Optimizing the performance of catalytic traps for hydrocarbon abatement during the cold-start of a gasoline engine

A key target to reduce current hydrocarbon emissions from vehicular exhaust is to improve their abatement under cold-start conditions. Herein, we demonstrate the potential of factorial analysis to design a highly efficient catalytic trap. The impact of the synthesis conditions on the preparation of copper-loaded ZSM-5 is clearly revealed by XRD, N2 sorption, FTIR, NH3-TPD, SEM and TEM. A high concentration of copper nitrate precursor in the synthesis improves the removal of hydrocarbons, providing both strong adsorption sites for hydrocarbon retention at low temperature and copper oxide nanoparticles for full hydrocarbon catalytic combustion at high temperature. The use of copper acetate precursor leads to a more homogeneous dispersion of copper oxide nanoparticles also providing enough catalytic sites for the total oxidation of hydrocarbons released from the adsorption sites, although lower copper loadings are achieved. Thus, synthesis conditions leading to high copper loadings jointly with highly dispersed copper oxide nanoparticles would result in an exceptional catalytic trap able to reach superior hydrocarbon abatement under highly demanding operational conditions.

Development of exfoliated layered stannosilicate for hydrogen adsorption

The use of hydrogen as an energy vector leads to the development of materials with high hydrogen adsorption capacity. In this work, a new layered stannosilicate, UZAR-S3, is synthesized and delaminated, producing UZAR-S4. UZAR-S3, with the empirical formula Na4SnSi5O14·3.5H2O and lamellar morphology, is a layered stannosilicate built from SnO6 and SiO4 polyhedra. The delamination process used here comprises three stages: protonation with acetic acid, swelling with nonylamine and the delamination itself with an HCl/H2O/ethanol solution. UZAR-S4 is composed of sheets a few nanometers thick with a high aspect ratio and a surface area of 236 m2/g, twenty times higher than that of UZAR-S3. At −196 °C for UZAR-S4, H2 adsorption reached remarkable values of 3.7 and 4.2 wt% for 10 and 40 bar, respectively, the latter value giving a high volumetric H2 storage capacity of 26.2 g of H2/L.

Non-covalent immobilization of RhDuphos on carbon nanotubes and carbon xerogels

The immobilization of the chiral complex RhDuphos, by electrostatic or π–π (adsorption) interactions, on carbon nanotubes and carbon xerogels is investigated. To promote such interactions, the supports were either oxidized or heat treated to create carboxylic type surface groups or an apolar surface, respectively. The catalysts were tested in the hydrogenation of methyl 2-acetamidoacrylate. The prepared hybrid catalysts are less active than the homogeneous RhDuphos, but most of them show a high enantioselectivity and the one prepared with the oxidized carbon xerogel is also reusable, being able to give a high substrate conversion, keeping as well a high enantioselectivity. The anchorage by electrostatic interactions is more interesting than the anchorage by π–π interactions, as the π–π adsorption method produces a modification of the metal complex structure leading to an active hybrid catalyst but without enantioselectivity. The creation of carboxylic groups on the support surface has led to some hindering of the complex leaching.

Synthesis of Robust Hierarchical Silica Monoliths by Surface-Mediated Solution/Precipitation Reactions over Different Scales: Designing Capillary Microreactors for Environmental Applications

A synthetic procedure to prepare novel materials (surface-mediated fillings) based on robust hierarchical monoliths is reported. The methodology includes the deposition of a (micro- or mesoporous) silica thin film on the support followed by growth of a porous monolithic SiO2 structure. It has been demonstrated that this synthesis is viable for supports of different chemical nature with different inner diameters without shrinkage of the silica filling. The formation mechanism of the surface-mediated fillings is based on a solution/precipitation process and the anchoring of the silica filling to the deposited thin film. The interaction between the two SiO2 structures (monolith and thin film) depends on the porosity of the thin film and yields composite materials with different mechanical stability. By this procedure, capillary microreactors have been prepared and have been proved to be highly active and selective in the total and preferential oxidation of carbon monoxide (TOxCO and PrOxCO).

Mesoporous materials for clean energy technologies

Alternative energy technologies are greatly hindered by significant limitations in materials science. From low activity to poor stability, and from mineral scarcity to high cost, the current materials are not able to cope with the significant challenges of clean energy technologies. However, recent advances in the preparation of nanomaterials, porous solids, and nanostructured solids are providing hope in the race for a better, cleaner energy production. The present contribution critically reviews the development and role of mesoporosity in a wide range of technologies, as this provides for critical improvements in accessibility, the dispersion of the active phase and a higher surface area. Relevant examples of the development of mesoporosity by a wide range of techniques are provided, including the preparation of hierarchical structures with pore systems in different scale ranges. Mesoporosity plays a significant role in catalysis, especially in the most challenging processes where bulky molecules, like those obtained from biomass or highly unreactive species, such as CO2 should be transformed into most valuable products. Furthermore, mesoporous materials also play a significant role as electrodes in fuel and solar cells and in thermoelectric devices, technologies which are benefiting from improved accessibility and a better dispersion of materials with controlled porosity.

