Chabazite (CHA) molecular sieves, which are industrial catalysts for the selective reduction of nitrogen oxides and the conversion of methanol into olefins, are also ideal materials in catalysis research because their crystalline frameworks contain one unique tetrahedral-site. The presence of a single lattice site allows for more accurate descriptions of experimental data using theoretical models, and consequently for more precise structure-function relationships of active sites incorporated into framework positions. A direct hydrothermal synthesis route to prepare pure-silica chabazite molecular sieves substituted with framework Sn atoms (Sn-CHA) is developed, which is required to predominantly incorporate Sn within the crystalline lattice. Quantitative titra-tion with Lewis bases (NH3, CD3CN, pyridine) demonstrates that framework Sn atoms behave as Lewis acid sites, which catalyze intermolecular propionaldehyde reduction and ethanol oxidation, as well as glucose-fructose isomerization. Aqueous-phase glucose isomerization turnover rates on Sn-CHA are four orders-of-magnitude lower than on Sn-Beta zeolites, but similar to those on amorphous Sn-silicates. Further analysis of Sn-CHA by dynamic nuclear polarization enhanced solid-state nuclear magnetic reso-nance (DNP NMR) spectroscopy enables measurement of 119Sn NMR chemical shift anisotropy (CSA) of Sn sites. Comparison of experimentally determined CSA parameters to those computed on cluster models using density functional theory supports the pres-ence of closed sites (Sn-(OSi)4) and defect sites ((HO)-Sn-(OSi)3) adjacent to a framework Si vacancy), which respectively be-come hydrated hydrolyzed-open sites and defect sites when Sn-CHA is exposed to ambient conditions or aqueous solution. Kinetic and spectroscopic data show that large substrates (e.g., glucose) are converted only on Sn sites located within disordered mesopo-rous voids of Sn-CHA, which are selectively detected and quantified in IR and 15N and 119Sn DNP NMR spectra using pyridine titrants. This integrated experimental and theoretical approach allows precise description of the primary coordination and secondary confining environments of Sn active sites isolated in crystalline silica frameworks, and clearly establishes the role of confinement within microporous voids for aqueous-phase glucose isomerization catalysis.
Date of this Version
Harris, James W.; Liao, Wei-Chih; Di Iorio, John R.; Henry, Alisa M.; Ong, Ta-Chung; Comas-Vives, Aleix; Coperet, Christopher; and Gounder, Rajamani, "Molecular Structure and Confining Environment of Sn Sites in Single-Site Chabazite Zeolites" (2017). School of Chemical Engineering Faculty Publications. Paper 4.
Available for download on Tuesday, September 18, 2018