Cyclic voltammetry was applied to investigate the permselective properties of electrode-supported ion-exchange polymer films intended for use in future molecular-scale spectroscopic studies of bipolar membranes. The ability of thin ionomer film assemblies to exclude mobile ions charged similarly to the polymer (co-ions) and accumulate ions charged opposite to the polymer (counterions) was scrutinized through use of the diffusible redox probe molecules [Ru(NH3)6]3+and [IrCl6]2−. With the anion exchange membrane (AEM) phase supported on a carbon disk electrode, bipolar junctions formed by addition of a cation exchange membrane (CEM) overlayer demonstrated high selectivity toward redox ion extraction and exclusion. For junctions formed using a Fumion®AEM phase and a Nafion®overlayer, [IrCl6]2−ions exchanged into Fumion®prior to Nafion®overcoating remained entrapped and the Fumion®excluded [Ru(NH3)6]3+ions for durability testing periods of more than 20 h under conditions of interest for eventualin situspectral measurements. Experiments with the Sustainion®anion exchange ionomer uncovered evidence for [IrCl6]2−ion coordination to pendant imidazolium groups on the polymer. A cyclic voltammetric method for estimation of the effective diffusion coefficient and equilibrium extraction constant for redox active probe ions within inert, uniform density electrode-supported thin films was applied to examine charge transport mechanisms.
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Structure-Property Relationships in Hybrid Cellulose Nanofibrils/Nafion-Based Ionic Polymer-Metal Composites
Herein, we report the production of ionic polymer-metal composites (IPMCs) hybridized with cellulose nanofibrils (CNF) as a partial substitute for Nafion®. The aim is not only to reduce the production cost and enhance respective mechanical/thermal properties but also to bestow a considerable degree of biodegradability to such products. Formulations with dierent CNF/Nafion® ratios were produced in a thin-film casting process. Crack-free films were air-dried and plated by platinum (Pt) through an oxidation-reduction reaction. The produced hybrids were analyzed in terms of thermal stability, mechanical and morphological aspects to examine their performance compared to the Nafion-based IPMC prior to plating process. Results indicated that films with higher CNF loadings had improved tensile strengths and elastic moduli but reduced ductility. Thermogravimetric analysis (TGA) showed that the incorporation of CNF to the matrix reduced its thermal stability almost linearly, however, the onset of decomposition point remained above 120 C, which was far above the temperature the composite membrane is expected to be exposed to. The addition of a cross-linking agent to the formulations helped with maintaining the integrity of the membranes during the plating process, thereby improving surface conductivity. The focus of the current study was on the physical and morphological properties of the films, and the presented data advocate the potential utilization of CNF as a nontoxic and sustainable bio-polymer for blending with perfluorosulfonic acid-based co-polymers, such as Nafion®, to be used in electroactive membranes.
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- Award ID(s):
- 1757529
- PAR ID:
- 10129419
- Date Published:
- Journal Name:
- Materials
- Volume:
- 12
- Issue:
- 8
- ISSN:
- 1996-1944
- Page Range / eLocation ID:
- 1269
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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