Preparation of Methyl Viologen-Kaolinite Intercalation Compound: Controlled Release and Electrochemical Applications

This work reports the preparation of novel kaolinite nanohybrid material obtained by intercalation of methyl viologen (MV) in the interlayer space of kaolinite, using methoxykaolinite (K-M) as starting material. Characterization of the resulting material (K-MV) confirmed the presence of MV units in the interlayer space of K-M with lateral orientation, associated with a high amount of water molecules due to the hydrophilic nature of MV. The resulting structural formula of this organoclay based on thermogravimetric analysis was Si2Al2O5(OH)3.72(OCH3)0.28(MV)0.17(H2O)0.82. The release of MV from the K-MV composite was studied in order to evaluate the advantages of using this material for pesticide formulation with MV as active ingredient. The localization of MV in the interlayer space of K-M significantly slows its release in water. However, the interactions that retain MV in the interlayer space remain sufficiently less intense to ensure a complete release of MV in a relatively short time (2 h). On the basis of the interactions that ensure MV intercalation in methoxykaolinite, K-M was used as electrode modifier and applied for the electrochemical determination of MV. The electrochemical signal of MV on the K-M modified electrode was 2 times more intense compared to the pristine kaolinite modified electrode. After optimization of experimental parameters, a sensitivity of 3.91 μA M-1 and a detection limit of 0.14 nM were obtained at the K-M modified electrode. This performance represents one of the most important reported so far in the literature during the electrochemical determination of MV. The sensor was also found very efficient for MV determination in real water systems (well, spring, and tap water) despite the decrease of sensitivity due to the presence of interfering species.