Metallic nanoparticles platinum

The coordination of ligands at the surface of metal nanoparticles has to influence the reactivity of these particles. However, only a few examples of asymmetric heterogeneous catalysis have been reported, the most popular ones using a platinum cinchonidine system [65,66]. In order to demonstrate the directing effect of asymmetric ligands, we have studied their coordination on ruthenium, palladium, and platinum nanoparticles and the influence of their presence on selected catalytic transformations. 

In the early work on the thermolysis of metal complexes for the synthesis of metal nanoparticles, the precursor carbonyl complex of transition metals, e.g., Co2(CO)8, in organic solvent functions as a metal source of nanoparticles and thermally decomposes in the presence of various polymers to afford polymer-protected metal nanoparticles under relatively mild conditions [1-3]. Particle sizes depend on the kind of polymers, ranging from 5 to >100 nm. The particle size distribution sometimes became wide. Other cobalt, iron [4], nickel [5], rhodium, iridium, rutheniuim, osmium, palladium, and platinum nanoparticles stabilized by polymers have been prepared by similar thermolysis procedures. Besides carbonyl complexes, palladium acetate, palladium acetylacetonate, and platinum acetylac-etonate were also used as a precursor complex in organic solvents like methyl-wo-butylketone [6-9]. These results proposed facile preparative method of metal nanoparticles. However, it may be considered that the size-regulated preparation of metal nanoparticles by thermolysis procedure should be conducted under the limited condition. 

The solvent-free controlled thermolysis of metal complexes in the absence or presence of amines is the simple one-pot synthesis of the metal nanoparticles such as gold, silver, platinum, and palladium nanoparticles and Au-Ag, Au-Pt, and Ag-Pd alloy nanoparticles. In spite of no use of solvent, stabilizer, and reducing agent, the nanoparticles produced by this method can be well size regulated. The controlled thermolysis in the presence of amines achieved to produce narrow size dispersed small metal nanoparticles under milder condition. This synthetic method may be highly promising as a facile new route to prepare size-regulated metal nanoparticles. Finally, solvent-free controlled thermolysis is widely applicable to other metal nanoparticles such as copper and nickel... 

NMR measurements are very useful to understand the properties of the stabilizing reagents of metal nanoparticles. Author s group reported the structure of stabilization of non-ionic and cationic surfactants on platinum nanoparticles [22] and that of ternary amines on rhodium nanoparticles [23]. Such information is considerably important for applications of nanoparticles such as... 

Kaifer and coworkers showed interest in the modification of metal nanoparticles with organic monolayers prepared with suitable molecular hosts. They reported the preparation of water-soluble platinum and palladium nanoparticles modified with thiolated /1-cyclodexlrin (/ -CD) [69]. Nanoparticle synthesis was... 

The liquid-phase hydrogenation of various terminal and internal alkynes under mild conditions was largely described with metal nanoparticles deposited/in-corporated in inorganic materials [83, 84], although several examples of selective reduction achieved by stabilized palladium, platinum or rhodium colloids have been reported in the literature. 

Recently, Dupont and coworkers described the use of room-temperature imi-dazolium ionic liquids for the formation and stabilization of transition-metal nanoparticles. The potential interest in the use of ionic liquids is to promote a bi-phasic organic-organic catalytic system for a recycling process. The mixture forms a two-phase system consisting of a lower phase which contains the nanocatalyst in the ionic liquid, and an upper phase which contains the organic products. Rhodium and iridium [105], platinum [73] or ruthenium [74] nanoparticles were prepared from various salts or organometallic precursors in dry 1-bu-tyl-3-methylimidazolium hexafluorophosphate (BMI PF6) ionic liquid under hydrogen pressure (4 bar) at 75 °C. Nanoparticles with a mean diameter of 2-3 nm... 

Although several noble-metal nanoparticles have been investigated for the enantiomeric catalysis of prochiral substrates, platinum colloids remain the most widely studied. PVP-stabilized platinum modified with cinchonidine showed ee-values >95%. Several stabilizers have been also investigated such as surfactants, cinchonidinium salts and solvents, and promising ee-values have been observed. Details of a comparison of various catalytic systems are listed in Table 9.16 in one case, the colloid suspension was reused without any loss in enantioselectiv-ity. Clearly, the development of convenient two-phase liquid-liquid systems for the recycling of chiral colloids remains a future challenge. 

Zhang, FI. and FI. Cui, Synthesis and characterization of functionalized ionic liquid-stabilized metal (gold and platinum) nanoparticles and metal nanoparticle/carbon nanotube hybrids. Langmuir, 2009. 25(5) p. 2604-2612. 

Zhao et al (70) developed a method for the synthesis of dendrimer-encapsulated metal nanoparticles based on sorbing metal ions into (modified) PAMAM dendrimers followed by a reduction. Dendrimers encapsulating copper, palladium, and platinum nanoparticles have been prepared. Hydroxyl-terminated PAMAM dendrimers were used to prepare encapsulated palladium (PAMAM generations 4, 6, and 8) and platinum (PAMAM generations 4 and 6) nanoparticles. The dendrimer-encapsulated palladium and platinum nanocomposites catalyzed the hydrogenation reaction of allyl alcohol and N-isopropyl acrylamide in water 71). 

