Electrocatalytic reduction of Molecular Oxygen with a Copper (II) Coordination Polymer

Oxygen reduction at the polarized water/1,2‐dichloroethane (DCE) interface catalyzed by a Cu (II) coordination polymer (Cu–pol) was studied with two lipophilic electron donors ferrocene (Fc) and tetrathiafulvalene (TTF). The results of the ion transfer voltammetry and two‐phase shake flask experimen...

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Bibliographic Details
Published in:Applied organometallic chemistry 2020-05, Vol.34 (5), p.n/a
Main Authors: Kamyabi, Mohammad Ali, Soleymani‐Bonoti, Fatemeh, Taheri, Leila, Morsali, Ahmad, Hosseini‐Monfared, Hassan
Format: Article
Language:English
Subjects:
Chemical reduction
Chemistry
Coordination polymers
Copper
Cu (II) coordination polymer
Dichloroethane
Electron transfer
Electrons
Ferrocene
Hydrogen peroxide
Molecular structure
Oxidation
Oxygen
polarized water/1,2‐dichloroethane interface
Protons
reduction of oxygen
Tetrathiafulvalene
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Summary:Oxygen reduction at the polarized water/1,2‐dichloroethane (DCE) interface catalyzed by a Cu (II) coordination polymer (Cu–pol) was studied with two lipophilic electron donors ferrocene (Fc) and tetrathiafulvalene (TTF). The results of the ion transfer voltammetry and two‐phase shake flask experiments suggest proceeding of the catalytic reaction as proton‐coupled electron transfer reduction of oxygen to hydrogen peroxide and water. In this process, while the protons supplied from the aqueous phase, the electrons provided from the organic phase by the weak electron donor, Fc. The O2 molecule takes a superoxide structure with Cu–pol which resulted to hydrogen peroxide or water on reduction. Furthermore, the results revealed that the apparent rate constant of TTF + Cu‐pol is higher than that of Fc + Cu‐pol system due to the faster kinetic reaction of TTF with respect to Fc. The catalytic activation of copper coordination polymer on the oxygen reduction by two electron donors, ferrocene (Fc) and tetrathiafulvalene (TTF) was investigated at the water/DCE interface and this is the first study on an electrocatalyticoxygen reduction reaction by a copper coordination polymer at the liquid/liquidinterface. Although, TTF can only reduce O2 to H2O on its own, based on the significant amount of detected H2O2,the reaction proceeds via a mixture of 2e‐/2H+ and 4e‐/4H+reduction pathways.
ISSN:0268-2605
1099-0739
DOI:10.1002/aoc.5562