Formation of Zn-Al layered double hydroxides (LDH) during the interaction of ZnO nanoparticles (NPs) with γ-Al2O3

Abstract

Zinc and aluminum layered double hydroxides (Zn-Al LDH) are a common group of major Zn species in various Zn-contaminated soil/sediment environments, yet their formation pathways and underlying mechanisms under varied conditions are not well understood. This study investigated the formation of Zn-Al LDHs through the direct interaction of two solid substrates, ZnO nanoparticles (NPs) and a representative Al oxide, γ-Al₂O₃. Batch experiments and complementary microscopic and spectroscopic analyses were conducted to elucidate the reaction kinetics and mechanisms, as well as the morphologic and structural evolution of the products. Dissolved Zn and Al concentrations decreased significantly in a dual solid system compared to a single solid system. A bulk Zn-Al LDH phase was found to form under a wide pH range (6.5-9.5). Aside from Zn-Al LDH, γ-Al₂O₃ was the main remaining solid phase at pH 6.5, whereas ZnO NPs were the main residual solid phases at pH 9.5. Formation of amorphous Zn(OH)₂ was also observed at both pH values, likely due to Zn²⁺ release at low pH and Al(OH)₄^- adsorption at high pH. It is proposed that the formation of Zn-Al LDH occurs via a dissolution-sorption-coprecipitation process, where the solubility of ZnO NPs or γ-Al₂O₃ solid phases determines the reaction pathways and kinetics under varied pH conditions. The results from this work revealed the transformation mechanisms for ZnO NPs under conditions from weakly acidic to alkaline pH with highly available Al particles and shed light on the environmental fate of ZnO NPs in Zn or ZnO NP contaminated environments.

Keywords: Interaction; Layered double hydroxides; Transformation; ZnO nanoparticles; γ-Al(2)O(3).