Mechanistic model of the oxygen reduction catalyzed by a metal-free porphyrin in one- and two-phase liquid systems

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F13%3A00398341" target="_blank" >RIV/61388955:_____/13:00398341 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1016/j.electacta.2012.12.100" target="_blank" >http://dx.doi.org/10.1016/j.electacta.2012.12.100</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.electacta.2012.12.100" target="_blank" >10.1016/j.electacta.2012.12.100</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Mechanistic model of the oxygen reduction catalyzed by a metal-free porphyrin in one- and two-phase liquid systems

Popis výsledku v původním jazyce

Mechanistic model is presented, which allows simulating the experimentally observed catalytic effect of the 5,10,15,20-meso-tetraphenylporphyrin (H2TPP), as well as the effects of H+, tetrakis(pentafluorophenyl)borate anion (TB) and water concentrationson the catalytic rate of the oxygen reduction reaction (ORR) with ferrocene (Fc) in 1,2-dichloroethane (DCE). Model calculations are based on the assumption that the electron transfer between the complex {(H4TPP2+)(TB)O2} and Fc is the rate determining step (r.d.s.) in both the catalytic and electrocatalytic cycle. The model calculations are performed using the reported acid dissociation constants for mono- and diprotonated H2TPP forms, and the equilibrium constants of the extraction of the ligands L =O2, water, or TB from the porphyrin complex {(H4TPP2+)(TB)L} calculated by the DFT methods. The rate constant of r.d.s. evaluated from the initial rates is compared with that obtained by a numeric fit of the experimental Fc+ transients. M

Název v anglickém jazyce

Mechanistic model of the oxygen reduction catalyzed by a metal-free porphyrin in one- and two-phase liquid systems

Popis výsledku anglicky

Mechanistic model is presented, which allows simulating the experimentally observed catalytic effect of the 5,10,15,20-meso-tetraphenylporphyrin (H2TPP), as well as the effects of H+, tetrakis(pentafluorophenyl)borate anion (TB) and water concentrationson the catalytic rate of the oxygen reduction reaction (ORR) with ferrocene (Fc) in 1,2-dichloroethane (DCE). Model calculations are based on the assumption that the electron transfer between the complex {(H4TPP2+)(TB)O2} and Fc is the rate determining step (r.d.s.) in both the catalytic and electrocatalytic cycle. The model calculations are performed using the reported acid dissociation constants for mono- and diprotonated H2TPP forms, and the equilibrium constants of the extraction of the ligands L =O2, water, or TB from the porphyrin complex {(H4TPP2+)(TB)L} calculated by the DFT methods. The rate constant of r.d.s. evaluated from the initial rates is compared with that obtained by a numeric fit of the experimental Fc+ transients. M

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CG - Elektrochemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP208%2F11%2F0697" target="_blank" >GAP208/11/0697: Katalýza redukce kyslíku bezkovovými porfyriny na elektrochemicky polarizovaných kapalných rozhraních</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2013

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Electrochimica acta

ISSN

0013-4686

e-ISSN

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Svazek periodika

110

Číslo periodika v rámci svazku

NOV 2013

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

6

Strana od-do

816-821

Kód UT WoS článku

000329530300103

EID výsledku v databázi Scopus

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