title: Template-Framework Interactions in Tetraethylammonium-Directed Zeolite Synthesis.
abstract: Zeolites, having widespread applications in chemical industries, are often synthesized using organic templates. These can be cost-prohibitive, motivating investigations into their role in promoting crystallization. Herein, the relationship between framework structure, chemical composition, synthesis conditions and the conformation of the occluded, economical template tetraethylammonium (TEA+) has been systematically examined by experimental and computational means. The results show two distinct regimes of occluded conformer tendencies: 1) In frameworks with a large stabilization energy difference, only a single conformer was found (BEA, LTA and MFI). 2) In the frameworks with small stabilization energy differences (AEI, AFI, CHA and MOR), less than the interconversion of TEA+in solution, a heteroatom-dependent (Al, B, Co, Mn, Ti, Zn) distribution of conformers was observed. These findings demonstrate that host-guest chemistry principles, including electrostatic interactions and coordination chemistry, are as important as ideal pore-filling.
authors.affiliation: Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands.
authors.forename: Joel E
authors.identifier: 0000-0002-0039-2863
authors.initials: JE
authors.lastname: Schmidt
authors.affiliation: Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands.
authors.forename: Donglong
authors.identifier: 0000-0002-5680-6279
authors.initials: D
authors.lastname: Fu
authors.affiliation: Departments of Bioengineering and Physics & Astronomy, Rice University, Houston, TX, 77005, USA.
authors.forename: Michael W
authors.identifier: 0000-0002-4298-3450
authors.initials: MW
authors.lastname: Deem
authors.affiliation: Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands.
authors.forename: Bert M
authors.identifier: 0000-0001-5245-1426
authors.initials: BM
authors.lastname: Weckhuysen
keywords: Raman spectroscopy; computational chemistry; conformational analysis; host-guest systems; zeolites