DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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. https://doi.org/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. https://doi.org/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 = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C8RA05580G

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

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.

Save / Share:

Works referenced in this record:

Design of ultrathin nanostructured polyelectrolyte-based membranes with high perchlorate rejection and high permeability
journal, May 2015


Separation of Ions Using Polyelectrolyte-Modified Nanoporous Track-Etched Membranes
journal, July 2013

  • Armstrong, Jason A.; Bernal, Edxon Eduardo Licón; Yaroshchuk, Andriy
  • Langmuir, Vol. 29, Issue 32
  • DOI: 10.1021/la401934v

Membranes with Oriented Polyelectrolyte Nanodomains
journal, October 2006

  • Chen, Hong; Palmese, Giuseppe R.; Elabd, Yossef A.
  • Chemistry of Materials, Vol. 18, Issue 20
  • DOI: 10.1021/cm061422w

Layer-by-Layer Assembly of Polyelectrolyte Chains and Nanoparticles on Nanoporous Substrates: Molecular Dynamics Simulations
journal, December 2011

  • Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.
  • Langmuir, Vol. 28, Issue 2
  • DOI: 10.1021/la203940w

Fast Ion Conduction in Layer-By-Layer Polymer Films
journal, March 2003

  • DeLongchamp, Dean M.; Hammond, Paula T.
  • Chemistry of Materials, Vol. 15, Issue 5
  • DOI: 10.1021/cm020945a

Exceptional Flame Resistance and Gas Barrier with Thick Multilayer Nanobrick Wall Thin Films
journal, June 2015

  • Guin, Tyler; Krecker, Michelle; Milhorn, Aaron
  • Advanced Materials Interfaces, Vol. 2, Issue 11
  • DOI: 10.1002/admi.201500214

Fundamental insight into the effect of carbodiimide crosslinking on cellular recognition of collagen-based scaffolds
journal, February 2017


Growth Mechanism of Confined Polyelectrolyte Multilayers in Nanoporous Templates
journal, March 2010

  • Roy, C. J.; Dupont-Gillain, C.; Demoustier-Champagne, S.
  • Langmuir, Vol. 26, Issue 5
  • DOI: 10.1021/la903121e

Highly Ion Conductive Poly(ethylene oxide)-Based Solid Polymer Electrolytes from Hydrogen Bonding Layer-by-Layer Assembly
journal, June 2004

  • DeLongchamp, Dean M.; Hammond, Paula T.
  • Langmuir, Vol. 20, Issue 13
  • DOI: 10.1021/la049777m

Shift-Time Polyelectrolyte Multilayer Assembly: Fast Film Growth and High Gas Barrier with Fewer Layers by Adjusting Deposition Time
journal, June 2014

  • Hagen, David A.; Foster, Brendan; Stevens, Bart
  • ACS Macro Letters, Vol. 3, Issue 7
  • DOI: 10.1021/mz500276r

The Chemistry of Redox-Flow Batteries
journal, June 2015

  • Noack, Jens; Roznyatovskaya, Nataliya; Herr, Tatjana
  • Angewandte Chemie International Edition, Vol. 54, Issue 34
  • DOI: 10.1002/anie.201410823

Super Gas Barrier of All-Polymer Multilayer Thin Films
journal, March 2011

  • Yang, You-Hao; Haile, Merid; Park, Yong Tae
  • Macromolecules, Vol. 44, Issue 6
  • DOI: 10.1021/ma1026127

A review of flame retardant nanocoatings prepared using layer-by-layer assembly of polyelectrolytes
journal, July 2017

  • Holder, Kevin M.; Smith, Ryan J.; Grunlan, Jaime C.
  • Journal of Materials Science, Vol. 52, Issue 22
  • DOI: 10.1007/s10853-017-1390-1

MOF-Sensitized Solar Cells Enabled by a Pillared Porphyrin Framework
journal, February 2017

  • Spoerke, Erik D.; Small, Leo J.; Foster, Michael E.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 9
  • DOI: 10.1021/acs.jpcc.6b11251

Voltage-Controlled Metal Binding on Polyelectrolyte-Functionalized Nanopores
journal, May 2011

  • Actis, Paolo; Vilozny, Boaz; Seger, R. Adam
  • Langmuir, Vol. 27, Issue 10
  • DOI: 10.1021/la2005612

The Role of Nanopore Geometry for the Rectification of Ionic Currents
journal, March 2011

