Isotope-exchange dynamics in isostructural decametalates with profound differences in reactivity

Eric M. Villa, C. André Ohlin, James R. Rustad, William H. Casey

Research output: Contribution to journalArticle

35 Scopus citations

Abstract

Rates of oxygen-isotope exchange at all structural sites in two isostructural polyoxometalates, [HxNb10O 28](6-x)- and [HxTi2Nb 8O28](8-x)-, show that small changes in structure have surprising and profound effects: a single-site substitution of Ti(IV) for Nb(V) inverts the pH dependencies for rates throughout the structures. Within a given structure, all oxygens exhibit similar pH dependencies although they react over a range greater than ∼104, indicating that pathways involve concerted motions of the entire lattices. Profound sensitivity to changes in structure and composition suggests reaction pathways in polyoxometalate ions will be highly variable even within structural classes. The results also require new thinking about how ab initio simulations are used to understand reaction pathways involving extended structures, like the mineral-water interface. Our data indicate that reactions proceed via metastable intermediates and that the simulations must be structurally faithful or will miss the essential chemistry.

Original languageEnglish (US)
Pages (from-to)16488-16492
Number of pages5
JournalJournal of the American Chemical Society
Volume131
Issue number45
DOIs
StatePublished - Nov 27 2009
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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