Binderless thin films of zeolite-templated carbon electrodes useful for electrochemical microcapacitors with ultrahigh rate performance

Controlled nanozeolite deposits are prepared by electrochemical techniques on a macroporous carbon support and binderless thin film electrodes of zeolite-templated carbon are synthesized using the deposits as templates. The obtained film electrodes exhibit extremely high area capacitance (10–12 mF cm−2) and ultrahigh rate capability in a thin film capacitor.

Sonochemical synthesis of graphene oxide supported Pt–Pd alloy nanocrystals as efficient electrocatalysts for methanol oxidation

Pt–Pd bimetallic nanoparticles supported on graphene oxide (GO) nanosheets were prepared by a sonochemical reduction method in the presence of polyethylene glycol as a stabilizing agent. The synthetic method allowed for a fine tuning of the particle composition without significant changes in their size and degree of aggregation. Detailed characterization of GO-supported Pt–Pd catalysts was carried out by transmission electron microscopy (TEM), AFM, XPS, and electrochemical techniques. Uniform deposition of Pt–Pd nanoparticles with an average diameter of 3 nm was achieved on graphene nanosheets using a novel dual-frequency sonication approach. GO-supported bimetallic catalyst showed significant electrocatalytic activity for methanol oxidation. The influence of different molar compositions of Pt and Pd (1:1, 2:1, and 3:1) on the methanol oxidation efficiency was also evaluated. Among the different Pt/Pd ratios, the 1:1 ratio material showed the lowest onset potential and generated the highest peak current density. The effect of catalyst loading on carbon paper (working electrode) was also studied. Increasing the catalyst loading beyond a certain amount lowered the catalytic activity due to the aggregation of metal particle-loaded GO nanosheets.

Electrochemical behaviour of different redox probes on single wall carbon nanotube buckypaper-modified electrodes

In the present work, the electrochemical properties of single-walled carbon nanotube buckypapers (BPs) were examined in terms of carbon nanotubes nature and preparation conditions. The performance of the different free-standing single wall carbon nanotube sheets was evaluated via cyclic voltammetry of several redox probes in aqueous electrolyte. Significant differences are observed in the electron transfer kinetics of the buckypaper-modified electrodes for both the outer- and inner-sphere redox systems. These differences can be ascribed to the nature of the carbon nanotubes (nanotube diameter, chirality and aspect ratio), surface oxidation degree and type of functionalities. In the case of dopamine, ferrocene/ferrocenium, and quinone/hydroquinone redox systems the voltammetric response should be thought as a complex contribution of different tips and sidewall domains which act as mediators for the electron transfer between the adsorbate species and the molecules in solution. In the other redox systems only nanotube ends are active sites for the electron transfer. It is also interesting to point out that a higher electroactive surface area not always lead to an improvement in the electron transfer rate of various redox systems. In addition, the current densities produced by the redox reactions studied here are high enough to ensure a proper electrochemical signal, which enables the use of BPs in sensing devices.

Electrochemical Performance of Hierarchical Porous Carbon Materials Obtained from the Infiltration of Lignin into Zeolite Templates

Hierarchical porous carbon materials prepared by the direct carbonization of lignin/zeolite mixtures and the subsequent basic etching of the inorganic template have been electrochemically characterized in acidic media. These lignin-based templated carbons have interesting surface chemistry features, such as a variety of surface oxygen groups and also pyridone and pyridinic groups, which results in a high capacitance enhancement compared to petroleum-pitch-based carbons obtained by the same procedure. Furthermore, they are easily electro-oxidized in a sulfuric acid electrolyte under positive polarization to produce a large amount of surface oxygen groups that boosts the pseudocapacitance. The lignin-based templated carbons showed a specific capacitance as high as 250 F g−1 at 50 mA g−1, with a capacitance retention of 50 % and volumetric capacitance of 75 F cm−3 at current densities higher than 20 A g−1 thanks to their suitable porous texture. These results indicate the potential use of inexpensive biomass byproducts, such as lignin, as carbon precursors in the production of hierarchical carbon materials for electrodes in electrochemical capacitors.

