Understanding the Ion Exchange Process in LDH Nanomaterials by Fast In Situ XRPD and PCA-Assisted Kinetic Analysis. (25th February 2019) - Palin, Luca
Abstract : Layered double hydroxides (LDHs) are nanomaterials with interesting properties finding applications in many fields, such as catalysis, environmental chemistry, and pharmaceuticals. They are anionic clays with positively charged layers and anions within the layers to reach neutrality. Their properties are defined by both composition and morphology. The composition can be tuned by exchanging the interlayer anion. The far more stable, common, and highly prevalent among natural LDHs is the carbonate anion thanks to its double negative charge. To adapt the properties of LDHs for technological applications, the challenge is to exchange the carbonate with the functionalizing monovalent anions in an effective and cheap way. In this study, the exchange of carbonate with nitrate ions is studied by in situ X-ray powder diffraction (XRPD). The exchange is carried out by a liquid-assisted grinding approach, inserting the mechanically ground dry sample in a capillary and then wetting it with a drop of nitric acid, while measuring the XRPD pattern. The kinetics of the process was investigated by the Avrami-Erofe'ev method; the reaction mechanism was determined using the advancing interface model and by analyzing the XRD peak shapes, which evidentiate changes in the crystallinity during the reaction. The reaction starts from the faces perpendicular to the layers and occurs along the channels, increasingly limited by diffusion when approaching the internal part of the crystals.