  • Kubeil, Clemens; Bund, Andreas
  • The Journal of Physical Chemistry C, Vol. 115, Issue 16
  • DOI: 10.1021/jp111377h

Simple, Benign, Aqueous-Based Amination of Polycarbonate Surfaces
journal, March 2015

  • VanDelinder, Virginia; Wheeler, David R.; Small, Leo J.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 10
  • DOI: 10.1021/am508797h

Conical Nanopore Membranes. Preparation and Transport Properties
journal, April 2004

  • Li, Naichao; Yu, Shufang; Harrell, C. Chad
  • Analytical Chemistry, Vol. 76, Issue 7
  • DOI: 10.1021/ac035402e

Modifying the surface charge of single track-etched conical nanopores in polyimide
journal, February 2008


Ion transport in nanofluidic channels
journal, January 2010


Layer-by-layer deposition and photovoltaic property of Ru-based metal–organic frameworks
journal, January 2014

  • Lee, Deok Yeon; Kim, Eun-Kyung; Shin, Chan Yong
  • RSC Advances, Vol. 4, Issue 23
  • DOI: 10.1039/c4ra00397g

Layer-by-Layer Assembly of Polyelectrolyte Multilayers in Three-Dimensional Inverse Opal Structured Templates
journal, March 2012

  • Yeo, Seon Ju; Kang, Hyo; Kim, Young Hun
  • ACS Applied Materials & Interfaces, Vol. 4, Issue 4
  • DOI: 10.1021/am300072p

Peculiarities of Polyelectrolyte Multilayer Assembly on Patterned Surfaces
journal, July 2011

  • Kiryukhin, Maxim V.; Man, Shu Mei; Sadovoy, Anton V.
  • Langmuir, Vol. 27, Issue 13
  • DOI: 10.1021/la200939p

Diode-like single-ion track membrane prepared by electro-stopping
journal, November 2001

  • Apel, P. Yu.; Korchev, Yu. E.; Siwy, Z.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 184, Issue 3, p. 337-346
  • DOI: 10.1016/S0168-583X(01)00722-4

Light-controlled ion channels formed by amphiphilic small molecules regulate ion conduction via cis–trans photoisomerization
journal, January 2013

  • Liu, Tao; Bao, Chunyan; Wang, Haiyan
  • Chemical Communications, Vol. 49, Issue 87
  • DOI: 10.1039/c3cc45618h

Investigations into the Electrochemical, Surface, and Electrocatalytic Properties of the Surface-Immobilized Polyoxometalate, TBA 3 K[SiW 10 O 36 (PhPO) 2 ]
journal, January 2015

  • Yaqub, Mustansara; Imar, Shahzad; Laffir, Fathima
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 2
  • DOI: 10.1021/am5017864

Combined Ionic and Hydrogen Bonding in Polymer Multilayer Thin Film for High Gas Barrier and Stretchiness
journal, August 2015


Control of Nanopore Wetting by a Photochromic Spiropyran: A Light-Controlled Valve and Electrical Switch
journal, May 2006

  • Vlassiouk, Ivan; Park, Choong-Do; Vail, Sean A.
  • Nano Letters, Vol. 6, Issue 5
  • DOI: 10.1021/nl060313d

Layer-by-Layer Assembly of Polyelectrolytes into Ionic Current Rectifying Solid-State Nanopores: Insights from Theory and Experiment
journal, June 2010

  • Ali, Mubarak; Yameen, Basit; Cervera, Javier
  • Journal of the American Chemical Society, Vol. 132, Issue 24
  • DOI: 10.1021/ja101014y

Through-Plane Conductivities of Membranes for Nonaqueous Redox Flow Batteries
journal, January 2015

  • Hudak, Nicholas S.; Small, Leo J.; Pratt, Harry D.
  • Journal of The Electrochemical Society, Vol. 162, Issue 10
  • DOI: 10.1149/2.0901510jes

Mechanism of Crosslinking of Proteins by Glutaraldehyde I: Reaction with Model Compounds
journal, January 1982


Layer-by-Layer Assembly of Polyelectrolytes in Nanofluidic Devices
journal, March 2010

  • DeRocher, Jonathan P.; Mao, Pan; Han, Jongyoon
  • Macromolecules, Vol. 43, Issue 5
  • DOI: 10.1021/ma902451s

Asymmetric Ion Transport through Ion-Channel-Mimetic Solid-State Nanopores
journal, January 2013

