Nanoparticles by reduction

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. 

Chen, M., Tang, B., and Nddes, D.E., Preparation of iron nanoparticles by reduction of P-FeOOH particles, IEEE Trans. Magn., 34, 1141, 1998. 

In our research we previously experienced the synthesis of Pd nanoparticles by reduction of Na2PdCl4 aqueous solutions in the presence of various stabilizing agents such as PVA (polyvinylalcohol), sodium citrate, PDDA (polydiallyl-... 

The formation of palladium nanoparticles by reduction with H2 in THF in the presence of a chiral diphosphine based on xylose (6.94) allowed small sized, monodispersed particles to be obtained . These Pd nanoparticles have proven to be good asymmetric catalysts for the CC coupling reaction in the alkylation of (rac)-3-acetoxy-l,3-diphenyl-1-propene by dimethylmalonate under basic conditions (Figure 6.72). 

D. Synthesis of Polymer-Immobilized Nanoparticles by Reductive Methods... 

Recent study described an efficient approach for the preparation of Rh(0) nanoparticles by reduction of RhCb with NaBH4 (scheme 2) followed by the stabilized by different isomers of bipyridine (scheme 3), the most used was 2,2 -bipyridine as ligand (Leger et al., 2008). These colloidal suspensions have shown interesting activities and selectivity for the hydrogenation of aromatic compounds in several non-aqueous ionic liquids according to the nature of the anion and cation fragments (scheme 2). 

Schematic diagrams for the synthetic schemes are illustrated in Fig. 15.5. To briefly summarize, silica nanoparticles were synthesized by the Stober-method and then coated with a Sn layer, which acts as a linker site for gold deposition. Gold layers were coated on the Sn-functionaUzed silica nanoparticles by reduction of HAuCLt. Finally, the gold-coated silica nanoparticles were covered...

Herein we briefly mention historical aspects on preparation of monometallic or bimetallic nanoparticles as science. In 1857, Faraday prepared dispersion solution of Au colloids by chemical reduction of aqueous solution of Au(III) ions with phosphorous [6]. One hundred and thirty-one years later, in 1988, Thomas confirmed that the colloids were composed of Au nanoparticles with 3-30 nm in particle size by means of electron microscope [7]. In 1941, Rampino and Nord prepared colloidal dispersion of Pd by reduction with hydrogen, protected the colloids by addition of synthetic pol5mer like polyvinylalcohol, applied to the catalysts for the first time [8-10]. In 1951, Turkevich et al. [11] reported an important paper on preparation method of Au nanoparticles. They prepared aqueous dispersions of Au nanoparticles by reducing Au(III) with phosphorous or carbon monoxide (CO), and characterized the nanoparticles by electron microscopy. They also prepared Au nanoparticles with quite narrow... 

The synthesis of bimetallic nanoparticles is mainly divided into two methods, i.e., chemical and physical method, or bottom-up and top-down method. The chemical method involves (1) simultaneous or co-reduction, (2) successive or two-stepped reduction of two kinds of metal ions, and (3) self-organization of bimetallic nanoparticle by physically mixing two kinds of already-prepared monometallic nanoparticles with or without after-treatments. Bimetallic nanoparticle alloys are prepared usually by the simultaneous reduction while bimetallic nanoparticles with core/shell structures are prepared usually by the successive reduction. In the preparation of bimetallic nanoparticles, one of the most interesting aspects is a core/shell structure. The surface element plays an important role in the functions of metal nanoparticles like catal5dic and optical properties, but these properties can be tuned by addition of the second element which may be located on the surface or in the center of the particles adjacent to the surface element. So, we would like to use following marks to inscribe the bimetallic nanoparticles composed of metal 1, Mi and metal 2, M2. 

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]. 

Shanker et al. [120] prepared bimetallic Au-core/ Ag-shell nanoparticles by the simultaneous reduction of Au(III) and Ag(I) ions in the presence of neem (Azadirachta indica) leaf broth as an extracting agent. 

Michaelis and Henglein [131] prepared Pd-core/Ag-shell bimetallic nanoparticles by the successive reduction of Ag ions on the surface of Pd nanoparticles (mean radius 4.6 nm) with formaldehyde. The core/shell nanoparticles, however, became larger and deviated from spherical with an increase in the shell thickness. The Pd/Ag bimetallic nanoparticles had a surface plasmon absorption band close to 380 nm when more than 10-atomic layer of Ag are deposited. When the shell thickness is less than 10-atomic layer, the absorption band is located at shorter wavelengths and the band disappears below about three-atomic layer. 

Vinodgopal et al. prepared Pt/Ru bimetallic nanoparticles by sonochemical reduction of Pt(II) and Ru(III) in aqueous solutions. TEM images indicated that sequential reduction of the Pt(II) followed by the Ru(III) produced Pt-core/Ru-shell bimetallic nanoparticles. In the presence of sodium dodecyl sulfate (SDS), as a stabilizer, the nanoparticles had diameters between 5 and 10 nm. When PVP was used as the stabilizer, the rate of reduction is much faster, giving ultrasmall bimetallic nanoparticles of ca. 5nm diameter [141]. 

Kan et al. reported preparation of Au-core/Pd-shell bimetallic nanoparticles by successive or simultaneous sonochemical irradiation of their metal precursors in ethylene glycol, respectively. In the successive method, Pd clusters or nanoparticles are first formed by reduction of Pd(N03)2, followed by adding HAUCI4 solution. As a result, Au-core/Pd-shell structured particles are formed, although Pd-core/Au-shell had been expected. In their investigations, the successive method was more effective than the simultaneous one in terms of the formation of the Au-core/Pd-shell nanoparticles [143]. 

In 1993, we examined formation processes of PVP-protected AuPt bimetallic nanoparticles by in-situ UV-Vis spectroscopy during the reduction [53]. Figure 8 shows the in-situ UV-Vis spectra during the simultaneous reduction of Au(III) and Pt(IV) ions. In the case of PVP-protected AuPt bimetallic system, Au(III) ions are... 

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]. 

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