Electrochemical Bubbles Generation by Hydrazine and Water Oxidation for Tuning of Surface Morphology and Hydrophobicity of Electrodeposited Polymers Films

POSSETTO DAVID; GABRIELA MARZARI; PEDRAZA DAZA DAMIAN; RUEDA BUENO HECTOR; CARLOS SUCHETTI; GIANLUCA POZZI; FERNANDO FUNGO

Mar del Plata

Congreso; 34th Topical Meeting of the International Society of Electrochemistry; 2023

Here, it is describing a methodology to get in situ electrochemical control of electrodeposited conductivepolymers nanostructures. The development of organic conductive polymers is continually boosting due totheir wide potential for a variety of applications that demand to use of these materials in solid-state. Thus,controlling the surface structures of conducting polymers films at the micro-nanoscale is an importantissue.1Exist many wet methods for polymer film formation between then it stands the electrochemicaltechniques, which only require that the monomer is soluble in the electrolyte solution allowing to formfilms at room temperature with fine film thickness control. An elegant electrochemical strategy to buildnanostructures, it is during the electropolymerization process concomitantly forms oxygen or hydrogenbubbles by electrochemically discharge of water in the electrode surface. Consequently, the bubbles act asa template and make that the polymer precipitation forms ordered porous structures modulating morphologyfilm. From its discovery, the interest in this technique hascontinuously increased. However, new precursors thatproduce gas through their electrochemical discharge havenot been explored. In this context, we showed the in situelectrochemical nitrogen bubbles generation bydischarging hydrazine (N2H4) in organic electrolytes, as atemplate to manipulate conducting polymers structures atthe micro-nanoscale morphology.2 Our findings show thatthrough the electrochemical parameters control is possibleto get a precise tuning of the diameter and density ofporous or hollow structures on a conducting polymer filmsynthesized by a one-step electrochemical method. On theother hand, Carbazole−Fluorene−Carbazole (CFC)conjugated monomers are interesting precursors ofelectrodeposited coatings films over conductivesubstrates.3, Their molecular design allows to bond tailoredsubstituents to the sp3 carbon atom at the 9-position offluorene ring. We showed that the introduction of linear orbranched polyfluoroalkyl pendant chains at 9-position inCFC materials (Figure 1) significantly facilitates the CFCthin-film electrodeposition improving their surfacemorphology, water repellency, and electrochromicbehavior regarding alkyl chains of similar lengths. We nowpresented a study on the influence of the gas bubble natureon the nanostructural features of electrodeposited CFCfilms in organic electrolyte. Thus, bubble templates weregenerated from the discharge of two different bubbleprecursors: water and hydrazine. This with the aim to analyze the pro and cons of both techniques gasprecursors. The films' morphologies were characterized by SEM and 3D laser techniques and the obtainedresults clearly show the contrasting behavior between long and short alkyl chains CFC monomers. Thus,through molecular design, fine electrochemical control and use of the different precursors, it was possibleto adjust the wettability of the soft templated film leading in superhydrophobic surfaces.1 Y. Xue, S. Chen, J. Yu, B. R. Bunes, Z. Xue, J. Xu, B. Lu, L. Zang, J. Mater. Chem. C 2020, 8, 10136-10159.2D. Possetto, L. Fernández, G. Marzari, F. Fungo RSC Adv., 2021, 11, 110203 D. Possetto, I. Pecnikaj, G. Marzari, S. Orlandi, S. Sereno, M. Cavazzini, G. Pozzi, F. Fungo, ChemPhysChem 2022, e202200371.