Modulation of the Electrochemical Reactivity of Solubilized Redox Active Polymers via Polyelectrolyte Dynamics

Mark Burgess, Kenneth Hernández-Burgos, Jonathon K. Schuh, Jasmine Davila, Elena C. Montoto, Randy H Ewoldt, Joaquin Rodriguez Lopez

Research output: Contribution to journalArticle

Abstract

Redox active polymers (RAPs) are electrochemically versatile materials that find key applications in energy storage, sensing, and surface modification. In spite of the ubiquity of RAP-modified electrodes, a critical knowledge gap exists in the understanding of the electrochemistry of soluble RAPs and their relation to polyelectrolyte dynamics. Here, we explore for the first time the intersection between polyelectrolyte behavior and the electrochemical response that highly soluble and highly substituted RAPs with viologen, ferrocene, and nitrostyrene moieties elicit at electrodes. This comprehensive study of RAP electrolytes over several orders of magnitude in concentration and ionic strength reveals distinct signatures consistent with surface confined, colloidal, and bulk-like electrochemical behavior. These differences emerge across polyelectrolyte packing regimes and are strongly modulated by changes in RAP coil size and electrostatic interactions with the electrode. We found that, unlike monomer motifs, simple changes in the ionic strength caused variations over 1 order of magnitude in the current measured at the electrode. In addition, the thermodynamics of adsorbed RAP films were also affected, giving rise to standard reduction potential shifts leading to redox kinetic effects as a result of the mediating nature of the RAP film in equilibrium with the solution. Full electrochemical characterization via transient and steady-state techniques, including the use of ultramicroelectrodes and the rotating disk electrode, were correlated to dynamic light scattering, ellipsometry, and viscometric analysis. These methods helped elucidate the relationship between electrochemical behavior and RAP coil size, film thickness, and polyelectrolyte packing regime. This study underscores the role of electrostatics in modulating the reactivity of redox polyelectrolytes.

Original languageEnglish (US)
Pages (from-to)2093-2104
Number of pages12
JournalJournal of the American Chemical Society
Volume140
Issue number6
DOIs
StatePublished - Feb 14 2018

Fingerprint

Polyelectrolytes
Oxidation-Reduction
Polymers
polymer
Modulation
electrode
Electrodes
Ionic strength
Static Electricity
Polymer films
Osmolar Concentration
Viologens
electrochemistry
Electrochemistry
light scattering
electrolyte
Ellipsometry
Rotating disks
Dynamic light scattering
Coulomb interactions

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Modulation of the Electrochemical Reactivity of Solubilized Redox Active Polymers via Polyelectrolyte Dynamics. / Burgess, Mark; Hernández-Burgos, Kenneth; Schuh, Jonathon K.; Davila, Jasmine; Montoto, Elena C.; Ewoldt, Randy H; Rodriguez Lopez, Joaquin.

In: Journal of the American Chemical Society, Vol. 140, No. 6, 14.02.2018, p. 2093-2104.

Research output: Contribution to journalArticle

Burgess, Mark ; Hernández-Burgos, Kenneth ; Schuh, Jonathon K. ; Davila, Jasmine ; Montoto, Elena C. ; Ewoldt, Randy H ; Rodriguez Lopez, Joaquin. / Modulation of the Electrochemical Reactivity of Solubilized Redox Active Polymers via Polyelectrolyte Dynamics. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 6. pp. 2093-2104.
@article{3b89334dd31c44d290b9a52c2f7a5ec1,
title = "Modulation of the Electrochemical Reactivity of Solubilized Redox Active Polymers via Polyelectrolyte Dynamics",
abstract = "Redox active polymers (RAPs) are electrochemically versatile materials that find key applications in energy storage, sensing, and surface modification. In spite of the ubiquity of RAP-modified electrodes, a critical knowledge gap exists in the understanding of the electrochemistry of soluble RAPs and their relation to polyelectrolyte dynamics. Here, we explore for the first time the intersection between polyelectrolyte behavior and the electrochemical response that highly soluble and highly substituted RAPs with viologen, ferrocene, and nitrostyrene moieties elicit at electrodes. This comprehensive study of RAP electrolytes over several orders of magnitude in concentration and ionic strength reveals distinct signatures consistent with surface confined, colloidal, and bulk-like electrochemical behavior. These differences emerge across polyelectrolyte packing regimes and are strongly modulated by changes in RAP coil size and electrostatic interactions with the electrode. We found that, unlike monomer motifs, simple changes in the ionic strength caused variations over 1 order of magnitude in the current measured at the electrode. In addition, the thermodynamics of adsorbed RAP films were also affected, giving rise to standard reduction potential shifts leading to redox kinetic effects as a result of the mediating nature of the RAP film in equilibrium with the solution. Full electrochemical characterization via transient and steady-state techniques, including the use of ultramicroelectrodes and the rotating disk electrode, were correlated to dynamic light scattering, ellipsometry, and viscometric analysis. These methods helped elucidate the relationship between electrochemical behavior and RAP coil size, film thickness, and polyelectrolyte packing regime. This study underscores the role of electrostatics in modulating the reactivity of redox polyelectrolytes.",
author = "Mark Burgess and Kenneth Hern{\'a}ndez-Burgos and Schuh, {Jonathon K.} and Jasmine Davila and Montoto, {Elena C.} and Ewoldt, {Randy H} and {Rodriguez Lopez}, Joaquin",
year = "2018",
month = "2",
day = "14",
doi = "10.1021/jacs.7b08353",
language = "English (US)",
volume = "140",
pages = "2093--2104",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Modulation of the Electrochemical Reactivity of Solubilized Redox Active Polymers via Polyelectrolyte Dynamics

