Inorganic-organic hybrid materials were synthesized by covalent attachment of epoxides to the surface of zirconium phosphate (ZrP) nanoplatelets. X-ray powder diffraction, FTIR, and TGA were utilized to confirm the presence of the modifiers and exclusive functionalization of the ZrP surface. NMR experiments were conducted to confirm the formation of P-O-C bonds between surface phosphate groups and epoxide rings. The applicability of the organically modified products was demonstrated by their use as fillers in a polymer matrix. Subsequently, a two step intercalation and surface modification procedure was utilized to prepare polymer nanocomposites that were imparted with functionality through the encapsulation of molecules within the interlayer of surface modified ZrP.

Organically surface-modified α-zirconium phosphate was obtained by reacting the surface P–O–H groups of α-zirconium phosphate nanoparticles (α-ZrP) with octadecyl­trichloro­silane (OTS). Surface functionalization of α-ZrP with OTS was accomplished using a one-step synthesis producing highly hydrophobic nanoparticles. The formation of P–O–Si bonds arising from nucleophilic attack of POH to the silane was confirmed by solid-state NMR experiments. The surface coverage of the organic modifier was characterized by TGA, AFM, and FTIR. In addition, we show the applicability of this system with a photoinduced electron-transfer reaction in a nonpolar solvent. Using an organically surface-modified α-ZrP previously loaded with tris(2,2′-bipyridyl)­ruthenium(II) (Ru(bpy)3 2+), the quenching of the luminescence of Ru(bpy)3 2+ in the presence of p-benzoquinone was monitored; a static quenching constant (K s) value of 8.82 × 102 M–1 and a dynamic quenching constant (K D) value of 6.99 × 102 M–1 were obtained.

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The intercalation of inorganic layered materials has resulted in a wide range of applicability. In such cases the applicability of the material is largely dependent upon the species intercalated within the layer, and the layered material acts largely as a host. Recently, the surface modification of inorganic layered materials has been investigated and it has been shown that the exterior layers can be exclusively functionalized. The advent of surface chemistry allows for the synthesis of particles with both a controlled interlayer and surface. This approach can be used to tailor nanoparticles for specific applications. Herein we review the surface chemistry of α-zirconium bis(monohydrogen orthophosphate) monohydrate (Zr(HPO4)2·H2O, α-ZrP) along with some applications of recent interest. Not only can these reactions be applied to α-ZrP, but similar chemistry can also be expanded to other layered materials and systems.