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Title: Polyelectrolyte layer-by-layer deposition on nanoporous supports for ion selective membranes

Abstract

This work demonstrates that the ionic selectivity and ionic conductivity of nanoporous membranes can be controlled independently via layer-by-layer (LbL) deposition of polyelectrolytes and subsequent selective cross-linking of these polymer layers. LbL deposition offers a scalable, inexpensive method to tune the ion transport properties of nanoporous membranes by sequentially dip coating layers of cationic polyethyleneimine and anionic poly(acrylic acid) onto polycarbonate membranes. The cationic and anionic polymers are self-assembled through electrostatic and hydrogen bonding interactions and are chemically crosslinked to both change the charge distribution and improve the intermolecular integrity of the deposited films. Both the thickness of the deposited coating and the use of chemical cross-linking agents influence charge transport properties significantly. Increased polyelectrolyte thickness increases the selectivity for cationic transport through the membranes while adding polyelectrolyte films decreases the ionic conductivity compared to an uncoated membrane. Once the nanopores are filled, no additional decrease in conductivity is observed with increasing film thickness and, upon cross-linking, a portion of the lost conductivity is recovered. The cross-linking agent also influences the ionic selectivity of the resulting polyelectrolyte membranes. Increased selectivity for cationic transport occurs when using glutaraldehyde as the cross-linking agent, as expected due to the selective cross-linking of primarymore » amines that decreases the net positive charge. Altogether, these results inform deposition of chemically robust, highly conductive, ion-selective membranes onto inexpensive porous supports for applications ranging from energy storage to water purification.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]
  1. Sandia National Laboratories, Albuquerque, USA 87185
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1473717
Alternate Identifier(s):
OSTI ID: 1485462
Report Number(s):
SAND-2018-11714J
Journal ID: ISSN 2046-2069; RSCACL
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 8 Journal Issue: 57; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Percival, Stephen J., Small, Leo J., Spoerke, Erik D., and Rempe, Susan B. Polyelectrolyte layer-by-layer deposition on nanoporous supports for ion selective membranes. United Kingdom: N. p., 2018. Web. doi:10.1039/C8RA05580G.
Percival, Stephen J., Small, Leo J., Spoerke, Erik D., & Rempe, Susan B. Polyelectrolyte layer-by-layer deposition on nanoporous supports for ion selective membranes. United Kingdom. doi:10.1039/C8RA05580G.
Percival, Stephen J., Small, Leo J., Spoerke, Erik D., and Rempe, Susan B. Mon . "Polyelectrolyte layer-by-layer deposition on nanoporous supports for ion selective membranes". United Kingdom. doi:10.1039/C8RA05580G.
@article{osti_1473717,
title = {Polyelectrolyte layer-by-layer deposition on nanoporous supports for ion selective membranes},
author = {Percival, Stephen J. and Small, Leo J. and Spoerke, Erik D. and Rempe, Susan B.},
abstractNote = {This work demonstrates that the ionic selectivity and ionic conductivity of nanoporous membranes can be controlled independently via layer-by-layer (LbL) deposition of polyelectrolytes and subsequent selective cross-linking of these polymer layers. LbL deposition offers a scalable, inexpensive method to tune the ion transport properties of nanoporous membranes by sequentially dip coating layers of cationic polyethyleneimine and anionic poly(acrylic acid) onto polycarbonate membranes. The cationic and anionic polymers are self-assembled through electrostatic and hydrogen bonding interactions and are chemically crosslinked to both change the charge distribution and improve the intermolecular integrity of the deposited films. Both the thickness of the deposited coating and the use of chemical cross-linking agents influence charge transport properties significantly. Increased polyelectrolyte thickness increases the selectivity for cationic transport through the membranes while adding polyelectrolyte films decreases the ionic conductivity compared to an uncoated membrane. Once the nanopores are filled, no additional decrease in conductivity is observed with increasing film thickness and, upon cross-linking, a portion of the lost conductivity is recovered. The cross-linking agent also influences the ionic selectivity of the resulting polyelectrolyte membranes. Increased selectivity for cationic transport occurs when using glutaraldehyde as the cross-linking agent, as expected due to the selective cross-linking of primary amines that decreases the net positive charge. Altogether, these results inform deposition of chemically robust, highly conductive, ion-selective membranes onto inexpensive porous supports for applications ranging from energy storage to water purification.},
doi = {10.1039/C8RA05580G},
journal = {RSC Advances},
number = 57,
volume = 8,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8RA05580G

Figures / Tables:

Figure 1 Figure 1: FTIR spectra of the bare polycarbonate (A) and polyelectrolyte on polycarbonate membranes showing the effect of cross-linking agent (B) and increasing number of bilayers (C). The positions of the carboxylic acid C=0 stretch and the primary amine N-H bend are shown with the dotted lines in each.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.