title: Trifluoroethanol and 19F magic angle spinning nuclear magnetic resonance as a basic surface hydroxyl reactivity probe for zirconium(IV) hydroxide structures.
abstract: A novel technique for determining the relative accessibility and reactivity of basic surface hydroxyl sites by reacting various zirconium(IV) hydroxide materials with 2,2,2-trifluoroethanol (TFE) and characterizing the resulting material using (19)F magic angle spinning (MAS) nuclear magnetic resonance (NMR) is presented here. Studied here are three zirconium hydroxide samples, two unperturbed commercial materials, and one commercial material that is crushed by a pellet press. Factors, such as the ratio of bridging/terminal hydroxyls, surface area, and pore size distribution, are examined and found to affect the ability of the zirconium(IV) hydroxide to react with TFE. X-ray diffraction, nitrogen isotherms, and (1)H MAS NMR were used to characterize the unperturbed materials, while thermogravitric analysis with gas chromatography and mass spectrometry along with the (19)F MAS NMR were used to characterize the materials that were reacted with TFE. Zirconium hydroxide materials with a high surface area and a low bridging/terminal hydroxyl ratio were found to react TFE in the greatest amounts.
authors.affiliation: Edgewood Chemical Biological Center, 5183 Blackhawk Road, Building 3549, Aberdeen Proving Ground, Maryland 21010-5424, USA. jared.b.decoste.ctr@us.army.mil
authors.forename: Jared B
authors.initials: JB
authors.lastname: DeCoste
authors.forename: T Grant
authors.initials: TG
authors.lastname: Glover
authors.forename: Gregory
authors.initials: G
authors.lastname: Mogilevsky
authors.forename: Gregory W
authors.initials: GW
authors.lastname: Peterson
authors.forename: George W
authors.initials: GW
authors.lastname: Wagner
mesh_terms: D005461:Fluorine / Q000737:chemistry*; D006878:Hydroxides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D013499:Surface Properties; D014270:Trifluoroethanol / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
chemical_list: D006878:Hydroxides; C470523:zirconium hydroxide; D005461:Fluorine; D014270:Trifluoroethanol; C031356:hydroxide ion; D015040:Zirconium