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Structures of Alkali Metals in Silica Gel Nanopores: New Materials for Chemical Reductions and Hydrogen Production

Structures of Alkali Metals in Silica Gel Nanopores: New Materials for Chemical Reductions and Hydrogen Production

Mouath Shatnawi, Gianluca Paglia, James L Dye, Kevin C Cram, Michael Lefenfeld, Simon J L Billinge

J Am Chem Soc. 2007 Feb 7;129(5):1386-92.

PMID: 17263423

Abstract:

Alkali metals and their alloys can be protected from spontaneous reaction with dry air by intercalation (with subsequent heating) into the pores of silica gel (SG) at loadings up to 40 wt %. The resulting loose, black powders are convenient materials for chemical reduction of organic compounds and the production of clean hydrogen. The problem addressed in this paper is the nature of the reducing species present in these amorphous materials. The atomic pair distribution function (PDF), which considers both Bragg and diffuse scattering components, was used to examine their structures. Liquid Na-K alloys added to silica gel at room temperature (stage 0) or heated to 150 degrees C (stage I) as well as stage I Na-SG, retain the overall pattern of pure silica gel. Broad oscillations in the PDF show that added alkali metals remain in the pores as nanoscale metal clusters. 23Na MAS NMR studies confirm the presence of Na(0) and demonstrate that Na+ ions are formed as well. The relative amounts of Na(0) and Na(+) depend on both the overall metal loading and the average pore size. The results suggest that ionization occurs near or in the SiO2 walls, with neutral metal present in the larger cavities. The fate of the electrons released by ionization is uncertain, but they may add to the silica gel lattice, or form an "electride-like plasma" near the silica gel walls. A remaining mystery is why the stage I material does not show a melting endotherm of the encapsulated metal and does not react with dry oxygen. Na-SG when heated to 400 degrees C (stage II) yields a dual-phase reaction product that consists of Na(4)Si(4) and Na(2)SiO(3).

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
LS72521	Sodium silica gel Stage II			Price

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