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Diastereomeric Monomers Enable Anion-Exchange Membranes With Controlled Local Polymer Backbone Flexibility and High Conductivity

Chen, Si LU ; Lyu, Xuchen LU ; Luong, Triet Nguyen Dai LU and Jannasch, Patric LU orcid (2026) In Advanced Science
Abstract
Multiple interdependent properties govern the performance of ion-exchange membranes. Here, we demonstrate a polymer backbone design that allows a constrained local flexibility, suppressing excessive hydration while facilitating high hydroxide conductivity in poly(arylene piperidinium) anion-exchange membranes (AEMs). This structural design builds on a pair of diastereomeric arene monomers with vicinal methyl substitutions that introduce local conformational constraints and enable systematic investigation of how subtle stereochemical variations influence hydration behavior, ion transport, and device performance without altering the overall polymer composition. Two corresponding membrane series are synthesized that differ only in... (More)
Multiple interdependent properties govern the performance of ion-exchange membranes. Here, we demonstrate a polymer backbone design that allows a constrained local flexibility, suppressing excessive hydration while facilitating high hydroxide conductivity in poly(arylene piperidinium) anion-exchange membranes (AEMs). This structural design builds on a pair of diastereomeric arene monomers with vicinal methyl substitutions that introduce local conformational constraints and enable systematic investigation of how subtle stereochemical variations influence hydration behavior, ion transport, and device performance without altering the overall polymer composition. Two corresponding membrane series are synthesized that differ only in stereochemistry, providing a composition-conserved platform for studies of structure–property relationships. The diastereomeric units in the AEMs facilitate the formation of ion-conducting domains, providing membranes combining high hydroxide conductivity with controlled water uptake. Hence, the syn-enriched membranes consistently exhibit higher water uptake than their anti-enriched counterparts at comparable ion-exchange capacities, resulting in higher hydroxide conductivity and improved anion exchange membrane water electrolysis performance. In comparison, the anti-enriched membranes display improved mechanical robustness and higher hydration efficiency for ion transport. Overall, this work establishes a stereochemistry-based synthetic strategy that enables systematic investigation and control of membrane properties through minimal structural variation, providing a molecular platform for rational AEM design.Multiple interdependent properties govern the performance of ion-exchange membranes. Here, we demonstrate a polymer backbone design that allows a constrained local flexibility, suppressing excessive hydration while facilitating high hydroxide conductivity in poly(arylene piperidinium) anion-exchange membranes (AEMs). This structural design builds on a pair of diastereomeric arene monomers with vicinal methyl substitutions that introduce local conformational constraints and enable systematic investigation of how subtle stereochemical variations influence hydration behavior, ion transport, and device performance without altering the overall polymer composition. Two corresponding membrane series are synthesized that differ only in stereochemistry, providing a composition-conserved platform for studies of structure–property relationships. The diastereomeric units in the AEMs facilitate the formation of ion-conducting domains, providing membranes combining high hydroxide conductivity with controlled water uptake. Hence, the syn-enriched membranes consistently exhibit higher water uptake than their anti-enriched counterparts at comparable ion-exchange capacities, resulting in higher hydroxide conductivity and improved anion exchange membrane water electrolysis performance. In comparison, the anti-enriched membranes display improved mechanical robustness and higher hydration efficiency for ion transport. Overall, this work establishes a stereochemistry-based synthetic strategy that enables systematic investigation and control of membrane properties through minimal structural variation, providing a molecular platform for rational AEM design. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
epub
subject
in
Advanced Science
article number
e76588
publisher
John Wiley & Sons Inc.
ISSN
2198-3844
DOI
10.1002/advs.76588
language
English
LU publication?
yes
id
c98cfe83-8a24-43b2-84f2-e6ab9d46bf88
date added to LUP
2026-04-17 17:51:28
date last changed
2026-08-19 12:51:11
@article{c98cfe83-8a24-43b2-84f2-e6ab9d46bf88,
  abstract     = {{Multiple interdependent properties govern the performance of ion-exchange membranes. Here, we demonstrate a polymer backbone design that allows a constrained local flexibility, suppressing excessive hydration while facilitating high hydroxide conductivity in poly(arylene piperidinium) anion-exchange membranes (AEMs). This structural design builds on a pair of diastereomeric arene monomers with vicinal methyl substitutions that introduce local conformational constraints and enable systematic investigation of how subtle stereochemical variations influence hydration behavior, ion transport, and device performance without altering the overall polymer composition. Two corresponding membrane series are synthesized that differ only in stereochemistry, providing a composition-conserved platform for studies of structure–property relationships. The diastereomeric units in the AEMs facilitate the formation of ion-conducting domains, providing membranes combining high hydroxide conductivity with controlled water uptake. Hence, the syn-enriched membranes consistently exhibit higher water uptake than their anti-enriched counterparts at comparable ion-exchange capacities, resulting in higher hydroxide conductivity and improved anion exchange membrane water electrolysis performance. In comparison, the anti-enriched membranes display improved mechanical robustness and higher hydration efficiency for ion transport. Overall, this work establishes a stereochemistry-based synthetic strategy that enables systematic investigation and control of membrane properties through minimal structural variation, providing a molecular platform for rational AEM design.Multiple interdependent properties govern the performance of ion-exchange membranes. Here, we demonstrate a polymer backbone design that allows a constrained local flexibility, suppressing excessive hydration while facilitating high hydroxide conductivity in poly(arylene piperidinium) anion-exchange membranes (AEMs). This structural design builds on a pair of diastereomeric arene monomers with vicinal methyl substitutions that introduce local conformational constraints and enable systematic investigation of how subtle stereochemical variations influence hydration behavior, ion transport, and device performance without altering the overall polymer composition. Two corresponding membrane series are synthesized that differ only in stereochemistry, providing a composition-conserved platform for studies of structure–property relationships. The diastereomeric units in the AEMs facilitate the formation of ion-conducting domains, providing membranes combining high hydroxide conductivity with controlled water uptake. Hence, the syn-enriched membranes consistently exhibit higher water uptake than their anti-enriched counterparts at comparable ion-exchange capacities, resulting in higher hydroxide conductivity and improved anion exchange membrane water electrolysis performance. In comparison, the anti-enriched membranes display improved mechanical robustness and higher hydration efficiency for ion transport. Overall, this work establishes a stereochemistry-based synthetic strategy that enables systematic investigation and control of membrane properties through minimal structural variation, providing a molecular platform for rational AEM design.}},
  author       = {{Chen, Si and Lyu, Xuchen and Luong, Triet Nguyen Dai and Jannasch, Patric}},
  issn         = {{2198-3844}},
  language     = {{eng}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Advanced Science}},
  title        = {{Diastereomeric Monomers Enable Anion-Exchange Membranes With Controlled Local Polymer Backbone Flexibility and High Conductivity}},
  url          = {{http://dx.doi.org/10.1002/advs.76588}},
  doi          = {{10.1002/advs.76588}},
  year         = {{2026}},
}