Deciphering the Role of p-Type ZnCo2O4 Semiconductor Nanoflakes for Selective Enhancement of Voltammetric Responses Toward Redox Species System: Interfacial Electron-Transfer Kinetics and Adsorption Capacity

Abstract

In this study, we describe experimental efforts to decipher the role of ZnCo2O4 nanoflakes (ZCO-NFs) for selective enhancement of voltammetric responses of screen-printed electrode (SPE) toward redox species system. The ZCO-NFs sample was characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and UV–vis spectroscopy. The electrochemical characterization of bare SPE and modified SPE electrodes was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Mott−Schottky analysis. A series of redox systems including paracetamol (PA), dopamine (DA), chloramphenicol (CAP), furazolidone (FZD), p-nitrophenol (p-NP), carbaryl (CBR), ofloxacin (OXF), and erythromycin (ERY) were selected to investigate for (i) reversible redox process, (ii) irreversible electrochemical oxidation process, and (iii) irreversible electrochemical reduction process on both bare-SPE and ZCO-NFs/SPE electrodes. The obtained results showed that ZCO-NFs possess the selective enhancement of electrochemical response for redox systems with an increase of 24%–90% for PAR, DA, FZD, CAP, and CBR and a decrease of 13%–49% for p-NP, ERY, and OFX. The different electrochemical response of redox species at nanostructured semiconductor electrodes is attributed to the contribution of both the adsorption capacity of redox species and the interfacial electron transfer process between electrode and redox species. An insight into the interfacial electron transfer kinetics and its contribution to the enhancement of electrochemical response on p-type semiconductor electrode is helpful in designing high-performance sensing platforms based on spinel oxide nanostructures.