title: Epitaxial Growth of ZSM-5@Silicalite-1: A Core-Shell Zeolite Designed with Passivated Surface Acidity.
abstract: The design of materials with spatially controlled chemical composition has potential advantages for wide-reaching applications that span energy to medicine. Here, we present a method for preparing a core-shell aluminosilicate zeolite with continuous translational symmetry of nanopores and an epitaxial shell of tunable thickness that passivates Brønsted acid sites associated with framework Al on exterior surfaces. For this study, we selected the commercially relevant MFI framework type and prepared core-shell particles consisting of an aluminosilicate core (ZSM-5) and a siliceous shell (silicalite-1). Transmission electron microscopy and gas adsorption studies confirmed that silicalite-1 forms an epitaxial layer on ZSM-5 crystals without blocking pore openings. Scanning electron microscopy and dynamic light scattering were used in combination to confirm that the shell thickness can be tailored with nanometer resolution (e.g., 5-20 nm). X-ray photoelectron spectroscopy and temperature-programmed desorption measurements revealed the presence of a siliceous shell, while probe reactions using molecules that were either too large or adequately sized to access MFI pores confirmed the uniform shell coverage. The synthesis of ZSM-5@silicalite-1 offers a pathway for tailoring the physicochemical properties of MFI-type materials, notably in the area of catalysis, where surface passivation can enhance product selectivity without sacrificing catalyst activity. The method described herein may prove to be a general platform for zeolite core-shell design with potentially broader applicability to other porous materials.
authors.affiliation: †Department of Chemical and Biomolecular Engineering, University of Houston, 4800 Calhoun Road, Houston, Texas 77204, United States.
authors.forename: Arian
authors.initials: A
authors.lastname: Ghorbanpour
authors.affiliation: ‡Department of Chemical, Biological, and Materials Engineering, University of Oklahoma, 100 East Boyd Street, Norman, Oklahoma 73019, United States.
authors.forename: Abhishek
authors.initials: A
authors.lastname: Gumidyala
authors.affiliation: †Department of Chemical and Biomolecular Engineering, University of Houston, 4800 Calhoun Road, Houston, Texas 77204, United States.
authors.forename: Lars C
authors.initials: LC
authors.lastname: Grabow
authors.affiliation: ‡Department of Chemical, Biological, and Materials Engineering, University of Oklahoma, 100 East Boyd Street, Norman, Oklahoma 73019, United States.
authors.forename: Steven P
authors.initials: SP
authors.lastname: Crossley
authors.affiliation: †Department of Chemical and Biomolecular Engineering, University of Houston, 4800 Calhoun Road, Houston, Texas 77204, United States.
authors.forename: Jeffrey D
authors.initials: JD
authors.lastname: Rimer
keywords: MFI; core−shell; epitaxy; heterogeneous catalysis; passivation; zeolite