Structural characterization of interfaces in silica core-alumina shell microspheres by solid-state NMR spectroscopy

Atomic-scale description of surfaces and interfaces in core-shell aluminosilicate materials is not fully elucidated, partially due to their amorphous character and complex mechanisms that govern their properties. In this paper, new insights into nanostructured core-shell aluminosilicates have been demonstrated, by using different solid-state NMR methods, i.e ²⁹Si, ²⁹Si cross-polarization (CP), ²⁷Al, ²⁷Al triple-quantum (3Q), and ¹H–²⁷Al heteronuclear correlation (HETCOR) MAS NMR. For this purpose, nanostructured silica core-alumina shell microspheres, undoped and doped with gadolinium ions respectively, obtained by a chemical synthesis based on the Stöber method for the silica core and electrostatic attraction for developing the alumina shell were studied. As a result, a new alumino-silicate layer formation was proved at the interface between silica core, where aluminum diffuses, on small scale, in the silica network, and alumina shell, where silicon ions migrate, on a larger scale, in the alumina network, leading to a stable core-shell structure. Moreover, this process is accompanied by significant local structural changes in the transition zone, particularly at the aluminum neighborhood, which is quite well understood now, with the power of solid-state NMR spectroscopy.