Colloid salt reduction

The reduction of transition metal salts in solution is the most widely practiced method for synthesis of metal colloidal suspensions [7]. In the preparation process, polymer is often used in order to prevent the agglomeration of metal particles as well as to control their size. Ahmadi et al. [5] reported that the concentration of the capping polymer affects the shape of platinum particles obtained by salt reduction. This means that the addition of a... 

The main advantage of the salt reduction method in the liquid phase is that it is reproducible and allows colloidal nanoparticles with narrow size distribution to be prepared. 

More direct and successful methods for the preparation of non-aqueous metal sols are desirable. Especially valuable would be a method that avoids the metal salt reduction step (and thus avoids contamination by other reagents), avoids electrical discharge methods which decompose organic solvents, and avoids macromolecule stabilization. Such a method would provide pure, non-aqueous metal colloids and should make efficient use of precious metals employed. Such colloids would be valuable technologically in many ways. They would also be valuable to study so that more could be learned about particle stabilization mechanisms in non-aqueous media, of which little is known at the present time. 

Figure 3.1 Formation of nanostructured metal colloids via the salt reduction method. (Adapted from Maase, M., Neue Methoden zur grolJen- und formselektiven Darstellung von Metallkolloiden., Ph.D. thesis, Bochum, Germany, 1998.)...

There are several bottom-up methods for the preparation of nanoparticles and also colloidal nanometals. Amongst these, the salt-reduction method is one of the most powerful in obtaining monodisperse colloidal particles. Electrochemical methods, which gained prominence recently after the days of Faraday, are not used to prepare colloidal nanoparticles on a large scale [26, 46], The decomposition of lower valent transitional metal complexes is gaining momentum in recent years for the production of uniform particle size nanoparticles in multigram amounts [47,48],... 

The design of the interstices filling in colloidal crystals with appropriate media and subsequently fluid-solid transformation is central to the whole synthesis. Fluid precursors in the voids of crystal arrays can solidify by polymerization and sol-gel hydrolysis. More recently, many methods have been developed including salt precipitation and chemical conversion, chemical vapor deposition (CVD), spraying techniques (spray pyrolysis, ion spraying, and laser spraying), nanocrystal deposition and sintering, oxide and salt reduction, electrodeposition, and electroless deposition. 

Figure 3 Formation of nanostructured metal colloids via the salt-reduction method. (From Ref. 42a.)...

Reductions often pose scale-up concerns. The primary difficulty is that hydrogen is used or generated, which requires additional considerations and equipment for safe handling. At the end of a reaction, safely quenching any residual reducing capability is a concern on scale. Work-up can be tedious, especially if colloidal salts are formed. Disposing of metal salt by-products can be costly, and environmental concerns arise. Considerable attention to details is necessary to develop a reliable reduction for scale-up. In spite of these potential drawbacks, once the process has been developed and the appropriate equipment has been commissioned, reductions can be extremely reliable. 

The ceric salts are derivatives of Ce02> which is feebly basic. As a consequence they are considerably hydrolyzed in solution and give an acid reaction. Normal ceric salts of weak adds are unknown, and even the chloride and nitrate are known only as double or complex salts. Reduction to cerous compounds is easily done in acid solution, but much more difficult to accomplish in alkaline media, Ceric compounds easily form colloidal solutions which do not appear to be basic salts of the ordinary type. 

The radiation method was described by Rogninski and Schalnikoff for the first time and is based on condensation of the metal atoms after collision [154]. Reetz et al. prepared nanoparticles via electrochemical synthesis [155]. Salt reduction was developed by Bonnemann to obtain mono- and bi-metallic nanoparticles in solution [156]. Salt reduction is the most widely practised method for the synthesis of colloidal metal suspensions. Faraday synthesised gold particles by the reduction of HAuCb [157]. 

A survey of the literature reveals that many of the various methods reported for the preparation of colloidal metal are applicable to a number of metals across the periodic table. For example, salt reduction using main group hydride redudng agents, or metal vapor routes, have been used for many metals in turn. It is not the goal of this section to provide a directory of all the reports on colloid syntheses, but only to give examples of the principal types of preparative methods which can be used. 

Palladium catalysts have been prepared by fusion of palladium chloride in sodium nitrate to give palladium oxide by reduction of palladium salts by alkaline formaldehyde or sodium formate, by hydrazine and by the reduction of palladium salts with hydrogen.The metal has been prepared in the form of palladium black, and in colloidal form in water containing a protective material, as well as upon supports. The supports commonly used are asbestos, barium carbonate, ... 

Effluent pretreatment is necessary when RO is used as tertiary treatment in order to prevent membranes filters form being blocked or abraded. UF offers a powerful tool for the reduction of fouling potential of RO/NF membranes [57]. A typical pretreatment consist of a MF allowing the removal of the large suspended solids form the WWTP effluent followed by UF unit which removes thoroughly suspended solids, colloidal material, bacteria, viruses and organic compounds from the filtrated water. The UF product is sent to the RO unit where dissolved salts are removed. 

The use of tetraoctylammonium salt as phase transfer reagent has been introduced by Brust [199] for the preparation of gold colloids in the size domain of 1-3 nm. This one-step method consists of a two-phase reduction coupled with ion extraction and self-assembly using mono-layers of alkane thiols. The two-phase redox reaction controls the growth of the metallic nuclei via the simultaneous attachment of self-assembled thiol monolayers on the growing clusters. The overall reaction is summarized in Equation (5). 

As alternatives to amphiphilic betaines, a wide range of cationic, anionic, and non-ionic surfactants including environmentally benign sugar soaps have been successfully used as colloidal stabilizers [201]. Electrochemical reduction of the metal salts provides a very clean access to water soluble nanometal colloids [192]. 

PVP, a water soluble amine-based pol5mer, was found to be an optimum protective agent because the reduction of noble metal salts by polyols in the presence of other surfactants often resulted in non-homogenous colloidal dispersions. PVP was the first material to be used for generating silver and silver-palladium stabilized particles by the polyol method [231-233]. By reducing the precur-sor/PVP ratio, it is even possible to reduce the size of the metal particles to few nanometers. These colloidal particles are isolable but surface contaminations are easily recognized because samples washed with the solvent and dried in the air are subsquently not any more pyrophoric [231,234 236]. 

A strategy to solve this problem is to separate the core formation process from the reduction of metal ions in the cores as shown in Scheme 1, and use solvent (EG) and simple ions (OH , etc.) as the stabilizers [11]. In the first step of this process, metal salts hydrolyzed in the alkaline solution of EG to give rise to metal hydroxide or oxide colloids, which were then reduced by EG at elevated temperature to produce colloidal metal nanoclusters in the... 

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