Platinum nanoparticle

More recently, Qu et al. examined composite Ru02/Ti02 nanotube and nanoparticle platinum electrodes [66], In a 0.5 M NaHC03 solution at -0.8V (versus SCE), the nanoparticle-based electrodes yielded faradaic efficiencies for methanol of 40%, compared to 61% for the nanotube composites However, no explanation was offered as to why the nanotube-based electrodes provided an increased catalytic activity. 

The heart of a fuel cell is the membrane electrode assembly (MEA). In the simplest form, the electrode component of the MEA would consist of a thin film containing a highly dispersed nanoparticle platinum catalyst. This catalyst layer is in good contact with the ionomeric membrane, which serves as the reactant gas separator and electrolyte in this cell. The membrane is about 25-100 p,m thick. The MEA then consists of an ionomeric membrane with thin catalyst layers bonded on each side. Porous and electrically conducting carbon paper/cloth current collectors act as gas distributors (Figure 27.1). Since ohmic losses occur within the ionomeric membrane, it is important to maximize the proton conductivity of the membrane, without sacrificing the mechanical and chemical stability. 

Dendrimer-encapstdated catalysts are another area of active research for polymer-supported catalysts. The nanoparticles are stabilized by the dendrimers preventing precipitation and a omeration. Bimetallic nanoparticles with encapsulated metals (dendrimer-encapsulated catalyst DEC) from commercially available fourth-generation PAMAM dendrimers and palladium and platinum metal salts were prepared via reduction by Crooks and co-workers [34], following previous work in this area [35], The simultaneous incorporation of Pt and Pd reflects the concentrations in solution. The bimetallic DECs are more active than the physical mixture of single-metal DEC [35, 36] in the case of the hydrogenahon of allyl alcohol in water, with a maximum TOP of 230 h compared to TOP = 190 h obtained for monometallic palladium nanoparticles (platinum TOP = 50 h ). 

In the one-step synthesis of FePt nanoparticles, platinum acetylacetonate (Pt(acac)2) and iron pentacarbonyl (Fe(CO)5) and Fe(CO)5 was mixed at excess of stabilizers at 100 °C, then the mixture was heated to more than 200 °C, and kept it at that temperature for Ih, before it was heated to reflux [215, 223]. It was found that with benzyl ether as solvent and oleic acid and oleylamine as stabilizers, one-pot reaction of Fe(CO)5 and Pt(acac)2 could give nanosized FePt particles (3 - 4 nm). Size, composition, and shape of the particles were controlled by varying the synthetic parameters such as molar ratio of stabilizers to metal precursor, addition sequence of the stabilizers and metal precursors, heating rate, heating temperature, and heating duration. Monodisperse FePt nanocrystals were prepared by hydrolysis of pentacarbonyl iron and reduction of metal complexes in the presence of oleic acid and oleylamine [215]. 

F1 NMR of chemisorbed hydrogen can also be used for the study of alloys. For example, in mixed Pt-Pd nanoparticles in NaY zeolite comparaison of the results of hydrogen chemisorption and F1 NMR with the formation energy of the alloy indicates that the alloy with platinum concentration of 40% has the most stable metal-metal bonds. The highest stability of the particles and a lowest reactivity of the metal surface are due to a strong alloying effect. 

These P-CD/adamantyl pseudorotaxane-terminated dendrimers can be used as nanoreactors in the preparation of gold and platinum nanoparticles in water... 

This technique is the most widely used and the most useful for the characterization of molecular species in solution. Nowadays, it is also one of the most powerful techniques for solids characterizations. Solid state NMR techniques have been used for the characterization of platinum particles and CO coordination to palladium. Bradley extended it to solution C NMR studies on nanoparticles covered with C-enriched carbon monoxide [47]. In the case of ruthenium (a metal giving rise to a very small Knight shift) and for very small particles, the presence of terminal and bridging CO could be ascertained [47]. In the case of platinum and palladium colloids, indirect evidence for CO coordination was obtained by spin saturation transfer experiments [47]. 

Fig. 6 TEM micrograph of hexadecylamine stabilized platinum nanoparticles showing the formation of nanowires...

Thiols are known to be excellent hgands for the stabilization of gold and platinum nanoparticles. In this respect, we did not observe any Iluxional behavior [31,52] in solution NMR experiments for thiols coordinated to the surface of noble metal particles (Fig. 8). However, in the case of rutheniiun, we foimd the slow catalytic formation of alkyl disulfides [31]. After exclud-... 

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. 

Similarly to Iridium and rhodium nanoparticle studies, Dupont describes benzene hydrogenation in various media by platinum(O) nanoparticles prepared by simple decomposition of Pt2(dba)3 in BMI PFe at 75 °C and under 4 bar H2 [68]. The Pt nanoparticles were isolated by centrifugation and char-... 

Other one-pot preparations of bimetallic nanoparticles include NOct4(BHEt3) reduction of platinum and ruthenium chlorides to provide Pto.sRuo.s nanoparticles by Bonnemann et al. [65-67] sonochemical reduction of gold and palladium ions to provide AuPd nanoparticles by Mizukoshi et al. [68,69] and NaBH4 reduction of dend-rimer—PtCl4 and -PtCl " complexes to provide dend-rimer-stabilized PdPt nanoparticles by Crooks et al. [70]. 

Dendrimer-protected colloids are capable of adsorbing carbon monoxide while suspended in solution, but upon removal from solution and support on a high surface area metal oxide, CO adsorption was nil presumably due to the collapse of the dendrimer [25]. It is proposed that a similar phenomena occurs on PVP-protected Pt colloids because removal of solvent molecules from the void space in between polymer chains most likely causes them to collapse on each other. Titration of the exposed surface area of colloid solution PVP-protected platinum nanoparticles demonstrated 50% of the total metal surface area was available for reaction, and this exposed area was present as... 

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