Mixed metal precipitates

The reaction is driven to completion by distilling the lower boiling alcohol. Metal methoxides are frequentiy insoluble and caimot be employed as starting materials in this reaction by the same token, they can be convenientiy prepared from solutions of higher alkoxides by precipitation with methanol. Alcoholysis also gives mixed metal alkoxides ... 

The anticancer agent Methotrexate (MTX) was conjugated with LDH by a coprecipitation method. To synthesize the MTX-LDH conjugate, powdered MTX was dissolved in decarbonated water, and titrated with NaOH (0.5 M) solution to give a 0.043 M solution of MTX at pH 7. The mixed metal solution of Mg(N03)2-6H20 and A1 (N03)3-9H20 with molar ratio Mg/Al = 2/1 was added to the MTX solution and the solution was titrated with NaOH solution until pH 9.5 to produce yellowish precipitates [7,26]. 

These reactions have been studied in detail for materials such as silica, and understanding of reaction mechanisms, as well as of the role of the precursor and catalyst (acid or base), has been well documented.63,64 Similar studies have been carried out in other material systems, most notably, lead zirconate titanate [Pb(Zr,Ti)03 PZT].52,65-68 For multicomponent (mixed-metal) systems such as those noted, prehydrolysis of less reactive alkoxides is sometimes employed to improve solution compositional uniformity. Other synthetic strategies to achieve molecular level mixing of reagents have also been employed. Here, synthesis of mixed-metal alkoxides has been a focus of investigators.40-42 A key point is to restrict the amount of water and to control how it is added to form solubalizable precursor species, rather than to induce precipitation.1,52,69,70... 

In some instances, this approach has proven successful, with comparatively low crystallization temperatures being observed. For example, Eichorst and Payne in the synthesis of LiNb03 noted crystallization temperatures of 400-500 °C for a mixed-metal alkoxide precursor.111 In other instances, these attempts have proven less successful. Numerous attempts have been made to synthesize Pb-Zr and Pb-Ti precursors, each with the 1 1 cation stoichiometry of the desired PbZr03 and PbTi03 compounds.83,84 Unfortunately, 1 1 stoichiometric ratio compounds have not always been obtained, with crystalline compounds of other stoichiometries precipitating from the solution, as illustrated in Fig. 2.11.83 This figure shows the crystal structure of PbTi2[p(4)—... 

In the case of MnO/ ( it is known to reduce on the surface of CNTs and graphene spontaneously to produce Mn02 NPs [182,183]. Solvothermal assisted precipitation of metal oxides can occur in milder solutions [184]. For example, mixed metal oxide NPs of CoFe204 have been deposited on GO from metallic salt precursors via the addition of ethanolamine followed by incubation at 180 °C in a sealed vessel [185]. Mixing GO with Cd2+ in DMSO followed by solvothermal treatment has been shown to both reduce GO to RGO and coat with CdS QDs [186]. 

For mixed metal oxides obtained from their hydroxide or carbonate precursors after calcination, it is generally difficult to determine whether the as-prepared precursor is a single-phase or multiphase solid solution [35]. Non-aqueous solvents appear superior for achieving two dissimilar metal oxides such as MM Oz or MM 04 precipitates such reactions cannot be carried out simultaneously in aqueous solution due to the large variations in pH necessary to induce precipitations [41,42]. Table 6.1 summarizes some of the nanoparticulate semiconducting metal oxides and mixed metal oxides prepared via co-precipitation techniques. The general procedure of achieving metal loaded nanoparticles on an oxide support is shown in Fig.6.5. 

Lime or caustic precipitation is the most commonly used method for treating aqueous wastes with non-complexed metals. Alkaline reagents such as lime, or caustic raises the pH of the wastewater and causes metals to precipitate out of the solution as metal hydroxides. For many metals there is a specific pH at which the metal hydroxide is least soluble, as shown in Figure 1. Because several metals co-exist in a waste in most cases, it is not possible to operate a treatment system at a single pH value that is optimum for all metal removals. As a compromise, a pH between 9.5 and 12.0 is maintained for typical mixed metals removal. A typical precipitation reaction is as follows ... 

Electronic parts makers, platers and other metal finishers require clean water rinses to remove plating chemicals from parts prior to the next process. The rinse water is sometimes expensive or in short supply. Furthermore, if the water is of poor quality, it must be pre-treated prior to use. The water is discarded after one use with conventional waste treatment, precipitation and clarification and a hazardous mixed metal sludge is generated which must be shipped to a hazardous waste landfill. 

In the Nippon Mining Company process,163 the aqueous feed consists of a solution of cobalt, nickel and other metal sulfates obtained by the high-pressure oxidative leaching of a mixed metal sulfide ore. Following the removal of iron and copper by chemical precipitation methods, and the successive extraction of zinc and cobalt by organophosphorus acid reagents (Section 63.3.2.2) under weakly acidic conditions, the pH value of the solution is adjusted to between 9 and 9.5 with ammonia, and nickel is extracted into a 25% solution of LIX 64N in an alkane solvent. 

The reaction is typically performed in diethyl ether, and the dication is precipitated as a red-brown solid or oil. Mixed-metal molybdenum-cobalt and tungsten-cobalt systems have also been obtained by this technique.75,76... 

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