Journal
ELECTROCHIMICA ACTA
Volume 55, Issue 2, Pages 439-450Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2009.04.027
Keywords
Neutron reflectivity; Conducting polymer; Bithiophene; Pentafluorophenyl-pyrrole; Crown ether; Modified electrode; Spatial distribution; Salvation
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Crown ether functionalised conducting polymer films were used to complex barium ions from acetonitrile solution. It was found that fully-functionalised N-derivatized polypyrrole films do not possess adequate mechanical stability, but dilution with unfunctionalised bithiophene co-monomer leads to a series of copolymer films with excellent stability. Film reactivity, composition and structure were investigated using electrochemical, nanogravimetric, FTIR, XPS and neutron reflectivity techniques. The first three of these provided spatially integrated barium populations and neutron reflectivity provided spatially resolved compositional profiles. Measurements at various stages of film fabrication yielded spatial distributions of co-monomer. crown ether, solvent and barium (as perchlorate) components. Critically, the amount of free volume to accommodate crown motifs and barium within the film was limited by the film's internal microstructure and solvent content; the low solvent volume fraction creates a different local environment to solution. (C) 2009 Elsevier Ltd. All rights reserved.
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