Electrochemical Impedance Spectroscopic Investigations of Nanocomposite Thin-Film Formation at an Electrified Micro Liquid-Liquid Interface

Abstract

Herein, the interface between two immiscible electrolyte solutions (ITIES) has been exploited as a pristine platform for electropolymerization of the 2D and 3D nanocomposite materials, i.e., metal nanoparticles (NPs) embedded within a conductive polymer matrix that are electrogenerated/electropolymerized simultaneously The free-standing conductive thin film can be prepared with an adjustable loading of metallic NPs, to be tailored for a variety of applications, including as catalytic electrodes in fuel cells, or act as a bioreceptor in a biosensor. Electrochemical impedance spectroscopy (EIS) has been used to investigate mechanistic aspects of film growth through two types of charge transfer processes, ion and electron transfer, that occur during electropolymerization. The thermodynamics of a heterogeneous electron transfer (HET) between redox centers, KAuCl4(aq) and terthiophene (TT, org), across the interface governs the electropolymerization reaction, including the rate, which is itself affected by the rate of diffusion of reactants toward the interface, ohmic resistance of the two electrolyte solutions, distance between reactants due to arrangement of ions at the interface, and reorganization energy of the involved species in the reaction. Electropolymerization is controlled through application of an applied external potential difference and monitored voltammetrically as well as by EIS. Curve fitting of EIS data was performed using an equivalent circuit incorporating a phase constant element (CPE) parallel to a resistor for non-ideal interfacial capacitance, and HET resistance across the film as it forms at the ITIES. Next, those elements are parallel to a resistor (R), and a Warburg element (W) to approximate ion transfer across the ITIES/porous thin-film as it grows (Fig. 1). Data suggest that the films electronic conductivity improves with increasing the [TT]:[KAuCl4] ratio. Increased capacitance was hypothesized to be linked to an increase in the effective surface area of the polymer film during its growth phase versus the molecularly smooth ITIES. Higher [TT]:[KAuCl4] ratios elicited higher capacitance as well as diffusion resistance which can be attributed to formation of a more compact film structure. Cyclic voltammetric and potential step methods are compared and discussed, highlighting the formed films final properties, including film thickness and conductivity. Figure 1