Study of the composition and structure of ion-conducting membranes based on polyvinyl alcohol by ¹H NMR spectroscopy

One of the alternative types of proton-conducting membranes for a hydrogen-air solid polymer fuel cell is the type of hybrid membranes based on polyvinyl alcohol (PVA) crosslinked with aldehyde, modified with sulfonic acid. Earlier, for the first time, we obtained new ion – conducting membranes based on furfural-crosslinked PVA modified with amino sulfonic acid (ASA) and tetraethoxysilane (TEOS), as well as membranes not crosslinked with furfural (FUR) or unmodified ASA and TEOS, by a liquid-phase synthesis method, in an organic medium-dimethyl sulfoxide. The values of their ionic conductivity and the degree of swelling in water are presented. In this work, the composition and structure of the obtained ion-conducting membranes are studied using liquid-phase nuclear magnetic resonance (NMR) spectroscopy on ¹H nuclei. In the ¹H NMR spectrum of an ion – conducting membrane not cross-linked with the «PVA/ASA», the signal of free OH groups of PVA is observed to disappear, but at the same time a characteristic triplet at 7.1 m.d. is preserved, having a constant of ~51 Hz and components of the same intensity (1:1:1), which corresponds to protons of ¹⁴NH₄⁺ hydrolyzed ASA. The disappearance of the expanded signal at 9.6 m. d. of protons of the free sulfo group of ASA and a narrow singlet signal at 5.8 m. d. of free protons of the NH₂ group of ASA indicates the interaction of ASA with OH groups of PVA. In the ¹H NMR spectrum of an ion – conducting membrane crosslinked with FUR – «PVA/ASA/FUR», signals of protons of the furan ring of FUR and a signal of its aldehyde group are observed, which is shifted to a strong field, which is determined by the formation of a chemical bond between FUR and the polymer chain of PVA. In the ¹H NMR spectra of all membranes modified by ASA, the appearance of a second weaker-field ¹⁴NH₄ triplet is observed, and in the spectra of a number of ion – conducting hybrid membranes modified by TEOS – «PVA/ASA/FUR/TEOS», signals of the third type of ¹⁴NH₄⁺ triplets shifted in a strong field relative to the other two ¹⁴NH₄⁺ triplets were detected. The appearance of additional ¹⁴NH₄⁺ triplets indicates the formation of several bound forms of the ammonium ion.

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