  • Guo, Wei; Tian, Ye; Jiang, Lei
  • Accounts of Chemical Research, Vol. 46, Issue 12
  • DOI: 10.1021/ar400024p

Polymer-Modified Mesoporous Silica Thin Films for Redox-Mediated Selective Membrane Gating
journal, November 2013

  • Elbert, Johannes; Krohm, Fabio; Rüttiger, Christian
  • Advanced Functional Materials, Vol. 24, Issue 11
  • DOI: 10.1002/adfm.201302304

Manipulation of Molecular Transport into Mesoporous Silica Thin Films by the Infiltration of Polyelectrolytes
journal, April 2011

  • Brunsen, Annette; Calvo, Alejandra; Williams, Federico J.
  • Langmuir, Vol. 27, Issue 8
  • DOI: 10.1021/la200501h

Ionic conduction, rectification, and selectivity in single conical nanopores
journal, March 2006

  • Cervera, Javier; Schiedt, Birgitta; Neumann, Reinhard
  • The Journal of Chemical Physics, Vol. 124, Issue 10
  • DOI: 10.1063/1.2179797

Electroactive Nanotube Membranes and Redox-Gating
journal, February 2007


Layer-by-Layer Assembly of Polyelectrolytes in Nanopores
journal, May 2007

  • Alem, Halima; Blondeau, Françoise; Glinel, Karine
  • Macromolecules, Vol. 40, Issue 9
  • DOI: 10.1021/ma0703251

Ultrasensitive Humidity Detection Using Metal–Organic Framework-Coated Microsensors
journal, August 2012

  • Robinson, Alex L.; Stavila, Vitalie; Zeitler, Todd R.
  • Analytical Chemistry, Vol. 84, Issue 16, p. 7043-7051
  • DOI: 10.1021/ac301183w

Pushing the Size Limits in the Replication of Nanopores in Anodized Aluminum Oxide via the Layer-by-Layer Deposition of Polyelectrolytes
journal, June 2012

  • Raoufi, Mohammad; Tranchida, Davide; Schönherr, Holger
  • Langmuir, Vol. 28, Issue 26
  • DOI: 10.1021/la3017062

Chlorine Resistant Glutaraldehyde Crosslinked Polyelectrolyte Multilayer Membranes for Desalination
journal, March 2015

  • Cho, Kwun Lun; Hill, Anita J.; Caruso, Frank
  • Advanced Materials, Vol. 27, Issue 17
  • DOI: 10.1002/adma.201405783

Mimicking pH-Gated Ionic Channels by Polyelectrolyte Complex Confinement Inside a Single Nanopore
journal, March 2017


Conical-Nanotube Ion-Current Rectifiers:  The Role of Surface Charge
journal, September 2004

  • Siwy, Zuzanna; Heins, Elizabeth; Harrell, C. Chad
  • Journal of the American Chemical Society, Vol. 126, Issue 35
  • DOI: 10.1021/ja047675c

Light-Gating Titania/Alumina Heterogeneous Nanochannels with Regulatable Ion Rectification Characteristic
journal, August 2013

  • Zhang, Qianqian; Hu, Ziying; Liu, Zhaoyue
  • Advanced Functional Materials, Vol. 24, Issue 4
  • DOI: 10.1002/adfm.201301426

Electrochemically enabled polyelectrolyte multilayer devices: from fuel cells to sensors
journal, January 2007

  • Lutkenhaus, Jodie L.; Hammond, Paula T.
  • Soft Matter, Vol. 3, Issue 7
  • DOI: 10.1039/b701203a

Electrochemical Characterization of Ultrathin Cross-Linked Metal Nanoparticle Films
journal, August 2016


Controlling Ion-Transport Selectivity in Gold Nanotubule Membranes
journal, September 2001


Polyelectrolyte Layer-by-Layer Deposition in Cylindrical Nanopores
journal, June 2010

  • Lazzara, Thomas D.; Lau, K. H. Aaron; Abou-Kandil, Ahmed I.
  • ACS Nano, Vol. 4, Issue 7
  • DOI: 10.1021/nn1007594

Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity
journal, January 2015

  • Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.
  • Nanoscale, Vol. 7, Issue 40
  • DOI: 10.1039/C5NR02939B

Science and technology for water purification in the coming decades
journal, March 2008

  • Shannon, Mark A.; Bohn, Paul W.; Elimelech, Menachem
  • Nature, Vol. 452, Issue 7185, p. 301-310
  • DOI: 10.1038/nature06599

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