Platinum–tin/carbon catalysts for ethanol oxidation: Influence of Sn content on the electroactivity and structural characteristics

Carbon-supported Pt–Sn catalysts commonly contain Pt–Sn alloy and/or Pt–Sn bimetallic systems (Sn oxides). Nevertheless, the origin of the promotion effect due to the presence of Sn in the Pt–Sn/C catalyst towards ethanol oxidation in acid media is still under debate and some contradictions. Herein, a series of Ptx–Sny/C catalysts with different atomic ratios are synthesized by a deposition process using formic acid as the reducing agent. Catalysts structure and chemical compositions are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and their relationship with catalytic behavior towards ethanol electro-oxidation was established. Geometric structural changes are producing by highest Sn content (Pt1–Sn1/C) promoted the interaction of Pt and Sn forming a solid solution of Pt–Sn alloy phase, whereas, the intermediate and lowest Sn content (Pt2–Sn1/C and Pt3–Sn1/C, respectively) promoted the electronic structure modifications of Pt by Sn addition without the formation of a solid solution. The amount of Sn added affects the physical and chemical characteristics of the bimetallic catalysts as well as reducing the amount of Pt in the catalyst composition and maintaining the electrocatalytic activities at the anode. However, the influence of the Sn oxidation state in Pt–Sn/C catalysts surfaces and the alloy formation between Pt and Sn as well as with the atomic ratio on their catalytic activity towards ethanol oxidation appears minimal. Similar methodologies applied for synthesis of Ptx–Sny/C catalysts with a small change show differences with the results obtained, thus highlighting the importance of the conditions of the preparation method.

Understanding the structure of the first atomic contact in gold

We have studied experimentally jump-to-contact (JC) and jump-out-of-contact (JOC) phenomena in gold electrodes. JC can be observed at first contact when two metals approach each other, while JOC occurs in the last contact before breaking. When the indentation depth between the electrodes is limited to a certain value of conductance, a highly reproducible behaviour in the evolution of the conductance can be obtained for hundreds of cycles of formation and rupture. Molecular dynamics simulations of this process show how the two metallic electrodes are shaped into tips of a well-defined crystallographic structure formed through a mechanical annealing mechanism. We report a detailed analysis of the atomic configurations obtained before contact and rupture of these stable structures and obtained their conductance using first-principles quantum transport calculations. These results help us understand the values of conductance obtained experimentally in the JC and JOC phenomena and improve our understanding of atomic-sized contacts and the evolution of their structural characteristics.

Impacto y consecuencias sociales contemporáneas de las políticas de tutela estatal en las reservas indígenas canadienses

Este artículo tiene como objetivo examinar el impacto y las consecuencias sociales contemporáneas del mantenimiento del sistema de organización social denominado «reserva indígena» en Canadá. Mediante un estudio de caso, se explora cómo la política organizacional y la estructura institucional contemporánea en las reservas indígenas canadienses están alimentando problemas psicosociales y de salud mental como, por ejemplo, abuso de sustancias psicoactivas, depresión, negligencia parental o violencia doméstica. Tres características estructurales se identifican como problemas inherentes en la estructura organizacional de las reservas contemporáneas: el desempleo estructural, la dependencia de programas de asistencia social y el faccionalismo comunitario.

A GIS-based methodology to quantitatively define an Adjacent Protected Area in a shallow karst cavity: The case of Altamira cave

Different types of land use are usually present in the areas adjacent to many shallow karst cavities. Over time, the increasing amount of potentially harmful matter and energy, of mainly anthropic origin or influence, that reaches the interior of a shallow karst cavity can modify the hypogeal ecosystem and increase the risk of damage to the Palaeolithic rock art often preserved within the cavity. This study proposes a new Protected Area status based on the geological processes that control these matter and energy fluxes into the Altamira cave karst system. Analysis of the geological characteristics of the shallow karst system shows that direct and lateral infiltration, internal water circulation, ventilation, gas exchange and transmission of vibrations are the processes that control these matter and energy fluxes into the cave. This study applies a comprehensive methodological approach based on Geographic Information Systems (GIS) to establish the area of influence of each transfer process. The stratigraphic and structural characteristics of the interior of the cave were determined using 3D Laser Scanning topography combined with classical field work, data gathering, cartography and a porosity–permeability analysis of host rock samples. As a result, it was possible to determine the hydrogeological behavior of the cave. In addition, by mapping and modeling the surface parameters it was possible to identify the main features restricting hydrological behavior and hence direct and lateral infiltration into the cave. These surface parameters included the shape of the drainage network and a geomorphological and structural characterization via digital terrain models. Geological and geomorphological maps and models integrated into the GIS environment defined the areas involved in gas exchange and ventilation processes. Likewise, areas that could potentially transmit vibrations directly into the cave were identified. This study shows that it is possible to define a Protected Area by quantifying the area of influence related to each transfer process. The combined maximum area of influence of all the processes will result in the new Protected Area. This area will thus encompass all the processes that account for most of the matter and energy carried into the cave and will fulfill the criteria used to define the Protected Area. This methodology is based on the spatial quantification of processes and entities of geological origin and can therefore be applied to any shallow karst system that requires protection.

