Advanced

Proton dissociation of sulfonated polysulfones: influence of molecular structure and conformation

Wohlfarth, Andreas; Smiatek, Jens; Kreuer, Klaus-Dieter; Takamuku, Shogo LU ; Jannasch, Patric LU and Maier, Joachim (2015) In Macromolecules 48(4). p.1134-1143
Abstract
The dissociation behavior of proton conducting sulfonated polysulfones has been investigated by combining electrophoretic NMR, pulsed magnetic field gradient NMR and conductivity meas- urements on monomeric and polymeric samples with concentrations of ionic groups in the range where dissociation is not complete (IEC = 4.55 – 7.04 meq g-1). In this regime, counterion con- densation is shown to critically depend on details of the molecular structure, and all atom MD simulations reveal the formation of well-defined ionic aggregates (e.g. triple ions). The corre- sponding global minima of the free energy are suggested to be the result of a delicate balance of the energetics involved in conformational changes, formation of ionic aggregates and... (More)
The dissociation behavior of proton conducting sulfonated polysulfones has been investigated by combining electrophoretic NMR, pulsed magnetic field gradient NMR and conductivity meas- urements on monomeric and polymeric samples with concentrations of ionic groups in the range where dissociation is not complete (IEC = 4.55 – 7.04 meq g-1). In this regime, counterion con- densation is shown to critically depend on details of the molecular structure, and all atom MD simulations reveal the formation of well-defined ionic aggregates (e.g. triple ions). The corre- sponding global minima of the free energy are suggested to be the result of a delicate balance of the energetics involved in conformational changes, formation of ionic aggregates and solvation. This goes beyond Manning’s counterion condensation theory and has important implications for the development of membranes with high ionic conductivity as needed for many electrochemical applications such as fuel cells and batteries. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Macromolecules
volume
48
issue
4
pages
1134 - 1143
publisher
The American Chemical Society
external identifiers
  • wos:000350193900028
  • scopus:84923331718
ISSN
0024-9297
DOI
10.1021/ma502550f
language
English
LU publication?
yes
id
e0b4058d-0f08-41a2-b791-b7b88779c1fe (old id 4882450)
alternative location
http://pubs.acs.org/doi/abs/10.1021/ma502550f
date added to LUP
2015-03-09 17:43:17
date last changed
2017-08-20 03:04:33
@article{e0b4058d-0f08-41a2-b791-b7b88779c1fe,
  abstract     = {The dissociation behavior of proton conducting sulfonated polysulfones has been investigated by combining electrophoretic NMR, pulsed magnetic field gradient NMR and conductivity meas- urements on monomeric and polymeric samples with concentrations of ionic groups in the range where dissociation is not complete (IEC = 4.55 – 7.04 meq g-1). In this regime, counterion con- densation is shown to critically depend on details of the molecular structure, and all atom MD simulations reveal the formation of well-defined ionic aggregates (e.g. triple ions). The corre- sponding global minima of the free energy are suggested to be the result of a delicate balance of the energetics involved in conformational changes, formation of ionic aggregates and solvation. This goes beyond Manning’s counterion condensation theory and has important implications for the development of membranes with high ionic conductivity as needed for many electrochemical applications such as fuel cells and batteries.},
  author       = {Wohlfarth, Andreas and Smiatek, Jens and Kreuer, Klaus-Dieter and Takamuku, Shogo and Jannasch, Patric and Maier, Joachim},
  issn         = {0024-9297},
  language     = {eng},
  number       = {4},
  pages        = {1134--1143},
  publisher    = {The American Chemical Society},
  series       = {Macromolecules},
  title        = {Proton dissociation of sulfonated polysulfones: influence of molecular structure and conformation},
  url          = {http://dx.doi.org/10.1021/ma502550f},
  volume       = {48},
  year         = {2015},
}