Polyoxometallate‐Based Layered Composite Films on Electrodes: Preparation Through Alternate Immersions in Modification Solutions

Abstract

An approach for the modification of electrode surfaces with thin films composed of polyoxometallate anions and large water‐soluble cationic species is described. In the procedure, a ca. monolayer of the iso‐ or heteropolyanion is first adsorbed onto the electrode surface. By immersing the resulting system into a solution containing a large monovalent, multivalent, or polyvalent cation, a composite layer is formed due to the interaction between the adsorbed polyanion and the solution cation. After rinsing, this electrode is reimmersed into the solution of the polyanion, and immobilization of an additional quantity of the polyanion takes place. By the repeated and alternate immersions into the anionic and cationic modification solutions, the amount of material on the electrode can be increased systematically in a controlled fashion leading to stable three‐dimensional multilayered molecular assemblies. The immobilized polyanions (isopolymolybdate, phosphotungstate, or silicotungstate) have redox characteristics similar to those of their solution counterparts. The precipitate‐forming cationic species include tetrabutylammonium and tris(1,10‐phenanthroline)‐iron(II) ions, as well as protonated poly(4‐ vinylpyridine). Composite films of heteropoly‐12‐tungstate anions with protonated poly(4‐vinylpyridine) are the most robust. The approach permits introduction of multiple redox centers into the thin films on electrodes, formation of bilayer‐type systems, and, in some cases, even insulating coatings. Details of the preparation and physicochemical, particularly electrochemical, properties of the produced systems are described.