Oxidative Inorganic Multilayers for Polypyrrole Film Generation

Abstract

A controlled nanoscale fabrication of conducting polymer films sets severe requirements for the preparation method and substrate. A new and versatile approach for producing thin polypyrrole films on a variety of surfaces is presented. Purely inorganic thin films are first prepared from poly(metaphosphate) and tetravalent metal ions using a sequential layer‐by‐layer technique. Redox‐active cerium(IV) polyphosphate multilayer and redox‐inactive zirconium(IV) and hafnium(IV) polyphosphate multilayers are prepared. Cerium‐based polyphosphate films grow exponentially with the number of layers but multilayers containing zirconium or hafnium exhibit a linear buildup process. All the studied systems produce relatively smooth films with initial bilayer thickness less than 2 nm. The cerium(IV) containing film is redox‐active, which is shown by its capability to form a polypyrrole layer on its surface by oxidation of pyrrole monomers in the adjacent aqueous solution. This is a general method to produce thin oxidative films of arbitrary size and form on a wide variety of surfaces.

Short versus long chain polyelectrolyte multilayers: a direct comparison of self-assembly and structural properties

“…Therefore, the exchange of complexes between film and solution may occur within experimental times. As a result of that, stable multilayering of pairs of oligomeric electrolytes has been reported so far only in exceptional cases, typically requiring additional interactions, such as hydrophobic or p-p-stacking forces [40][41][42][43][44][45] in addition to electrostatic ones.…”

Oxidative Layer-By-Layer Multilayers Based on Metal Coordination: Influence of Intervening Graphene Oxide Layers

“…Both display an exponential growth in the beginning, as reported earlier. 38 The film mass increase is considerably higher upon adsorption of a PP layer than after a Ce layer, but PP addition leads only to negligible changes in the spectra, so that the multilayer spectra can be attributed to cerium species in the film. On the other hand, the aqueous solutions of Ce(IV) display very high molar absorptivity below 250 nm and a shift in the maximum around 300 nm, which implies a different coordination environment of cerium in the films.…”

“…The X-ray photoelectron spectra (XPS) were recorded as described previously. 38 The polarization modulation infrared reflection-absorption spectra (PM-IRRAS) were recorded on the Nexus 870 FTIR spectrometer (Nicolet) equipped with a liquid nitrogen cooled mercury–cadmium–telluride (MCT-A) detector and a PEM-90 photoelastic modulator (HINDS Instruments); see the Supporting Information for details.…”

“…We have studied oxidative [polyphosphate(PP)/Ce] multilayers consisting of Ce(IV) and PP, which allow an electroless polymerization of monomers, such as pyrrole (Py), aniline, 3,4-ethylenedioxythiophene (EDOT), or 5,6-dihydroxyindole, to conducting polymer or melanin-type films on their surface. 38 − 40 Cerium acts as an oxidant in these films, but it also brings resilience to the film structure. In these oxidative multilayers, the limiting factor is the amount of oxidants in the film.…”

Nano Fibrous Cerium(IV) Hydrogen Phosphate Membrane Self Supported Indole Polymerization Agent

“…Belonging to this class are polyaniline, polypyrrole, polybenzimidazole and others. Polyppyrole polymerization by fibrous ceium phosphate has been reported [31,32].…”