For example, alkyl ammonium-stabilized metal nanoparticles were generated by electrochemical process. A target bulk metal sheet is settled as an anode in an electrochemical cell as shown in Figure 9.1.1. Metal cations are generated at the anode and move to the cathode. Metal ions are reduced there by electrons generated from the cathode to form zero-valence metal atoms. In many cases, the zero-valence metal atoms are deposited onto the cathode metal sheet (usually platinum) or precipi-... 

The fabrication of regular arrays of metallic nanoparticles by molecular templating is of great interest in order to prepare nanometre structures for future use in nanoelectronics, optical and chemical devices.43 A sensitive, rapid and powerful direct analytical method is required for the quantitative analysis of high purity platinum or palladium nanoclusters produced by biomolecular... 

Directly applying Gubkin s concept of a plasma cathode, Koo et al. produced isolated metal nanoparticles by reduction of a platinum salt at the free surface of its aqueous solution [39]. The authors used an AC discharge as cathode over the surface of an aqueous solution of ITPtCk. Platinum particles with a diameter of about 2 nm were deposited at the plasma liquid electrolyte interface by reduction with free electrons from the discharge. 

There are a number of different ways to prepare metal overlayers in practical nanoscale fuel cell electrocatalysts. One approach is schematically shown in Figure 3.3.13A, where a spherical alloy nanoparticle consisting of a noble metal (grey), platinum, and a nonnoble metal (red), such as copper, is subject to a corrosive electrochemical... 

The deposition-precipitation method as proposed by Haruta et al. (1993) provides another way to synthesize composite materials with noble metal nanoparticles over metal-oxide supports. The synthesis of gold and platinum nanoparticles supported on various metal oxide substrates (such as Ti02, ZnO, Ce02, C03O4 and Fe203) (Bamwenda, Tsubota, Nakamura and Haruta 1995 Boccuzzi, Chiorino, Tsubota and Haruta 1996 Centeno, Carrizosa and Odriozola 2003 Moon, Lee, Park and Hong 2004 Zanella, Delannoy and Louis 2005 Li, Comotti and Schuth 2006) has been continually reported in the past one and a half decades. 

Figure 4.7 Experimental observations of the TOF variations for supported platinum catalysts Pt/Al203 as a function of the size of cata-lytically active metal nanoparticles during the stationary occurrence of the methane deep oxidation at 430 C [1].

EBL was used to fabricate uniform platinum nanoparticle arrays on Si02 (mean platinum particle diameter 30-1000 nm 52,53,106,107,398)), and evaporation techniques were used to prepare smaller particles and a continuous platinum film. The EBL microfabrication technique allows the production of model catalysts consisting of supported metal nanoparticles of uniform size, shape, and interparticle distance. Apart from allowing investigations of the effects of particle size, morphology, and surface structure (roughness) on catalytic activity and selectivity, these model catalysts are particularly well suited to examination of diffusion effects by systematic variations of the particle separation (interparticle distance) or particle size. The preparation process (see Fig. 1 in Reference 106)) is described only briefly here, and detailed descriptions can be found in References 53,106,399). 

In contrast to standard borohydride reductive nanoparticle synthesis, we have developed an alternative strategy to amino acid encapsulated nanoparticles by utilizing a metal nanoparticle (M°-(Ligand))/metal ion (M"+) precursor redox pair with matched oxidation/reduction potentials. Simply, a metal nanoparticle such as Pt°-(Cys) acts as the principal reductant to a complimentary selected metal ion of Au + resulting in a new stabilized metal nanoparticle of Au°-(Cys) and the oxidation product of the original nanoparticle Pt"+. Malow et al. have reported a metathesis/transmetallation type reaction between a platinum colloid and a Au cyanide compound. Similarly, we employed a Pt°-(Cys)/AuCl4 pair and 0.5-2.0 equivalents of Au to Pt -(Cys). XRD analysis of the nanoparticle products revealed differences in crystallinity... 

Radiolysis has been used successfully in order to synthesize various noble (such as silver, gold and platinum) and non-noble (such as nickel and iron) metal nanoparticles in aqueous solution and also in other solvents such as alcohols. Due to their relatively low redox potential compared to that of the bulk, metal clusters can be oxygen-sensitive. However, the deoxygenation (by bubbling with an inert gas such as argon or nitrogen) of the solutions prior to irradiation and their study under inert atmosphere prevent their oxidation. Moreover, since water radiolysis leads to the formation of protons in addition to that of hydrated electrons, radio-induced acidification of the medium may lead to non-noble metal clusters corrosion. Therefore, to avoid the oxidation by protons, the solutions can be prepared in slightly basic medium. 

---