Effects of Ultrasound Irradiation on the Synthesis of Metal Oxide Nanostructures

High intensity ultrasound can be used for the production of novel nanomaterials, including metal oxides. According to previous works in this field, the most notable effects are consequence of acoustic cavitation. In this context, we have studied the preparation of different materials in the presence of ultrasound, including N-doped TiO2 nanopowder, NiTiO3 nanorods and MnOx thin films. Ultrasound did not show a significant effect in all the cases. Exclusively for NiTiO3 nanorods a reduction of the final particle size occurs upon ultrasonic irradiation. From these results, it can be concluded that the ultrasound irradiation does not always play a key role during the synthesis of metal oxides. The effects seem to be particularly relevant in those cases where mass transport is highly hindered and in those procedures that require the rupture of nanoparticle aggregates to obtain a homogenous dispersion.

Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

The electro-oxidation of carbon materials enormously degrades their performance and limits their wider utilization in multiple electrochemical applications. In this work, the positive influence of phosphorus functionalities on the overall electrochemical stability of carbon materials has been demonstrated under different conditions. We show that the extent and selectivity of electroxidation in P-containing carbons are completely different to those observed in conventional carbons without P. The electro-oxidation of P-containing carbons involves the active participation of phosphorus surface groups, which are gradually transformed at high potentials from less-to more-oxidized species to slow down the introduction of oxygen groups on the carbon surface (oxidation) and the subsequent generation of (C*OOH)-like unstable promoters of electro-gasification. The highest-oxidized P groups (–C–O–P-like species) seem to distribute the gained oxygen to neighboring carbon sites, which finally suffer oxidation and/or gasification. So it is thought that P-groups could act as mediators of carbon oxidation although including various steps and intermediates compared to electroxidation in P-free materials.

Study on Electrochemical Capacitance using Templated Carbons

The template carbonization technique enables the production of porous carbons and carbon-based composites with precisely designed, controlled pore structures. The resulting templated carbons are therefore useful to investigate and understand the relation between carbon nanostructure and electrocapacitive properties. In this short review paper, we introduce our works on electrochemical capacitance using zeolite-templated carbons and carbon-coated anodic aluminum oxide.

Photogeneration of Hydrogen from Water by Hybrid Molybdenum Sulfide Clusters Immobilized on Titania

Two new hybrid molybdenum(IV) Mo3S7 cluster complexes derivatized with diimino ligands have been prepared by replacement of the two bromine atoms of [Mo3S7Br6]2− by a substituted bipyridine ligand to afford heteroleptic molybdenum(IV) Mo3S7Br4(diimino) complexes. Adsorption of the Mo3S7 cores from sample solutions on TiO2 was only achieved from the diimino functionalized clusters. The adsorbed Mo3S7 units were reduced on the TiO2 surface to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction by approximately 0.3 V (for 1 mA cm−2) with a turnover frequency as high as 1.4 s−1. The nature of the actual active molybdenum sulfide species has been investigated by X-ray photoelectron spectroscopy. In agreement with the electrochemical results, the modified TiO2 nanoparticles show a high photocatalytic activity for H2 production in the presence of Na2S/Na2SO3 as a sacrificial electron donor system.

Successful functionalization of superporous zeolite templated carbon using aminobenzene acids and electrochemical methods

A novel and selective electrochemical functionalization of a highly reactive superporous zeolite templated carbon (ZTC) with two different aminobenzene acids (2-aminobenzoic and 4-aminobenzoic acid) was achieved. The functionalization was done through potentiodynamic treatment in acid media under oxidative conditions, which were optimized to preserve the unique ZTC structure. Interestingly, it was possible to avoid the electrochemical oxidation of the highly reactive ZTC structure by controlling the potential limit of the potentiodynamic experiment in presence of aminobenzene acids. The electrochemical characterization demonstrated the formation of polymer chains along with covalently bonded functionalities to the ZTC surface. The functionalized ZTCs showed several redox processes, producing a capacitance increase in both basic and acid media. The rate performance showed that the capacitance increase is retained at scan rates as high as 100 mV s−1, indicating that there is a fast charge transfer between the polymer chains formed inside the ZTC porosity or the new surface functionalities and the ZTC itself. The success of the proposed approach was also confirmed by using other characterization techniques, which confirmed the presence of different nitrogen groups in the ZTC surface. This promising method could be used to achieve highly selective functionalization of highly porous carbon materials.

