of 193 nm immersion lithography is the development of high refractive index immersion fluids and resists. Increases in the refractive index (RI) of the immersion fluid will result in increases in the numerical aperture and depth of focus. Increasing the RI of resist polymers will improve exposure latitude for the process. A challenge for increasing the RI of resist polymers is to do so without detrimentally affecting other properties of the polymer such as transparency, line edge roughness, adhesion and plasma etch resistance. It is well known in the literature that introducing sulfur, bromine or aromatic groups into a polymer structure will increase its RI. However, due to the relatively strong absorption of phenyl groups at 193 nm these groups have to be avoided. Furthermore, the use of bromine poses problems associated with contamination of the silicon wafer. Hence, in this study, a systematic approach has been used to increase the sulfur content of 193 nm type resist polymers, by synthesis of sulfur-containing monomers and by performing bulk modifications of the polymer. The effect of sulfur content on the RI at 193 nm was then investigated. A broad study of the relationship between molecular structure and RI dispersion from 250-180 nm has also been undertaken, and conclusions drawn using QSPR methodologies. Finally, the effect of sulfur content on other lithography parameters, such as transparency, adhesion and plasma etch resistance, was also evaluated

THE Exchange Rate Determinants in Morocco: An Empirical Investigation

One of the most important instruments of economic policy of the opened countries is the exchange rate. It is considered both a mean of monetary regulation and a tool of outside competitiveness. Morocco plans to adopt the floating exchange rate regime, in the end of 2009. Indeed, the question which arises today is to know what type of floating exchange rate regime will be applied. Under the economic, technical and institutional factors, we ask if Morocco is ready and able to adopt this regime. In the light of this report, this paper will deal with the impact of the exchange rate policy on the real economy in Morocco through an empirical model called « The Behavioural Equilibrium Exchange Rate » supported by Clark and MacDonald (1997). Firstly, our investigation deals with the efficiency of exchange rate policy adopted by Morocco, secondly, it deals with the capacity of Dirham to resist to the shocks caused by the misalignments and finely, with the Moroccan monetary authorities’ capacity to manage the existing exchange regime. Under using the cointegration method, the error correction model and the analysis of the shocks by using the method of the decomposition of variance, our results confirm that the dynamics of the exchange rate in Morocco is determined by the variables such as the terms of trade, the foreign assets and the foreign debt. Similarly, in terms of short-term fluctuations in the exchange rate and in the analysis of the shocks, the supply and demand dynamics the dirham seems determining.Exchange Rate Policy; Exchange Rate regime; efficiency; shocks and misalignments; Cointegration Tests; Stability; Dirham.

Non-CA resists for 193nm immersions lithography: Effects of chemical structure on sensitivity

Initial studies are presented on the use of polysulfones as non-chemically amplified resists (non-CARs) for 193 nm immersion lithography. Polynorbornene sulfone films on silicon wafers have been irradiated with 193 nm photons in the absence of a photo-acid generator. Chemical contrast curves and contrast curves were obtained via spectroscopic ellipsometry and grazing angle - attenuated total reflectance FTIR spectroscopy. Results were consistent with previously reported mechanisms for the degradation of aliphatic polysulfones with ionizing radiation. It was shown that E0 values could be reduced significantly by using a post exposure bake step, which propagated depolymerization of the polymer. Initial patterning results down to 50 nm half pitch were demonstrated with EUV photons

Development of an operational high refractive index resist for 193nm immersion lithography

Generation-three (Gen-3) immersion lithography offers the promise of enabling the 32nm half-pitch node. For Gen-3 lithography to be successful, however, there must be major breakthroughs in materials development: The hope of obtaining numerical aperture imaging 1.70 is dependent on a high index lens, fluid, and resist. Assuming that a fluid and a lens will be identified, this paper focuses on a possible path to a high index resist. Simulations have shown that the index of the resist should be 1.9 with any index higher than 1.9 leading to an increased process latitude. Creation of a high index resist from conventional chemistry has been shown to be unrealistic. The answer may be to introduce a high index, polarizable material into a resist that is inert relative to the polymer behavior, but will this too degrade the performance of the overall system? The specific approach is to add very high index (~2.9) nanoparticles to an existing resist system. These nanoparticles have a low absorbance; consequently the imaging of conventional 193nm resists does not degrade. Further, the nanoparticles are on the order of 3nm in diameter, thus minimizing any impact on line edge roughness (LER)

Temperature programmed desorption study of pre-irradiated TiO2_2 anatase in the presence of ethanol. Effect of conduction band electrons on reaction selectivity

The work addresses one of the fundamentals of photocatalytic reactions, the fate of conduction-band (CB) electrons of a photo-excited TiO$_2$-anatase. Some of these CB-electrons are self-trapped as large-polarons. We have studied by Infrared-spectroscopy these polarons upon UV-excitation in the presence and absence of O$_2$. Moreover, the effect of CB-electrons on chemical reactions was investigated by temperature-programmed-desorption. Over the non-irradiated TiO$_2$, the dehydration and oxidation products dominated, while over that prior UV-irradiated in the presence of ethanol the dehydrogenation product increased and the oxidation pathway was partly suppressed. These changes are attributed to CB-electrons that made the near-surface more metallic

Continuous catalytic upgrading of ethanol to n-butanol and >C-4 products over Cu/CeO2 catalysts in supercritical CO2

n-Butanol (BuOH) often has superior properties as a bio-fuel compared to ethanol (EtOH). However finding sustainable sources of BuOH is proving difficult. In this paper, direct production of BuOH from EtOH is compared over custom-synthesized six Cu catalysts, supported on different solid acids. These catalysts were tested in a continuous flow supercritical CO2 (scCO2) reactor, and were found to catalyse the dehydrogenation, aldol condensation and hydrogenation steps of the so-called Guerbet reaction converting EtOH to BuOH. BuOH yields and selectivities were significantly different over the four catalysts. Cu on high surface area CeO2 showed the best activity for BuOH formation, with yields above 30% achieved with good selectivity. In addition high pressure CO2 is shown to have a positive effect on the reaction, possibly due to the redox cycle of Ce2O3 and CeO2