Anhydrous superprotonic polymer by superacid protonation of cross-linked (PNCl2)n

Younes Ansari, Kazuhide Ueno, Zuofeng Zhao, Charles Angell

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We describe a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The degree of protonation of the polymer is presumed to be higher than that for the unpolymerized molecular liquid (PNCl2)3, where NMR analysis suggests the protonation is about 20%, because the conductivity of the latter is much lower. At a mole fraction of HOTf of x = 0.5 (i.e., H:N = 1), we find that the cross-linked polymer is also much more conductive than the linear polymer with same HOTf mole fraction, implying an increased proton decoupling conduction mechanism. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but with the present measurements, we cannot establish whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2 - component.

Original languageEnglish (US)
Pages (from-to)1548-1553
Number of pages6
JournalJournal of Physical Chemistry C
Volume117
Issue number4
DOIs
StatePublished - Jan 31 2013

Fingerprint

Protonation
Polymers
conductivity
polymers
decoupling
Relaxation time
Protons
relaxation time
protons
Rubber
rubber
Nitrogen
Nuclear magnetic resonance
nitrogen
conduction
nuclear magnetic resonance
Liquids
liquids

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Anhydrous superprotonic polymer by superacid protonation of cross-linked (PNCl2)n . / Ansari, Younes; Ueno, Kazuhide; Zhao, Zuofeng; Angell, Charles.

In: Journal of Physical Chemistry C, Vol. 117, No. 4, 31.01.2013, p. 1548-1553.

Research output: Contribution to journalArticle

Ansari, Younes ; Ueno, Kazuhide ; Zhao, Zuofeng ; Angell, Charles. / Anhydrous superprotonic polymer by superacid protonation of cross-linked (PNCl2)n In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 4. pp. 1548-1553.
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AB - We describe a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The degree of protonation of the polymer is presumed to be higher than that for the unpolymerized molecular liquid (PNCl2)3, where NMR analysis suggests the protonation is about 20%, because the conductivity of the latter is much lower. At a mole fraction of HOTf of x = 0.5 (i.e., H:N = 1), we find that the cross-linked polymer is also much more conductive than the linear polymer with same HOTf mole fraction, implying an increased proton decoupling conduction mechanism. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but with the present measurements, we cannot establish whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2 - component.

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