Determination of the depth profile distribution of guest species in microporous materials using the voltammetry of immobilized particles methodology: application to lapachol attachment to palygorskite and kaolinite.

Abstract

A model for determining the in-depth profile distribution of electroactive species hosted in inorganic microporous matrixes using the voltammetry of immobilized particles methodology is described. The method, based on the analysis of cyclic voltammetric data at different potential scan rates, allows us to determine the in-depth profile variation of the concentration of electroactive guest species as well as the evaluation of the (oxidized form)/(reduced form) concentration ratio in cases where two oxidation states of the electroactive species coexist. The application to Maya blue-type materials prepared from lapachol, a naphtoquinonic dye, and palygorskite and kaolinite clays is reported. The determination of the in-depth distribution of guest molecules is not easy due to the heterogeneity of the clay particle size distribution and the appearance of cyclization and redox tuning reactions. Electrochemical data revealed differences in the in-depth distribution of the dye molecules in the grains of the channelled (palygorskite) and the laminar (kaolinite) clays that suggest that lapachol compounds can ingress into the channels of the palygorskite framework whereas remain externally adsorbed onto the kaolinite crystals.