Biphasic Voltammetry and Spectroelectrochemistry in Polymer of Intrinsic Microporosity—4-(3-Phenylpropyl)-Pyridine Organogel/Aqueous Electrolyte Systems: Reactivity of MnPc Versus MnTPP

Vellaichamy Ganesan, Elena Madrid, R. Malpass-Evans, M. Carta, N B. Mckeown, Frank Marken

Research output: Contribution to journalArticle

Abstract

A hydrophobic polymer of intrinsic microporosity (PIM-EA-TB) is employed to stabilize an organogel/aqueous electrolyte phase boundary based on an organic water-insoluble 4-(3-phenylpropyl)-pyridine phase. The organogel with electrocatalytic metal complexes embedded is immobilized on glassy carbon or on transparent mesoporous tin-doped indium oxide (ITO) electrodes. Liquid/liquid ion transfer voltammetry is investigated for a 4-(3-phenylpropyl)-pyridine organogel/aqueous electrolyte interface for two types of redox systems: tetraphenylporphyrinato-Mn(III/II) (MnTPP) and phthalocyanato-Mn(III/II) (MnPc). Electron transfer is shown to be coupled to reversible liquid/liquid anion transfer processes for PF6−, ClO 4 −, SCN −, and NO 3 −, with a change in mechanism for the more hydrophilic anions Cl−,F −, and SO42−. In situ UV-Vis spectroelectrochemistry reveals reversible Mn(III/II) redox processes coupled to ion transfer for MnTPP. But further complexity and a detrimental side reaction are observed for MnPc causing gradual loss of the electrochemical response in the presence of dioxygen.
Original languageEnglish
Pages (from-to)295-304
JournalElectrocatalysis
Volume10
Issue number4
DOIs
Publication statusPublished - 15 Jul 2019

Cite this

Biphasic Voltammetry and Spectroelectrochemistry in Polymer of Intrinsic Microporosity—4-(3-Phenylpropyl)-Pyridine Organogel/Aqueous Electrolyte Systems: Reactivity of MnPc Versus MnTPP. / Ganesan, Vellaichamy; Madrid, Elena; Malpass-Evans, R.; Carta, M.; Mckeown, N B.; Marken, Frank.

In: Electrocatalysis, Vol. 10, No. 4, 15.07.2019, p. 295-304.

Research output: Contribution to journalArticle

@article{d999414a6f6b4aa29bc45d9d3859b5b6,
title = "Biphasic Voltammetry and Spectroelectrochemistry in Polymer of Intrinsic Microporosity—4-(3-Phenylpropyl)-Pyridine Organogel/Aqueous Electrolyte Systems: Reactivity of MnPc Versus MnTPP",
abstract = "A hydrophobic polymer of intrinsic microporosity (PIM-EA-TB) is employed to stabilize an organogel/aqueous electrolyte phase boundary based on an organic water-insoluble 4-(3-phenylpropyl)-pyridine phase. The organogel with electrocatalytic metal complexes embedded is immobilized on glassy carbon or on transparent mesoporous tin-doped indium oxide (ITO) electrodes. Liquid/liquid ion transfer voltammetry is investigated for a 4-(3-phenylpropyl)-pyridine organogel/aqueous electrolyte interface for two types of redox systems: tetraphenylporphyrinato-Mn(III/II) (MnTPP) and phthalocyanato-Mn(III/II) (MnPc). Electron transfer is shown to be coupled to reversible liquid/liquid anion transfer processes for PF6−, ClO 4 −, SCN −, and NO 3 −, with a change in mechanism for the more hydrophilic anions Cl−,F −, and SO42−. In situ UV-Vis spectroelectrochemistry reveals reversible Mn(III/II) redox processes coupled to ion transfer for MnTPP. But further complexity and a detrimental side reaction are observed for MnPc causing gradual loss of the electrochemical response in the presence of dioxygen.",
author = "Vellaichamy Ganesan and Elena Madrid and R. Malpass-Evans and M. Carta and Mckeown, {N B.} and Frank Marken",
year = "2019",
month = "7",
day = "15",
doi = "10.1007/s12678-018-0497-8",
language = "English",
volume = "10",
pages = "295--304",
journal = "Electrocatalysis",
issn = "1868-2529",
publisher = "Springer Publishing Company",
number = "4",

}

TY - JOUR

T1 - Biphasic Voltammetry and Spectroelectrochemistry in Polymer of Intrinsic Microporosity—4-(3-Phenylpropyl)-Pyridine Organogel/Aqueous Electrolyte Systems: Reactivity of MnPc Versus MnTPP

AU - Ganesan, Vellaichamy

AU - Madrid, Elena

AU - Malpass-Evans, R.

AU - Carta, M.

AU - Mckeown, N B.

AU - Marken, Frank

PY - 2019/7/15

Y1 - 2019/7/15

N2 - A hydrophobic polymer of intrinsic microporosity (PIM-EA-TB) is employed to stabilize an organogel/aqueous electrolyte phase boundary based on an organic water-insoluble 4-(3-phenylpropyl)-pyridine phase. The organogel with electrocatalytic metal complexes embedded is immobilized on glassy carbon or on transparent mesoporous tin-doped indium oxide (ITO) electrodes. Liquid/liquid ion transfer voltammetry is investigated for a 4-(3-phenylpropyl)-pyridine organogel/aqueous electrolyte interface for two types of redox systems: tetraphenylporphyrinato-Mn(III/II) (MnTPP) and phthalocyanato-Mn(III/II) (MnPc). Electron transfer is shown to be coupled to reversible liquid/liquid anion transfer processes for PF6−, ClO 4 −, SCN −, and NO 3 −, with a change in mechanism for the more hydrophilic anions Cl−,F −, and SO42−. In situ UV-Vis spectroelectrochemistry reveals reversible Mn(III/II) redox processes coupled to ion transfer for MnTPP. But further complexity and a detrimental side reaction are observed for MnPc causing gradual loss of the electrochemical response in the presence of dioxygen.

AB - A hydrophobic polymer of intrinsic microporosity (PIM-EA-TB) is employed to stabilize an organogel/aqueous electrolyte phase boundary based on an organic water-insoluble 4-(3-phenylpropyl)-pyridine phase. The organogel with electrocatalytic metal complexes embedded is immobilized on glassy carbon or on transparent mesoporous tin-doped indium oxide (ITO) electrodes. Liquid/liquid ion transfer voltammetry is investigated for a 4-(3-phenylpropyl)-pyridine organogel/aqueous electrolyte interface for two types of redox systems: tetraphenylporphyrinato-Mn(III/II) (MnTPP) and phthalocyanato-Mn(III/II) (MnPc). Electron transfer is shown to be coupled to reversible liquid/liquid anion transfer processes for PF6−, ClO 4 −, SCN −, and NO 3 −, with a change in mechanism for the more hydrophilic anions Cl−,F −, and SO42−. In situ UV-Vis spectroelectrochemistry reveals reversible Mn(III/II) redox processes coupled to ion transfer for MnTPP. But further complexity and a detrimental side reaction are observed for MnPc causing gradual loss of the electrochemical response in the presence of dioxygen.

U2 - 10.1007/s12678-018-0497-8

DO - 10.1007/s12678-018-0497-8

M3 - Article

VL - 10

SP - 295

EP - 304

JO - Electrocatalysis

JF - Electrocatalysis

SN - 1868-2529

IS - 4

ER -