Synchrotron SAXS and Impedance Spectroscopy Unveil Nanostructure Variations in Redox-Responsive Porous Membranes from Poly(ferrocenylsilane) Poly(ionic liquid)s

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Abstract

Nanostructured cellular polymeric materials with controlled cell sizes, dispersity, architectures, and functional groups provide opportunities in separation technology, smart catalysts, and controlled drug delivery and release. This paper discusses porous membranes formed in a simple electrostatic complexation process using a NH3 base treatment from redox responsive poly(ferrocenysilane) (PFS)-based poly(ionic liquid)s and poly(acrylic acid) (PAA). These porous membranes exhibit reversible switching between more open and more closed structures upon oxidation and reduction. The porous structure and redox behavior that originate from the PFS matrix are investigated by small-angle X-ray scattering (SAXS) using synchrotron radiation combined with electrochemical impedance spectroscopy. In order to gain more insight into structure variations during electrochemical treatment, the scattering signal of the porous membrane is detected directly from the films at the electrode surface in situ, using a custom-built SAXS electrochemical cell. All experiments confirm the morphology changing between more “open” and more “closed” cells with approximately 30% variation in the value of the equivalent radius (or correlation length), depending on the redox state of ferrocene in the polymer main chain. This property may be exploited in applications such as reference-electrode-free impedance sensing, redox-controlled gating, or molecular separations.
Original languageEnglish
Pages (from-to)296-302
Number of pages7
JournalMacromolecules
Volume50
Issue number1
DOIs
Publication statusPublished - 2017

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Ionic Liquids
X ray scattering
Synchrotrons
Ionic liquids
Nanostructures
Spectroscopy
Membranes
carbopol 940
Controlled drug delivery
Electrodes
Electrochemical cells
Polymers
Synchrotron radiation
Complexation
Electrochemical impedance spectroscopy
Functional groups
Acrylics
Electrostatics
Scattering
Oxidation

Keywords

  • METIS-320165
  • IR-102829
  • EWI-27858

Cite this

@article{395b417172c94fd79a78cacbee3c48e1,
title = "Synchrotron SAXS and Impedance Spectroscopy Unveil Nanostructure Variations in Redox-Responsive Porous Membranes from Poly(ferrocenylsilane) Poly(ionic liquid)s",
abstract = "Nanostructured cellular polymeric materials with controlled cell sizes, dispersity, architectures, and functional groups provide opportunities in separation technology, smart catalysts, and controlled drug delivery and release. This paper discusses porous membranes formed in a simple electrostatic complexation process using a NH3 base treatment from redox responsive poly(ferrocenysilane) (PFS)-based poly(ionic liquid)s and poly(acrylic acid) (PAA). These porous membranes exhibit reversible switching between more open and more closed structures upon oxidation and reduction. The porous structure and redox behavior that originate from the PFS matrix are investigated by small-angle X-ray scattering (SAXS) using synchrotron radiation combined with electrochemical impedance spectroscopy. In order to gain more insight into structure variations during electrochemical treatment, the scattering signal of the porous membrane is detected directly from the films at the electrode surface in situ, using a custom-built SAXS electrochemical cell. All experiments confirm the morphology changing between more “open” and more “closed” cells with approximately 30{\%} variation in the value of the equivalent radius (or correlation length), depending on the redox state of ferrocene in the polymer main chain. This property may be exploited in applications such as reference-electrode-free impedance sensing, redox-controlled gating, or molecular separations.",
keywords = "METIS-320165, IR-102829, EWI-27858",
author = "Laura Folkertsma-Hendriks and Kaihuan Zhang and Orsolya Czakkel and {de Boer}, {Hans L.} and Hempenius, {Mark A.} and {van den Berg}, Albert and Mathieu Odijk and Vancso, {Gyula J.}",
year = "2017",
doi = "10.1021/acs.macromol.6b02318",
language = "English",
volume = "50",
pages = "296--302",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Synchrotron SAXS and Impedance Spectroscopy Unveil Nanostructure Variations in Redox-Responsive Porous Membranes from Poly(ferrocenylsilane) Poly(ionic liquid)s

AU - Folkertsma-Hendriks, Laura

AU - Zhang, Kaihuan

AU - Czakkel, Orsolya

AU - de Boer, Hans L.

AU - Hempenius, Mark A.

AU - van den Berg, Albert

AU - Odijk, Mathieu

AU - Vancso, Gyula J.

PY - 2017

Y1 - 2017

N2 - Nanostructured cellular polymeric materials with controlled cell sizes, dispersity, architectures, and functional groups provide opportunities in separation technology, smart catalysts, and controlled drug delivery and release. This paper discusses porous membranes formed in a simple electrostatic complexation process using a NH3 base treatment from redox responsive poly(ferrocenysilane) (PFS)-based poly(ionic liquid)s and poly(acrylic acid) (PAA). These porous membranes exhibit reversible switching between more open and more closed structures upon oxidation and reduction. The porous structure and redox behavior that originate from the PFS matrix are investigated by small-angle X-ray scattering (SAXS) using synchrotron radiation combined with electrochemical impedance spectroscopy. In order to gain more insight into structure variations during electrochemical treatment, the scattering signal of the porous membrane is detected directly from the films at the electrode surface in situ, using a custom-built SAXS electrochemical cell. All experiments confirm the morphology changing between more “open” and more “closed” cells with approximately 30% variation in the value of the equivalent radius (or correlation length), depending on the redox state of ferrocene in the polymer main chain. This property may be exploited in applications such as reference-electrode-free impedance sensing, redox-controlled gating, or molecular separations.

AB - Nanostructured cellular polymeric materials with controlled cell sizes, dispersity, architectures, and functional groups provide opportunities in separation technology, smart catalysts, and controlled drug delivery and release. This paper discusses porous membranes formed in a simple electrostatic complexation process using a NH3 base treatment from redox responsive poly(ferrocenysilane) (PFS)-based poly(ionic liquid)s and poly(acrylic acid) (PAA). These porous membranes exhibit reversible switching between more open and more closed structures upon oxidation and reduction. The porous structure and redox behavior that originate from the PFS matrix are investigated by small-angle X-ray scattering (SAXS) using synchrotron radiation combined with electrochemical impedance spectroscopy. In order to gain more insight into structure variations during electrochemical treatment, the scattering signal of the porous membrane is detected directly from the films at the electrode surface in situ, using a custom-built SAXS electrochemical cell. All experiments confirm the morphology changing between more “open” and more “closed” cells with approximately 30% variation in the value of the equivalent radius (or correlation length), depending on the redox state of ferrocene in the polymer main chain. This property may be exploited in applications such as reference-electrode-free impedance sensing, redox-controlled gating, or molecular separations.

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KW - IR-102829

KW - EWI-27858

U2 - 10.1021/acs.macromol.6b02318

DO - 10.1021/acs.macromol.6b02318

M3 - Article

VL - 50

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JO - Macromolecules

JF - Macromolecules

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