Controlled fabrication of multilayered 4-(pyrrole-1-yl) benzoate supported poly(3,4-ethylenedioxythiophene) linked hybrid films of Prussian blue type nickel hexacyanoferrate

The ability of 4-(pyrrole-1-yl) benzoic acid (PyBA) to form monolayer-type carboxylate-derivatized ultra-thin organic films on solid electrode surfaces was explored here to attract coordinatively and immobilize Ni2+ ions at the electrode/electrolyte interface. In the next step, the system was exposed to Fe(CN)63− or Fe(CN)64− solution to form a robust nickel hexacyanoferrate (NiHCF) layer. By repeated and alternate treatments in solutions of PyBA, Ni2+ cations, and Fe(CN)63− or Fe(CN)64− anions, the amount of the material could be increased systematically in a controlled fashion to form three-dimensional multilayered NiHCF-based assemblies. The layer-by-layer method was also extended to the growth of hybrid conducting polymer stabilized NiHCF films in which the initial PyBA-anchored NiHCF layer (formed on glassy carbon) was subsequently exposed (a desired number of times) through alternate immersions to the monomer (3,4-ethylenedioxythiophene), Fe(CN)63− and Ni2+ solutions. During voltammetric potential cycling (electropolymerization) in the external supporting electrolyte solution, poly(3,4-ethylenedioxythiophene) or PEDOT linked NiHCF-based multilayered films were produced. They were characterized by good stability and high dynamics of charge transport.