Support nanoparticles

Abstract A review of the thermolytic molecular precursor (TMP) method for the generation of multi-component oxide materials is presented. Various adaptations of the TMP method that allow for the preparation of a wide range of materials are described. Further, the generation of isolated catalytic centers (via grafting techniques) and mesoporous materials (via use of organic templates) is simimarized. The implications for syntheses of new catalysts, catalyst supports, nanoparticles, mesoporous oxides, and other novel materials are discussed. 

PtRu nanoparticles can be prepared by w/o reverse micro-emulsions of water/Triton X-lOO/propanol-2/cyclo-hexane [105]. The bimetallic nanoparticles were characterized by XPS and other techniques. The XPS analysis revealed the presence of Pt and Ru metal as well as some oxide of ruthenium. Hills et al. [169] studied preparation of Pt/Ru bimetallic nanoparticles via a seeded reductive condensation of one metal precursor onto pre-supported nanoparticles of a second metal. XPS and other analytical data indicated that the preparation method provided fully alloyed bimetallic nanoparticles instead of core/shell structure. AgAu and AuCu bimetallic nanoparticles of various compositions with diameters ca. 3 nm, prepared in chloroform, exhibited characteristic XPS spectra of alloy structures [84]. 

Arene and olefin compounds, pure or in admixture, are efficient ligands in promoting the aggregation of platinum atoms from mononuclear species to ligand-stabilized soluble clusters and solid-supported nanoparticles (Scheme 14). 

The mass activity MA (in A g ) of the Pt catalyst is, of course, the product of the specific activity js (in A m ) and the specitic surface area 5mass (in ni g ) MA = js mass- Because S ass is inversely proportional to the particle diameter dpt, the use of supported Pt nanoparticles is effective for increasing MA, if js is a constant independent of dpt- However, even at pure Pt, conflicting results on the values of js and P(H202) have been reported, suggesting the presence of differences in electrochemical properties between bulk and supported nanoparticles. For example, Bregoli [1978]... 

KovalyovEV, Resnyanskii ED, Elokhin VI, Bal zhinimaev BS, Myshlyavtsev AV. 2003. Novel statistical lattice model for the supported nanoparticle. Features of the reaction performance influenced by the dynamically changed shape and surface morphology of the supported active particle. Phys Chem Chem Phys 5 784-790. 

Information on the chemical state of iridium on going from the molecular precursors, and its adsorption on the surface of the support can be obtained by Ir Mossbauer spectroscopy. It allows to estimate the composition of the Ir-containing alloys that are possibly formed during the activation treatment of supported bimetallic systems. The main results obtained in the application of Ir Mossbauer spectroscopy to characterize two Ir-containing bimetallic supported nanoparticles, i.e., Pt-Ir on amorphous silica and Fe-Ir on magnesia are presented and discussed... 

Johanek, V., Schauermann, S., Laurin, M. et al. (2004) On the role of different adsorption and reaction sites on supported nanoparticles during a catalytic reaction NO decomposition on a Pd/alumina model catalyst , J. Phys. Chem. B, 108, 14244. 

To determine the phase properties of the calcined bimetallic nanoparticles, a detailed x-ray diffraction (XRD) study was carried out. The XRD data of AuPt/C showed that the diffraction patterns for the carbon-supported nanoparticles show a series of broad Bragg peaks, a picture typical for materials of limited structural coherence. Nevertheless, the peaks are defined well enough to allow a definitive phase identification and structural characterization. The diffraction patterns of Au/C and Pt/C could be unambiguously indexed into an fcc-type cubic lattice occurring with bulk gold and platinum. We estimated the corresponding lattice parameters by carefully determining... 

Molecular-level studies of mechanisms of proton and water transport in PEMs require quantum mechanical calculations these mechanisms determine the conductance of water-filled nanosized pathways in PEMs. Also at molecular to nanoscopic scale, elementary steps of molecular adsorption, surface diffusion, charge transfer, recombination, and desorption proceed on the surfaces of nanoscale catalyst particles these fundamental processes control the electrocatalytic activity of the accessible catalyst surface. Studies of stable conformations of supported nanoparticles as well as of the processes on their surface require density functional theory (DFT) calculations, molecular... 

