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Search results for: AND PROPERTIES OF THE INDIUM-TIN-OXIDE (ITO) ELECTRODES
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Featuring Semitransparent p–i–n Perovskite Solar Cells for High-Efficiency Four-Terminal/Silicon Tandem Solar Cells
PublicationTwo issues need to be resolved when fabricating p–i–n semitransparent perovskite solar cells (ST-PVSCs) for four-terminal (4 T) perovskite/silicon tandem solar cells: 1) damage to the underlying absorber (MAPbI3), electron transporting layer ([6,6]-phenyl-C61-butyric acid methyl ester, PCBM), and work function (WF) modifier (polyethylenimine, PEI), resulting from the harsh sputtering conditions for the transparent electrodes (TEs)...
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Badanie właściwości czujników wilgotności na bazie nanocząstek tlenku cynku
PublicationW celu pomiaru wilgotności szeroko stosowane są czujniki elektryczne. Warstwą czynną, zmieniającą swoje właściwości pod wpływem pary wodnej, stanowią najczęściej materiały ceramiczne lub polimerowe. Tlenek cynku jest jednym z materiałów ceramicznych będących dobrym kandydatem do zastosowania go jako warstwy czynną w czujnikach wilgotności. W tej pracy przedstawiono wyniki badań właściwości struktur czujnikowych z warstwą tlenku...
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Wpływ procesu redukcji na właściwości strukturalne i mechaniczne szkieł tlenkowych z grupy (Pb,Bi)-(Si,Ge)-O = Influence of reduction process on the structural and mechanical properties of (Pb,Bi)-(Si,Ge)-O oxide glasses
PublicationThe effect of the reduction process in H2 at 380 °C on the microstructure and elemental composition of a glass Bi0.4Pb0.2Si0.4Ox has been investigated. It has been shown that after reduction a clearly separated top layer with a thickness of approx. 50 µm was formed on the surface of the sample. This layer is depleted of oxygen and has higher electrical conductivity than the interior of the glass. It has also been found that some...
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Wpływ kształtu elektrody woltamperometrycznej na jej właściwości metrologiczne w dziedzinie czasu
PublicationW artykule omówiono właściwości metrologiczne elektrod woltamperometrycznych. Wykazano, że w przypadku oznaczania małych wartości stężeń jonów metali, elektrody te zachowują się tak jak przetworniki pomiarowe I rzędu. Ich właściwości metrologiczne opisuje czułość i stała czasowa. Wartości tych wielkości są uzależnione od mechanizmu transportu jonów do/od powierzchni elektrod oraz od ich kształtu. Wykonano symulacje wpływu kształtu...
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Is the Solid Electrolyte Interphase an Extra-Charge Reservoir in Li-Ion Batteries?
PublicationAdvanced metal oxide electrodes in Li-ion batteries usually show reversible capacities exceeding the theoretically expected ones. Despite many studies and tentative interpretations, the origin of this extra-capacity is not assessed yet. Lithium storage can be increased through different chemical processes developing in the electrodes during charging cycles. The solid electrolyte interface (SEI), formed already during the first...
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Composite Materials Based on Silicon Oxycarbide as Anodes for Lithium-Ion Batteries
PublicationIn this work, the properties of binary SiOC/graphite and SiOC/tin, as well as ternary SiOC/graphite/tin obtained from various preceramic precursors are described. During the first step, the materials were synthesized using various techniques such as sol-gel and hydrosilylation. To prevent sedimentation and agglomeration of graphite particles during the gelation stage without using surfactants and thickeners, a new gelation technique...
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Binder-induced surface structure evolution effects on Li-ion battery performance
PublicationA comparative investigation on binder induced chemical and morphological evolution of Li4Ti5O12 electrodes was performed via X-ray photoemission spectroscopy, scanning electron microscopy, and electrochemical measurements. Composite electrodes were obtained using three different binders (PAA, PVdF, and CMC) with 80:10:10 ratio of active material:carbon:binder. The electrochemical performances of the electrodes, were found to be...
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An Aqueous Exfoliation of WO3 as a Route for Counterions Fabrication—Improved Photocatalytic and Capacitive Properties of Polyaniline/WO3Composite
PublicationIn this paper, we demonstrate a novel, electrochemical route of polyaniline/tungsten oxide (PANI)/WO3) film preparation. Polyaniline composite film was electrodeposited on the FTO (fluorine-doped tin oxide) substrate from the aqueous electrolyte that contained aniline (monomer) and exfoliated WO3 as a source of counter ions. The chemical nature of WO3 incorporated in the polyaniline matrix was investigated using X-ray photoelectron...
