Independent Configurable Architecture for Reliable Operation of Unmanned Systems with Distributed Onboard Services

This paper presents the development of ICAROUS-2 (Independent Configurable Architecture for Reliable Operation of Unmanned Systems with Distributed Onboard Services), the second generation of a software architecture that integrates several algorithms as distributed onboard services to enable robust autonomous UAS applications. In particular, the ICAROUS architecture defines a framework to perform detect and avoid, geofencing, path monitoring, path planning, and autonomous decision making to ensure safety and mission progress. Most of the core algorithms implemented in ICAROUS are formally verified using an interactive theorem prover. These algorithms are composed together using a plan execution engine, whose operational semantics is formally specified. A description of the integrated architecture, services currently available, and flight test results highlighting the capability of ICAROUS are presented

On the activation energy of the formic acid oxidation reaction on platinum electrodes

A temperature dependent study on the formic acid oxidation reaction has been carried out in order to determine the activation energy of this reaction on different platinum single crystal electrodes, namely Pt(1 0 0), Pt(1 1 1), Pt(5 5 4) and Pt(5 4 4) surfaces. The chronoamperometric transients obtained with pulsed voltammetry have been analyzed to determine the current densities through the active intermediate and the CO formation rate. From the temperature dependency of those parameters, the activation energy for the direct reaction and the CO formation step have been calculated. For the active intermediate path, the activation energy are in the range of 50–60 kJ/mol. On the other hand, a large dependence on the electrode potential is found for the activation energy of the CO formation reaction on the Pt(1 0 0) electrode, and the activation energy values for this process range between 20 and 100 kJ/mol. These results have been explained using a reaction mechanism in which the oxidation of formic acid requires the presence of a pre-adsorbed anion on the electrode surface

Effects of the anion adsorption and pH on the formic acid oxidation reaction on Pt(111) electrodes

The effects of solution pH and anion adsorption for the formic acid oxidation reaction on the Pt(111) electrode have been examined using electrochemical techniques. Regarding the pH effects, it has been found that oxidation currents for this reaction increase with pH, which indicates that solution formate is involved in the reaction mechanism. Unexpectedly, the adsorption of sulfate on the Pt(111) electrode has a positive effect on the oxidation of formic acid, which also suggests that adsorbed anions are also involved in the mechanism. The activation energy calculated from temperature dependent measurements diminishes with the solution pH and also in the presence of adsorbed sulfate. These measurements corroborate the involvement of solution formate and anions in the oxidation mechanism. Using these results, a rate equation for the oxidation of formic acid is proposed. The current values calculated from this equation are in very good agreement with the experimental currents in perchloric acid solutions.This work has been financially supported by the MICINN (Spain)(project CTQ2010-16271) and Generalitat Valenciana (project PROMETEO/2009/045, FEDER)

Understanding the Effect of the Adatoms in the Formic Acid Oxidation Mechanism on Pt(111) Electrodes

The engineered search for new catalysts requires a deep knowledge about reaction mechanisms. Here, with the support of a combination of computational and experimental results, the oxidation mechanism of formic acid on Pt(111) electrodes modified by adatoms of the p block is elucidated for the first time. DFT calculations reveal that some adatoms, such as Bi and Pb, have positive partial charge when they are adsorbed on the bare surface, whereas others, such as Se and S, remain virtually neutral. When the partial charge is correlated with previously reported experimental results for the formic acid oxidation reaction, it is found that the partial positive charge is directly related to the increase in catalytic activity of the modified surface. Further, it is obtained that such a positive partial charge is directly proportional to the electronegativity difference between the adatom and Pt. Thus, the electronegativity difference can be used as an effective descriptor for the expected electrocatalytic activity. This partial positive charge on the adatom drives the formic acid oxidation reaction, since it favors the formation and adsorption of formate on the adatom. Once adsorbed, the neighboring platinum atoms assist in the C–H bond cleavage. Finally, it is found that most of the steps involved in the proposed oxidation mechanism are barrierless, which implies a significant diminution of the activation barriers in comparison to that of the unmodified Pt(111) electrode. This diminution in the activation barrier has been experimentally corroborated for the Bi–Pt(111) electrode, supporting the proposed mechanism.This work has been financially supported by the MINECO (Spain) (project CTQ2013-44083-P) and Generalitat Valenciana (project PROMETEOII/2014/013)

Charge effects on the behavior of CTAB adsorbed on Au(111) electrodes in aqueous solutions

The behavior of adsorbed CTAB on Au(111) electrodes has been studied using electrochemical and FTIR experiments in different aqueous solutions. The results show that the adsorbed layer is stable in acidic solutions in the whole potential range of study. The observed electrochemical and FTIR behavior is compatible with the formation of a membrane of CTA+ on the electrode surface with the polar amino groups in contact with the surface. When the electrode charge is negative, the polar groups are attracted to the surface, so that the capacitance of the electrode is smaller than that recorded for the unmodified Au(111) electrode. As the charge becomes positive, the membrane detaches from the surface and water molecules permeate through it, changing the capacitance of the electrode and giving rise to characteristic peaks in the voltammetric profile. At potentials higher than these peaks, the behavior of the electrode is comparable to that observed for the unmodified electrode. The stability of the membrane is facilitated by the incorporation of anions of the supporting electrolyte. Those anions remain on the membrane even when the electrode is transferred to a different solution, as the electrochemical behavior shows.Financial support from Ministerio de Ciencia e Innovación (Project PID2019-105653GB-100 ) and Generalitat Valenciana (Project PROMETEO/2020/063 ) is acknowledged

