title: Ruthenium nanoparticles inside porous [Zn4O(bdc)3] by hydrogenolysis of adsorbed [Ru(cod)(cot)]: a solid-state reference system for surfactant-stabilized ruthenium colloids.
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 (13)C 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 (13)C MAS NMR, PXRD, and TEM.
authors.affiliation: Lehrstuhl für Anorganische Chemie II-Organometallics & Materials, Ruhr-Universität, Universitätsstrasse 150, D-44780 Bochum, Germany.
authors.forename: Felicitas
authors.initials: F
authors.lastname: Schröder
authors.forename: Daniel
authors.initials: D
authors.lastname: Esken
authors.forename: Mirza
authors.initials: M
authors.lastname: Cokoja
authors.forename: Maurits W E
authors.initials: MW
authors.lastname: van den Berg
authors.forename: Oleg I
authors.initials: OI
authors.lastname: Lebedev
authors.forename: Gustaaf
authors.initials: G
authors.lastname: Van Tendeloo
authors.forename: Bernadeta
authors.initials: B
authors.lastname: Walaszek
authors.forename: Gerd
authors.initials: G
authors.lastname: Buntkowsky
authors.forename: Hans-Heinrich
authors.initials: HH
authors.lastname: Limbach
authors.forename: Bruno
authors.initials: B
authors.lastname: Chaudret
authors.forename: Roland A
authors.initials: RA
authors.lastname: Fischer