Poly nanoparticles

For the preparation of nanoparticles based on two aqueous phases at room temperature one phase contains chitosan and poly(ethylene oxide) and the other contains sodium tripolyphosphate. The particle size (200-1000 nm) and zeta potential (between -i- 20 mV and -l- 60 mV) could be modulated by varying the ratio chitosan/PEO-PPO. These nanoparticles have great proteinloading capacity and provide continuous release of the entrapped protein (particularly insulin) for up to one week [100,101]. 

Ohya et al. reported poly(ethyleneglycol)-grafted chitosan nanoparticles as peptide drug carriers. The incorporation and release of insulin was dependent on the extent of the reaction of poly(ethyleneglycol) with chitosan [190]. 

Carrot, G. Scholz, S. M. Plummer, C. J. G. Hilbron, J. G. and Hedrick, L. J. (1999). Synthesis and Characterization of Nanoscopic Entitles Based on Poly(Caprolactone)-Grafted Cadmium Sulfide Nanoparticles. Chem. Mater., 11, 3571-3577. 

The generation of semicondnctor nanoparticles below spread monolayers was first reported by Fendler [134]. Poly(styrenephosphonate diethyl ester) and its 1 1 copolymer with... 

The use of a polymer monolayer to form LB films to be gas treated to form CdS nanoparticles has been reported [174]. The polymer use was poly (maleic anhydride) ester-... 

Steric stabilization is brought about by large organic molecules such as poly(A-vinyl-2-p5Trolidone) (PVP) that are firmly adsorbed on the surface of the nanoparticle [47,57]. Polymeric stabilizers establish many weak bonds with the nanoparticle s surface rather than forming less strong bonds at specific sites of the particles. This mode of stabilization has been shown to be very versatile (see Section 3.6). 

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... 

In Figure 12a (Pd Pt = 1 2) and 12b (Pd Pt = 1 1), only the spectral feature of CO adsorbed on the Pt atoms, i.e., a strong band at 2068 cm and a very weak broad band at around 1880 cm was observed, while that derived from CO adsorbed on Pd atoms at 1941 cm is completely absent, which proved that the Pd-core has been completely covered by a Pt-shell. Recently we also characterized Au-core/Pd-shell bimetallic nanoparticles by the CO-IR [144]. Reduction of two different precious metal ions by refluxing in ethanol/ water in the presence of poly(A-vinyl-2-pyrrolidone) (PVP) gave a colloidal dispersion of core/shell structured bimetallic nanoparticles. In the case of Pd and Au ions, the bimetallic nanoparticles with a Au-core/Pd-shell structure are usually produced. In contrast, it is difficult to prepare bimetallic nanoparticles with the inverted core/shell, i.e., Pd-core/Au-shell structure. A sacrificial hydrogen strategy is useful to construct the inverted core/shell structure, where the colloidal dispersions of Pd cores are treated with hydrogen and then the solution of the second element, Au ions, is slowly... 

Solla-Gullon et al. [Ill] carried out FT-IRs experiments of adsorbed CO for PdPt nanoparticles prepared by reduction of H2PtCl6 and K2PdCl4 with hydrazine in a w/o microemulsion of water/poly(ethyleneglycol) dodecyl ether (BRIJ(R)30)/ -heptane. The experiments gave information on the relative amount of linear- and bridge-bonded CO, which is known to depend on the surface distribution of the two elements. 

In 1989, we developed colloidal dispersions of Pt-core/ Pd-shell bimetallic nanoparticles by simultaneous reduction of Pd and Pt ions in the presence of poly(A-vinyl-2-pyrrolidone) (PVP) [15]. These bimetallic nanoparticles display much higher catalytic activity than the corresponding monometallic nanoparticles, especially at particular molecular ratios of both elements. In the series of the Pt/Pd bimetallic nanoparticles, the particle size was almost constant despite composition and all the bimetallic nanoparticles had a core/shell structure. In other words, all the Pd atoms were located on the surface of the nanoparticles. The high catalytic activity is achieved at the position of 80% Pd and 20% Pt. At this position, the Pd/Pt bimetallic nanoparticles have a complete core/shell structure. Thus, one atomic layer of the bimetallic nanoparticles is composed of only Pd atoms and the core is completely composed of Pt atoms. In this particular particle, all Pd atoms, located on the surface, can provide catalytic sites which are directly affected by Pt core in an electronic way. The catalytic activity can be normalized by the amount of substance, i.e., to the amount of metals (Pd + Pt). If it is normalized by the number of surface Pd atoms, then the catalytic activity is constant around 50-90% of Pd, as shown in Figure 13. 

After our success in preparation of the colloidal dispersions of Pt-core/Pd-shell bimetallic nanoparticles by simultaneous reduction of PdCl2 and H2PtCl6 in refluxing ethanol/water in the presence of poly(V-vinyl-2-pyrroli-done) [15,16] several reports have appeared on the formation of the core/shell-structured bimetallic nanoparticles by simultaneous reactions [5,52,68,183]. 

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.

Figure 3. Morphological distribution of Pt nanoparticles obtained by using (A) poly-NIPA (LCST = 37.5 °C) and (B) poly-NEA (LCST = 69.2 °C), at different temperatures.

A square and triangular Pt nanoparticle obtained by using poly-NIPA and poly-NEA, respectively, was observed by high resolution TEM (HRTEM) (JEM-2010F). The images (Figure 4) show a crystalline structure with clearly resolved lattice fringes. The square Pt nanoparticle... 

Figure 8. Comparison between catalytic properties of Pt(poly-crystalline)/Al203 (Engelhard) and Pt(l 00)/Al203 (morphologically controlled Pt nanoparticles) the NO/CH4 reaction conversion (X) and yield (Y), and the reaction products at 500 °C.

By using thermosensitive poly-acrylamides, it is possible to prepare cubic Pt nanocrystals (with predominant (1 0 0) facets) and tetrahedral Pt nanocrystals (rich in (111) facets). These Pt nanocrystals can be supported on oxide (alumina) and used as a catalyst in structure-sensitive reaction, NO reduction by CH4. The results proved that morphologically controlled metal nanoparticles supported on adequate support give us a novel tool to connect the worlds of surface science with that of real catalysis. 

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