The influence of lateral flake size in graphene/graphite paste electrodes: an electroanalytical investigation

Abstract

We report the electroanalytical properties of graphene and graphite paste electrodes comprising varying lateral flake sizes. The fabricated electrodes are first electrochemically validated using a standard redox probe prior to the influence of their heterogeneous electron transfer (HET) kinetics/flake sizes being explored towards sensing applications. Electrochemical analysis is employed using a range of relevant biomolecules and prominent drugs of abuse. It is inferred that smaller lateral flake sizes result in an increased number of edge plane sites ‘available’ upon the electrode surface, leading to greater sensitivity and Limit of Detection (LOD) values. Calibration plots show an improvement in LODs from 0.7 to 0.19 μM and sensitivity from 0.023 to 0.038 A M⁻¹ for the detection of ascorbic acid and LODs from 3.43 to 1.3 μM and sensitivities from 0.009 to 0.025 A M⁻¹ for the detection of β-nicotinamide adenine dinucleotide (NADH) when comparing ‘typical’ (12.2 μm) and ‘small’ (0.5 μm) lateral flake sizes. In the case of uric acid, the reported sensitivity and LOD with typical sizes is 0.046 A M⁻¹ and 1.42 μM, in comparison to 0.168 A M⁻¹ and 0.85 μM with smaller flakes, with dopamine also supporting these findings. In terms of the drugs of abuse considered, methamphetamine exhibits an improved LOD from 0.82 to 0.65 μg mL⁻¹ and sensitivity from 0.15 to 0.25 A μg mL⁻¹ when comparing typical and small flakes respectively. However, cocaine and 3,4-methylenedioxymethamphetamine (MDMA) exhibit variable results, likely due to complex oxidation mechanisms and each paste electrode's specific heterogeneous surface nature. This work demonstrates the sensing capabilities of graphene and graphite paste electrodes comprising varying lateral flake sizes. It is inferred that smaller lateral flake sizes give rise to improved electroanalytical responses and enhanced graphitic based electrochemical sensors; which is important to consider when designing and optimising carbon based electrochemical sensor devices and likely has wider implications in the energy sector when utilising such electrodes.