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Tailoring Structure-Property Relationships in π-Conjugated Heterocyclic Poly(arylene alkylene) Anion-Exchange Membranes for High-Performance Water Electrolysis

Wang, Qian ; Huang, Riyang ; Zhao, Wenzhe ; Chen, Si LU ; Guo, Yunpeng ; Wu, Yang ; Zhao, Yun ; Jannasch, Patric LU orcid and Yang, Jingshuai LU (2026) In Advanced Science
Abstract
Anion-exchange membrane water electrolysis (AEMWE) is a promising technology for sustainable hydrogen production, but practical applications are limited by the trade-off between hydroxide conductivity and alkaline stability of anion-exchange membranes (AEMs). Here, we report a molecular design strategy that regulates ion transport pathways and membrane stability by tethering quaternary ammonium cations via flexible side chains to π-conjugated heterocyclic backbone polymers. Durable cationic copolymers containing p-terphenyl with dibenzofuran (DBF) or dibenzothiophene (DBT) units are synthesized. Combined experimental and theoretical studies establish structure-property relationships linking heteroatom chemistry to the hydration,... (More)
Anion-exchange membrane water electrolysis (AEMWE) is a promising technology for sustainable hydrogen production, but practical applications are limited by the trade-off between hydroxide conductivity and alkaline stability of anion-exchange membranes (AEMs). Here, we report a molecular design strategy that regulates ion transport pathways and membrane stability by tethering quaternary ammonium cations via flexible side chains to π-conjugated heterocyclic backbone polymers. Durable cationic copolymers containing p-terphenyl with dibenzofuran (DBF) or dibenzothiophene (DBT) units are synthesized. Combined experimental and theoretical studies establish structure-property relationships linking heteroatom chemistry to the hydration, microphase morphology, and ion transport. DBF-units promote dense hydrogen bonding networks, whereas DBT-units strengthen ion-dipole interactions and induce more pronounced microphase separation. Consequently, optimized DBF- and DBT-based membranes exhibit hydroxide conductivities exceeding 180 and 200 mS cm−1, respectively, at 80°C. In AEMWEs using non-precious-metal catalysts, these membranes deliver current densities above 4.1 and 5.1 A cm−2 at 2 V, respectively. The DBT-based membrane also maintains stable operation for over 1600 h at 1 A cm−2 and 60°C. This work establishes structure-performance relationships and provides a practical molecular design strategy for highly conductive, durable AEMs based on π-conjugated heterocyclic backbone units. (Less)
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organization
publishing date
type
Contribution to journal
publication status
epub
subject
in
Advanced Science
article number
e77491
pages
16 pages
publisher
John Wiley & Sons Inc.
ISSN
2198-3844
DOI
10.1002/advs.77491
language
English
LU publication?
yes
id
60b0783d-87d3-4f35-ab53-914fb38ad96e
date added to LUP
2026-04-03 12:48:12
date last changed
2026-09-02 15:00:12
@article{60b0783d-87d3-4f35-ab53-914fb38ad96e,
  abstract     = {{Anion-exchange membrane water electrolysis (AEMWE) is a promising technology for sustainable hydrogen production, but practical applications are limited by the trade-off between hydroxide conductivity and alkaline stability of anion-exchange membranes (AEMs). Here, we report a molecular design strategy that regulates ion transport pathways and membrane stability by tethering quaternary ammonium cations via flexible side chains to π-conjugated heterocyclic backbone polymers. Durable cationic copolymers containing <i>p</i>-terphenyl with dibenzofuran (DBF) or dibenzothiophene (DBT) units are synthesized. Combined experimental and theoretical studies establish structure-property relationships linking heteroatom chemistry to the hydration, microphase morphology, and ion transport. DBF-units promote dense hydrogen bonding networks, whereas DBT-units strengthen ion-dipole interactions and induce more pronounced microphase separation. Consequently, optimized DBF- and DBT-based membranes exhibit hydroxide conductivities exceeding 180 and 200 mS cm<sup>−1</sup>, respectively, at 80°C. In AEMWEs using non-precious-metal catalysts, these membranes deliver current densities above 4.1 and 5.1 A cm<sup>−2</sup> at 2 V, respectively. The DBT-based membrane also maintains stable operation for over 1600 h at 1 A cm<sup>−2</sup> and 60°C. This work establishes structure-performance relationships and provides a practical molecular design strategy for highly conductive, durable AEMs based on π-conjugated heterocyclic backbone units.}},
  author       = {{Wang, Qian and Huang, Riyang and Zhao, Wenzhe and Chen, Si and Guo, Yunpeng and Wu, Yang and Zhao, Yun and Jannasch, Patric and Yang, Jingshuai}},
  issn         = {{2198-3844}},
  language     = {{eng}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Advanced Science}},
  title        = {{Tailoring Structure-Property Relationships in π-Conjugated Heterocyclic Poly(arylene alkylene) Anion-Exchange Membranes for High-Performance Water Electrolysis}},
  url          = {{http://dx.doi.org/10.1002/advs.77491}},
  doi          = {{10.1002/advs.77491}},
  year         = {{2026}},
}