title: Effects of adsorbate molecules on the quadrupolar interaction of framework aluminum atoms in dehydrated zeolite H,Na-Y.
abstract: The effect of adsorbate molecules on the quadrupolar interaction of framework aluminum atoms with the electric field gradient in dehydrated zeolite H,Na-Y has been studied by (27)Al MAS NMR and (27)Al MQMAS NMR spectroscopy at magnetic fields of 9.4 and 17.6 T. Upon adsorption of molecules interacting with bridging OH groups by hydrogen bonds (acetonitrile and acetone), the quadrupole coupling constant of framework aluminum atoms was found to decrease from 16.0 MHz (unloaded zeolite) to 9.4 MHz. Adsorption of molecules, which cause a proton transfer from the zeolite framework to the adsorbates (ammonia and pyridine), reduces the quadrupole coupling constant to 3.8 MHz for coverages of 0.5-2 molecules per bridging OH group. The experiments indicate that the quadrupole coupling constant of framework aluminum atoms in dehydrated zeolite H,Na-Y reflects the chemical state of adsorbate complexes formed at bridging OH groups. In agreement with earlier investigations it was found that a proton affinity of the adsorbate molecules of PA = 812-854 kJ/mol is necessary to induce a proton transfer from the zeolite framework to the adsorbed compounds. This proton transfer is accompanied by a strong improvement of the tetrahedral symmetry of zeolitic framework AlO(4) tetrahedra and a decrease of the electric field gradient.
authors.affiliation: Institute of Chemical Technology, University of Stuttgart, 70550 Stuttgart, Germany.
authors.forename: Jian
authors.initials: J
authors.lastname: Jiao
authors.forename: Johanna
authors.initials: J
authors.lastname: Kanellopoulos
authors.forename: Babita
authors.initials: B
authors.lastname: Behera
authors.forename: Yijiao
authors.initials: Y
authors.lastname: Jiang
authors.forename: Jun
authors.initials: J
authors.lastname: Huang
authors.forename: V R
authors.initials: VR
authors.lastname: Reddy Marthala
authors.forename: Siddharth S
authors.initials: SS
authors.lastname: Ray
authors.forename: Wei
authors.initials: W
authors.lastname: Wang
authors.forename: Michael
authors.initials: M
authors.lastname: Hunger