Pseudocapacitance of zeolite-templated carbon in organic electrolytes

Carbon and graphene-based materials often show some amount of pseudocapacitance due to their oxygen-functional groups. However, such pseudocapacitance is generally negligible in organic electrolytes and has not attracted much attention. In this work, we report a large pseudocapacitance of zeolite-templated carbon (ZTC) based on the oxygen-functional groups in 1 M tetraethylammonium tetrafluoroborate dissolved in propylene carbonate (Et4NBF4/PC). Due to its significant amount of active edge sites, a large amount of redox-active oxygen functional groups are introduced into ZTC, and ZTC shows a high specific capacitance (330 F g−1). Experimental results suggest that the pseudocapacitance could be based on the formation of anion and cation radicals of quinones and ethers, respectively. Moreover, ZTC shows pseudocapacitance also in 1 M lithium hexafluorophosphate dissolved with a mixture of ethylene carbonate and diethyl carbonate (LiPF6/EC+DEC) which is used for lithium-ion batteries and lithium-ion capacitors.

Saint Petersburg Region, Russia, 1817 (Raster Image)

This layer is a georeferenced raster image of the historic, topographic paper map entitled: [Topograficheskai͡a karta okruzhnosti Sanktpetersburga : Ispravlennaia 1817 goda]. It was published by Voenno-Topograficheskom Depo pri Glavnom Shtabie ego Impertorskafo Velichestva in [1817]. Scale [ca. 1:42,000]. Covers Saint Petersburg Region, Russia. Map in Russian.The image inside the map neatline is georeferenced to the surface of the earth and fit to the European Datum 1950, Universal Transverse Mercator (UTM) Zone 36N projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map.This is a typical topographic map portraying both natural and manmade features. It shows and names works of nature, such as mountains, valleys, lakes, rivers, vegetation, etc. It also identify the principal works of humans, such as roads, railroads, boundaries, transmission lines, major buildings, etc. Relief is shown by hachures. This layer is part of a selection of digitally scanned and georeferenced historic maps from The Harvard Map Collection as part of the Imaging the Urban Environment project. Maps selected for this project represent major urban areas and cities of the world, at various time periods. These maps typically portray both natural and manmade features at a large scale. The selection represents a range of regions, originators, ground condition dates, scales, and purposes.

A interpretação constitucional no controle difuso de constitucionalidade ante a omissão do Estado na efetivação dos direitos fundamentais

O Poder Judiciário expressa a vontade política do Estado interpretando o direito e mantendo a força normativa da Constituição, sobretudo frente as normas que expressam direitos fundamentais por sua alta carga valorativa, sendo o juiz o último intérprete da norma, o qual não deve tutelar sempre o direito fundamental sob maior ataque, mas sim encontrando critérios científicos que leve em consideração sua efetividade e as medidas restritivas a ele impostas. No estudo abordou-se sem exclusividade os métodos de interpretação constitucional, e seu princípios interpretativos, visando harmonizá-los e não valorizar partes do texto constitucional, ante sua força decorrer da unidade. Abordados os princípios da supremacia da Constituição, da unidade de seu texto, máxima efetividade de suas disposições, e força normativa, com enfoque no princípio da interpretação conforme, não só no controle concentrado como também no difuso de constitucionalidade. Analisou-se técnicas de decisão no controle de constitucionalidade, não só a declaração de inconstitucionalidade com e sem redução do texto, como sua diferenciação da interpretação conforme. Explanadas ainda as ações de controle concentrado perante o Supremo Tribunal Federal, e esclarecidas a repercussão geral em recurso extraordinário, o mandado de injunção, as súmulas vinculantes e impeditivas de recursos, a reclamação constitucional, o controle de constitucionalidade no âmbito dos Tribunais estaduais, e o praticado pelos juízes de primeiro grau. E no controle difuso de constitucionalidade foi abordada o controle de convencionalidade dos tratados internacionais sobre direitos humanos. Finalizando com a omissão do Estado frente aos direitos fundamentais, reconhecendo seu papel de destaque no ordenamento jurídico constitucional por não estarem só naquele texto, mas espargidos por todo o sistema jurídico interno e externo. Ao final tratou-se das omissões estatais da assistência judiciária gratuita, da regulamentação do direito de greve dos servidores públicos, e das omissões nas prestações dos serviços públicos de saúde e educação.

