Water determination of precursor solutions with oxidant cations by the Karl Fischer method: the YBCO-TFA case

Uncontrolled water content in non-aqueous precursor solutions can be a source of irreproducibility in thin film performance through changes in the gel network. Towards gaining control on the solution properties, water determination in metalorganic solutions of YBCO-TFA has been studied by the Karl Fischer titration in a volumetric-type unit. However, oxidizing cations usually present when preparing functional oxides by chemical solution routes severely interfere in the Karl Fischer analysis. In the case of YBCO-TFA, cupric ions in the initial solution oxidize the iodide produced in the Karl Fischer reaction back to iodine, which in turn feeds the titration reaction and consumes more water, causing a negative error in the analysis, which can be as large as 70%. However, such chemical interference of cupric salts can be modelled and quantified. A corrected Karl Fischer methodology is proposed for accurately measuring water content in YBCO-TFA solutions, which could be potentially extended to other precursor solutions containing oxidant cations.     

Origin of the size dependence of Au nanoparticles toward molecular oxygen dissociation

Density functional theory calculations using a plane-wave basis set and a generalized gradient approach exchange-correlation potential have been carried out to study the dissociation of molecular oxygen by Au nanoparticles and its dependence with particle size. The analysis of the energy related data shows that the reactivity is dominated by the energy barrier height from adsorbed O₂ to the dissociated state and by the stability of molecular oxygen on the nanoparticle. The energy barrier is found to be only slightly dependent on the particles size where large variations are found for the adsorption energy of the O₂ molecule on the different nanoparticles. A careful analysis of the electronic structure shows that the driving force for O₂ adsorption by these nanoparticles is the existence of a clear gap between occupied and unoccupied states for the naked particle. This allows accommodating bonding states with O₂ below the Fermi level resulting in a strong interaction. On the contrary, the Au nanoparticles with a more metallic electronic structure have necessarily to accommodate bonding and antibonding states below the Fermi level with a concomitant weaker interaction with O₂.     

An ab initio study of the interaction of atomic hydrogen with cluster models simulating the (100) and (110) silver surfaces

Ab initio calculations have been carried out for the interactions of atomic hydrogen with Ag₅ cluster models, simulating the adsorption on the one-fold and four-fold sites of the (100) and (110) silver surfaces. It is found that one-layer cluster models lead to unreasonable results as a consequence of their high instability. Chemisorption on the one-fold site is found to be the preferred one. This results is easily interpreted on the basis of symmetry properties of the higher occupied molecular orbitals.     

Synthesis of precocenes with ionoforic groups

Preparation of potential insect antijuvenile hormone agents with polyoxyethyl and glycosyl groups at C-8 position of the 2-H-chromene ring of precocenes is described.     

Monitoring the effect of chemicals on biological communities. The biofilm as an interface

Biofilms can be regarded as early warning systems for detection of the effects of toxicants on aquatic systems, because they have been successfully used for detection of other environmental stressors (e.g. pH, salinity, organic pollution). A variety of methods is used for detection of the effects of toxicants by use of biofilms. The methods range from structurally-based to functionally-based, and from in vitro-based to systemic approaches. Physiological approaches may be appropriate for detection of acute effects. Among these methods, photosynthesis is more related to the effect of toxicants affecting algal communities, directly or indirectly, and extracellular enzyme activity is less specific. Selecting one or the other may depend on the suspected direct effect of the toxicant. Integrated studies have revealed the relevance of toxicants to top-down or bottom-up regulation of the biofilm community. Persistent or chronic effects should affect other biofilm indicators, for example growth or biomass-related factors (e.g. chlorophyll), or community composition. Among these, community composition might better reflect the effects of the toxicant(s), because this may cause a shift from a sensitive to a progressively tolerant community. Community composition-based approaches do not usually adequately reflect cause–effect relationships and require complementary analysis of properties affected in the short-term, for example physiological properties. The current array of methods available must be wisely combined to disentangle the effects of chemicals on biofilms, and whether these effects are transient or persistent, to successfully translate the chemical action of toxicants into the effect they might have on the river ecosystem.     