M. Eikerling, J. Meier, and U. Stimming. Hydrogen evolution at a single supported nanoparticle A kinetic model. Zeitschrift fur Phystkalische Chemie 217 (2003) 395-414. 

Carbon-supported platinum (Pt) and platinum-rathenium (Pt-Ru) alloy are one of the most popular electrocatalysts in polymer electrolyte fuel cells (PEFC). Pt supported on electrically conducting carbons, preferably carbon black, is being increasingly used as an electrocatalyst in fuel cell applications (Parker et al., 2004). Carbon-supported Pt could be prepared at loadings as high as 70 wt.% without a noticeable increase of particle size. Unsupported and carbon-supported nanoparticle Pt-Ru, ,t m catalysts prepared using the surface reductive deposition... 

Nanoparticles, which often show enhanced catalytic abilities [32, 33] unusual optical properties [34], and novel quantum size effects [35], have been widely used in fields such as catalysis [36, 37], sensing [38], optoelectronics [39], and microelectronics [40]. Nanoparticle catalysis is industrially and experimentally important because a large variety of C-C coupling [41] and alcohol oxidation [32] can be effectively catalyzed by nanoparticles. In this part, we will present a brief review on recent advances in supported nanoparticle heterogeneous catalysts on various mesoporous materials. Heterogeneous nanoparticle catalysts have several... 

Some Applications of Supported Nanoparticles Modified by Organometallics 117... 

When the hydrogenation of citral is performed with supported nanoparticles of rhodium metal, for example Rh/Si02 under classical conditions [liquid phase, rhodium dispersion 80% (particles in the range of 1-2nm), citral/Rhs = 200, P(ti2) = 80bar, T = 340 K], the catalytic activity is very high but most of the above products are obtained and the reaction is totally non-selective, even if the major product was citronellal. 

Supported nanoparticles are related to the idea of starting with polynuclear cluster precursors. While there is no clear line that divides polynuclear clusters from nanoparticles, clusters are generally small, low nuclearity (MnL n = 3-20), structurally well-characterized species approximately 1-2 nm in size. Nanoparticles are larger (>2 nm) and frequently defined by a size distribution rather than a discrete number of atoms and ligands [41]. In the area of catalysis, gold nanopar-... 

Supported nanoparticles (1-1.5 nm) based on Ru4Pt2 entities have been obtained by using a Ru4Pt2(CO)i8 precursor on carbon black and fullerene soot [63]. XANES analysis showed differences between the interaction of nanoparticles with both carbon black and fullerene supports. In particular, a change in the electronic properties of the nanoparticles on fullerene is proposed this change was related to a strong interaction between the nanoparticle and a surface-atom, probably via the formation of a Ru-carbide phase. 

Chan SC, Barteau MA (2005) Preparation of highly uniform Ag/Ti02 and Au/Ti02 supported nanoparticles catalyst by photodeposition. Langmuir 23 5588-5595... 

Once molecular complex precursors are successfully synthesized, they may be used for supported nanoparticles in the form of thin films. Hursthouse et al. (28) synthe-... 

Now possibilities of the MC simulation allow to consider complex surface processes that include various stages with adsorption and desorption, surface reaction and diffusion, surface reconstruction, and new phase formation, etc. Such investigations become today as natural analysis of the experimental studying. The following papers [282-285] can be referred to as corresponding examples. Authors consider the application of the lattice models to the analysis of oscillatory and autowave processes in the reaction of carbon monoxide oxidation over platinum and palladium surfaces, the turbulent and stripes wave patterns caused by limited COads diffusion during CO oxidation over Pd(110) surface, catalytic processes over supported nanoparticles as well as crystallization during catalytic processes. 

An interpretation of the results for catalytic reaction kinetics on active supported nanoparticles on the scale down to 10nm has been obtained by the MC technique [285]. The technique allows the peculiarities of the reaction performance on the nanometer scale, including the inherent heterogeneity of metal crystallites as well as spontaneous and adsorbate-induced changes of the shape and degree of dispersion of supported catalysts. 

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