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Characterization and Analytical Application of Cobalt Pyridinoporfyrazinate as a Non-Platinum Mediator in Hydrogen Electrocatalysis
Klusáčková, Monika
This work reports on the cobalt pyridinoporphyrazinate (CoTmtppa) as a platinum-group metal-free catalyst for hydrogen evolution and oxidation reactions with the possibility of use in hydrogen energy and hydrogen potentiometric sensing. A different interaction of CoTmtppa with various electrode substrates, highly oriented pyrolytic graphite (HOPG) and annealed gold (Au(111)), affects its electrocatalytic behaviour in hydrogen reactions. The formation of a hydride-type complex with the bonding of hydrogen atoms to cobalt centre is supposed to be the rate-determining step. In the case of hydrogen evolution, the maximum catalytic activity of mediator was reached at pH = 11,0, when the HOPG/CoTmtppa showed overpotential decrease by 300 mV and an almost 60-fold increase of current densities compared to HOPG. The electrocatalytic activity of Au(111)/CoTmtppa resulted in a further decrease of overpotential by 175 mV in comparison with HOPG/Co(I)Tmtppa. The electrochemical oxidation of hydrogen was found to depend on hydrogen source which was electrochemically generated on-site or molecular hydrogen supplied from an external source. In the case of electrochemically generated hydrogen, the maximum activity of HOPG/CoTmtppa was reached at pH = 2.1 and an additional it was observed 50 % increase in current...
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Characterization and Analytical Application of Cobalt Pyridinoporfyrazinate as a Non-Platinum Mediator in Hydrogen Electrocatalysis
Klusáčková, Monika
This work reports on the cobalt pyridinoporphyrazinate (CoTmtppa) as a platinum-group metal-free catalyst for hydrogen evolution and oxidation reactions with the possibility of use in hydrogen energy and hydrogen potentiometric sensing. A different interaction of CoTmtppa with various electrode substrates, highly oriented pyrolytic graphite (HOPG) and annealed gold (Au(111)), affects its electrocatalytic behaviour in hydrogen reactions. The formation of a hydride-type complex with the bonding of hydrogen atoms to cobalt centre is supposed to be the rate-determining step. In the case of hydrogen evolution, the maximum catalytic activity of mediator was reached at pH = 11,0, when the HOPG/CoTmtppa showed overpotential decrease by 300 mV and an almost 60-fold increase of current densities compared to HOPG. The electrocatalytic activity of Au(111)/CoTmtppa resulted in a further decrease of overpotential by 175 mV in comparison with HOPG/Co(I)Tmtppa. The electrochemical oxidation of hydrogen was found to depend on hydrogen source which was electrochemically generated on-site or molecular hydrogen supplied from an external source. In the case of electrochemically generated hydrogen, the maximum activity of HOPG/CoTmtppa was reached at pH = 2.1 and an additional it was observed 50 % increase in current...
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Characterization and Analytical Application of Cobalt Pyridinoporfyrazinate as a Non-Platinum Mediator in Hydrogen Electrocatalysis
Klusáčková, Monika ; Nesměrák, Karel (advisor) ; Opekar, František (referee) ; Gál, Miroslav (referee)
This work reports on the cobalt pyridinoporphyrazinate (CoTmtppa) as a platinum-group metal-free catalyst for hydrogen evolution and oxidation reactions with the possibility of use in hydrogen energy and hydrogen potentiometric sensing. A different interaction of CoTmtppa with various electrode substrates, highly oriented pyrolytic graphite (HOPG) and annealed gold (Au(111)), affects its electrocatalytic behaviour in hydrogen reactions. The formation of a hydride-type complex with the bonding of hydrogen atoms to cobalt centre is supposed to be the rate-determining step. In the case of hydrogen evolution, the maximum catalytic activity of mediator was reached at pH = 11,0, when the HOPG/CoTmtppa showed overpotential decrease by 300 mV and an almost 60-fold increase of current densities compared to HOPG. The electrocatalytic activity of Au(111)/CoTmtppa resulted in a further decrease of overpotential by 175 mV in comparison with HOPG/Co(I)Tmtppa. The electrochemical oxidation of hydrogen was found to depend on hydrogen source which was electrochemically generated on-site or molecular hydrogen supplied from an external source. In the case of electrochemically generated hydrogen, the maximum activity of HOPG/CoTmtppa was reached at pH = 2.1 and an additional it was observed 50 % increase in current...
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Influence of electrode preparation on electrocatalytic activity of water soluble porphyrazine complex to hydrogen
Klusáčková, Monika ; Janda, Pavel ; Tarábková, Hana
The influence of electrode preparation and used electrode substrate on electrocatalytic activity of N, N`,N``,N```tetramethyl-tetra-3,4-pyridinopor-phyrazinocobalt (CoTmt-3,4-ppa) complex deposited on electrode surface for hydrogen reaction has been studied. Electrochemical deposition, spontaneous adsorption, and spin coating have been used to the modification of two different electrode substrates: annealed gold and highly oriented pyrolytic graphite. Prepared electrodes have been characterized using cyclic voltammetry, backscattering VIS spectroscopy and atomic force microscopy. The detailed comparison of surface morphology, surface coverage, surface roughness parameters, and thickness of deposited layers of CoTmt-3,4-ppa mediatoronhydrogen reaction has been investigated.
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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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Effect of substrate hydrophobicity on the electrocatalytic behaviour of phthalocyanine
Klusáčková, Monika ; Janda, Pavel ; Tarábková, Hana
In this work, the electrocatalytic activity of pyridinoporphyrazine mediator deposited on two substrates with different hydrophobicity has been presented. We focused on hydrophobic highly oriented pyrolytic graphite (HOPG) as well as hydrophilic annealed gold electrode (Au111). The immobilization of mediator has been carried out spontaneous adsorption from aqueous solution on electrode surfaces. The different hydrophobicity surface resulted in change the electrocatalytic activities of mediator to hydrogen in aqueous solution. For this purpose, electrochemical, in situ spectroelectrochemical, and ex situ microscopically characterizations have been performed. The detailed comparison of surface morphology, surface coverage, surface roughness parameters, thickness of deposited layers of mediator, and pH solution has been studied.
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Influence of Electrode Preparation on Electrocatalytic Activity of Tetrapyridinoporphyrazinato Cobalt(II) Complex to Propylene
Klusáčková, Monika ; Janda, Pavel ; Tarábková, Hana
The water-soluble complex N ,N' ,N' ',N' "-Tetramethyl-tetra-3,4-pyridinoporphyrazinocobalt (CoTmt-3,4-ppa) has been deposited by different techniques on two substrate. Electrochemical deposition, spontaneous adsorption, and spin coating have been used to the modification of two electrode material: annealed gold as hydrophilic substrate and highly oriented pyrolytic graphite as hydrophobic substrate. The modified electrodes have been characterized using cyclic voltammetry, backscattering VIS spectroscopy and atomic force microscopy. The influence of substrate material and modification techniques on electrocatalytic activity of CoTmt-3,4-ppa modified electrodes for propylene oxidation has been studied.
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Gaseous nanodomains at solid/liquid interface
Janda, Pavel ; Tarábková, Hana ; Klusáčková, Monika
Existence of gaseous nanodomains at solid liquid interface (surface nanobubbles) has been presumed first by Phil Attard and his fellow workers (1) based on discovery of long range attractive forces between two adjacent planar solid surfaces immersed in water. Attard et al. ascribed forces and their discontinuous character to sub-micro bubbles bridging both immersed surfaces.
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