On the performance of carbon-based screen-printed electrodes for (in)organic hydroperoxides sensing in rainwater

Hydroperoxides play important roles in atmospheric chemical processes since they act as strong oxidants. This paper details with the modification, characterization and performance of different carbon-based screen-printed electrodes to develop a sensor that allows to analyze organic and inorganic hydroperoxides in atmospheric samples. Commercial electrodes made up of graphite, graphene, carbon nanotubes and graphene oxide were electrochemically activated and subsequently modified by layer-by-layer method with a conducting polymer of azure-A and electrodeposited platinum nanoparticles. Characterization of modified electrodes was performed by FE-SEM, XPS, Raman spectroscopy, cyclic voltammetry, and impedance spectroscopy. Even though all modified carbonaceous substrates enabled the development of competitive electrochemical sensors for (in)organic hydroperoxides detection, carbon nanotubes underlying substrate exhibited the best performances in terms of sensitivity, stability, limit of detection and linear range. This amperometric sensor displayed linear responses to hydroperoxides over 0.081-450 μM with detection limits in the range of 24-558 nM and sensitivity values among 0.0628±1.6E-4 and 0.0112±0.71E-4 μA/μM for the different hydroperoxides herein studied. The developed electrochemical sensor was successfully applied to the analysis of (in)organic hydroperoxides in rainwater samples. Measurements in rainwater were performed in a city located in the East of Spain and collected at two different sites (downtown and suburban area) on two different dates (July and November 2020). The presented results demonstrated high sensitivity and selectivity for the detection of hydroperoxides among a plethora of substances naturally present in rainwater.