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Immobilization of Alkynyl Functionalized Manganese Phthalocyanine Via Click Electrochemistry for Electrocatalytic Oxygen Evolution Reaction

Abstract

Peripherally and non-peripherally terminal alkynyl substituted manganese phthalocyanines (MnPc) were synthesized and characterized and then used as functional materials in modified electrodes. MnPcs were substituted with alkynyl groups which are reactive moieties in click electrochemistry (CEC) reactions. Mn (III) cations were incorporated into the cavity of Pc ring in order to increase redox activity of the complexes. Electrochemical characterizations of the complexes were determined with the voltammetric and in situ spectroelectrochemical measurements in order to determine their possible technological applications. MnPc complexes illustrated five redox couples and these redox couples were assigned as [Cl-MnIIIPc−2]/[Cl-MnIIPc−2]1-, [Cl-MnIIPc−2]1-/[Cl-MnIPc−2]2-, [Cl-MnIPc−2]2-/[ Cl-MnIPc−3]3-, and [Cl-MnIIIPc−2]/[Cl-MnIIPc−1]1+ redox processes. Position of the substituents affected the mechanism of the redox reactions, influenced tendency to react with the molecular oxygen. Moreover changing the position of the substituents slightly influenced the peak potentials and reversibility of the redox processes. For the applications, modified electrodes (ITO/PANI-N3-MnPc and GCE/PANI-N3-MnPc) were constructed with CEC reaction between azido functionalized polyaniline (PANI-N3) and terminally alkynyl substituted MnPcs and these electrodes. Voltammetric characterizations of the modified electrodes illustrated suitable redox activity and conductivity for the practical applications. Finally GCE/PANI-N3-MnPc electrodes were tested as potential electrocatalyst for water splitting reaction. Although, GCE/PANI-N3-MnPc electrodes did not catalyze hydrogen evolution reaction (HER), they significantly catalyzed oxygen evolution reaction (OER) in aqueous solution.

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Publication details

The article was received on 28 Jun 2017, accepted on 07 Sep 2017 and first published on 07 Sep 2017


Article type: Paper
DOI: 10.1039/C7CP04354F
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    Immobilization of Alkynyl Functionalized Manganese Phthalocyanine Via Click Electrochemistry for Electrocatalytic Oxygen Evolution Reaction

    B. Öztaş , D. Akyüz and A. Koca, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP04354F

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