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Published July 21, 2014 | Supplemental Material + Published
Journal Article Open

Novel surfactant-free route to delaminated all-silica and titanosilicate zeolites derived from a layered borosilicate MWW precursor

Abstract

Layered borosilicate zeolite precursor ERB-1P (Si/B = 11) is delaminated via simultaneous deboronation and SDA removal, to yield material DZ-1 consisting of silanol nests, using a simple aqueous Zn(NO_3)_2 treatment. Characterization of this synthesis process by PXRD shows loss of long-range order, and transmission electron microscopy (TEM) demonstrates transformation of rectilinear layers in the layered zeolite precursor to single and curved layers in the delaminated material. N_2 physisorption confirms the expected decrease of micropore volume and increase in external surface area for delaminated materials relative to their calcined 3D zeolite counterpart. Elemental analysis shows loss of B and absence of Zn in the delaminated material. Resonances corresponding to silanol nests are evident via^(29)Si solid-state NMR spectroscopy in DZ-1, which should be located within 12-MR pockets near the external surface. We have successfully utilized these nests as tetrahedral recognition sites for incorporation of Ti within an isolated framework coordination environment in material Ti-DZ-1. Diffuse-reflectance ultraviolet (DR-UV) spectroscopy of Ti-DZ-1 confirms isolated framework Ti sites, which are assigned to bands in the range of 210 nm–230 nm. Infrared spectra of Ti-DZ-1 consist of a distinct absorption band at 960 cm^(−1), which is absent in DZ-1 prior to Ti incorporation and has been previously correlated with the presence of framework Ti species. Infrared spectra after pyridine adsorption demonstrate bands consistent with Lewis-acid sites in the resulting Ti-substituted delaminated zeolite. The accessibility of these Lewis-acid sites is confirmed when using Ti-DZ-1 as a catalyst for cyclohexene epoxidation using tert-butyl hydroperoxide as the organic oxidant – a reaction for which both DZ-1 and TS-1 are inactive.

Additional Information

© 2014 Royal Society of Chemistry. Received 5th February 2014, Accepted 19th March 2014. First published online 19 Mar 2014. The authors are grateful to the Management and Transfer of Hydrogen via Catalysis Program funded by Chevron Corporation. The NMR facility at Caltech was supported by the National Science Foundation under Grant Number 9724240 and partially supported by the MRSEC Program of the NSF under Award Number DMR-520565. X.O. is also grateful of Dr. Cong-Yan Chen of Chevron Corporation for providing Na-kanemite.

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August 20, 2023
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