Neutral Red as a Redox Probe for Comparative Evaluation of Electrochemical Performance of Bismuth Modified Electrodes

Abstract

For the first time, Neutral Red (NR) has been used as a redox probe for comparative evaluation of the electrochemical performance of screen-printed carbon electrodes (SPCEs) modified with bismuth under different potentiostatic pre-plating conditions (Bi/SPCEs). It was shown that protonated NR undergoes quasi-reversible redox transformations at bare-SPCE and Bi/SPCEs in the pH range 5–6 in phosphate buffer solutions (PBS) in the potential range of (−0.2)–(−0.8) V, where bismuth is not electroactive. Bi/SPCEs have been characterized morphologically by scanning electron microscopy (SEM) and electrochemically by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) employing NR as a redox probe. The obtained SEM, CV, and EIS data are in good agreement. The highest charge transfer resistance (Rct) values (3.9 and 3.3 kΩ) were obtained at bare-SPCE and Bi/SPCE having low degree of bismuth coverage. Contrarily, the lowest Rct value (8 Ω) was recorded at Bi/SPCE, with the highest degree of bismuth coverage. CV experiments showed a significant increase in the electrochemical performances of Bi/SPCEs, whose surface is half or more covered with bismuth, in comparison to the bare-SPCE. Nickel (II) ions and formaldehyde (FM), in the form of formaldehyde hydrazone (FAH), were used as model analytes to determine the electroanalytical performance of Bi/SPCEs. A comparison of roughness factor and sensitivity toward both analytes for Bi/SPCEs with two-tailed Pearson’s criterion showed a high degree of correlation between their electrochemical and electroanalytical characteristics. The data acquired indicates that the use of NR as a redox probe may be quite helpful to control modification processes when developing novel bismuth-containing sensors.