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The Effect of Increasing the Amount of Indium Alloying Material on the Efficiency of Sacrificial Aluminium Anodes
PublicationAl-Zn-In alloys having 4.2% zinc content and various indium content in the range of 0.02–0.2% were tested with respect to the most important electrochemical properties of sacrificial anodes in a cathodic protection, i.e., the current capacity and potential of the operating anode. The distribution of In and Zn in the tested alloys was mapped by means of the EDX technique, which demonstrated that these elements dissolve well in the...
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Organic semiconductor rubrene thin films deposited by pulsed laser evaporation of solidified solutions
PublicationOrganic semiconductor rubrene (C42H28) belongs to most preferred spintronic materials because of the high charge carrier mobility up to 40 cm2(V·s)-1. However, the fabrication of a defect-free, polycrystalline rubrene for spintronic applications represents a difficult task. We report preparation and properties of rubrene thin films deposited by pulsed laser evaporation of solidified solutions. Samples of rubrene dissolved in aromatic...
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The Influence of Iron Doping on Performance of SrTi1-XFexO3-δ Perovskite Oxygen Electrode for SOFC
PublicationSolid Oxide Fuel Cells (SOFC) are based on electrolytes and mixed ionic and electronic conductivity (MIEC) materials. The need to reduce costs causes an increase in interest of new compounds suitable for operating temperatures between 600 °C and 800 °C. The SrTi1-xFexO3 (STF) perovskite material is a perspective material that could be used for the oxygen electrodes. In this work STF materials with different content of iron (x =...
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Laser patterned platform with PEDOT–graphene composite film for NO2 sensing
PublicationThis work presents a simple and fully electrochemical route used for fabricating of a NO2 gas sensor made of reduced-graphene-oxide-poly(3,4-ethylenedioxythiophene) composite film. The sensing platform was fabricated from alumina substrate and equipped with gold interdigitated electrodes and built-in heater.The temperature distribution on the surface of interdigitated electrodes was investigated by a thermalimaging camera and compared...
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Properties of Nasicon-based CO2 sensor with Bi8Nb2O17 reference electrode
PublicationGas sensors are useful for the carbon dioxide concentration monitoring in many applications. The major challenge is to develop a potentiometric sensor working without the necessity of a reference gas and without a need of the reference electrode encapsulation. Important issue is a selection of reference electrode material, which should provide stable reference potential. For example as reference electrode material in sensor based...
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Few-Layer Black Phosphorus/Chitosan Nanocomposite Electrodes via Controlled Electrodeposition for Enhanced Electrochemical Kinetic Performance
PublicationThis study presents the preparation and characterization of few-layer black phosphorus (FLBP) chitosan electrodes by controlled electrochemical deposition of chitosan nanoparticles on FLBP-modified glassy carbon electrodes. FLBP was prepared by solvent-assisted exfoliation of bulk BP and was further modified with chitosan forming together a nanocomposite, including easy cross-linking with nanomaterials and film-forming properties....
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Efficiency of exciton splitting in organic photovoltaic cells within EQE spectrum
PublicationThe paper presents a procedure of estimating the efficiency of exciton splitting at ED/EA interface. The procedure consists in evaluation of splitting of excitons into electron-hole pairs on the basis of the external quantum efficiency spectra of planar cells and spectra of absorbance of active organic layers. The fitting parameters are the exciton splitting probabilities at ED/EA interface. The presented procedure was applied...
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Badania stabilności chemicznej kompozytowego elektrolitu 3-YSZ-Al2O3 w stosunku do materiałów elektrodowych do zastosowania w średniotemperaturowych ogniwach paliwowych
PublicationJednym z podstawowych wymogów stawianych mate- riałom na elektrolity do średniotemperaturowych ogniw paliwowych IT-SOFC (ang. intermediate-temperature solid oxide fuel cells) jest ich kompatybilność chemiczna z elektrodami w temperaturach zarówno eksploatacji, jak i wytwarzania ogniw. W celu sprawdzenia, czy badany w pracy kompozytowy elektrolit o osnowie z częściowo stabilizowanego ditlenku cyrkonu i z wtrąceniami tlenku glinu...
