title: Characterization of Phosphate and Arsenate Adsorption onto Keggin-Type Al30 Cations by Experimental and Theoretical Methods.
abstract: Keggin-type aluminum oxyhydroxide species such as the Al30 (Al30O8(OH)56(H2O)26(18+)) polycation can readily sequester inorganic and organic forms of P(V) and As(V), but there is a limited chemical understanding of the adsorption process. Herein, we present experimental and theoretical structural and chemical characterization of [(TBP)2Al2(μ4-O8)(Al28(μ2-OH)56(H2O)22)](14+) (TBP = t-butylphosphonate), denoted as (TBP)2Al30-S. We go on to consider the structure as a model for studying the reactivity of oxyanions to aluminum hydroxide surfaces. Density functional theory (DFT) calculations comparing the experimental structure to model configurations with P(V) adsorption at varying sites support preferential binding of phosphate in the Al30 beltway region. Furthermore, DFT calculations of R-substituted phosphates and their arsenate analogues consistently predict the beltway region of Al30 to be most reactive. The experimental structure and calculations suggest a shape-reactivity relationship in Al30, which counters predictions based on oxygen functional group identity.
authors.affiliation: Department of Chemistry, University of Iowa , Iowa City, Iowa 52242, United States.
authors.forename: Katie W
authors.initials: KW
authors.lastname: Corum
authors.affiliation: Department of Chemistry, University of Iowa , Iowa City, Iowa 52242, United States.
authors.forename: Melissa
authors.initials: M
authors.lastname: Fairley
authors.affiliation: Department of Chemistry, University of Iowa , Iowa City, Iowa 52242, United States.
authors.forename: Daniel K
authors.initials: DK
authors.lastname: Unruh
authors.affiliation: Department of Chemistry, University of Iowa , Iowa City, Iowa 52242, United States.
authors.forename: Maurice K
authors.initials: MK
authors.lastname: Payne
authors.affiliation: Department of Chemistry, University of Iowa , Iowa City, Iowa 52242, United States.
authors.forename: Tori Z
authors.initials: TZ
authors.lastname: Forbes
authors.affiliation: Department of Chemistry, University of Iowa , Iowa City, Iowa 52242, United States.
authors.forename: Sara E
authors.initials: SE
authors.lastname: Mason