American Chemical Society
cm9b04037_si_026.mp4 (527.71 kB)

Group Vibrational Mode Assignments as a Broadly Applicable Tool for Characterizing Ionomer Membrane Structure as a Function of Degree of Hydration

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posted on 2020-02-26, 22:40 authored by Neili Loupe, Khaldoon Abu-Hakmeh, Shuitao Gao, Luis Gonzalez, Matthew Ingargiola, Kayla Mathiowetz, Ryan Cruse, Jonathan Doan, Annie Schide, Isaiah Salas, Nicholas Dimakis, Seung Soon Jang, William A. Goddard, Eugene S. Smotkin
Infrared spectra of Nafion, Aquivion, and the 3 M membrane were acquired during total dehydration of fully hydrated samples. Fully hydrated exchange sites are in a sulfonate form with a C3V local symmetry. The mechanical coupling of the exchange site to a side chain ether link gives rise to vibrational group modes that are classified as C3V modes. These mode intensities diminish concertedly with dehydration. When totally dehydrated, the sulfonic acid form of the exchange site is mechanically coupled to an ether link with no local symmetry. This gives rise to C1 group modes that emerge at the expense of C3V modes during dehydration. Membrane IR spectra feature a total absence of C3V modes when totally dehydrated, overlapping C1 and C3V modes when partially hydrated and a total absence of C1 modes when fully hydrated. DFT calculated normal-mode analyses complemented with molecular dynamics simulations of Nafion with overall λ (λAvg) values of 1, 3, 10, 15, and 20 waters/exchange site were sectioned into subcubes to enable the manual counting of the distribution of λlocal values that integrate to λAvg values. This work suggests that at any state of hydration, IR spectra are a consequence of a distribution of λlocal values. Bond distances and the threshold value of λlocal, for exchange site dissociation, were determined by DFT modeling and used to correlate spectra to manually counted λlocal distributions.