The effect of carbon nanofillers on the performance of electromechanical polyaniline-based composite actuators

Different types of crystalline carbon nanomaterials were used to reinforce polyaniline for use in electromechanical bilayer bending actuators. The objective is to analyze how the different graphitic structures of the nanocarbons affect and improve the in situ polymerized polyaniline composites and their subsequent actuator behavior. The nanocarbons investigated were multiwalled carbon nanotubes, nitrogen-doped carbon nanotubes, helical-ribbon carbon nanofibers and graphene oxide, each one presenting different shape and structural characteristics. Films of nanocarbon-PAni composite were tested in a liquid electrolyte cell system. Experimental design was used to select the type of nanocarbon filler and composite loadings, and yielded a good balance of electromechanical properties. Raman spectroscopy suggests good interaction between PAni and the nanocarbon fillers. Electron microscopy showed that graphene oxide dispersed the best, followed by multiwall carbon nanotubes, while nitrogen-doped nanotube composites showed dispersion problems and thus poor performance. Multiwall carbon nanotube composite actuators showed the best performance based on the combination of bending angle, bending velocity and maximum working cycles, while graphene oxide attained similarly good performance due to its best dispersion. This parallel testing of a broad set of nanocarbon fillers on PAni-composite actuators is unprecedented to the best of our knowledge and shows that the type and properties of the carbon nanomaterial are critical to the performance of electromechanical devices with other conditions remaining equal.

Dynamic investigation of an ancient masonry bell tower with operational modal analysis: a non-destructive experimental technique to obtain the dynamic characteristics of a structure

This paper shows the results of an experimental analysis on the bell tower of “Chiesa della Maddalena” (Mola di Bari, Italy), to better understand the structural behavior of slender masonry structures. The research aims to calibrate a numerical model by means of the Operational Modal Analysis (OMA) method. In this way realistic conclusions about the dynamic behavior of the structure are obtained. The choice of using an OMA derives from the necessity to know the modal parameters of a structure with a non-destructive testing, especially in case of cultural-historical value structures. Therefore by means of an easy and accurate process, it is possible to acquire in-situ environmental vibrations. The data collected are very important to estimate the mode shapes, the natural frequencies and the damping ratios of the structure. To analyze the data obtained from the monitoring, the Peak Picking method has been applied to the Fast Fourier Transforms (FFT) of the signals in order to identify the values of the effective natural frequencies and damping factors of the structure. The main frequencies and the damping ratios have been determined from measurements at some relevant locations. The responses have been then extrapolated and extended to the entire tower through a 3-D Finite Element Model. In this way, knowing the modes of vibration, it has been possible to understand the overall dynamic behavior of the structure.

Structural Analysis with ANSYS on Stone Constructions in the Historical Spanish Heritage

According to the importance of rehabilitation and recovery of Architectural Heritage in the live of people, this paper is aimed to strengthen the traditional methods of stone vaults calculation taking advantage of the technological characteristics of the powerful program ANSYS Workbench. As an example of this, it could find out the possible pathologies that could arise during the construction history of the building. To limit this research, the upper vault of the main chapel of the Santiago parish church in Orihuela -Alicante- is selected as a reference which is a Jeronimo Quijano´s important building work in the XVI century in the Renaissance. Moreover, it is an innovative stone masonry vault that consists of 8 double intercrossed arches with each other and braced by severies. During the seventeenth century there was a lantern in the central cap and it is unknown why it was removed. Its construction could justify the original constructive solution with intercrossed arches that freed the center to create a more enlightened and comfortable presbytery. By similarity with other Quijano’s works, it is considered a small lantern drilling the central spherical cap. It is proposed to carry out a comparative study of it with different architectural solutions from the same period and based on several common parameters such as: a vault of square plant with spherical surround, intercrossed arches, a possible lantern, the dimension of the permitted space, similar states of loads and compact limestone masonry. The three solutions are mainly differentiated by their size and the type of lantern and its comparison lets us know which one is the most resistant and stable. The other two building works maintain some connection with the Quijano's professional scope. It has selected the particular case of the Communion chapel of the Basilica in Elche (a large prismatic lantern with a large cylindrical drum that starts from the own arches and an upper hemispherical dome), for its conservation, its proximity to Orihuela and its implementation during the century XVIII. Finally, a significant Dome Spanish Renaissance complete the selection: a cross vault of the Benavides Chapel of the Saint Francisco Convent in Baeza - Jaén-, designed by Andres of Vandelvira in the sixteenth century (a large hemispherical dome that starts from the own arcs). To simplify the calculation and standardize the work that have to be contrasted, all of them were considered with some similar characteristics: 30 cm constant thickness, the intercrossed arches were specifically analyzed and had identical loads, Young's modulus and Poisson's ratio. Regarding the calculation solutions, in general terms, the compressive stresses predominate, influencing on it the joint collaboration of the filling material on the vault, the vault itself, the thick side walls, the buttresses and the top cover weight . In addition, the three solutions are suitable, being the Orihuela one the safest and the Baeza one the riskiest for its large dimensions. Thus, the idea of intercrossed arches with suitable thickness would allow carry out the heaviest lantern and this would confirm it as a Renaissance architectural typology built in stone.