LeveragingC<sub>2</sub>H<sub>4</sub>N<sub>3</sub><sup>+</sup>CH<sub>3</sub>SO<sub>3</sub><sup>–</sup> IonicLiquid-Embedded MOF-808 and Biobased Vitamin E for Enhanced Performanceand Oxidative Tolerance in Zero-Humidified PEMFCs

Integration of diverse functional materials offers a multifaceted approach to tackle the challenges of developing highly conductive, durable, and cost-effective membrane electrolytes for energy applications. A simple, low cost protic ionic liquid (PIL) “triazolium methanesulfonate” (C<sub>2</sub>H<sub>4</sub>N<sub>3</sub><sup>+</sup>CH<sub>3</sub>SO<sub>3</sub><sup>–</sup>) was entrapped into the pores of zirconium-based metal–organic framework (MOF), MOF 808 (Zr<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(BTC)<sub>2</sub>(HCOO)<sub>5</sub>(H2O)<sub>1</sub>(OH)<sub>1</sub>) to develop a hybrid proton conductor (TrzIL@M). This generated a new class of material that can harness the intrinsic properties of rigid host-soft guest, resulting in synergistic interplay that forms ordered, long-range ion conducting ducts and prevents PIL leaching when incorporated in a polymer matrix. Further, electrolytes are susceptible to degradation by reactive oxygen species. To combat this, we drew inspiration from biological systems and utilized the renewable antioxidant vitamin E (α-tocopherol) as a potent radical scavenger. Finally, a mixed matrix membrane electrolyte was developed by incorporating TrzIL@M and vitamin E into a SPEEK matrix. The resulting membrane (SP/TrzIL@ME) exhibited a high conductivity of 0.035 S/cm at 100 °C ∼2.7 times upsurge in comparison to pristine SPEEK membrane, while PIL loss was reduced by 18%. SP/TrzIL@ME achieved maximum current density of 1327 mA/cm<sup>2</sup> and peak power density 245 mW/cm<sup>2</sup> in zero-humidified conditions. SP/TrzIL@ME operated effectively in nonhumidified state mitigating flooding, swelling, and dimensional distortion associated with humidity-dependent membranes. Notably, the membrane could retain 91% of open-circuit voltage after five cycles (50 h) durability testing attributed to the scavenging activity and recyclability of vitamin E, establishing the PEM as a potential candidate for proton exchange membrane fuel cells.

Publication Details

Journal
Figshare
Published
2025-03-24
DOI
https://doi.org/10.1021/acsaem.4c02795.s001
Primary Topic
Fuel Cells and Related Materials
Type
article
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article

LeveragingC2H4N3+CH3SO3– IonicLiquid-Embedded MOF-808 and Biobased Vitamin E for Enhanced Performanceand Oxidative Tolerance in Zero-Humidified PEMFCs

Figshare
Fuel Cells and Related Materials
article

LeveragingC2H4N3+CH3SO3– IonicLiquid-Embedded MOF-808 and Biobased Vitamin E for Enhanced Performanceand Oxidative Tolerance in Zero-Humidified PEMFCs

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Abstract

Integration of diverse functional materials offers a multifaceted approach to tackle the challenges of developing highly conductive, durable, and cost-effective membrane electrolytes for energy applications. A simple, low cost protic ionic liquid (PIL) “triazolium methanesulfonate” (C<sub>2</sub>H<sub>4</sub>N<sub>3</sub><sup>+</sup>CH<sub>3</sub>SO<sub>3</sub><sup>–</sup>) was entrapped into the pores of zirconium-based metal–organic framework (MOF), MOF 808 (Zr<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(BTC)<sub>2</sub>(HCOO)<sub>5</sub>(H2O)<sub>1</sub>(OH)<sub>1</sub>) to develop a hybrid proton conductor (TrzIL@M). This generated a new class of material that can harness the intrinsic properties of rigid host-soft guest, resulting in synergistic interplay that forms ordered, long-range ion conducting ducts and prevents PIL leaching when incorporated in a polymer matrix. Further, electrolytes are susceptible to degradation by reactive oxygen species. To combat this, we drew inspiration from biological systems and utilized the renewable antioxidant vitamin E (α-tocopherol) as a potent radical scavenger. Finally, a mixed matrix membrane electrolyte was developed by incorporating TrzIL@M and vitamin E into a SPEEK matrix. The resulting membrane (SP/TrzIL@ME) exhibited a high conductivity of 0.035 S/cm at 100 °C ∼2.7 times upsurge in comparison to pristine SPEEK membrane, while PIL loss was reduced by 18%. SP/TrzIL@ME achieved maximum current density of 1327 mA/cm<sup>2</sup> and peak power density 245 mW/cm<sup>2</sup> in zero-humidified conditions. SP/TrzIL@ME operated effectively in nonhumidified state mitigating flooding, swelling, and dimensional distortion associated with humidity-dependent membranes. Notably, the membrane could retain 91% of open-circuit voltage after five cycles (50 h) durability testing attributed to the scavenging activity and recyclability of vitamin E, establishing the PEM as a potential candidate for proton exchange membrane fuel cells.

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Fuel Cells and Related Materials
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LeveragingC<sub>2</sub>H<sub>4</sub>N<sub>3</sub><sup>+</sup>CH<sub>3</sub>SO<sub>3</sub><sup>–</sup> IonicLiquid-Embedded MOF-808 and Biobased Vitamin E for Enhanced Performanceand Oxidative Tolerance in Zero-Humidified PEMFCs · Figshare (2025) | TGRS Research Map | TGRS