Direct Drawing Method of Graphite onto Paper for High-Performance Flexible Electrochemical Sensors

A simple and fast fabrication method to create high-performance pencil-drawn electrochemical sensors is reported for the first time. The sluggish electron transfer observed on bare pencil-drawn surfaces was enhanced using two electrochemical steps: first oxidizing the surface and then reducing it in a subsequent step. The heterogeneous rate constant was found to be 5.1 × 10^-3 cm s^-1, which is the highest value reported so far for pencil-drawn surfaces. We mapped the origin of such performance by atomic force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Our results suggest that the oxidation process leads to chemical and structural transformations on the electrode surface. As a proof-of-concept, we modified the pencil-drawn surface with Meldola's blue to electrocatalytically detect nicotinamide adenine dinucleotide (NADH). The electrochemical device exhibited the highest catalytic constant (1.7 × 10⁵ L mol^-1 s^-1) and the lowest detection potential for NADH reported so far in paper-based electrodes.