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Potentiometric Oxygen Sensor with Solid State Reference Electrode
PublicationThe concentration or the partial pressure of oxygen in an environment can be determined using different measuring principles. For high temperature measurements of oxygen, ceramic-based sensors are the most practical. They are simple in construction, exploration and maintenance. A typical oxygen potentiometric sensor consists of an oxygen ion conducting solid electrolyte and two electrodes deposited...
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A telemedical and an outpatient thoracic impedance measurements - a validation algorithm of the electrodes placement
PublicationThis paper presents the algorithm for validation of electrodes locations for the thoracic impedance measurements. In particular the presented algorithm was designed to perform the telemetric sleep apnea monitoring. One of the problems, during the clinical tests of a developed device, was to preserve the repeatability of measurements. It strongly depended on the appropriate electrodes placement on the examined person’s thorax. It...
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Nanotubular oxide layers and hydroxyapatite coatings on ‘Ti–13Zr–13Nb’ alloy
PublicationThe presented research was aimed to determine the mechanical properties of the nanotubular oxide layer covered with hydroxyapatite coating. The Ti–13Zr–13Nb alloy was oxidised in 1M phosphoric acid with an addition of 0?5% HF for HF solution at 20 V voltage. The electrochemically assisted deposition of hydroxyapatite was performed at cyclic polarisation in NH4H2PO4 and CaCl2 solution at 80uC. The mechanical properties were determined...
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Electrolytic deposition of reactive element thin films on Crofer 22 APU and evaluation of the resulting high-temperature corrosion protection properties at 700 °C–900 °C
PublicationThis article presents electrolytic deposition of thin Rare Earth (RE) coatings on Crofer 22 APU stainless steel substrates for high temperature applications, such as interconnects in solid oxide cell stacks. The deposition of coatings based on yttrium-, gadolinium-, lanthanum-, and cerium nitrates is discussed. The high temperature corrosion properties of surface-modified steels were examined using thermogravimetry and electrical...
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Protonic Ceramic Fuel Cells as novel electrochemical devices
PublicationProton ceramic conductors are novel materials which are interesting from the application point of view. For example, Protonic Ceramic Fuel Cells (PCFCs) is a type of a solid oxide fuel cell, which uses proton ceramic conductors as an electrolyte. Scientists are looking for the most efficient materials for these devices. In recent years main focus has been put on the search for new proton and mixed proton-electron conductors which...
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Calix[4]arenes appended with thioamide moieties as powerful tool for heavy metals recognition
PublicationSelectivity of new thioamide derivatives was assessed using those ligands as sensor materials in ion-selective membrane electrodes and tested towards Pb2+ - selectivity. The influence of the nature of the thioamide function (linear, branched or cyclic substituents) on their ionophoric properties was investigated. Electrodes based on cyclic thioamide moieties are promising analytical tools for monitoring Pb2+ concentration in natural...
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Polyurethane Nanocomposites Containing Reduced Graphene Oxide, FTIR, Raman, and XRD Studies
PublicationRecently, graphene and other graphene-based materials have become an essential part of composite science and technology. Their unique properties are not only restricted to graphene but also shared with derivative compounds like graphene oxide, reduced graphene oxide, functionalized graphene, and so forth. One of the most structurally important materials, graphene oxide (GO), is prepared by the oxidation of graphite. Though removal...
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Interrelated shape memory and Payne effect in polyurethane/graphene oxide nanocomposites
PublicationWe report the fabrication of graphene oxide (GO) based polyurethane (PU) nanocomposites by a simple method of mixing and their shape memory properties at different temperatures. Both the polymer and the filler were synthesized in the laboratory by simple and easy methods – PU by pre-polymer method and GO by improved graphene oxide synthesis method. High molecular level dispersion of GO platelets within the PU matrix and thus good...
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Pulsed Laser Deposition of Bismuth Vanadate Thin Films—The Effect of Oxygen Pressure on the Morphology, Composition, and Photoelectrochemical Performance
PublicationThin layers of bismuth vanadate were deposited using the pulsed laser deposition technique on commercially available FTO (fluorine-doped tin oxide) substrates. Films were sputtered from a sintered, monoclinic BiVO4 pellet, acting as the target, under various oxygen pressures (from 0.1 to 2 mbar), while the laser beam was perpendicular to the target surface and parallel to the FTO substrate. The oxygen pressure strongly affects...