New insights on electrochemical hydrogen storage in nanoporous carbons by in situ Raman spectroscopy

In situ Raman spectroscopy was exploited to analyze the interaction between carbon and hydrogen during electrochemical hydrogen storage at cathodic conditions. Two different activated carbons were used and characterized by different electrochemical techniques in two electrolytes (6 M KOH and 0.5 M Na2SO4). The in situ Raman spectra collected showed that, in addition to the D and G bands associated to the graphitic carbons, two bands appear simultaneously at about 1110 and 1500 cm−1 under cathodic conditions, and then they disappear when the potential increases to more positive values. This indicates that carbon–hydrogen bonds are formed reversibly in both electrolytes during cathodic conditions. Comparing the two activated carbons, it was confirmed that, in both electrolytes, the hydrogenation of carbon atoms is produced more easily for the sample with lower amount of surface oxygen groups. In KOH medium, for the two samples, the formation of carbon–hydrogen bonds proceeds at more positive potential with respect to the thermodynamic potential value for hydrogen evolution. Furthermore, changes in the shape of the D band (due to an intensity increase of the D1 band) during the formation of carbon–hydrogen bonds suggest that hydrogenation of the carbon atoms increases the number of edge planes.

Tailoring the Surface Chemistry of Activated Carbon Cloth by Electrochemical Methods

This paper presents a systematic study of the effect of the electrochemical treatment (galvanostatic electrolysis in a filter-press electrochemical cell) on the surface chemistry and porous texture of commercial activated carbon cloth. The same treatments have been conducted over a granular activated carbon in order to clarify the effect of morphology. The influence of different electrochemical variables, such as the electrode polarity (anodic or cathodic), the applied current (between 0.2 and 1.0 A) and the type of electrolyte (HNO3 and NaCl) have also been analyzed. The anodic treatment of both activated carbons causes an increase in the amount of surface oxygen groups, whereas the cathodic treatment does not produce any relevant modification of the surface chemistry. The HNO3 electrolyte produced a lower generation of oxygen groups than the NaCl one, but differences in the achieved distribution of surface groups can be benefitial to selectively tune the surface chemistry. The porous texture seems to be unaltered after the electro-oxidation treatment. The validity of this method to introduce surface oxygen groups with a pseudocapacitive behavior has been corroborated by cyclic voltammetry. As a conclusion, the electrochemical treatment can be easily implemented to selectively and quantitatively modify the surface chemistry of activated carbons with different shapes and morphologies.

High-Pressure Methane Storage in Porous Materials: Are Carbon Materials in the Pole Position?

Natural gas storage on porous materials (ANG) is a promising alternative to conventional on-board compressed (CNG) or liquefied natural gas (LNG). To date, Metal–organic framework (MOF) materials have apparently been the only system published in the literature that is able to reach the new Department of Energy (DOE) value of 263 cm3 (STP: 273.15 K, 1 atm)/cm3; however, this value was obtained by using the ideal single-crystal density to calculate the volumetric capacity. Here, we prove experimentally, and for the first time, that properly designed activated carbon materials can really achieve the new DOE value while avoiding the additional drawback usually associated with MOF materials (i.e., the low mechanical stability under pressure (conforming), which is required for any practical application).

Using a RGB-D camera for 6DoF SLAM

This paper presents a method for fast calculation of the egomotion done by a robot using visual features. The method is part of a complete system for automatic map building and Simultaneous Localization and Mapping (SLAM). The method uses optical flow in order to determine if the robot has done a movement. If so, some visual features which do not accomplish several criteria (like intersection, unicity, etc,) are deleted, and then the egomotion is calculated. We use a state-of-the-art algorithm (TORO) in order to rectify the map and solve the SLAM problem. The proposed method provides better efficiency that other current methods.

RGBD Human-Hand recognition for the Interaction with Robot-Hand

New low cost sensors and the new open free libraries for 3D image processing are permitting to achieve important advances for robot vision applications such as tridimensional object recognition, semantic mapping, navigation and localization of robots, human detection and/or gesture recognition for human-machine interaction. In this paper, a method to recognize the human hand and to track the fingers is proposed. This new method is based on point clouds from range images, RGBD. It does not require visual marks, camera calibration, environment knowledge and complex expensive acquisition systems. Furthermore, this method has been implemented to create a human interface in order to move a robot hand. The human hand is recognized and the movement of the fingers is analyzed. Afterwards, it is imitated from a Barret hand, using communication events programmed from ROS.

