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    Mass and charge transport in highly mesostructured polyelectrolyte/electroactive-surfactant multilayer films

    Year: 2021

    Journal: J. Colloid Interface Sci., Volume 581, JAN 1, page 595–607

    Authors: Piccinini, Esteban; Gonzalez, Graciela A.; Azzaroni, Omar; Battaglini, Fernando

    Organizations: Universidad de Buenos Aires [UBACYT 20020170100341BA]; PIP CONICET [11220150100291CO]; Universidad Nacional de La Plata (UNLP) [PPID-X016]; ANPCYT, Argentina [PICT 2015-0801, 2016-1680, 2017-1523]; CONICET [PIP-0370]

    Keywords: Spatially addressed redox sites; Layer-by-layer; Mesostructured films; Electrochemical quartz crystal microbalance; Rigid film; Electron transfer; Mass transfer

    Hypothesis: Dimensionally stable electroactive films displaying spatially addressed redox sites is still a challenging goal due to gel-like structure. Polyelectrolyte and surfactants can yield highly mesostructured films using simple buildup strategies as layer-by-layer. The use of redox modified surfactants is expected to introduce order and an electroactive response in thin films. Experiments: The assembly of polyacrylic acid and different combinations of redox-modified and unmodified hexadecyltrimethylammonium bromide yields highly structured and electroactive thin films. The growth, viscoelastic properties, mass, and electron transport of these films were studied by combining electrochemical and quartz crystal balance with dissipation experiments. Findings: Our results show that the films are highly rigid and poorly hydrated. The mass and charge transport reveal that the ingress (egress) of the counter ions during the electrochemical oxidation (reduction) is accompanied with a small amount of water, which is close to their hydration sphere. Thus, the generated mesostructured films present an efficient charge transport with negligible changes in their structures during the electron transfer process. The control over the meso-organization and its stability represents a promising tool in the construction of devices where the vectorial transfer of electrons, or ions, is required. (C) 2020 Elsevier Inc. All rights reserved.
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