In the quest to find powerful modifiers of screen-printed electrodes for sensing applications, a set of rare earth-doped Ca10-xREx(PO4)6(OH)2 (RE = La, Nd, Sm, Eu, Dy, and Tm and x = 0.01, 0.02, 0.10, and 0.20) hydroxyapatite (HAp) samples were subjected to an in-depth electrochemical characterization using electrochemical impedance spectroscopy and cyclic and square wave voltammetry. Among all of these, the inorganic phosphates doped with lanthanum proved to be the most reliable, revealing robust analytical performances in terms of sensitivity, repeatability, reproducibility, and reusability, hence paving the way for their exploitation in sensing applications. Structural data on La-doped HAp samples were also provided by using different techniques, including optical microscopy, X-ray diffraction, Rietveld refinement from X-ray data, Fourier transform infrared, and Raman vibrational spectroscopies, to complement the electrochemical characterization.
Water pollution is nowadays a global problem and the effective detection of pollutants is of fundamental importance. Herein, a facile, efficient, robust, and rapid (response time < 2 min) method for the determination of important quinone-based industrial pollutants such as hydroquinone and benzoquinone is reported. The recognition method is based on the use of screen-printed electrodes as sensing platforms, enhanced with carbon-based nanomaterials. The enhancement is achieved by modifying the working electrode of such platforms through highly sensitive membranes made of Single- or Multi-Walled Carbon Nanotubes (SWNTs and MWNTs) or by graphene nanoplatelets. The modified sensing platforms are first carefully morphologically and electrochemically characterized, whereupon they are tested in the detection of different pollutants (i.e., hydroquinone and benzoquinone) in water solution, by using both cyclic and square-wave voltammetry. In particular, the sensors based on film-deposited nanomaterials show good sensitivity with a limit of detection in the nanomolar range (0.04 and 0.07 µM for SWNT- and MWNT-modified SPEs, respectively) and a linear working range of 10 to 1000 ppb under optimal conditions. The results highlight the improved performance of these novel sensing platforms and the large-scale applicability of this method for other analytes (i.e., toxins, pollutants).