An improvement of a SLAM RGB-D method with movement prediction derived from a study of visual features

This paper presents a method for the fast calculation of a robot’s egomotion using visual features. The method is part of a complete system for automatic map building and Simultaneous Location and Mapping (SLAM). The method uses optical flow to determine whether the robot has undergone a movement. If so, some visual features that do not satisfy several criteria are deleted, and then egomotion is calculated. Thus, the proposed method improves the efficiency of the whole process because not all the data is processed. We use a state-of-the-art algorithm (TORO) to rectify the map and solve the SLAM problem. Additionally, a study of different visual detectors and descriptors has been conducted to identify which of them are more suitable for the SLAM problem. Finally, a navigation method is described using the map obtained from the SLAM solution.

Preliminary interpretation of shaking-table response of a full-scale 3-storey building composed of thin reinforced concrete sandwich walls

In the last few decades, the use of cast in situ reinforced concrete sandwich panels for the construction of low- to mid-rise buildings has become more and more widespread due to several interesting properties of this construction technique, such as fast construction and high thermal and acoustic performances. Nonetheless the level of knowledge of the structural behavior of systems made of squat reinforced concrete sandwich panels is still not so consolidated, especially with reference to the seismic response, due to the lack of experimental studies. In recent years, while various experimental tests have been conducted on single panels aimed at assessing their seismic capacity, only few tests have been carried out on more complex structural systems. In this paper, the experimental results of a series of shaking-table tests performed on a full-scale 3-storey building are presented in detail. The main goal is to give to the scientific community the possibility of develop independent interpretation of these experimental results. An in-depth interpretation of the discrepancies between the analytical predictions and the experimental results is beyond the objective of this paper and is still under development. Nonetheless, preliminary interpretations indicate that both the stiffness and the strength of the building under dynamic excitation appear quite superior with respect to those expected from the results of previous pseudo-static cyclic tests conducted on simple specimens.

Logic-Based Outer Approximation for the Design of Discrete-Continuous Dynamic Systems with Implicit Discontinuities

We address the optimization of discrete-continuous dynamic optimization problems using a disjunctive multistage modeling framework, with implicit discontinuities, which increases the problem complexity since the number of continuous phases and discrete events is not known a-priori. After setting a fixed alternative sequence of modes, we convert the infinite-dimensional continuous mixed-logic dynamic (MLDO) problem into a finite dimensional discretized GDP problem by orthogonal collocation on finite elements. We use the Logic-based Outer Approximation algorithm to fully exploit the structure of the GDP representation of the problem. This modelling framework is illustrated with an optimization problem with implicit discontinuities (diver problem).

Logic-Based Outer-Approximation Algorithm for Solving Discrete-Continuous Dynamic Optimization Problems

We present an extension of the logic outer-approximation algorithm for dealing with disjunctive discrete-continuous optimal control problems whose dynamic behavior is modeled in terms of differential-algebraic equations. Although the proposed algorithm can be applied to a wide variety of discrete-continuous optimal control problems, we are mainly interested in problems where disjunctions are also present. Disjunctions are included to take into account only certain parts of the underlying model which become relevant under some processing conditions. By doing so the numerical robustness of the optimization algorithm improves since those parts of the model that are not active are discarded leading to a reduced size problem and avoiding potential model singularities. We test the proposed algorithm using three examples of different complex dynamic behavior. In all the case studies the number of iterations and the computational effort required to obtain the optimal solutions is modest and the solutions are relatively easy to find.

Industry-specific effect of CSR initiatives: hotels and airlines

Purpose – This study aims to examine the relationships between a firm's corporate social responsibility (CSR) activities and its performance and risk. The authors hypothesize that industry-level effects are highly determinant of the sign and magnitude of these relationships to establish a ranking of industries to identify the position of the most prominent tourism-related industries: hotels and airlines. Based on the cybernetic model of decision making and the heuristics thereof, shareholders base their investment decisions derived from CSR announcements on the idea that the industries behave differently; their fixed costs being a relevant factor. Design/methodology/approach – The authors estimate the industry-specific effects of CSR initiatives on firms' performance and risk using a sample of 583 announcements from the Spanish Stock Market. Findings – The results show that while CSR announcements have a positive effect on performance when the authors do not account for industry-specific factors, once the authors incorporate these factors into the analysis, the authors find that firm performance and risk vary quite substantially as a function of the industry to which the firm belongs. Interestingly, while the hotel industry presents an average behavior (standing at 9th position in returns, 15th in terms of risk, and 8th according to the ratio returns/volatility), the airline industry presents the worst situation of all industries: last in performance and last in risk. Practical implications – The results help managers assess their decisions and allocate CSR resources optimally. Originality/value – This article is the first attempt to empirically test and comprehensively detect the different relationships between CSR and firm performance across industries.