Surface acidity of tin dioxide nanomaterials revealed with ³¹P solid-state NMR spectroscopy and DFT calculations

Tin dioxide (SnO₂) nanomaterials are important acid catalysts. It is therefore crucial to obtain details about the surface acidic properties in order to develop structure-property relationships. Herein, we apply ³¹P solid-state NMR spectroscopy combined with a trimethylphosphine (TMP) probe molecule, to study the facet-dependent acidity of SnO₂ nanosheets and nanoshuttles. With the help of density functional theory calculations, we show that the tin cations exposed on the surfaces are Lewis acid sites and their acid strengths rely on surface geometries. As a result, the (001), (101), (110), and (100) facets can be differentiated by the ³¹P NMR shifts of adsorbed TMP molecules, and their fractions in different nanomaterials can be extracted according to deconvoluted ³¹P NMR resonances. The results provide new insights on nanosized oxide acid catalysts.