Effect of Intercalants inside Birnessite-Type Manganese Oxide Nanosheets for Sensor Applications

Hydrazine is a common reducing agent widely used in many industrial and chemical applications; however, its high toxicity causes severe human diseases even at low concentrations. To detect traces of hydrazine released into the environment, a robust sensor with high sensitivity and accuracy is required. An electrochemical sensor is favored for hydrazine detection owing to its ability to detect a small amount of hydrazine without derivatization. Here, we have investigated the electrocatalytic activity of layered birnessite manganese oxides (MnO₂) with different intercalants (Li⁺, Na⁺, and K⁺) as the sensor for hydrazine detection. The birnessite MnO₂ with Li⁺ as an intercalant (Li-Bir) displays a lower oxidation peak potential, indicating a catalytic activity higher than the activities of others. The standard heterogeneous electron transfer rate constant of hydrazine oxidation at the Li-Bir electrode is 1.09- and 1.17-fold faster than those at the Na-Bir and K-Bir electrodes, respectively. In addition, the number of electron transfers increases in the following order: K-Bir (0.11 mol) < Na-Bir (0.17 mol) < Li-Bir (0.55 mol). On the basis of the density functional theory calculation, the Li-Bir sensor can strongly stabilize the hydrazine molecule with a large adsorption energy (-0.92 eV), leading to high electrocatalytic activity. Li-Bir also shows the best hydrazine detection performance with the lowest limit of detection of 129 nM at a signal-to-noise ratio of ∼3 and a linear range of 0.007-10 mM at a finely tuned rotation speed of 2000 rpm. Additionally, the Li-Bir sensor exhibits excellent sensitivity, which can be used to detect traces of hydrazine without any effect of interference at high concentrations and in real aqueous-based samples, demonstrating its practical sensing applications.