Reaction Dynamics of the Decaniobate Ion [HxNb10O28](6–x)– in Water

Villa, Eric M.; Ohlin, C. André; Balogh, Edina; Anderson, Travis M.; Nyman, May D.; Casey, William H.

doi:10.1002/anie.200801125

Reaction Dynamics of the Decaniobate Ion [H_xNb₁₀O₂₈]^(6–x)– in Water

Journal Article · Mon Jun 09 00:00:00 EDT 2008 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.200801125· OSTI ID:2543076

Villa, Eric M. ^[1]; Ohlin, C. André ^[1]; Balogh, Edina ^[1]; Anderson, Travis M. ^[2]; Nyman, May D. ^[2]; Casey, William H. ^[1]

University of California, Davis, CA (United States)
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Key questions in geo- and environmental chemistry concern interactions between water and metal-oxide/mineral surfaces as these are responsible for weathering and for the elimination of pollutants. Large oxide ions could be enormously useful to geochemists in testing hypotheses about reaction pathways at mineral surfaces, but most dissociate rapidly, exchange oxygens too quickly, or have such complicated acid-base chemistry that they aren't helpful. Simultaneously, the polyoxometalate (POM) community needs information about reaction pathways in these ions to understand the degradation of catalysts and the structural evolutions among different POMs. Here, the nanometer-size decaniobate ion ([H_xNb₁₀O₂₈]^(6-x)-) is unique in aqueous niobate chemistry as it does not strongly protonate when dissolved into water and is stable at near-neutral pH. We report here, with unprecedented clarity and detail, the rates of steady isotope exchange at all the seven structural types of oxygens in this ion (labeled A-G in Figure 1-A) as a function of solution composition. Separately we follow the pathways for dissociation and identify the reaction products. Our results indicate that the entire structure is involved in the reaction dynamics. For example, rates of steady oxygen-isotope exchanges also increase with pH, even when they are much more rapid than dissociation. Furthermore, base-induced dissociation leaves much of the molecule intact, illustrating pathways for interconversion of all known aqueous isopolyniobate types.

Research Organization:: University of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-05ER15693

OSTI ID:: 2543076

Alternate ID(s):: OSTI ID: 2507332

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 26 Vol. 47; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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