Enhanced performance of pencil-drawn paper-based electrodes by laser-scribing treatment

Electrochemical Paper-based Analytical Devices (ePADs) are an alternative to traditional portable analytical techniques due to features such as low-cost, easy surface modification with different materials, and high sensitivity. A fast and simple method to fabricate enhanced ePADs using pencil-drawing which involves the CO₂ laser treatment of the carbon surface deposited on paper is described. The electrochemical performances of the devices were evaluated using cyclic voltammetry (CV) with different redox probes and electrochemical impedance spectroscopy (EIS). The electrochemical results show that a treated surface presents a lower resistance to charge transfer and changes the approach of the probe and the overlap of its orbitals with the electrode. To investigate the effects of the laser treatment process, chemical and structural characteristics were evaluated using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. These results indicated that laser treatment promoted the restoration of carbon-carbon double bonds and removed a thin layer of nanodebris present in commercial pencils, resulting in an improvement of the electrochemical kinetics. As a proof-of-concept, the Pencil-Drawing Electrode (PDE) was used for the detection and quantification of furosemide (FUR) in a sample of synthetic urine, exhibiting a limit of detection (LOD) of 2.4 × 10^-7 mol L^-1. The percentages of recovery of the FUR added to the samples A and B were 95% and 110%, respectively. The analysis using CO₂ laser-treated PDE resulted in a fast, simple, and reliable method for this doping agent.