December 1 - 6, 2024
Boston, Massachusetts
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2024 MRS Fall Meeting & Exhibit
CH02.04.20

Nanophase Evolution, Local Water Content Distributions and Protonation Levels in Nafion—A Vibrational Spectroscopic and Molecular Dynamics Approach

When and Where

Dec 3, 2024
8:00pm - 10:00pm
Hynes, Level 1, Hall A

Presenter(s)

Co-Author(s)

Dan Donnelly III1,Moon Young Yang2,Seung Soon Jang3,Nicholas Dimakis4,William A. Goddard III2,Eugene Smotkin1

Northeastern University1,California Institute of Technology2,Georgia Institute of Technology3,The University of Texas at Rio Grande Valley4

Abstract

Dan Donnelly III1,Moon Young Yang2,Seung Soon Jang3,Nicholas Dimakis4,William A. Goddard III2,Eugene Smotkin1

Northeastern University1,California Institute of Technology2,Georgia Institute of Technology3,The University of Texas at Rio Grande Valley4
Nafion has been a dominant ionomer membrane for low-temperature (~80 °C) fuel cells and electrolyzers for nearly 50 years, because of its superior chemical-mechanical stability and high protonic conductivity. Nafion morphology comprises hydrophobic (semicrystalline), interphasial (interphasial), and water-rich domains. The hydration-level-dependent size, shape, and interconnectivity of domains remains elusive, and has limited ionomer development for high-temperature operations.

For any hydrated Nafion membrane, characterized by a bulk H2O/SO3(H) ratio (λ), our classical molecular dynamics (CMD) simulations show a wide distribution of local λ values (λloc). We used density functional theory (DFT) based vibrational normal mode analysis to generate unique λloc = 0-15 spectra, each of which contributes to overall membrane FTIR transmission spectra. For λloc < 3, the SO3H proton remains covalently bound (i.e., C1 local symmetry), and yields normal modes that correspond to IR bands ~1414 and ~910 cm-1 (C1 bands). For λloc ≥ 3, the proton dissociates to form SO3 (C3V local symmetry), which yields normal modes corresponding to C3V bands ~1060 and ~970 cm-1. We now correlate the coexistence of C1 and C3V bands during membrane hydration/dehydration to SO3/SO3H ratios (i.e., protonation levels) generated by reactive force field (ReaxFF) MD simulations.

CMD simulations, governed by classical equations of motion, fail to model the dynamic exchange of protons between SO3(H) groups (i.e., exchange sites) and water/hydronium. We used ReaxFF in Nafion MD simulations to model this exchange, and to derive λ-dependent protonation levels. This is the first such use of ReaxFF, to the best of our knowledge. Our MD systems comprised 320 exchange sites, and were hydrated as follows: λ = 0, 1, 2, 3, 5, 7, 10, 15, 20. We relate the ReaxFF generated protonation levels to C1 and C3V transmission-IR band intensity changes, resulting from sub-λ aliquots of water vapor injected into an initially dehydrated Nafion membrane. Illustrations of ReaxFF MD structures reveal nano-phase segregation and heterogeneity in water environments. Inner-sphere waters contribute to λloc values and outer-sphere waters do not. Inner sphere waters either bridge multiple exchange sites (bridged) or hydrate single SO3(H) groups (non-bridged). Outer-sphere waters are either isolated or bulk-like. The applicability of our coordinated experimental/theoretical approach to hydrocarbon-based ionomers will be described.

Keywords

infrared (IR) spectroscopy | morphology

Symposium Organizers

Ye Cao, The University of Texas at Arlington
Jinghua Guo, Lawrence Berkeley National Laboratory
Amy Marschilok, Stony Brook University
Liwen Wan, Lawrence Livermore National Laboratory

Session Chairs

Jinghua Guo
Liwen Wan

In this Session