Hydrogen photoproduction in a continuous flow system with u.v.-light and aqueous suspensions of RuOx/Pt/TiO2

Water photolysis has been studied in liquid phase, using neutral aqueous suspensions of RuO_x/Pt/TiO₂ particles and u.v. light. A continuous gas flow apparatus of ca 350 cm³ of total volume and holding 150 cm³ of catalyst suspension was designed and tested. Hydrogen generation rates up to 110 μmol h^?1 have been obtained. Influence of photoproducts and catalyst concentration on the process rate is studied. Discussion is centred in the role played by oxygen in catalyst activity and process dynamics.     

Differential evolution solution to the SLAM problem

A new solution to the Simultaneous Localization and Modelling problem is presented in this paper. The algorithm is based on the stochastic search for solutions in the state space to the global localization problem by means of a differential evolution algorithm. This non linear evolutive filter, called Evolutive Localization Filter (ELF), searches stochastically along the state space for the best robot pose estimate. The set of pose solutions (the population) focuses on the most likely areas according to the perception and up to date motion information. The population evolves using the log-likelihood of each candidate pose according to the observation and the motion errors derived from the comparison between observed and predicted data obtained from the probabilistic perception and motion model.The proposed SLAM algorithm operates in two steps: in the first step the ELF filter is used at local level to re-localize the robot based on the robot odometry, the laser scan at a given position and a local map where only a low number of the last scans have been integrated. In the second step, the aligned laser measures and the corrected robot poses are used to detect whether the robot is revisiting a previously crossed area (i.e., a cycle in the robot trajectory exists). Once a cycle is detected, the Evolutive Localization Filter is used again to estimate the accumulated residual drift in the detected loop and then to re-estimate the robot poses in order to integrate the sensor measures in the global map of the environment.The algorithm has been tested in different environments to demonstrate the effectiveness, robustness and computational efficiency of the proposed approach.     

Robust quantification of the exposure to operational risk: Bringing economic sense to economic capital

Operational risk is commonly analyzed in terms of the distribution of aggregate yearly losses. Risk measures can then be computed as statistics of this distribution that focus on the region of extreme losses. Assuming independence among the operational risk events and between the likelihood that they occur and their magnitude, separate models are made for the frequency and for the severity of the losses. These are then combined to estimate the distribution of aggregate losses. While the detailed form of the frequency distribution does not significantly affect the risk analysis, the choice of model for the severity often has a significant impact on operational risk measures. For heavy-tailed distributions these measures are dominated by extreme losses, whose probability cannot be reliably extrapolated from the available data. With limited empirical evidence, it is difficult to distinguish among alternative models that produce very different values of the risk measures. Furthermore, the estimates obtained can be unstable and overly sensitive to the presence or absence of single extreme events. Setting a bound on the maximum amount that can be lost in a single event reduces the dependence on the distributional assumptions and improves the robustness and stability of the risk measures, while preserving their sensitivity to changes in the risk profile. This bound should be determined by expert assessment on the basis of economic arguments and validated by the regulator, so that it can be used as a control parameter in the risk analysis.     

Unsaturated Copolyesters from Macrolactone/Norbornene: Toward Reaction Kinetics of Metathesis Copolymerization Using Ruthenium Carbene Catalysts

Unsaturated copolyesters are of great interest in polymer science due to their broad potential applications and sustainability. Copolyesters were synthesized from the ring-opening metathesis copolymerization of ω-6-hexadecenlactone (HDL) and norbornene (NB) using ruthenium-alkylidene [Ru(Cl₂)(=CHPh)(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(PCy₃)] (Ru1), [Ru(Cl)₂(=CHPh)(PCy₃)₂] (Ru2), and ruthenium-vinylidene [RuCl₂(=C=CH(p-C₆H₄CF₃))(PCy₃)₂] (Ru3) catalysts, respectively, yielding HDL-NB copolymers with different ratios of the monomer HDL in the feed. The activity of N-heterocyclic-carbene (NHC) (Ru1) and phosphine (Ru2 and Ru3) ligands containing ruthenium-carbene catalysts were evaluated in the synthesis of copolymer HDL-NB. The catalysts Ru1 with an NHC ligand showed superior activity and stability over catalysts Ru2 and Ru3 bearing PCy₃ ligands. The incorporation of the monomers in the copolymers determined by ¹H-NMR spectroscopy was similar to that of the HDL-NB values in the feed. Experiments, at distinct monomer molar ratios, were carried out using the catalysts Ru1–Ru3 to determine the copolymerization reactivity constants by applying the Mayo–Lewis and Fineman–Ross methods. The copolymer distribution under equilibrium conditions was studied by the ¹³C NMR spectra, indicating that the copolymer HDL-NB is a gradient copolymer. The main factor determining the decrease in melting temperature is the inclusion of norbornene units, indicating that the PNB units permeate trough the HDL chains. The copolymers with different molar ratios [HDL]/[NB] have good thermal stability up to 411 °C in comparison with the homopolymer PHDL (384 °C). Further, the stress–strain measurements in tension for these copolymers depicted the appreciable increment in stress values as the NB content increases.     

