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AFM Imaging of Adsorbed Nafion Polymer on Mica and Graphite at Molecular Level

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Electrochemical Energy Research Laboratory, GM Research and Development, 10 Carriage Street, Honeoye Falls, New York 14472-1039, United States
Department of Chemistry and Biomolecular Science, Clarkson University, 8 Clarkson Avenue Potsdam, New York 13699-5810, United States
§ Trison Business Solutions, Honeoye Falls, New York 14472-1039, United States
Tel.: 315-268-3807. Fax: 315-268-6610. E-mail: [email protected]
Cite this: Langmuir 2011, 27, 16, 10157–10166
Publication Date (Web):July 7, 2011
https://doi.org/10.1021/la201283a
Copyright © 2011 American Chemical Society

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    Abstract

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    Perfluorosulfonic acid ionomer (PFSA, specifically Nafion at EW = 975 g/mol) was visualized at the single molecule level using atomic force microscopy (AFM) in liquid. The diluted commercial Nafion dispersion shows an apparent Mw = 1430 kg/mol and Mw/Mn = 3.81, which is assigned to chain aggregation. PFSA aggregates, imaged on mica and HOPG during adsorption from EtOH–H2O solvent at pH(e) 3.0 (below isoelectric point), showed a stable, segmented rod-like conformation. This structure is consistent with earlier NMR, SAXS/SANS, and TEM results that support a stiff helical Nafion conformation with long persistence length, a sharp solvent–polymer interface, and an extension of the sulfonated side chain into solution. Adsorption of Nafion structures on HOPG was observed at even higher pH(e) from EtOH due to screening of the repulsive electrostatic interaction in lower dielectric constant solvent, while the chain adopted an expanded coil conformation. These measurements provided direct evidence of the chain aggregation in EtOH–H2O solution and revealed their equilibrium conformations for adsorption on two model surfaces, highly ordered pyrolitic graphite (HOPG) and mica. The commercial Nafion dispersion was autoclaved at 0.10% w/w in nPrOH/H2O = 4:1 v/v solvent at 230 °C for 6 h to give a single-chain dispersion with Mw = 310 kg/mol and Mw/Mn = 1.60. The autoclaved chains adopt an electrostatically stabilized compact globule conformation as observed by AFM imaging of the single PFSA molecules after rapid deposition on mica and HOPG at a low surface coverage.

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