Layer-by-Layer Fabrication of Core–Shell Fe₃O₄@UiO-66-NH₂ with High Catalytic Reactivity toward the Hydrolysis of Chemical Warfare Agent Simulants

Abstract

Detoxifying materials against chemical warfare agents (CWAs) and their simulants are highly desired for proper handling of contamination by and destruction of CWAs. Herein, we report a facile layer-by-layer fabrication of core-shell Fe₃O₄@UiO-66-NH₂ and its application in fast degradation of CWA simulants. The Fe₃O₄@UiO-66-NH₂ composite was prepared through a layer-by-layer epitaxial growth strategy, by alternately immersing Fe₃O₄ nanoparticles in ethanol solutions of a metal node [Zr₆O₄(OH)₄]¹²⁺ precursor and organic linkers [NH₂-BDC, 2-aminoterephthalic acid], respectively, and separating using a magnet. As confirmed by characterization results, the Fe₃O₄@UiO-66-NH₂ composites with 24.4 μmol/g Zr₆ node content showed a well-defined core-shell structure as well as good thermal and chemical stability. These core-shell magnetic metal-organic frameworks (MOFs) were further tested in the catalytic hydrolysis of dimethyl-4-nitrophenyl phosphate (a nerve agent simulant) and demonstrated 36 times higher catalytic activity than the UiO-66-NH₂ powder due to their highly defective surface, high percentage of MOFs on the surface, and their rich mesoporous structure. Since magnetism was retained after the coating of MOFs, Fe₃O₄@UiO-66-NH₂ could be easily recovered and reused after catalysis.