Layered double hydroxide/sepiolite hybrid nanoarchitectures for the controlled release of herbicides

In this work, organic-inorganic hybrid nanoarchitectures were prepared in a single coprecipitation step by assembling magnesium-aluminum layered double hydroxides (MgAl-LDH) and a sepiolite fibrous clay, with the simultaneous encapsulation of the herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) as the MgAl-LDH retains its ion exchange properties. The synthetic procedure was advantageous in comparison to the incorporation of MCPA by ion exchange after the formation of the LDH/sepiolite nanoarchitecture in a previous step, as it was less time consuming and gave rise to a higher loading of MCPA. The resulting MCPA-LDH/sepiolite nanoarchitectures were characterized by various physicochemical techniques (XRD, FTIR and ²⁹Si NMR spectroscopies, CHN analysis and SEM) that revealed interactions of LDH with the sepiolite fibers through the silanol groups present on the outer surface of sepiolite, together with the intercalation of MCPA in the LDH confirmed by the increase in the basal spacing from 0.77 nm for the pristine LDH to 2.32 nm for the prepared materials. The amount of herbicide incorporated in the hybrid nanoarchitectures prepared by the single-step coprecipitation method surpassed the CEC of LDH (ca. 330 mEq/100 g), with values reaching 445 mEq/100 g LDH for certain compositions. This suggests a synergy between the inorganic solids that allows the nanoarchitecture to exhibit better adsorption properties than the separate components. Additionally, in the release assays, the herbicide incorporated in the hybrid nanoarchitectures could be completely released, which confirms its suitability for agricultural applications. In order to achieve a more controlled release of the herbicide and to act for several days on the surface of the soil, the hybrid nanoarchitectures were encapsulated in a biopolymer matrix of alginate/zein and shaped into spheres. In in vitro tests carried out in bidistilled water, a continuous release of MCPA from the bionanocomposite beads was achieved for more than a week, while the non-encapsulated materials released the 100% of MCPA in 48 h. Besides, the encapsulation may allow for better handling and transport of the herbicide.