Nanoporous Cauliflower-like Pd-Loaded Functionalized Carbon Nanotubes as an Enzyme-Free Electrocatalyst for Glucose Sensing at Neutral pH: Mechanism Study.

In this work, we propose a novel functionalized carbon nanotube (f-CNT) supporting nanoporous cauliflower-like Pd nanostructures (PdNS) as an enzyme-free interface for glucose electrooxidation reaction (GOR) in a neutral medium (pH 7.4). The novelty resides in preparing the PdNS/f-CNT biomimetic nanocatalyst using a cost-effective and straightforward method, which consists of drop-casting well-dispersed f-CNTs over the Screen-printed carbon electrode (SPCE) surface, followed by the electrodeposition of PdNS. Several parameters affecting the morphology, structure, and catalytic properties toward the GOR of the PdNS catalyst, such as the PdCl precursor concentration and electrodeposition conditions, were investigated during this work. The electrochemical behavior of the PdNS/f-CNT/SPCE toward GOR was investigated through Cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), and amperometry. There was also a good correlation between the morphology, structure, and electrocatalytic activity of the PdNS electrocatalyst. Furthermore, the LSV response and potential-pH diagram for the palladium-water system have enabled the proposal for a mechanism of this GOR. The proposed mechanism would be beneficial, as the basis, to achieve the highest catalytic activity by selecting the suitable potential range. Under the optimal conditions, the PdNS/f-CNT/SPCE-based biomimetic sensor presented a wide linear range (1-41 mM) with a sensitivity of 9.3 µA cm mM and a detection limit of 95 µM (S/N = 3) toward glucose at a detection potential of +300 mV vs. a saturated calomel electrode. Furthermore, because of the fascinating features such as fast response, low cost, reusability, and poison-free characteristics, the as-proposed electrocatalyst could be of great interest in both detection systems (glucose sensors) and direct glucose fuel cells.