O Contributo dos Fatores Psicológicos na Ocorrência do Parto Pré-termo

Some psychological variables of women seem to be in close relationship with the clinical course of pregnancy and delivery outcome. However, about risk factors for preterm birth, it is necessary to deepen the knowledge of the psychological risk area to enable more effective prevention. Aim: To relate the result of delivery, with regard to gestational age, mode of delivery and infant characteristics with psychological variables assessed during pregnancy, prenatal maternal attachment, psychopathological symptomatology and coping. Methodology: A prospective, descriptive correlational study; participants were 395 women at the second trimester of pregnancy and at postpartum, who attended antenatal clinics at the center of Portugal. The following instruments were used: Clinical Questionnaire about the Result of Delivery; Sociodemographic and Clinical Questionnaire in Pregnancy; Maternal Antenatal Attachment Scale; Brief Symptoms Inventory (BSI); Problems’ Resolution Inventory (PRI). Results: Gestational age and birth weight of the baby, on one side, and variables of prenatal attachment, BSI and PRI, on the other side, did not correlate significantly. The quality of prenatal maternal attachment was higher in women who came to have a delivery by forceps or vacuum extraction, compared with those that had caesarean birth (p = .05). The majority of women had a healthy pregnancy (75.7%). Coping strategies like Interpersonal Sensitivity and Help-seeking seem to influence the occurrence of obstetrical pathology. Women with higher scores on Total Prenatal Attachment and Intensity of Preocupation are more likely to have newborns with health problems. There is an association between clinical variables, the newborn´s health at birth and obstetric pathology of the II and III trimesters. Conclusion: Prenatal psychological factors such as prenatal attachment do not seem to influence the obstetric condition or the result of delivery but appear to play an important role about how pregnant women experience pregnancy and labor.

Modélisation de l’activité électrique des oreillettes avant et après ablation par cathéter

- Réalisé au centre de recherche de l'hospital du Sacré-Coeur de Montréal. - Programme conjoint entre Université de Montréal et École Polytechnique de Montréal.

Réadaptation et performance visuelle chez la personne hémianopsique : une étude de cas portant sur les saccades oculaires et le blindsight

But: La perte unilatérale du cortex visuel postérieur engendre une cécité corticale controlatérale à la lésion, qu’on appelle hémianopsie homonyme (HH). Celle-ci est notamment accompagnée de problèmes d’exploration visuelle dans l’hémichamp aveugle dus à des stratégies oculaires déficitaires, qui ont été la cible des thérapies de compensation. Or, cette perte de vision peut s’accompagner d’une perception visuelle inconsciente, appelée blindsight. Notre hypothèse propose que le blindsight soit médié par la voie rétino-colliculaire extrastriée, recrutant le colliculus supérieur (CS), une structure multisensorielle. Notre programme a pour objectif d’évaluer l’impact d’un entraînement multisensoriel (audiovisuel) sur la performance visuelle inconsciente des personnes hémianopsiques et les stratégies oculaires. Nous essayons, ainsi, de démontrer l’implication du CS dans le phénomène de blindsight et la pertinence de la technique de compensation multisensorielle comme thérapie de réadaptation. Méthode: Notre participante, ML, atteinte d’une HH droite a effectué un entraînement d’intégration audiovisuel pour une période de 10 jours. Nous avons évalué la performance visuelle en localisation et en détection ainsi que les stratégies oculaires selon trois comparaisons principales : (1) entre l’hémichamp normal et l’hémichamp aveugle; (2) entre la condition visuelle et les conditions audiovisuelles; (3) entre les sessions de pré-entraînement, post-entraînement et 3 mois post-entraînement. Résultats: Nous avons démontré que (1) les caractéristiques des saccades et des fixations sont déficitaires dans l’hémichamp aveugle; (2) les stratégies saccadiques diffèrent selon les excentricités et les conditions de stimulations; (3) une adaptation saccadique à long terme est possible dans l’hémichamp aveugle si l’on considère le bon cadre de référence; (4) l’amélioration des mouvements oculaires est liée au blindsight. Conclusion(s): L’entraînement multisensoriel conduit à une amélioration de la performance visuelle pour des cibles non perçues, tant en localisation qu’en détection, ce qui est possiblement induit par le développement de la performance oculomotrice.