About: Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin

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An Entity of Type : http://linked.opendata.cz/ontology/domain/vavai/Vysledek, within Data Space : linked.opendata.cz associated with source document(s)

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	Stopped- fl ow kinetic measurements, UV vis spectroscopy, rotating disk voltammetry, and quantum chemical calculations are used to clarify the role of water in the homogeneous two-electron reduction of O 2 to H 2 O 2 in 1,2-dichloroethane (DCE) using ferrocene (Fc) as an electron donor, tetrakis(penta fl uorophenyl)boric acid (HTB) as a proton donor, and [5,10,15,20-tetraphenyl-21 H ,23 H - porphine]cobalt(II) (Co II TTP) as a catalyst. Kinetic analysis suggests that the reaction is controlled by the intramolecular proton coupled electron transfer to the O 2 molecule coordinated to the metal center producing the O 2 H radical. This rate- determining step is common to both the O 2 reduction by Fc catalyzed by Co II TPP and the O 2 reduction by Co II TPP itself. Experimental data point to the competitive coordination of water to the metal center leading to a strong inhibition of the catalytic reaction. In agreement with this finding, quantum chemical calculations indicate that water is bound to the metal center much more strongly than triplet O2. A similar effect is demonstrated also for the O2 reduction catalyzed by the porphyrin free base (H2 TPP), though its rate is lower by 2 orders of magnitude. Stopped- fl ow kinetic measurements, UV vis spectroscopy, rotating disk voltammetry, and quantum chemical calculations are used to clarify the role of water in the homogeneous two-electron reduction of O 2 to H 2 O 2 in 1,2-dichloroethane (DCE) using ferrocene (Fc) as an electron donor, tetrakis(penta fl uorophenyl)boric acid (HTB) as a proton donor, and [5,10,15,20-tetraphenyl-21 H ,23 H - porphine]cobalt(II) (Co II TTP) as a catalyst. Kinetic analysis suggests that the reaction is controlled by the intramolecular proton coupled electron transfer to the O 2 molecule coordinated to the metal center producing the O 2 H radical. This rate- determining step is common to both the O 2 reduction by Fc catalyzed by Co II TPP and the O 2 reduction by Co II TPP itself. Experimental data point to the competitive coordination of water to the metal center leading to a strong inhibition of the catalytic reaction. In agreement with this finding, quantum chemical calculations indicate that water is bound to the metal center much more strongly than triplet O2. A similar effect is demonstrated also for the O2 reduction catalyzed by the porphyrin free base (H2 TPP), though its rate is lower by 2 orders of magnitude. (en)
Title	Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin (en)
skos:prefLabel	Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin Inhibitory Effect of Water on the Oxygen Reduction Catalyzed by Cobalt(II) Tetraphenylporphyrin (en)
skos:notation	RIV/61388955:_____/14:00427152!RIV15-GA0-61388955
http://linked.open...avai/riv/aktivita	I P
http://linked.open...avai/riv/aktivity	I, P(GAP208/11/0697)
http://linked.open...iv/cisloPeriodika	11
http://linked.open...vai/riv/dodaniDat	2015
http://linked.open...aciTvurceVysledku	Kvapilová, Hana Samec, Zdeněk Langmaier, Jan Záliš, Stanislav Trojánek, Antonín
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...dnocenehoVysledku	21857
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/14:00427152
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	electrochemistry; porphyrins; biomimetic catalysts (en)
http://linked.open.../riv/klicoveSlovo	porphyrins biomimetic catalysts electrochemistry
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[04CC1B9F469C]
http://linked.open...i/riv/nazevZdroje	Journal of Physical Chemistry A
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	5 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	Catalysis of the oxygen reduction by metal-free porphyrins at the electrochemically polarized liquid-liquid interfaces
http://linked.open...UplatneniVysledku	2014
http://linked.open...v/svazekPeriodika	118
http://linked.open...iv/tvurceVysledku	Langmaier, Jan Záliš, Stanislav Samec, Zdeněk Trojánek, Antonín Kvapilová, Hana
http://linked.open...ain/vavai/riv/wos	000333381700006
issn	1089-5639
number of pages	11 (xsd:int)
http://bibframe.org/vocab/doi	10.1021/jp500057x

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