Selective active site placement in Lewis acid zeolites and implications for catalysis of oxygenated compounds.

The selective incorporation of isolated framework Lewis acid sites at specific crystallographic positions in high-silica zeolites was achieved by applying a rationalized post-synthetic grafting methodology. The removal of framework Ge atoms from a Ge-BEC zeolite with low concentrations of Ge in the framework (Si/Ge ∼ 150) followed by grafting allows the synthesis of Sn-BEC zeolites with Sn atoms positionally biased into the double-4-ring (D4R) crystallographic positions of the BEC framework. Spectroscopic characterization using solid-state nuclear magnetic resonance (NMR) coupled with theoretical calculations revealed that Sn atoms preferentially form open Sn sites in the D4R of Sn-BEC. This observation was supported by IR spectra of adsorbed deuterated acetonitrile (CD3CN), a known titrant of Sn sites in zeolites. The catalytic implications of selective incorporation of open Sn sites in Sn-BEC were probed using the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction. Although the MPVO turnover rates normalized by the total number of open Sn sites were comparable on Sn-BEC and a conventional Sn-Beta catalyst synthesized in fluoride media (Sn-Beta(F)), Sn-BEC demonstrated higher per gram reaction rates because of its larger fraction of open sites compared to Sn-Beta(F). These results highlight the advantage of placing active sites in targeted locations within a zeolite structure. The methodology presented here to selectively place catalytic active sites via sacrificial heteroatoms, such as Ge, can be generalized for the design of many other tetrahedrally-coordinated metal-containing zeolites.