Extreme Two‐Phase Cooling from Laser‐Etched Diamond and Conformal,Template‐Fabricated Microporous Copper

This paper reports the first integration of laser‐etched polycrystalline diamond microchannels with template‐fabricated microporous copper for extreme convective boiling in a composite heat sink for power electronics and energy conversion. Diamond offers the highest thermal conductivity near room temperature, and enables aggressive heat spreading along triangular channel walls with 1:1 aspect ratio. Conformally coated porous copper with thickness 25 µm and 5 µm pore size optimizes fluid and heat transport for convective boiling within the diamond channels. Data reported here include 1280 W cm^?2 of heat removal from 0.7 cm² surface area with temperature rise beyond fluid saturation less than 21 K, corresponding to 6.3 × 10⁵ W m^?2 K^?1. This heat sink has the potential to dissipate much larger localized heat loads with small temperature nonuniformity (5 kW cm^?2 over 200 µm × 200 µm with <3 K temperature difference). A microfluidic manifold assures uniform distribution of liquid over the heat sink surface with negligible pumping power requirements (e.g., <1.4 × 10^?4 of the thermal power dissipated). This breakthrough integration of functional materials and the resulting experimental data set a very high bar for microfluidic heat removal.     

Semiconductor-to-metallic phase transition of VO<Subscript>2</Subscript> by laser excitation

VO₂ thin films deposited on MgO and fused silica glass substrates were prepared by the pulsed laser deposition (PLD) technique, which shows phase transition (PT) from the monoclinic semiconductor phase to a metallic tetragonal rutile structure at temperatures over 68°C. The observed PT is reversible, showing a typical hysteresis. The PT can also be induced through optical pumping by laser excitation. In this case, it was found that the optically induced PT is ultrafast and passive, but not thermally initiated. In order to understand the PT mechanism, a study of transient holography using degenerate-four-wavemixing (DFWM) measurement was conducted. A Nd:YAG pulsed laser with pulse duration of 30 psec operating at 532 nm was employed as the coherent light source. This showed that the observed transient holography in VO₂ thin film is associated with the excited state dynamical process, which essentially causes the structural change, or so-called optically induced PT. The observed extremely large polarizability is believed to relate to the large offset in the potential well minimum between the ground state and excited state. Through an unidentified intermediate state, the transient lattice distortion triggered the structural change.     

Unprecedented Improvement of Single Li‐Ion Conductive Solid Polymer Electrolyte Through Salt Additive

Solid‐state lithium metal (Li°) batteries (SSLMBs) are believed to be the most promising technologies to tackle the safety concerns and the insufficient energy density encountered in conventional Li‐ion batteries. Solid polymer electrolytes (SPEs) inherently own good processability and flexibility, enabling large‐scale preparation of SSLMBs. To minimize the growth of Li° dendrites and cell polarization in SPE‐based SSLMBs, an additive‐containing single Li‐ion conductive SPE is reported. The characterization results show that a small dose of electrolyte additive (2 wt%) substantially increases the ionic conductivity of single Li‐ion conductive SPEs as well as the interfacial compatibility between electrode and SPE, allowing the cycling of SPE‐based cells with good electrochemical performance. This work may provide a paradigm shift on the design of highly cationic conductive electrolytes, which are essential for developing safe and high‐performance rechargeable batteries.     

Transparent,Anisotropic Biofilm with Aligned Bacterial Cellulose Nanofibers

Cellulose nanofibrils are attractive as building blocks for advanced photonic, optoelectronic, microfluidic, and bio‐based devices ranging from transistors and solar cells to fluidic and biocompatible injectable devices. For the first time, an ultrastrong and ultratough cellulose film, which is composed of densely packed bacterial cellulose (BC) nanofibrils with hierarchical fibril alignments, is successfully demonstrated. The molecular level alignment stems from the intrinsic parallel orientation of crystalline cellulose molecules produced by Acetobacter xylinum. These aligned long‐chain cellulose molecules form subfibrils with a diameter of 2–4 nm, which are further aligned to form nanofibril bundles. The BC film yields a record‐high tensile strength (≈1.0 GPa) and toughness (≈25 MJ m^?3). Being ultrastrong and ultratough, yet the BC film is also highly flexible and can be folded into desirable shapes. The BC film exhibits a controllable manner of alignment and is highly transparent with modulated optical properties, paving the way to enabling new functionalities in mechanical, electrical, fluidic, photonics, and biocompatible applications.