Chemistry on the edge: A microscopic analysis of the intercalation, exfoliation, edge functionalization, and monolayer surface tiling reactions of α-Zirconium phosphate

David M. Kaschak, Stacy A. Johnson, Daniel E. Hooks, Hyuk Nyun Kim, Michael Ward, Thomas E. Mallouk

Research output: Contribution to journalArticle

Abstract

The intercalation and exfoliation reactions of α-zirconium phosphate, Zr(HPO4)2·H2O (α-ZrP), were studied microscopically by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The reaction of α-ZrP with tetra(n-butylammonium) hydroxide (TBA+OH-) initially produces intercalation compounds, which then transform to unilamellar colloids. The rate-determining step in intercalation is the opening of the interlamellar galleries. Subsequent diffusion of TBA+ ions into the opened galleries is rapid. The hydrolysis reaction of α-ZrP colloids proceeds from the edges inward, forming ~4-nm hydrated zirconia particles that decorate the edges of the sheets. The reaction does not go to completion, as it is limited by equilibrium associated with the release of phosphate into the solution. The hydrolysis reaction is negligible at 0°C, which permits the synthesis of hydrolysis-free unilamellar colloids. Remarkably, these colloids form monolayer films on amine-derivatized silicon surfaces with a high density that suggests significant surface mobility during the adsorption process. Addition of appropriate phosphonic acids to colloidal α-ZrP suspensions enables modification of the sheet edges, illustrated here by the anchoring of osmium oxide particles to the sheet edges by a vinylphosphonate linker.

Original languageEnglish (US)
Pages (from-to)10887-10894
Number of pages8
JournalJournal of the American Chemical Society
Volume120
Issue number42
DOIs
StatePublished - Oct 28 1998

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Surface reactions
Colloids
Intercalation
Zirconium
Monolayers
Phosphates
Hydrolysis
Phosphorous Acids
Osmium
Intercalation compounds
Atomic Force Microscopy
Silicon
Transmission Electron Microscopy
Zirconia
Oxides
Adsorption
Amines
Atomic force microscopy
Suspensions
Ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Chemistry on the edge : A microscopic analysis of the intercalation, exfoliation, edge functionalization, and monolayer surface tiling reactions of α-Zirconium phosphate. / Kaschak, David M.; Johnson, Stacy A.; Hooks, Daniel E.; Kim, Hyuk Nyun; Ward, Michael; Mallouk, Thomas E.

In: Journal of the American Chemical Society, Vol. 120, No. 42, 28.10.1998, p. 10887-10894.

Research output: Contribution to journalArticle

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