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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)
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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)
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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)
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skos:notation
| - RIV/61388955:_____/14:00427152!RIV15-GA0-61388955
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http://linked.open...avai/riv/aktivita
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http://linked.open...avai/riv/aktivity
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http://linked.open...iv/cisloPeriodika
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http://linked.open...vai/riv/dodaniDat
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http://linked.open...aciTvurceVysledku
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http://linked.open.../riv/druhVysledku
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http://linked.open...iv/duvernostUdaju
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http://linked.open...titaPredkladatele
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http://linked.open...dnocenehoVysledku
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http://linked.open...ai/riv/idVysledku
| - RIV/61388955:_____/14:00427152
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http://linked.open...riv/jazykVysledku
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http://linked.open.../riv/klicovaSlova
| - electrochemistry; porphyrins; biomimetic catalysts (en)
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http://linked.open.../riv/klicoveSlovo
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http://linked.open...odStatuVydavatele
| - US - Spojené státy americké
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http://linked.open...ontrolniKodProRIV
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http://linked.open...i/riv/nazevZdroje
| - Journal of Physical Chemistry A
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http://linked.open...in/vavai/riv/obor
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http://linked.open...ichTvurcuVysledku
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http://linked.open...cetTvurcuVysledku
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http://linked.open...vavai/riv/projekt
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http://linked.open...UplatneniVysledku
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http://linked.open...v/svazekPeriodika
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http://linked.open...iv/tvurceVysledku
| - Langmaier, Jan
- Záliš, Stanislav
- Samec, Zdeněk
- Trojánek, Antonín
- Kvapilová, Hana
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http://linked.open...ain/vavai/riv/wos
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issn
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number of pages
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http://bibframe.org/vocab/doi
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