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Fabrication and structural properties of Y and Fe co-doped SrTiO3 nanoceramics for SOFC
PublicationYttria and iron co-doped strontium titanate perovskites, (Y0,07Sr0,93Ti1-xFexO3-δx=0,1; 0,2) samples were fabricated by two methods: solid-state synthesis (SS) and the Pechinisol-gel modified method. The morphology of samples were measured by SEM and X-raydiffraction. Results were compared and discussed. The strong relationship between fabricationprocedure and microstructure has been proven. It was also observed, that the nanoceramicsobtained...
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Synthesis and modification of reduced graphene oxide aerogels for biofuel cell applications
PublicationWe have carried out the preparation of reduced graphene oxide aerogels using eco-friendly method that is based on the Hummers method of graphite oxidation without the use of NaNO3 that produces toxic gases. To obtain a porous 3D structure of reduced graphene oxide, we performed the hydrothermal reduction at elevated temperature. We also prepared the rGO aerogel/CNT composite using multiwalled carbon nanotubes as linkers. The rGO...
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Submicron inorganic particles as an additional filler in hybrid epoxy matrix composites reinforced with glass fibres
PublicationIn this study, the effect of selected submicron metal oxide (zinc oxide, titanium oxide) or non-metal oxide (silicon dioxide) particles on mechanical and thermo-mechanical properties of epoxy/glass composites was investigated. The applied epoxy resin was a diglycidyl ether of bisphenol-A cured with triethylenetetramine. As a reinforcement twill weave E-glass fabric was used. Hybrid composites (contained particulate and fibrous...
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Insightful Analysis of Phenomena Arising at the Metal|Polymer Interphase of Au-Ti Based Non-Enzymatic Glucose Sensitive Electrodes Covered by Nafion
PublicationThis paper focuses on the examination of glucose oxidation processes at an electrode material composed of gold nanoparticles embedded in a titanium template. Three dierent conditions were investigated: the chloride content in the electrolyte, its ionic conductivity and the presence of a Nafion coating. The impact of the provided environment on the oxidation reaction was evaluated by cyclic voltammetry (CV) and electrochemical impedance...
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Development of iron doped strontium titanates as oxygen electrode for solid oxide fuel cells
PublicationProducing efficient solid oxide fuel cells (SOFC) without the use of harmful elements is one of the current challenges. Increasing the safety of people and reducing production costs is possible, among others, thanks to the use of iron doped strontium titanates as porous oxygen electrodes. In this thesis, the results of research on iron doped strontium titanates as potential oxygen electrodes for SOFC are presented. The research...
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Hydrogen Production Mechanism in Low-Temperature Methanol Decomposition Catalyzed by Ni3Sn4 Intermetallic Compound: A Combined Operando and Density Functional Theory Investigation
PublicationHydrogen production from methanol decomposition to syngas (H2 + CO) is a promising alternative route for clean energy transition. One major challenge is related to the quest for stable, cost-effective, and selective catalysts operating below 400 °C. We illustrate an investigation of the surface reactivity of a Ni3Sn4 catalyst working at 250 °C, by combining density functional theory, operando X-ray absorption spectroscopy, and high-resolution...
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Semi-transparent ordered TiO2 nanostructures prepared by anodization of titanium thin films deposited onto the FTO substrate
PublicationIn a significant amount of cases, the highly ordered TiO2nanotube arrays grow through anodic oxidationof a titanium metal plate immersed in electrolyte containing fluoride ions. However, for some practicalapplications, e.g. solar cells or electrochromic windows, the semi-transparent TiO2formed directly onthe transparent, conductive substrate is very much desired. This work shows that high-quality Ti coatingcould be formed at room...
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Applying of Doped Graphene Oxide Coatings for Corrosion Prevention
PublicationINTRODUCTION Graphene is a carbonaceous material characterized by extraordinary properties (high electron mobility, high surface area, high mechanical strength of 1100 GPa, very dense network hindering the passage of even the smallest helium atoms) [1]. Therefore, it found many applications, also as an anti-corrosive layer [2]. Electrophoretic Deposition (EPD) is one of the methods to deposit coatings. However, due to slight solubility...
