Metal clusters hydrogen activation

High catalytic activity is exhibited when one unit cell of NHCO is occupied by one (Pt)2 or (Pt)3 cluster. Hydrogen activation is caused by decomposition of H2 molecules to the atomic state with subsequent formation of the hydride complex. Oxidation-reduction titration as well as electron-microscopy measurements show the incorporation of Pd crystallites inside nylon grains [114]. Most have a mean diameter of about 30 A. However, under the assumption that all the metal is located on the polymeric support surface, the calculated accessible metal surface amounts to several hundred Angstroms. Therefore, during preparation of the Pd-nylon catalyst, part of the metal penetrates into the organic matrix. 

Copper clusters, as reported by the Rice group(lc), do not react with hydrogen. Hydrogen chemisorption on copper surfaces is also an activated process. Surface beam scattering experiments place this barrier between 4-7 kcal/mole(33). This large value is consistent with the activated nature oT hydrogen chemisorption on metal clusters, and the trend toward bulk behavior for relatively small clusters (>25 atoms in size). 

A series of papers by Shustorovi ch(63) and/or Baetzo1d(64) summarized in a recent article(65) have addressed the problem of chemisorption on metal surfaces in terms of electron accepting and donating interactions. Saillard and Hoffmann (66) developed qualitatively identical pictures of these interactions but starting from fragment orbital type analysis. These papers are only a few of the theoretical discussions that consider hydrogen activation, however we will use their approach because it address the problem in a fashion that can interpolate between the organometallic cluster and the bulk. 

After TPD of hydrogen, the sample was reoxidized at the activation temperature by injecting pulses of pure oxygen in helium referenced to helium gas. After oxidation of the cobalt metal clusters, the number of moles of oxygen consumed... 

Catalytic experiments. The runs are performed in a 300mL static reactor (Autoclave Engineers Model AE 300) for 15hrs under an initial 20 bar pressure with a sample weight leading to 0.U mg-atom of metal. Neither the unloaded zeolites nor the molecular clusters are active in CO hydrogenation under our experimental conditions. 

Much emphasis has been placed in recent times on easily recoverable liquid bi-phasic catalysts, including metal clusters in nonconventional solvents. For instance, aqueous solutions of the complexes [Ru3(CO)12.x(TPPTS)x] (x=l, 2, 3 TPPTS = triphenylphosphine-trisulfonate, P(m-C6H4S03Na)3) catalyze the hydrogenation of simple alkenes (1-octene, cyclohexene, styrene) at 60°C and 60 bar H2 at TOF up to 500 h 1 [24], while [Ru i(CO)C (TPPMS) >,] (TPPMS = triphenylphos-phine-monosulfonate, PPh2(m-C6H4S03Na) is an efficient catalyst precursor for the aqueous hydrogenation of the C=C bond of acrylic acid (TOF 780 h 1 at 40 °C and 3 bar H2) and other activated alkenes [25]. The same catalysts proved to be poorly active in room temperature ionic liquids such as [bmim][BF4] (bmim= Tbutyl-3-methylimidazolium). No details about the active species involved are known at this point. 

H. Bonnemann, W. Brijoux, R. Brinkmann, E. Dinjus, T. Jouben, R. Fretzen, and B. Korall, Highly dispersed metal clusters and colloids for the preparation of active liquid-phase hydrogenation catalysts, J. Mol. Catal. 74,323-333 (1992). 

A size-selective synthesis of nanostructured transition metal clusters (Pd, Ni) has been reported166, as has the preparation of colloidal palladium in organic solvents167, the latter of which is an active and stable catalyst for selective hydrogenation. The use of microwaves in the preparation of palladium catalysts on alumina and silica resulted in hydrogenation catalysts with improved crystallite size and activity168. 

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