Preparação, caracterização e estudos eletroquimicos de eletrodos a base de carbono cerâmico aplicados na determinação de dopamina

Abstract

The study of carbon-based ceramic electrodes (CCE) has been significantly increased due to advantages over other electrodes. The CCE features as large surface area, high electrical conductivity and higher mechanical strength, increases their stability and durability. Different parameters of CCE preparation, such as type of precursor, carbon material, catalyst amount, among others, significantly influence the morphological properties and consequently their electrochemical responses. Based on these factors this work presents a 23 factorial design (2 levels and 3 factors) which the factors analyzed were catalyst amount (HCl 12 mol L-1), graphite / precursor ratio, and precursor type (TEOS - tetraethoxysilane and MTMOS - methyltrimetoxysilane). These variables were optimized by analyzing the electrochemical responses obtained in presence of potassium ferrocyanide (at fixed concentration of 1.0 x10-3 mol L-1). The design resulted in a significant third order interaction for anodic peak current values (Ipa), and also to the potential difference (E) between the factors studied which could not be observed using an univariated study. The optimized electrode was modified with ferrocenecarboxylic acid (designated as CCE/Ferrocene) mainly aiming at the increase the sensitivity to the unmodified one. SEM images indicated that the components are homogeneously dispersed in the sample but with some little agglomeration of segregated ferrocene particles. From cyclic voltammetric experiments, it was observed that the CCE/Ferrocene presented a redox pair at Epa = 390.3 mV and Epc = 298.7 mV (E = 91.7 mV), related to the ferrocene/ferrocenium process, since the non- modified CCE did not presented any redox peaks. Studies of the modified electrode in different scan rates resulted in a linear relationship between the anodic peak current values and the scan rate, a characteristic behavior for confined species in the surface electrode. In order to verify the possibility of using the CCE/Ferrocene as an electrochemical sensor, studies in presence of dopamine (DA) were carried out. In this case, it was observed that after DA addition in the electrolyte solution, a considerably increase in the redox currents were observed at same oxidation potential of ferrocene (Epa= 408.0 mV vs Ag/AgCl), different from the observed when using only CCE as electrode material, which the increase in the anodic peak was considerably lower and slightly dislocated to higher positive potential (Epa= 446.1 mV vs Ag/AgCl). Square wave voltammetry (SWV) experiments were evaluated in presence of DA, with optimized parameters. In these conditions, the proposed sensor has shown a linear response range from 0.2 to 1.0 molL-1 with a detection limit of 1.5 mol L-1 to CCE and 0.43 mol L-1 for CCE/Ferrocene. From SWV experiments, it was observed that the AA oxidation at CCE/Ferrocene occurred in a different potential of DA oxidation, with a peak separation of approximately 170.5 mV. Moreover, CCE/Ferrocene did not respond to different AA concentrations indicating that is possible with this electrode determine DA without the interference of AA.