Localization of Mn2+ ions in mesoporous NnS

Nanocrystalline cubic ZnS doped with 0.2% mol manganese, exhibiting a stable mesoporous structure, was synthesized at room temperature by a non toxic surfactant-assisted liquid-liquid reaction. The X-ray diffraction measurements demonstrate the formation of a sponge-like mesoporous material built from cubic ZnS nanocrystals of 1.8 nm average sizes, with a tight distribution of pores of 1.8 nm mean diameter. The transmission electron microscopy images confirm the formation of the mesoporous structure with walls of 3.1 nm mean thickness built from cubic ZnS nanocrystallites of 2.1 nm average size. The resulting tight distribution of crystallites and pores yields a well resolved Electron Paramagnetic Resonance spectrum, with the narrowest reported component lines attributed to three types of isolated Mn2+ centers, called Mn2+(I), Mn2+(II) and Mn2+(III). From the analysis of the spin Hamiltonian parameters it is shown that in the Mn2+(I) centers the paramagnetic ion is situated at substitutional Zn sites in the ZnS nanocrystals, being also subjected to a small axial distortion. The relative concentration changes under thermal treatment experiments strongly suggest that in both Mn2+(II) and Mn2+(III) centers the Mn2+ ion is localized on the surface of the ZnS nanocrystallites, being bond to an oxygen ion in the first case and to an additional water molecule in the second case.