Zinc-Intercalated Halloysite Nanotubes as Potential Nanocomposite Fertilizers with Targeted Delivery of Micronutrients

Abstract

This study reports on the development of nanocomposites utilizing a mineral inhibitor and a micronutrient filler. The objective was to produce a slow release fertilizer, with zinc sulfate as the filler and halloysite nanotubes as the inhibitor. The study seeks to chemically activate the intercalation of zinc into the macro-, meso-, and micropores of the halloysite nanotubes to enhance their performance. As a result, we obtained three nanocomposites in zinc sulfate solution with concentrations of 2%, 20%, and 40%, respectively, which we named Hly-7Å-Zn2, Hly-7Å-Zn20, and Hly-7Å-Zn40. We investigated the encapsulation of zinc sulfate in halloysite nanotubes using X-ray diffraction analysis, transmission electron spectroscopy, infrared spectroscopy (FTIR), and scanning electron microscopy with an energy-dispersive spectrometer. No significant changes were observed in the initial mineral parameters when exposed to a zinc solution with a concentration of 2 mol%. It was proven that zinc was weakly intercalated in the micropore space of the halloysite through the increase in its interlayer distance from 7.2 to 7.4. With an increase in the concentration of the reacted solution, the average diameter of the nanotubes increased from 96 nm to 129 nm, indicating that the macropore space of the nanotubes, also known as the “site”, was filled. The activated nanocomposites exhibit a maximum fixed content of adsorbed zinc on the nanotube surface of 1.4 wt%. The TEM images reveal an opaque appearance in the middle section of the nanotubes. S SEM images revealed strong adhesion of halloysite nanotubes to plant tissues. This property guarantees prolonged retention of the fertilizer on the plant surface and its resistance to leaching through irrigation or rainwater. Surface spraying of halloysite nanotubes offers accurate delivery of zinc to plants and prevents soil and groundwater contamination, rendering this fertilizer ecologically sound. The suggested approach of activating halloysite with a zinc solution appears to be a possible route forward, with potential for the production of tailored fertilizers in the days ahead.