title: Role of the hydroxyl-water hydrogen-bond network in structural transitions and selectivity toward cesium in Cs0.38(D1.08H0.54)SiTi2O7.(D0.86H0.14)2O crystalline silicotitanate.
abstract: The crystal structure of the selective Cs+ ion exchanger D1.6H0.4Ti2SiO7.D2.66H0.34O1.5, known as crystalline silicotitanate or CST, has been determined in both native (D-CST) and in the Cs+-exchanged forms ((Cs, D)-CST) from angle-dispersive and time-of-flight neutron diffraction studies. The final fully exchange Cs+ form transformed from D-CST with unit cell parameters a = 11.0704(3) A c = 11.8917(5) A and space group P42/mbc, to one with a = 7.8902(1) A c = 11.9051(4) A and space group P42/mcm. Rietveld structure refinements of both D-CST and (Cs, D)-CST suggest the transition, and ultimately the selectivity, is driven by changes in the positions of water molecules, in response to the initial introduction of Cs+. The changes in water position appear to disrupt the D-O-O-D dihedral associated with the CST framework in space group P42/mbc which ultimately leads to the structural transition. The new geometric arrangement of the water-deuteroxyl network in (Cs, D)-CST suggests that Dwater-Ddeuteroxyl repulsion forced by Cs+ exchange drives the structural transformation.
authors.affiliation: Department of Geosciences, Center for Environmental and Molecular Sciences, Stony Brook University, Stony Brook, NY 11794-2100, USA. aaron.celestian@gmail.com
authors.forename: Aaron J
authors.initials: AJ
authors.lastname: Celestian
authors.forename: John B
authors.initials: JB
authors.lastname: Parise
authors.forename: Ronald I
authors.initials: RI
authors.lastname: Smith
authors.forename: Brian H
authors.initials: BH
authors.lastname: Toby
authors.forename: Abraham
authors.initials: A
authors.lastname: Clearfield