Preparation of Noble Metal Colloids

PREPARATION OF NOBLE METAL COLLOIDS AND SELECTED STRUCTURES... 

The formation and stabilization of noble metal colloids in the aqueous phase are widely known. Platinum and palladium are most widely used in hydrogenation of C=C bonds but some results have been described with rhodium. Generally, surfactants are investigated as stabilizers for the preparation of rhodium nanoparticles for biphasic catalysis in water. In many cases, ionic surfactants, such as ammonium salts, which provide sufficiently hydrophilic character to maintain the catalytic species within the aqueous phase, are used. The obtained micelles constitute interesting nanoreactors for the synthesis of controlled size nanoparticles due to the confinement of the particles inside the micelle cores. Aqueous colloidal solutions are then obtained and can be easily used as catalysts. 

Kameo Azusa, Yoshimura Tomokazu, and Esumi Kunio. Preparation of noble metal nanoparticles in supercritical carbon dioxide. Colloids. Surf. A Physicochem. Eng. Asp. 215 no. 1-3 (2003) 181-189. 

In this chapter, we intend to introduce to the reader some of the most popular preparation methods of noble metal colloids, but do not intend by any means to thoroughly review the scientific literature on metal colloid synthesis. We have chosen examples of synthesis in aqueous and organic solvents, and differentiate between spherical and anisotropic nanoparticles (nanorods and nanoprisms). Additionally, in section 3 we shall describe one of the most popular recent procedures to assemble metal colloids into nanostructured materials (layer-by-layer assembly), as well as the properties of the resulting structures. 

Late transition metal or 3d-transition metal irons, such as cobalt, nickel, and copper, are important for catalysis, magnetism, and optics. Reduction of 3d-transition metal ions to zero-valent metals is quite difficult because of their lower redox potentials than those of noble metal ions. A production of bimetallic nanoparticles between 3d-transi-tion metal and noble metal, however, is not so difficult. In 1993, we successfully established a new preparation method of PVP-protected CuPd bimetallic nanoparticles [71-73]. In this method, bimetallic hydroxide colloid forms in the first step by adjusting the pH value with a sodium hydroxide solution before the reduction process, which is designed to overcome the problems caused by the difference in redox potentials. Then, the bimetallic species... 

The alkaline EG S5mthesis method is a very effective technology for the chemical preparation of unprotected metal and alloy nanoclusters stabilized by EG and simple ions. This method is characterized by two steps involving the formation of metal hydroxide or oxide colloidal particles and the reduction of them by EG in a basic condition. The strategy of separating the core formation from reduction processes provides a valid route to overcome the obstacle in producing stable unprotected metal nanoclusters in colloidal solutions with high metal concentrations. Noble metal and alloy nanoclusters such as Pt, Rh, Ru, Os, Pt/Rh and Pt/Ru nanoclusters with small particle... 

Sakka S., Kozuka H., Sol-gel preparation of coating fdms containing noble metal colloids, J. Sol-Gel Sci. Technol. 1998 13 701-705. 

Application of amphiphilic block copolymers for nanoparticle formation has been developed by several research groups. R. Schrock et al. prepared nanoparticles in segregated block copolymers in the sohd state [39] A. Eisenberg et al. used ionomer block copolymers and prepared semiconductor particles (PdS, CdS) [40] M. Moller et al. studied gold colloidals in thin films of block copolymers [41]. M. Antonietti et al. studied noble metal nanoparticle stabilized in block copolymer micelles for the purpose of catalysis [36]. Initial studies were focused on the use of poly(styrene)-folock-poly(4-vinylpyridine) (PS-b-P4VP) copolymers prepared by anionic polymerization and its application for noble metal colloid formation and stabilization in solvents such as toluene, THF or cyclohexane (Fig. 6.4) [42]. 

To maximize fluorophore excitation and increase the fluorescence quantum yield, the spectral properties of the metal nanoparticles need to be optimized. While spherical colloidal nanoparticles of noble metals have been well known for many years, it is only recently that there has been an explosion of reports on the preparation and properties of anisotropically-shaped materials. As will be discussed in the following sections, a wide range of morphologies can be produced, including triangular nanoplates (nanoprisms), cubes, octahedra, nanowires, nanorods and bi-pyramids. The last few years have also seen major developments in our understanding of the growth processes involved, so that now it is possible to prepare many types of shaped p>articles in a controlled fashion. 

Polymer-protected noble metallic colloids can be prepared by the one-step radiation-induced reduction of aqueous metallic ions with 2-propanol using y-irradiator or e-beam irradiator (see. Figures 19.1 and 19.2). In an aqueous solution, water molecules absorb the irradiation energy and generate many reactive species, such as solvated electrons (e q"), H, and OH" Equation 19.1... 

Sakka S, Kozuka H, Zhao G. Sol-gel preparation of metal particle/oxide nanocomposites. Sol-gel optics, vol. ni, J.D. Mackenzie, ed. SPIE Proc. 1994 2288 108-119 Sakka S., Kozuka H. Sol-gel preparation ofcoating films containing noble metal colloids. J. Sol-Gel Sci. Technol. 1998 13 701-705... 

The alkaline EG synthesis method described in this chapter is highly efficient for preparing colloidal solutions of small and narrowly distributed unprotected noble metal or alloy nanoclusters with high metal concentration. 

A new class of heterogeneous catalyst has emerged from the incorporation of mono- and bimetallic nanocolloids in the mesopores of MCM-41 or via the entrapment of pro-prepared colloidal metal in sol-gel materials [170-172], Noble metal nanoparticles containing Mex-MCM-41 were synthesized using surfactant stabilized palladium, iridium, and rhodium nanoparticles in the synthesis gel. The materials were characterized by a number of physical methods, showed that the nanoparticles were present inside the pores of MCM-41. They were found to be active catalysts in the hydrogenation of cyclic olefins such as cyclohexene, cyclooctene, cyclododecene, and... 

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