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Determination of Roughness Factor and Fractal Dimension of Zirconium in its Native and Surface Modified State using Atomic Force Microscopy. Effect of the Hydrogen Evolution Reaction on the Surface Structure
Novák, M. ; Kocábová, Jana ; Kolivoška, Viliam ; Pospíšil, Lubomír ; Macák, J. ; Cichoň, Stanislav ; Cháb, Vladimír ; Hromadová, Magdaléna
Atomic force microscopy (AFM) was used to characterize surface morphology of pristine zirconium, Si modified and FeSi modified zirconium electrodes prior and after hydrogen evolution at potentials negative of the open circuit potential value. Two main characteristic parameters were obtained from the ex situ AFM height images, namely, the roughness factor and fractal dimension of the studied surface. The effect of hydrogen evolution reaction on the electrode surface morphology was discussed. Fractal dimension values were used successfully to explain the non ideality of the interfacial capacitance.
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Investigation of Single Molecule Charge Transport Properties and Geometrical Arrangement in Terpyridine Architectures Supported by the Tetraphenylmethane Tripod
Kolivoška, Viliam ; Sebechlebská, Táňa ; Šebera, Jakub ; Gasior, Jindřich ; Lindner, M. ; Lukášek, J. ; Valášek, M. ; Mayor, M. ; Mészáros, G. ; Hromadová, Magdaléna
Tripodal platforms were engineered recently to realize a well-defined directional contact between metallic electrodes and molecular architectures dedicated to serve as working elements for electronic applications. In this work we employ cyclic voltammetry, scanning tunneling microscopy break junction technique and theoretical approaches based on the combination of density functional theory and non-equilibrium Green´s function to investigate the geometrical arrangement and single molecule charge transport in terpyridine-based architectures supported by tetraphenylmethane tripod. We demonstrate that this architecture adopts a favorable geometrical arrangement capable of forming highly conductive molecular junctions and is thus suitable to serve as a basis for working molecular switches.
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Effect of pH on the Oxide Film Formation on a Pristine Zr Electrode
Hromadová, Magdaléna ; Kocábová, Jana ; Kolivoška, Viliam ; Pospíšil, Lubomír
Effect of pH on the oxidation of zirconium metal was studied by cyclic voltammetry in\naqueous borate buffer solutions as a function of the potential scan rate and pH from 4.80 to\n9.17. The results show that the oxide growth kinetics depends on pH of the electrolyte\nsolution and the total amount of irreversibly formed oxide under the potentiodynamic\nconditions decreases with decreasing buffer pH in accord with thermodynamic considerations.\nCathodic current corresponding to hydrogen evolution reaction diminishes in the presence of\nanodically modified electrode compared to bare zirconium.
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Charge Transport through Molecular Towers Based on Tetraphenylmethane Tripods
Kolivoška, Viliam ; Šebera, Jakub ; Lindner, M. ; Valášek, M. ; Mayor, M. ; Mészáros, G. ; Gasior, Jindřich ; Hromadová, Magdaléna
Molecular platforms with multiple anchors were introduced recently to provide robust\ncoupling between molecular electronic components and metallic electrodes. In this work,\ncharge transport in tower-shaped single molecule conductors based on tetraphenylmethane\ntripod possessing three thiol anchors is investigated by scanning tunneling microscopy break\njunction technique. The effect of tripod substitution pattern and number of repeating units in\nmolecule is addressed. The substitution was found to influence conductance value in early\nstages of molecular junction evolution, where tower lays parallel to surface. In late stages, the\ncharge is transported through principal molecular axis and junction breaks thermally in tilted\nconfiguration.
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Characterization of electrode modified by pyridineporphyrazinate film and its utilization in electrochemical sensor
Klusáčková, Monika ; Nesměrák, Karel (advisor) ; Hromadová, Magdaléna (referee)
In the diploma thesis the charge transfer reaction on thin layer N,N',N'',N'''-tetramethyl-tetra-3,4-pyridinoporphyrazinocobalt mediator is studied. The mediator is deposited on electrode surface formed by basal plane of highly ordered pyrolytic graphite. The modified electrode, which displays electrocatalytic activity to oxidation of propylene, has been characterized by cyclic voltammetry, backscattering spectroscopy and atomic force microscopy.
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Dependence of Single-Molecule Conductance of Pyridinium Derivatives on Their Structure
Lachmanová, Štěpánka ; Hromadová, Magdaléna ; Kolivoška, Viliam ; Pospíšil, Lubomír ; Gasior, Jindřich ; Mészáros, G. ; Lainé, P. P.
The derivates of pyridinium belong to promising group of molecules applicable in molecular electronics. For this purpose, four expanded branched pyridinium compounds were synthetized and the influence of the molecular structure on their electrochemical properties and single-molecule conductances has been studied. The highest values of conductance provided compounds 9-(pyridin-4-yl)benzo[c]benzo[1,2]quinolizino[3,4,5,6-ija][1,6]naphthyridin-15-ium tetrafluoroborate and 3,5-dimethyl-2´,6´-diphenyl-[4,1´:4´,4´´-terpyridin]-1´-ium tetrafluoroborate. By the electrochemical reduction both of these compounds received two electrons in two separated one-electron steps. On the other hand, the compounds 2´,6´-diphenyl-[4,1´:4´,4´´-terpyridin]-1´-ium tetrafluoroborate and 2,6-diphenyl-4-(4-(pyridin-4-yl)phenyl)-[1,4´-bipyridin]-1-ium tetrafluoroborate are reduced by different mechanism and their conductance was lower.
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Comparison of Techniques for Single-Molecule Conductance Measurements of Expanded Pyridinium Molecules
Lachmanová, Štěpánka ; Hromadová, Magdaléna ; Sokolová, Romana ; Kocábová, Jana ; Gasior, Jindřich ; Mészáros, G. ; Lainé, P. P.
This work is focused on the comparison of two techniques of single-molecule conductance measurements: Scanning Tunneling Microscopy Break Junction technique and Mechanically Controlled Break Junction technique. The structure of studied compound 9-(pyridin-4-yl)benzo[c]benzo[1,2]quinolizino[3,4,5,6-ija][1,6]naphthyridin-15-ium allows the formation of the molecular bridge between two gold electrodes, which are connected to a source of the constant voltage in both of the used methods. The differences, advantages and disadvantages of both of the techniques will be discussed. Both techniques provided two values of conductance of studied compound depending on the experimantal conditions.
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