Reduction of metal salts

Using electrons for the electrolytic reduction of metal salts, Reetz and coworkers have introduced a further variation to the tetraalkylammoniumhalide-stabilization mode [192-198]. The overall electrochemical process can be divided into the following steps (i) oxidative dissolution of the sacrificial Metbuik anode, (ii) migration of Met ions to the cathode, (iii) reductive formation of... 

On the other hand, one of the mildest chemical procedures is an alcohol reduction of metal salts in the presence of the protective agents [4,5]. The reaction proceeds according to the Equation (3). 

Chemical reduction of metal salts in solution is the most widely used method of preparation of metal nanoparticles, especially in laboratories. In general, the reducing reagents are added into the solution of the precursor ions, but in some cases, a solvent works as a reductant. Various reducing reagents have been proposed to prepare metal nanoparticles. Ethanol or small alcohols can reduce precious metal ions such as Au, Pt", Pd, Ag, and so on [3j. Polymer-stabilized precious metal nanoparticles and their alloy particles can be used as good catalysts for various reactions. Polyols, such as ethylene glycol, were... 

This mechanism is the same as that implicated in the sonochemical reduction of metal salts to metal colloids. 

Generation of Activated Metals via the Reduction of Metal Salts... 

This approach frequently leads to the most active metals as the relatively short reduction times at low temperatures leads to reduced sintering of the metal particles and hence higher reactivity. Fujita, et aL(62) have recently shown that lithium naphthalide in tqluepe can be prepared by sonicating lithium, naphthalene, and N, N, N, N-tetramethylethylene-diamine (TMEDA) in toluene. This allows reductions of metal salts in hydrocarbon solvents. This proved to be especially beneficial with cadmium(49). An extension of this approach is to use the solid dilithium salt of the dianion of naphthalene. Use of this reducing agent in a hydrocarbon solvent is essential in the preparation of highly reactive uranium(54). This will be discussed in detail below. 

Cobalt represents an interesting contrast to the many activated metal powders generated by reduction of metal salts. As will be seen, the cobalt powders are highly reactive with regard to several different types of reactions. However, in contrast to the vast majority of metals studied to date, it shows limited reactivity toward oxidative addition with carbon halogen bonds. 

Activated metals, generation via the reduction of metal salts, 223-225 Activation of transition metal slurries, mechanisms, 202 Addition reactions... 

Further mechanistic insights into hydrogenations catalyzed by HRuCl(PPh3)3 (7, p. 83) have been obtained indirectly, from studies on hydrogenation of some ruthenium(III) phosphine complexes (83). A frequently considered mechanism for hydrogen reduction of metal salts involves slow formation of an intermediate monohydride, followed by a faster reaction between the hydride and starting complex (/, p. 72), Eqs. (2) and (3) ... 

Ffirai and Toshima have published several reports on the synthesis of transition-metal nanoparticles by alcoholic reduction of metal salts in the presence of a polymer such as polyvinylalcohol (PVA) or polyvinylpyrrolidone (PVP). This simple and reproducible process can be applied for the preparation of monometallic [32, 33] or bimetallic [34—39] nanoparticles. In this series of articles, the nanoparticles are characterized by different techniques such as transmission electronic microscopy (TEM), UV-visible spectroscopy, electron diffraction (EDX), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) or extended X-ray absorption fine structure (EXAFS, bimetallic systems). The great majority of the particles have a uniform size between 1 and 3 nm. These nanomaterials are efficient catalysts for olefin or diene hydrogenation under mild conditions (30°C, Ph2 = 1 bar)- In the case of bimetallic catalysts, the catalytic activity was seen to depend on their metal composition, and this may also have an influence on the selectivity of the partial hydrogenation of dienes. 

A synthetic alternative to this is the chemical reduction of metal salts in the presence of extremely hydrophilic surfactants have yielded isolable nanometal colloids having at least 100 mg of metal per litre of water [105], The wide range of surfactants conveniently used to prepare hydrosols with very good redispersibility properties include amphiphilic betaines A1-A4, cationic, anionic, nonionic and even environmentally benign sugar soaps. Table 3.1 presents the list of hydrophilic stabilizers used for the preparation of nanostructured colloidal metal particles, and Table 3.2 shows the wide variety of transition metal mono- and bi-metallic hydrosols formed by this method [105,120],... 

The reduction of metal salts can also produce nanocarbon-QD hybrids [167]. CNT-Cd0 8Zn0 2S QD hybrids have been obtained by first adsorbing Cd2+ and Zn2+ ions onto oxidized MWCNTs followed by reduction via addition of Na2S to precipitate the QDs... 

Transition-metal nanopartides are of fundamental interest and technological importance because of their applications to catalysis [22,104-107]. Synthetic routes to metal nanopartides include evaporation and condensation, and chemical or electrochemical reduction of metal salts in the presence of stabilizers [104,105,108-110]. The purpose of the stabilizers, which include polymers, ligands, and surfactants, is to control particle size and prevent agglomeration. However, stabilizers also passivate cluster surfaces. For some applications, such as catalysis, it is desirable to prepare small, stable, but not-fully-passivated, particles so that substrates can access the encapsulated clusters. Another promising method for preparing clusters and colloids involves the use of templates, such as reverse micelles [111,112] and porous membranes [106,113,114]. However, even this approach results in at least partial passivation and mass transfer limitations unless the template is removed. Unfortunately, removal of the template may re-... 

It has been previously reported [21, 22] that metal colloids are formed by radiochemical reactions in water/alcohol solutions, in which the reduction of metal salts takes place by solvated electrons and free radicals produced under UV or y-ray irradiation. Ichikawa et al. have applied this photoreduction method to the surface-mediated reaction of metallic ions and succeeded in synthesizing metal/aUoy nanowires in the constrained cavities of mesoporous supports such as FSM-16 and MCM-41 [18-20, 23-25]. The adsorbed water and alcohol work not only as solvents in the nanoscale silica void space but also as a source of reducing species for metallic ions to metals under UV-vis and y-ray [11, 18, 19] irradiation. The results indicate the dense formation of Pt nanowires inside the charmels of mesoporous supports, such as FSM-16, which act as the templates. In fact, no any Pt wire is observed on the external surface of FSM-16 or amorphous silica surface. Short wires, 10 nm long, are also observed as a minor species in the samples in the initial stage of UV and y-ray irradiation. 

Alkali metal reductions of metallic salts using an arene as electron carrier, lithium being the most used metallic component (Rieke method) . Although not belonging to this group of metals, magnesium-anthracene has found some apphcations in the activation of other metals . 

Metal colloids can be prepared by reduction of metal salts in solution using CO, hydroxylamine, oxalic acid, formaldehyde, citric acid or sodium citrate. 

Brust et al. have developed methods to fabricate MPC and MMPC systems that rely on the reduction of metal salts (Pd, Au, Ag, Pt) in the presence of capping ligands.5 The approach uses mild conditions and moderate reducing agents that are compatible... 

Highly active platinum, palladium, and nickel catalysts also can be obtained by reduction of metal salts with sodium borohydride (NaBH4). 

New routes to high quality colloidal NCs of varying compositions and shapes appear in the literature almost on a weekly basis. The most successful of these approaches to crystalline semiconductor NCs with excellent optical properties share the same basic premise of pyrolysis of metal-organic precursors in solutions of hot coordinating solvents. In contrast, the syntheses of noble metal NCs typically rely on the reduction of metal salts in the presence of citrate ions (e.g. An or Ag), in two-phase systems (e.g. An or Ag), or under high-temperature conditions in the presence of stabilizing... 

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