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Optimization of Graphene Oxide Synthesis and Its Reduction
PublicationIn this article, we present the review of the chemical methods of synthesis of graphene oxide and its reduction in order to obtain the so-called reduced graphene oxide (rGO) whose properties are similar to those of pure graphene. We also present our experiments and the results in this field and the comparison of the efficiency of different methods of synthesis as well as the reduction of graphene oxide. To characterize the obtained...
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Eco-Friendly Electromagnetic Interference Shielding Materials from Flexible Reduced Graphene Oxide Filled Polycaprolactone/Polyaniline Nanocomposites
PublicationHybrid nanocomposites have the unique ability of enhancing material properties due to the existing synergistic effect of the fillers. In this study, the authors report such an eco-friendly hybrid nanocomposite comprising of polyaniline and reduced graphene oxide in polycaprolactone. The conducting polyaniline improved the processability of polycaprolactone, and the final composites were prepared by incorporating graphene oxide...
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Dynamic Electrochemical Impedance Spectroscopy (DEIS) as a Tool for Analyzing Surface Oxidation Processes on Boron-Doped Diamond Electrodes
PublicationSurface oxidation processes play a key role in understanding electrochemical properties of boron-doped diamond (BDD) electrodes. The type of surface termination groups, which create the potential window of electrolytic water stability or hydrophobicity, influences such properties. In this study the kinetics of oxidation process under anodic polarization were studied in situ by means of Dynamic Electrochemical Impedance Spectroscopy...
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Chromogenic derivatives of new bis(phenylhydrazono-1H-tetrazol-5-yl-acetonitriles) - synthesis and properties
PublicationDerivatives of bis(phenylhydrazono-1H-tetrazol-5-yl-acetonitriles) with oxygen and sulphur atoms in the structure of aliphatic chains were successfully synthesised. The correlation between the ligand structure and its complexation properties was investigated by absorption spectroscopy. The formation of complexes of presented compounds with metal cations (Cu2+, Ni2+, Zn2+, Co2+, Fe2+ and Pb2+) was studied. Ligands 5-8 were additionally...
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Investigation of electrocatalytic gas sensor properties in presence of chlorine
PublicationProperties of sensor based on Nasicon with two round shaped platinum electrodes are investigated. Influence of different chlorine concentrations on the sensor response is presented. Measurements in different temperatures have been performed in order to determine optimal sensor working temperature.
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Improvement of Oxygen Electrode Performance of Intermediate Temperature Solid Oxide Cells by Spray Pyrolysis Deposited Active Layers
PublicationIntermediate temperature solid oxide fuel cells oxygen electrodes are modified by active interfacial layers. Spray pyrolysis is used to produce thin (≈500 nm) layers of mixed ionic and electronic conductors: Sm0.5Sr0.5CoO3−δ (SSC), La0.6Sr0.4CoO3−δ (LSC), La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF), and Pr6O11 (PrOx) on the electrode–electrolyte interface. The influence of the annealing temperature on the electrode polarization (area specific...
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Functionalization of graphene oxide coatings with phosphorus atoms and their corrosion resistance in sodium chloride environment
PublicationIn this work, we compared corrosion resistance of graphene oxide, and phosphorus functionalized reduced graphene oxide coatings obtained as a result of electrophoretic deposition on the copper substrate. Doping graphene oxide with phosphorus atoms was performed by a hydrothermal method in the presence of different amounts of phosphoric acid. Structural studies confirmed the insertion of phosphorus atoms into the graphene oxide...
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Lower Rim Substituted p-tert-Butyl-Calix[4]arene. Part 16. Synthesis of 25, 26, 27, 28-tetrakis(piperidinethiocarbonylmethylene)-p-tert-butylcalix[4]arene and its interaction with metal ions
PublicationThe synthesis, characterisation and X-ray crystal structures of p-tert-butyl-calix[4]arenethioamide L and its complex with lead L-Pb2+ is reported. The cation-binding properties in solution have been assessed by liquid-liquid extraction of the metal picrates from water into dichloromethane and by stability constants determination in acetonitrile using UV-absorption spectrophotometry or potentiometry. The compound was used as active...