Adsorption of carbon monoxide on Pt{100} surfaces: dependence of the CO stretching vibrational frequency on surface coverage

We have used the ab initio cluster model approach to study the dependence of the CO stretching frequency on CO surface coverage. We have also investigated the relative importance of the various factors that can affect the position of the CO stretching band as coverage increases. Two effects can change the CO stretching frequency: the adsorbate–adsorbate dipole coupling, which is a purely physical effect, and the changes in the 2π^* CO molecular orbitals, due to the different chemical environment at higher coverages. From our vibrational analysis, we conclude that CO–CO dipole coupling is the main cause of the upward shift of the CO stretching band when the CO coverage is increased. The population of the 2π^* CO molecular orbitals does not change at any coverage within the region considered. We have also estimated the ¹²CO–¹³CO dipole coupling, which previous studies have assumed to be weak. Our results demonstrate that the ¹²CO–¹³CO dipole coupling is indeed weak compared with the ¹²CO–¹²CO dipole coupling. At a CO surface coverage of 0.5 monolayers (ML), we have calculated a band shift of 40 cm⁻¹ to higher frequency. However, we should point out that when one ¹²CO molecule is surrounded by a ¹³CO environment, the ¹²CO stretching band shifts 10 cm⁻¹ upwards. We have also computed the heat of adsorption of CO on Pt{100}-(1×1) as a function of CO coverage. The initial heat of adsorption is calculated to be about 192 kJ mol⁻¹ and then drops to 180 kJ mol⁻¹ at 0.5 ML. These results agree quite well with recent calorimetric measurements. Besides that, we have estimated that the CO–CO interaction energy at 0.5 ML is repulsive and has a value of 5 kJ mol⁻¹.     

Theoretical study of CO2 activation on Pt(111) induced by coadsorbed K atoms

The adsorption of CO₂ on the clean and potassium-precovered Pt(111) surface has been studied by means of the cluster model approach within the hybrid B3LYP density functional theory-based method. On the clean surface, CO₂ is undistorted and weakly bound. The equilibrium position of this physisorbed species appears at a rather large distance from the surface. However, when coadsorbed K atoms are included in the model, a chemisorbed, bent CO₂ species on top of a surface Pt atom is found. The presence of the coadsorbed K is found to be necessary to promote CO₂ chemisorption and activation, the key step in activating the CO₂ molecule being a direct interaction with the coadsorbate. In addition, the calculated vibrational frequencies for this chemisorbed species are in agreement with available experimental data.     

Highly hydrophobic polyfluorinated azo dyes grafted on surfaces

Artificial hydrophobic surfaces have a great potential in a wide range of industrial applications owing to their self-cleaning, anti-fogging and anti-biofouling properties. A family of polyfluorinated reactive azo dyes has been prepared and some of them easily modified and grafted on cotton fabric and glass surfaces obtaining new coloured hydrophobic materials.     

Charge Polarization at a Au–TiC Interface and the Generation of Highly Active and Selective Catalysts for the Low‐Temperature Water–Gas Shift Reaction

Au atoms in contact with TiC(001) undergo significant charge polarization. Strong metal–support interactions make Au/TiC(001) an excellent catalyst for the low‐temperature water–gas shift (WGS), with turnover frequencies orders of magnitude larger than those observed for conventional metal/oxide catalysts. DFT calculations indicate that the WGS reaction follows an associative mechanism with HOCO as a key intermediate.     

Density functional studies of coinage metal nanoparticles: scalability of their properties to bulk

Density functional plane-wave calculations have been carried out for series of Cu _n ,Ag _n and Au _n particles containing up to 146 (Cu, Ag) and 225 (Au) atoms. Full geometry optimization has been performed for all particles starting from the structures created by cuts from the bulk. In line with previous studies, calculated average nearest-neighbour distances and cohesive energies of the particles linearly depend on such size-derived parameters as the average coordination number of metal atoms and the inverse of the mean particle radius, respectively. Rather accurate linear extrapolation of the observables under scrutiny to the bulk values has been achieved. However, we show that the scalability for particles made of various elements of the same d¹⁰s¹ electron configuration differs, e.g. for bond lengths in Au _n species it is noticeably less perfect than that for Cu _n and Ag _n ones. Implications of encountered structural peculiarities of the nanoparticles for their reactivity are outlined.