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. This journal is ; This work has been supported by the Spanish Government-MINECO through ''Severo Ochoa" (SEV-2016-0683), MAT2017-82288-C2-1-P (AEI/FEDER, UE) and RTI2018-101033-B-I00 (MCIU/AEI/FEDER, UE), and by Generalitat Valenciana through AICO/2019/060. JRD and YR-L thank the U.S. Department of Energy, Office of Basic Energy Sciences under Award No. DE-SC0016214 for support. ARF acknowledges the Spanish Government-MINECO for a FPU scholarship (FPU2017/01521). The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization.