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Fabrication of anti-corrosion nitrogen doped graphene oxide coatings by electrophoretic deposition
PublicationThis work assesses anti-corrosion properties of graphene and N-doped graphene coatings deposited on copper by an electrophoretic method. Graphene oxide (GO) precursor was synthesized by an improved Hummers' method, whereas N-doping was performed hydrothermally in the presence of ammonia. After nitrogenation, doped graphene oxide samples (NGO) contained a reduced amount of oxygen and about 9% w/w nitrogen as pyridinic, pyrrole,...
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Influence of the Square Wave Voltage on Dynamical Properties of a Flat Voltammetric Electrode in the Time Domain by the Electrochemical Reversible Reaction
PublicationIn this article there is a presentation of the analysis of the polarizing voltage shape influencing dynamic properties of voltammetric electrodes when on their surface reversible reaction takes place in the time domain. The electrode polarization with linearly increasing voltage and with a square component, was analyzed. The analysis that were conducted showed that the voltammetric electrode behaves like a first order transducer....
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Synthesis and properties of new 'N,'N-phenyltetrazole podand
PublicationThe synthesis of a new chromogenic N,N-phenyltetrazole receptor is reported here. The cationbinding properties of this receptor in solution were investigated by naked-eye colour change, electrochemical methods and UV-Vis spectroscopy in various solvents (CH3CN, dimethylsulphoxide (DMSO), DMSO/H2O, CH3CN/H2O and CH3CN/MeOH). In addition, the receptor was used as a sensing material in ion-selective membrane electrodes. The selectivity...
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NANOCRYSTALLINE CATHODES FOR SOLID OXIDE FUEL CELLS MADE OF NOBLE METALS
PublicationCathodes for solid oxide fuel cells prepared by the infiltration method at 600 °C are presented. The infiltration method allows to produce stable, nanostructured electrodes. Cathodes were prepared using gold, platinum, La2NiO4+δ (L2N) and La0.6Sr0.4Co0.2Fe0.8O3 δ (LSCF). Symmetrical cathode/electrolyte/cathode samples were prepared and examined with SEM microscopy and electrochemical impedance spectroscopy. Despite successful deposition...
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Electrodes criticality: the impact of CRMs in the leachate electrochemical oxidation
Publication. Landfill leachate possesses high concentrations of ammonia, micropollutants, and heavy metals, and are characterised for low biodegradability. For this reason, conventional treatment technologies may result ineffective for complete pollutant removal. Electrochemical oxidation allows most of the of recalcitrant pollutants to be oxidised effectively within an easy operational and acceptable retention time, without the need to provide...
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Spray deposited carbon nanotubes counter electrodes for dye-sensitized solar cells
PublicationCarbon nanotubes due to their catalytic properties are a promising alternative to platinum counter electrodes (CE) for dye-sensitized solar cells (DSSC). In this study, counter electrodes were made from double-walled carbon nanotube (DWCNT) ink using the spray printing technique and afterwards thermally treated at temperatures ranging from 120 to 300 °C. Morphology and structure was studied using scanning electron microscopy and...
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Spray-deposited carbon-nanotube counter-electrodes for dye-sensitized solar cells
PublicationCarbon nanotubes due to their catalytic properties are a promising alternative to platinum counter electrodes (CE) for dye-sensitized solar cells (DSSC). In this study, counter electrodes were made from double-walled carbon nanotube (DWCNT) ink using the spray printing technique and afterwards they were thermally treated at temperatures ranging from 120 to 300 °C. Morphology and structure was studied using scanning electron microscopy...
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Selection of Electrode Material for Inconel 617/P92 Steel SMAW Dissimilar Welds
PublicationThe present work aimed to investigate the microstructure and mechanical properties of the dissimilar shielded metal arc welded (SMAW) joint of Alloy 617 and P92 steel for advanced ultrasupercritical boilers. The SMAW joint was produced using three different types of electrodes, namely, ENiCrFe-3, ENiCrMo-3, and ENiCrCoMo-1. During microstructural observation of the welded joints, no possible cracking was detected in the weldments....
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Microextraction Techniques Used in the Procedures for Determining Organomercury and Organotin Compounds in Environmental Samples
PublicationDue to human activities, the concentrations of organometallic compounds in all parts of the environment have increased in recent decades. The toxicity and some biochemical properties of mercury and tin present in the environment depend on the concentration and chemical form of these two elements. The ever-increasing demand for determining compounds at very low concentration levels in samples with complex matrices requires...