Stable Metal-Organic Framework-Supported Niobium Catalysts.

Developing structurally well-defined, supported oxide catalysts remains a significant challenge. Here, we report the grafting of Nb(V) oxide sites onto the nodes of the Zr-based metal organic framework (MOF) NU-1000 as a stable, well-defined catalyst support. Nb(V) oxide was deposited with loadings up to 1.6 mmol/g via two postsynthetic methods: atomic layer deposition in a MOF, and solution-phase grafting in a MOF. Difference envelope density measurements indicated that the two synthetic methods resulted in different local structures of the Nb(V) ions within NU-1000. Despite their high Nb(V) loadings, which were equivalent to >60% surface coverage, nearly all Nb(V) sites of the MOF-supported catalysts were active sites for alkene epoxidation, as confirmed by phenylphosphonic acid titration. The MOF-supported catalysts were more selective than the control Nb-ZrO2 catalyst for cyclohexene epoxidation with aqueous H2O2 and were far more active on a gravimetric basis.