Templateless synthesis of polypyrrole nanowires by non-static solution-surface electropolymerization

Polypyrrole nanowires (PPy-NWs) are synthesized by a novel templateless approach based on non-static solution-surface (NSSS) electropolymerization. The mechanism responsible for PPy-NW formation is the simultaneous oxidation of pyrrole and water, with concomitant formation of hydroxyl radicals and dioxygen nanobubbles. In particular, a localized PPy-NW deposition at the solution-air interface is enabled by solution-surface electropolymerization due to the surface excess of the monomer at the interface favored by the large surface tension of the solvent. In the proposed approach, solution-surface electropolymerization is performed in non-static conditions (NSSS), as the solution-air interface is shifted by flowing the electrolyte solution over the electrode surface. This allows a PPy-NW homogeneous deposition on whatever large area electrode to be rapidly achieved. Parameters influencing the morphology of PPy-NWs are studied, particularly focusing on flow rate, pH of the electrolyte solution, and electropolymerization time. The growth process of PPy-NWs is examined and the way of tuning their resulting morphology is discussed. Morphological investigation by scanning electron microscopy and chemical/electrochemical characterization of PPy-NWs by X-ray photoelectron spectroscopy and cyclic voltammetry, respectively, further support the proposed nanowire formation mechanism. Nanowires with diameter in the range of 40-300 nm are obtained, and the possibility of depositing differently sized nanowires with a predetermined spatial distribution on the same substrate is also demonstrated.