Pt particles

Figure 17. PMC behavior in the accumulation region, (a) PMC potential curve and photocurrent-potential curve (dashed line) for silicon (dotted with Pt particles) in contact with propylene carbonate electrolyte containing ferrocene.21 (b) PMC potential curve and photocurrent-potential curve (dashed line) for a sputtered ZnO layer [resistivity 1,5 x 103 ft cm, on conducting glass (ITO)] in contact with an alkaline electrolyte (NaOH, pH = 12), measured against a saturated calomel electrode.22...

Figure 25. Effect of corrosion and prepolarization on (a) PMC voltage and (b) photocurrent voltage dependence. Left n-Si (covered with Pt particles) in contact with a 5 M HBr/0.05 M Br2 aqueous solution. A comparison is made of the PMC peak during the first and the third potential sweeps. Right n-WSe2 in contact with an aqueous 0.05 M Fe2+/3+ solution. The effect of cathodic prepolarization on position and height of the PMC peak is shown.

Mesoporous carbon materials were prepared using ordered silica templates. The Pt catalysts supported on mesoporous carbons were prepared by an impregnation method for use in the methanol electro-oxidation. The Pt/MC catalysts retained highly dispersed Pt particles on the supports. In the methanol electro-oxidation, the Pt/MC catalysts exhibited better catalytic performance than the Pt/Vulcan catalyst. The enhanced catalytic performance of Pt/MC catalysts resulted from large active metal surface areas. The catalytic performance was in the following order Pt/CMK-1 > Pt/CMK-3 > Pt/Vulcan. It was also revealed that CMK-1 with 3-dimensional pore structure was more favorable for metal dispersion than CMK-3 with 2-dimensional pore arrangement. It is eoncluded that the metal dispersion was a critical factor determining the catalytic performance in the methanol electro-oxidation. 

In a series of studies of carefully prepared catalysts of Pt on silica gel (7,10-12) we have shown that the Pt particles are equi-axed, (and de-finitely not cuboidal as is often assumed) that the size (or percent metal exposed) agrees with results from hydrogen chemisorption, and that the particles are free of microstrain faults or twins, except when the average size is similar to the pore size of the support. In this latter case, the particles are elongated, and there is microstrain, probably due to differ-... 

Reduction by hydrogen completely alters the chemical reactivity and its variation with size. At the same time, the Pt particle size is reduced. The mean-square amplitude of vibration follows this reactivity. 

Photocatalyzed H2 evolution inside vesicle cavity over tiny anchored Pt particles also has been reported (see [15] and refs, therein). 

The type catalyst, Pt/Ti02 reduced at 300 C behaves much like Pt/Si02, but reduction at 500°C largely eliminates its capacity for the chemisorption of H2 and hydrogenation while inducing activity for the hydrogenation of CO. Ti suboxide formed by reduction encapsulates the Pt particles. 

The activity and stability of catalysts for methane-carbon dioxide reforming depend subtly upon the support and the active metal. Methane decomposes to carbon and hydrogen, forming carbon on the oxide support and the metal. Carbon on the metal is reactive and can be oxidized to CO by oxygen from dissociatively adsorbed COj. For noble metals this reaction is fast, leading to low coke accumulation on the metal particles The rate of carbon formation on the support is proportional to the concentration of Lewis acid sites. This carbon is non reactive and may cover the Pt particles causing catalyst deactivation. Hence, the combination of Pt with a support low in acid sites, such as ZrO, is well suited for long term stable operation. For non-noble metals such as Ni, the rate of CH4 dissociation exceeds the rate of oxidation drastically and carbon forms rapidly on the metal in the form of filaments. The rate of carbon filament formation is proportional to the particle size of Ni Below a critical Ni particle size (d<2 nm), formation of carbon slowed down dramatically Well dispersed Ni supported on ZrO is thus a viable alternative to the noble metal based materials. 