ATR-SEIRAS study of CO adsorption and oxidation on Rh modified Au(111-25 nm) film electrodes in 0.1 M H2SO4

Rh modified Au(111-25 nm) electrodes, prepared by electron beam evaporation and galvanostatic deposition, were employed to study adsorption and electro-oxidation of CO on Rh in 0.1 M sulfuric acid solution by in situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). The results of ATR-SEIRAS experiments were compared with those obtained by infrared reflection absorption spectroscopy on three low-index Rh single crystal surfaces. The Rh film deposited on Au(111-25 nm) electrode consists of 3D clusters forming a highly stepped [n(111) × (111)]-like surface with narrow (111) terraces. When CO was dosed at the hydrogen adsorption potential region, CO adsorbed in both atop (COL) and bridge (COB) configurations, as well as coadsorbed water species, were detected on the Rh film electrode. A partial interconversion of spectroscopic bands due to the CO displacement from bridge to atop sites was found during the anodic potential scan, revealing that there is a potential-dependent preference of CO adsorption sites on Rh surfaces. Our data indicate that CO oxidation on Rh electrode surface in acidic media involves coadsorbed water and follows the nucleation and growth model of a Langmuir-Hinshelwood type reaction.The work was supported by the Research Center Jülich, the University of Bern, Swiss National Science Foundation (200020_144471, 200021-124643), the Spanish Ministerio de Economía y Competitividad (project CTQ2013-44083-P) and University of Alicante. QX acknowledges fellowships of the Research Center Jülich; IP acknowledges support by COST Action TD 1002; and AK acknowledges the financial support by CTI Swiss Competence Centers for Energy Research (SCCER Heat and Electricity Storage)

Development of learning objectives for neurology in a veterinary curriculum: Part II: Postgraduates

Background: Specialization in veterinary medicine in Europe is organized through the Colleges of the European Board of Veterinary Specialization. To inform updating of the curriculum for residents of the European College of Veterinary Neurology (ECVN) job analysis was used. Defining job competencies of diploma holders in veterinary neurology can be used as references for curriculum design of resident training. With the support of the diplomates of the ECVN and the members of the European Society of Veterinary Neurology (ESVN) a mixed-method research, including a qualitative search of objectives and quantitative ranking with 149 Likert scale questions and 48 free text questions in 9 categories in a survey was conducted. In addition, opinions of different groups were subjected to statistical analysis and the result compared. Results: A return rate of 62% (n = 213/341) was achieved. Of the competencies identified by the Delphi process, 75% objectives were expected to attain expert level; 24% attain advanced level; 1% entry level. In addition, the exercise described the 11 highly ranked competencies, the 3 most frequently seen diseases of the central and peripheral nervous systems and the most frequently used immunosuppressive, antiepileptic and chemotherapeutic drugs. Conclusion: The outcomes of this “Delphi job analysis” provide a powerful tool to align the curriculum for ECVN resident training and can be adapted to the required job competencies, based on expectations. The expectation is that for majority of these competencies diplomates should attain an expert level. Besides knowledge and clinical skills, residents and diplomates are expected to demonstrate high standards in teaching and communication. The results of this study will help to create a European curriculum for postgraduate education in veterinary neurology

An Aza-Fused pi-Conjugated Microporous Framework Catalyzes the Production of Hydrogen Peroxide

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/page/policy/articlesonrequest/index.html"[EN] In order to produce hydrogen peroxide in small-scale electrochemical plants, selective catalysts for the oxygen reduction reaction (ORR) toward the desired species are required. Here, we report about the synthesis, characterization, ORR electrochemical behavior, and reaction mechanism of an aza-fused pi-conjugated microporous polymer, which presents high selectivity toward hydrogen peroxide. It was synthesized by polycondensation of 1,2,4,5-benzenetetramine tetrahydrochloride and triquinoyl octahydrate. A cobalt-modified version of the material was also prepared by a simple postsynthesis treatment with a Co(II) salt. The characterization of the material is consistent with the formation of a conductive robust porous covalent laminar polyaza structure. The ORR properties of these catalysts were investigated using rotating disk and rotating disk ring arrangements. The results indicate that hydrogen peroxide is almost exclusively produced at very low overpotentials on these materials. Density functional theory calculations provide key elements to understand the reaction mechanism. It is found that, at the relevant potential for the reaction, half of the nitrogen atoms of the material would be hydrogenated. This hydrogenation process would destabilize some carbon atoms in the lattice and would provide segregated charge. On the destabilized carbon atoms, molecular oxygen would be chemisorbed with the aid of charge transferred from the hydrogenated nitrogen atoms and solvation effects. Due to the low destabilization of the carbon sites, the resulting molecular oxygen chemisorbed state, which would have the characteristics of a superoxide species, would be only slightly stable, promoting the formation of hydrogen peroxide.This work has been financially supported by the MCINN-FEDER (projects CTQ2016-76221-P, MAT2013-46753-C2-1-P, and MAT2014-52305-P) and Generalitat Valenciana (project PROMETEO/2014/013).Briega-Martos, V.; Ferre Vilaplana, A.; De La Peña, A.; Segura, J.; Zamora, F.; Feliu, J.; Herrero, E. (2017). An Aza-Fused pi-Conjugated Microporous Framework Catalyzes the Production of Hydrogen Peroxide. ACS Catalysis. 7(2):1015-1024. https://doi.org/10.1021/acscatal.6b03043S101510247