Schroeder, F. ; Esken, D. ; Cokoja, M. ; Berg, M. W. E. van den ; Lebedev, O. I. ; van Tendeloo, G. ; Walaszek, B. ; Buntkowsky, G. ; Limbach, H. H. ; Chaudret, B. ; Fischer, R. A. (2008)
Ruthenium nanoparticles inside porous Zn4O(bdC)(3) by hydrogenolysis of adsorbed Ru(cod)(cot): A solid-state reference system for surfactant-stabilized ruthenium colloids.
In: Journal of the American Chemical Society, 130 (19)
Artikel, Bibliographie

Kurzbeschreibung (Abstract)

The gas-phase loading of Zn4O(bdc)(3) (MOF-5; bdc = 1,4-benzenedicarboxylate) with the volatile compound Ru(cod)(cot) (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene) was followed by solid-state C-13 magic angle spinning (MAS) NMR spectroscopy. Subsequent hydrogenolysis of the adsorbed complex inside the porous structure of MOF-5 at 3 bar and 150 degrees C was performed, yielding ruthenium nanoparticles in a typical size range of 1.5-1.7 nm, embedded in the intact MOF-5 matrix, as confirmed by transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (PXRD), and X-ray absorption spectroscopy (XAS). The adsorption of CO molecules on the obtained Ru@MOF-5 nanocomposite was followed by IR spectroscopy. Solid-state 2 H NMR measurements indicated that MOF-5 was a stabilizing support with only weak interactions with the embedded particles, as deduced from the surprisingly high mobility of the surface Ru-D species in comparison to surfactant-stabilized colloidal Ru nanoparticles of similar sizes. Surprisingly, hydrogenolysis of the Ru(cod)(cot)(3.5)@MOF-5 inclusion compound at the milder condition of 25 degrees C does not lead to the quantitative formation of Ru nanoparticles. Instead, formation of a ruthenium-cyclooctadiene complex with the arene moiety of the bdc linkers of the framework takes place, as revealed by 13C MAS NMR, PXRD, and TEM.

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