When the amount of coke formed as a function of time on stream is compared to the decrease in catalytic activity (see Fig. 3), two regimes of deactivation can be noticed for the strongly deactivating catalysts, i e, a slow initial deactivation which is followed by a rapid loss of activity This first phase is characteristic of a slow transformation of the reactive carbon into less reactive coke. The second phase is attributed to carbon formed on the support which accumulates there and rapidly covers the Pt particles when its amount reaches a critical value causing the sudden decay of catalytic activity. 

Clusters of Co and Pt particles highly dispersed with Co at exdtange positions, and an adequate add fonction must necessarily be inintimate contact within the Mordenite dhannds to generate an effident cata for the NO with CH abatement (Figs. 1 and 2 and Table 2). 

Fig. 7 Reaction of SnBu4 on Pt particles supported on silica at 50 °C evolution of the stoichiometry of surface organotin species as a function of coverage and reaction time (see time in square boxes)...

Scheme 35 Various steps observed during the hydrogenolysis of SnBu4 at the surface of a Pt particle (sphere color-code Pt brown, H blue, C white, Sn green)...

The overall reaction pathway is probably similar to what has been presented for the reaction of SnBu4 with Pt particles, that is first hydrogenolysis of the As-C bond to form Nis[AsPh2] , species, which rapidly evolves into Nis[AsPh]jy, Nis[As]jy to give finally an alloy by migration of the As adatoms into the Ni lattice as evidenced by the formation of Nickeline (NiAs) according to XRD studies (Scheme 36). 

The mechanism of formation of Pt particles by the or-ganometallic reduction route, however, was found to proceed differently, for example in the reductive stabilization of Pt nanoparticles produced by reacting Pt-acetylacetonate with excess trimethylaluminium. Here, derivates of aluminium alkyls act as both reducing agents and colloidal stabilizers. As was shown by a combination... 

TEM imugv uf Pt particles prepared via polyol method (wilhoul sarfaclanl)... 

As an alternative approach towards the above requirement, Somorjai introduced the method of electron lithography [119] which represents an advanced HIGHTECH sample preparation technique. The method ensures uniform particle size and spacing e.g. Pt particles of 25 nm size could be placed with 50 nm separation. This array showed a uniform activity similar to those measured on single crystal in ethylene hydrogenation. The only difficulty with the method is that the particle size is so far not small enough. Comprehensive reviews have been lined up for the effect of dispersion and its role in heterogeneous catalysis [23,124,125]. 

Without sonication, Pt particles adsorb primarily on the external surface of SBA-15 and at the mesopore openings. Sonication promotes homogeneous inclusion and deposition of Pt nanoparticles on the inner surface of the support mesopores, because ca. 90% of the total surface area is from the inner pore walls. Heat treatment... 

The mechanical incorporation of active nanoparticles into the silica pore structure is very promising for the general synthesis of supported catalysts, although particles larger than the support s pore diameter cannot be incorporated into the mesopore structure. To overcome this limitation, pre-defined Pt particles were mixed with silica precursors, and the mesoporous silica structures were grown by a hydrothermal method. This process is referred to as nanoparticle encapsulation (NE) (Scheme 2) [16] because the resulting silica encapsulates metal nanoparticles inside the pore structure. 

The acidic conditions of standard SBA-15 synthesis [35] cause the precipitation of metal nanoparticles without silica encapsulation, or the formation of amorphous silica due to the presence of the polymer used for nanoparticle synthesis. Therefore, the SBA-15 framework was synthesized under neutral condition using sodium fluoride as a hydrolysis catalyst and tetramethylorthosilicate (TMOS) as the silica precursor. Pt particles with different sizes were dispersed in the aqueous template polymer solution sodium fluoride and TMOS were added to the reaction mixture. The slurry aged at 313 K for a day, followed by an additional day at 373 K. Pt(X)/SBA-15-NE (X = 1.7, 2.9, 3.6, and 7.1nm) catalysts were obtained by ex-situ calcination (see Section 3.2). TEM images of the ordered... 

Pt particles remain highly dispersed in the reaction mixture during mesostructure formation. All measurements including XRD, SAXS, and TEM indicate a well-ordered silica structure. N2 physisorption measurement indicated high surface areas (523-661 m g ) and meso-sized pores (112-113 A) for the silica supports produced in the presence of different Pt particles. 

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