Pt nanoparticles

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-... 

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... 

Pt/Pd bimetallic nanoparticles can be prepared by refluxing the alcohol/water (1 1, v/v) solution of palla-dium(II) chloride and hexachloroplatinic(IV) acid in the presence of poly(A-vinyl-2-pyrrolidone) (PVP) at ca. 95 °C for Ih [15,16,48]. The resulting Pd/Pt nanoparticles have a Pt-core/Pd-shell structure with a narrow size distribution and the dispersion is stable against aggregation for several years. The core/shell structure was confirmed by the technique of EAXFS. Composition of Pt/Pd nanoparticles can be controlled by the initially feed amount of two different metal ions, i.e., in this case one... 

Yang et al. found that Ag-core/Pt-shell nanoparticles with a core/shell could only be formed by the successive reduction method using Ag nanoparticles as the seeds. Results of measurements of UV-Vis, TEM, EDX, and XPS supported the core/shell structure of the bimetallic nanoparticles. The reverse order of preparation using Pt nanoparticles as the seeds did not provide any core/shell nanoparticles while a physical mixture of Ag nanoparticles and the original Pt seeds was obtained [140]. 

Recently characterization of bimetallic nanoparticles by EXAFS were extensively reported [122-124,176], Structural transformation of bimetallic Pd/Pt nanoparticles, which were prepared by a sequential loading of H2PtClg onto the Pd loaded catalyst, was investigated with EXAFS at high temperatures [176], The results of EXAFS at Pd K and Pt L-III edges showed that Pt was surface-enriched or anchored on the Pd metal core with an increase of the Pt content. The structure of the obtained bimetallic Pd/Pt nanoparticles seemed to be retained upon heating up to 1273 K under ambient condition [176], Pt/ Au bimetallic nanoparticles can be prepared by polyol method and stabilized by PVP [122], XANES and EXAFS studies were also performed on the samples and their results supported the idea of a Pt-core/Au-shell structure with the elements segregated from each other [122],... 

All Pt nanoparticles were monodisperse and the size distribution was less than 10%. The average particle sizes... 

Table 1. Yield and average size of shape-controlled Pt nanoparticles [15].

Two-Dimensional Deposition and Characterization of Pt Nanoparticles on Oxide Surfaces... 

Figure 6. Thermogravimetric analysis (TGA) of free 55 K PVP and 7.1 nm Pt-PVP nanoparticles in oxygen. Oxidative decomposition of free PVP begins at 573K, while significant weight loss due to the catalyzed oxidation of PVP on PVP-protected Pt nanoparticles occurs at 473 K. It appears that PVP layer is not a complete monolayer or the entanglement of PVP chains causes a porous polymer layer enabling oxygen diffusion to the nanoparticle surface [17]. (Reprinted from Ref [17], 2006, with permission from Springer.)...

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... 

Prior to inclusion of PVP-protected Pt nanoparticles the SBA-15 silica is calcined at 823K for 12h to remove residual templating polymer. Removal of PVP is required for catalyst activation. Due to the decomposition profile of PVP (Figure 6), temperatures > 623 K were chosen for ex situ calcination of Pt/SBA-15 catalysts. Ex-situ refers to calcination of 300-500 mg of catalyst in a tube furnace in pure oxygen for 12-24 h at temperatures ranging from 623 to 723 K (particle size dependent) [13]. Catalysts were activated in He for 1 h and reduced at 673 K in H2 for 1 h. After removal, the particle size was determined by chemisorption. Table 2 is a summary of chemisorption data for Cl catalysts as well as nanoparticle encapsulation (NE) catalysts (see description of these samples in proceeding section). 

Scheme 1. Inclusion of size-controlled PVP-protected Pt nanoparticles in calcined mesoporous SBA-15 silica matrices. Mechanical agitation by low-power sonication affords a high dispersion of nanoparticles ranging in size from 1 to 7nm in the mesopore channels. The method is referred to as capillary inclusion (Cl). The technique is limited by the size of nanoparticles that can fit into the 6-9 nm diameter mesopores [13]. (Reprinted from Ref [13], 2005, with permission from American Chemical Society.)...

Three-Dimensional Deposition of Pt Nanoparticles by Nanoparticle Encapsulation... 

Scheme 2. Encapsulation of size- and shape-controlled Pt nanoparticles under neutral hydrothermal synthesis conditions of SBA-15. Silica templating block copolymers and silica precursors were added to PVP-protected Pt nanoparticle solutions and subjected to the standard SBA-15 silica synthesis conditions. Neutral, rather than acidic pH conditions were employed to prevent particle aggregation and amorphous silica formation [16j. (Reprinted from Ref. [16], 2006, with permission from American Chemical Society.)...

An example of a Pt nanoparticle cube catalyst is shown Figure 12 [17]. 

Table 4. Ag/Pt molar ratio and its influence on ethylene hydrogenation rates and apparent activation energy for nanoparticle encapsulated shape-controlled Pt nanoparticles [17].

Recently, Somorjai, Yang et al. [143] examined this reaction over lwt.% Pt/SBA-15 utilizing an elaborate preparation protocol. Preformed Pt nanoparticle sols of five different mean sizes, obtained by alcohol reduction in the presence of a protecting polymer (PVP) were combined with SBA-15 silica exhibiting 9nm pores. After 3h low-power ultrasonic treatment, the Pt particles were evenly distributed throughout the pores of the support (Figure 12 (a)-(e)). 

Scheme 5. Covalent attachment to an amino-functionalized gel of pre-formed, polymer-stabilized metal (Rh, Pt) nanoparticles. (Reprinted from Ref. [33], 1991, with permission from the American chemical Society.)...

Synthesis of Morphologically Controlled Pt Nanoparticles and Their Application in Catalytic... 

In order to obtain Pt nanoparticles, aqueous solution of 10 M K2PtCl4, which contained 10 M (as monomer unit) of poly-NIPA or poly-NEA, was bubbled with Ar gas and then H2 gas. Then the reaction vessel was sealed tightly and kept in a water bath at a suitable temperature. At given reaction times, the vessels were opened and the samples for transmission electron microscopy (TEM) were prepared by soaking a grid (carbon substrate, Oken) in the colloidal solution and then drying it in the air. The TEM (Hitachi H-8100) was operated at 200 kV. 

Figure 2. TEM images of Pt nanoparticles obtained by using poly-NIPA as capping material at (A) 25 °C and (B) 40 °C, together with the images of particles obtained by using poly-NEA at (C) 40 °C and (D) 80 °C.

---