Journal article
Characterization of Phosphate and Arsenate Adsorption onto Keggin-Type Al sub(30) Cations by Experimental and Theoretical Methods
Inorganic chemistry, Vol.54(17), pp.8367-8374
09/08/2015
DOI: 10.1021/acs.inorgchem.5b01039
Abstract
Keggin-type aluminum oxyhydroxide species such as the Al sub(30) (Al sub(30)O sub(8)(OH) sub(56)(H sub(2)O) sub(26) super(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) sub(2)Al sub(2)( mu sub(4)-O sub(8))(Al sub(28)( mu sub(2)-OH) sub(56)(H sub(2)O) sub(22))] super(14+) (TBP = t-butylphosphonate), denoted as (TBP) sub(2)Al sub(30)-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 Al sub(30) beltway region. Furthermore, DFT calculations of R-substituted phosphates and their arsenate analogues consistently predict the beltway region of Al sub(30) to be most reactive. The experimental structure and calculations suggest a shape-reactivity relationship in Al sub(30), which counters predictions based on oxygen functional group identity.
Details
- Title: Subtitle
- Characterization of Phosphate and Arsenate Adsorption onto Keggin-Type Al sub(30) Cations by Experimental and Theoretical Methods
- Creators
- Katie W CorumMelissa FairleyDaniel K UnruhMaurice K PayneTori Z ForbesSara E Mason
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.54(17), pp.8367-8374
- DOI
- 10.1021/acs.inorgchem.5b01039
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Grant note
- DOI: 10.13039/100000165, name: National Science Foundation, award: CHE-1254127
- Language
- English
- Date published
- 09/08/2015
- Academic Unit
- Core Research Facilities; Chemistry; Civil and Environmental Engineering
- Record Identifier
- 9983986087002771
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