AU - Burgess, Mark

AU - Hernández-Burgos, Kenneth

AU - Schuh, Jonathon K.

AU - Davila, Jasmine

AU - Montoto, Elena C.

AU - Ewoldt, Randy H

AU - Rodriguez Lopez, Joaquin

PY - 2018/2/14

Y1 - 2018/2/14

N2 - Redox active polymers (RAPs) are electrochemically versatile materials that find key applications in energy storage, sensing, and surface modification. In spite of the ubiquity of RAP-modified electrodes, a critical knowledge gap exists in the understanding of the electrochemistry of soluble RAPs and their relation to polyelectrolyte dynamics. Here, we explore for the first time the intersection between polyelectrolyte behavior and the electrochemical response that highly soluble and highly substituted RAPs with viologen, ferrocene, and nitrostyrene moieties elicit at electrodes. This comprehensive study of RAP electrolytes over several orders of magnitude in concentration and ionic strength reveals distinct signatures consistent with surface confined, colloidal, and bulk-like electrochemical behavior. These differences emerge across polyelectrolyte packing regimes and are strongly modulated by changes in RAP coil size and electrostatic interactions with the electrode. We found that, unlike monomer motifs, simple changes in the ionic strength caused variations over 1 order of magnitude in the current measured at the electrode. In addition, the thermodynamics of adsorbed RAP films were also affected, giving rise to standard reduction potential shifts leading to redox kinetic effects as a result of the mediating nature of the RAP film in equilibrium with the solution. Full electrochemical characterization via transient and steady-state techniques, including the use of ultramicroelectrodes and the rotating disk electrode, were correlated to dynamic light scattering, ellipsometry, and viscometric analysis. These methods helped elucidate the relationship between electrochemical behavior and RAP coil size, film thickness, and polyelectrolyte packing regime. This study underscores the role of electrostatics in modulating the reactivity of redox polyelectrolytes.

AB - Redox active polymers (RAPs) are electrochemically versatile materials that find key applications in energy storage, sensing, and surface modification. In spite of the ubiquity of RAP-modified electrodes, a critical knowledge gap exists in the understanding of the electrochemistry of soluble RAPs and their relation to polyelectrolyte dynamics. Here, we explore for the first time the intersection between polyelectrolyte behavior and the electrochemical response that highly soluble and highly substituted RAPs with viologen, ferrocene, and nitrostyrene moieties elicit at electrodes. This comprehensive study of RAP electrolytes over several orders of magnitude in concentration and ionic strength reveals distinct signatures consistent with surface confined, colloidal, and bulk-like electrochemical behavior. These differences emerge across polyelectrolyte packing regimes and are strongly modulated by changes in RAP coil size and electrostatic interactions with the electrode. We found that, unlike monomer motifs, simple changes in the ionic strength caused variations over 1 order of magnitude in the current measured at the electrode. In addition, the thermodynamics of adsorbed RAP films were also affected, giving rise to standard reduction potential shifts leading to redox kinetic effects as a result of the mediating nature of the RAP film in equilibrium with the solution. Full electrochemical characterization via transient and steady-state techniques, including the use of ultramicroelectrodes and the rotating disk electrode, were correlated to dynamic light scattering, ellipsometry, and viscometric analysis. These methods helped elucidate the relationship between electrochemical behavior and RAP coil size, film thickness, and polyelectrolyte packing regime. This study underscores the role of electrostatics in modulating the reactivity of redox polyelectrolytes.

UR - http://www.scopus.com/inward/record.url?scp=85042057020&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042057020&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b08353

DO - 10.1021/jacs.7b08353

M3 - Article

VL - 140

SP - 2093

EP - 2104

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 6

ER -