Revealing nanostructure-driven oxidative protection in thiourea-functionalized sPEEK hybrid membranes for PEM…

Abstract

Achieving long-term oxidative stability in proton exchange membrane fuel cells (PEMFCs) remains a major challenge. Here, we investigate the morphological mechanisms underlying the oxidative stability of thiourea-functionalized sol–gel (SG)/sulfonated poly(ether ether ketone) (sPEEK) hybrid membranes, previously developed using two organosilane precursors, N,N′-bis[3-(triethoxysilyl)propyl] thiourea (HTU) and N-phenyl,N′-[3-(triethoxysilyl)propyl] thiourea (TTU). These thiourea groups, introduced as sacrificial antioxidants, are used to tune the nanoscale organization of the SG phase within the polymer matrix. Contrast-variation small-angle neutron scattering (CV-SANS) shows that the SG phase is distributed within ionic nanochannels and interbundle regions. Although TEM and AFM indicate homogeneous dispersion at the microscale, sub-resolution fluctuations likely account for the SANS signal. HTU forms well-defined spherical hybrid domains (∼5–6 nm), whereas TTU produces larger, less organized structures (∼18–22 nm). Under oxidative conditions, pristine sPEEK swells and degrades above 0.1 wt%, whereas hybrid membranes retain structural integrity and conductivity up to 0.3 wt% through a two-stage protection mechanism, consisting of a primary (total) SG-driven protection in ionic domains followed by a secondary protection in interbundle regions upon SG consumption. This sequential mechanism governs membrane integrity and proton transport under oxidative stress.

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Cite

BibTeX RIS

BibTeX

@article{tougne2026revealing,
  title = {{Revealing nanostructure-driven oxidative protection in thiourea-functionalized sPEEK hybrid membranes for PEM fuel cells}},
  author = {Claire Tougne and Meriem Daoudi and Evelise Ferri and Vincent H Mareau and Véronique Dufaud and Catherine Santini and Eliane Espuche and Olivier Lottin and Jean-Christophe Perrin and Jérôme Dillet and Assma El Kaddouri and Lionel Porcar and Laurent Gonon and Hakima Mendil-Jakani},
  journal = {Journal of Materials Chemistry A},
  year = {2026},
  month = sep,
  doi = {10.1039/d6ta03128e},
  url = {https://hal.science/hal-05762294v1},
  note = {CC BY 4.0},
}

RIS

TY  - JOUR
TI  - Revealing nanostructure-driven oxidative protection in thiourea-functionalized sPEEK hybrid membranes for PEM fuel cells
AU  - Claire Tougne
AU  - Meriem Daoudi
AU  - Evelise Ferri
AU  - Vincent H Mareau
AU  - Véronique Dufaud
AU  - Catherine Santini
AU  - Eliane Espuche
AU  - Olivier Lottin
AU  - Jean-Christophe Perrin
AU  - Jérôme Dillet
AU  - Assma El Kaddouri
AU  - Lionel Porcar
AU  - Laurent Gonon
AU  - Hakima Mendil-Jakani
PY  - 2026
DA  - 2026/09/24
JO  - Journal of Materials Chemistry A
DO  - 10.1039/d6ta03128e
UR  - https://hal.science/hal-05762294v1
AB  - Achieving long-term oxidative stability in proton exchange membrane fuel cells (PEMFCs) remains a major challenge. Here, we investigate the morphological mechanisms underlying the oxidative stability of thiourea-functionalized sol–gel (SG)/sulfonated poly(ether ether ketone) (sPEEK) hybrid membranes, previously developed using two organosilane precursors, N,N′-bis[3-(triethoxysilyl)propyl] thiourea (HTU) and N-phenyl,N′-[3-(triethoxysilyl)propyl] thiourea (TTU). These thiourea groups, introduced as sacrificial antioxidants, are used to tune the nanoscale organization of the SG phase within the polymer matrix. Contrast-variation small-angle neutron scattering (CV-SANS) shows that the SG phase is distributed within ionic nanochannels and interbundle regions. Although TEM and AFM indicate homogeneous dispersion at the microscale, sub-resolution fluctuations likely account for the SANS signal. HTU forms well-defined spherical hybrid domains (∼5–6 nm), whereas TTU produces larger, less organized structures (∼18–22 nm). Under oxidative conditions, pristine sPEEK swells and degrades above 0.1 wt%, whereas hybrid membranes retain structural integrity and conductivity up to 0.3 wt% through a two-stage protection mechanism, consisting of a primary (total) SG-driven protection in ionic domains followed by a secondary protection in interbundle regions upon SG consumption. This sequential mechanism governs membrane integrity and proton transport under oxidative stress.
SN  - 2050-7488
SN  - 2050-7496
ER  -