Quantitative 1H NMR analysis of chemical stabilities in anion-exchange membranes

Sean A. Nuñez, Michael Anthony Hickner

Research output: Contribution to journalArticle

132 Citations (Scopus)

Abstract

We compared the alkaline stability of three classes of anion exchange membranes that are leading candidates for applications in platinum-free fuel cells. A methodology is presented for the study of chemical stability of anion-exchange polymers in alkaline media that provides clear and quantitative 1H NMR spectroscopic data of dissolved polymers containing benzyltrimethylammonium functionalities. Recent studies have investigated the stabilities of benzimidazolium- and alkylimidazolium-bearing polymers using periodic 1H NMR sampling. These studies included varying alkaline concentrations, external heating sources, and excessive processing and contained no internal standard for absolute measurements. Key aspects of our time-resolved 1H NMR method include in situ heating and sampling within the spectrometer, fixed stoichiometric relationships between the benzyltrimethylammonium functionalities of each polymer and potassium deuteroxide (KOD), and the incorporation of an internal standard for the absolute measurement of the polymer degradation. In addition, our method permits the identification of the degradation products to find the underlying cause of chemical lability. Our results demonstrate that a styrene-based polymer containing benzyltrimethylammonium functional groups is remarkably stable when exposed to 20 equivalents per cation of KOD at 80 C with a half-life (t 1/2) of 231 h. Under these standard conditions, functionalized poly(phenylene oxide) and poly(arylene ether sulfone) copolymers, both bearing benzyltrimethylammonium functionalities were found to degrade with a half-lives of 57.8 and 2.7 h, respectively.

Original languageEnglish (US)
Pages (from-to)49-52
Number of pages4
JournalACS Macro Letters
Volume2
Issue number1
DOIs
StatePublished - Jan 24 2013

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Chemical stability
Anions
Ion exchange
Polymers
Negative ions
Nuclear magnetic resonance
Membranes
Bearings (structural)
Sampling
Heating
Degradation
Sulfones
Styrene
Platinum
Ether
Oxides
Functional groups
Potassium
Spectrometers
Cations

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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abstract = "We compared the alkaline stability of three classes of anion exchange membranes that are leading candidates for applications in platinum-free fuel cells. A methodology is presented for the study of chemical stability of anion-exchange polymers in alkaline media that provides clear and quantitative 1H NMR spectroscopic data of dissolved polymers containing benzyltrimethylammonium functionalities. Recent studies have investigated the stabilities of benzimidazolium- and alkylimidazolium-bearing polymers using periodic 1H NMR sampling. These studies included varying alkaline concentrations, external heating sources, and excessive processing and contained no internal standard for absolute measurements. Key aspects of our time-resolved 1H NMR method include in situ heating and sampling within the spectrometer, fixed stoichiometric relationships between the benzyltrimethylammonium functionalities of each polymer and potassium deuteroxide (KOD), and the incorporation of an internal standard for the absolute measurement of the polymer degradation. In addition, our method permits the identification of the degradation products to find the underlying cause of chemical lability. Our results demonstrate that a styrene-based polymer containing benzyltrimethylammonium functional groups is remarkably stable when exposed to 20 equivalents per cation of KOD at 80 C with a half-life (t 1/2) of 231 h. Under these standard conditions, functionalized poly(phenylene oxide) and poly(arylene ether sulfone) copolymers, both bearing benzyltrimethylammonium functionalities were found to degrade with a half-lives of 57.8 and 2.7 h, respectively.",
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Quantitative 1H NMR analysis of chemical stabilities in anion-exchange membranes. / Nuñez, Sean A.; Hickner, Michael Anthony.

In: ACS Macro Letters, Vol. 2, No. 1, 24.01.2013, p. 49-52.

Research output: Contribution to journalArticle

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