Anodic oxidation of metals method

The character of the processes that take place on anodic dissolution is dependent on the nature of metal. Those that have high enough negative potentials to dissolve directly in alcohols (lanthanides, for example) need only some additional anodic potential to overcome the overvoltage. The electric current yields (i.e., the ratio of the amount of alkoxide formed and that calculated 

The appearance of the alkali alkoxide can lead to formation of bimetallic alkoxides or bimetallic alkoxide halides as impurities. For example, lithium oxoalkoxocomplexes were isolated as side products of the anodic dissolution of Mo and W when LiCl was used as conductive additive [908], 

The electrochemical technique can be used also for direct synthesis of bimetallic alkoxides. For instance, the anodic dissolution of rhenium in the methanol-based electrolyte that already contained MoO(OMe)4, permitted to prepare with a good yield (60%) a bimetallic complex RevMov,02(OMe)7, with a single Re-Mo bond [904], Application of the same procedure permitted the preparation of complex alkoxide solutions with controlled composition for sol-gel processing of ferroelectric films [1777]. 

It should be mentioned that by changing the conditions of electrochemical synthesis — such as nature of the alcohol, the purity of the metal used as anode, the nature and concentration of the conductive additive, the voltage (usually 30 — 110 V DC is applied), the temperature, and even the construction of the cell — one can significantly effect the process of the anodic dissolution or even change its mechanism. As it has already been mentioned, the electrochemical dissolution of iron in alifatic alcohols gives insoluble iron (II) alkoxides [1005], while in 2-methoxyethanol a soluble iron (HI) complex is obtained [1514], Another example is provided by tantalum dissolution in isopropanol while high-purity metal is rapidly dissolved anodically [1639], the one containing impurities is passivated. Therefore, it is quite clear that each synthesis requires careful study, optimization of parameters of electrochemical synthesis, and isolation and purification of final products. 

An important advantage of the electrochemical technique lies in its simplicity because metals are much easier to handle than metal halides and are always commercially available the consumption of the solvents is also much smaller than for conventional techniques [1639, 1612]. The electrochemical method allows the creation of a highly efficient, low-waste continuous process for commercial production of metal alkoxides [948]. 

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Recently, the anodic oxidation of metals (method 2) was also applied for the preparation of the niobium and tantalum derivatives of M(OR)5 series (R= Me, Et, Pr, Bu ) [1478, 1616, 1639]. It should be mentioned that a crystalline oxoisopropoxideTa20(OPri)g,iPrOH (Fig. 4.1 c), was isolated from the PrOH-based electrolyte. It is destroyed on heating in vacuo, yielding Ta(OPri)J. 

The metatheis of acetates with the alkali alkoxides (method 5) can be used for the preparation of the methoxides and ethoxides of all three elements and is the only reaction leading to Hg(OR)2 [1623]. The trans-esterification of Zn(OMe)2 (method 6), according to [1121], can be carried out only in the presence of LiOR (forming soluble bimetallic complexes). The direct electrochemical synthesis on the anodic oxidation of metals in alcohols has been described for Zn(OEt)2 and a series of cadmium derivatives (Cd(OR)2 — obtained in the presence of such donor ligands as Dipy, Phen, and Dmso [98]) (method 2). 

At present the most perspective and ecologically pure route appears to be the anodic oxidation of metal in alcohols in the presence of a conductive additive (method 2), and industrial technology has been developed in Russia for Ti(OBu )4 [948]. 

The main route to rhenium alkoxides is the interaction of halids and oxy-halids with alkali alkoxides or alcohols in presence of amines (method 5). As the important starting reagents can serve also Re2(CO),0 and Re207 (method 3) The preparation ofrhenium (V) and (VI) oxoderivatives by the anodic oxidation of metal in alcohols has also been described (method 2) (see Table 12.22). The bimetallic alkoxides ofrhenium and heavy transition metals can most efficiently be obtained by interaction ofrhenium (VII) oxide with the alkoxides ofthese elements in refluxing toluene ... 

Attempts to prepare In(II) halide complexes by this method are unsuccessful. Anodic oxidation of In metal produces In which disproportionates to the clement and In(II) halide complexes- . 

The electrochemical preparation of metal chalcogenide compounds has been demonstrated by numerous research groups and reviewed in a number of publications [ 1-3]. For the most part, the methods that have been used comprise (a) cathodic co-reduction of the metal ion and a chalcogen oxoanion in aqueous solution onto an inert substrate (b) cathodic deposition from a solvent containing metal ions and the chalcogen in elemental form (the chalcogens are not soluble in water under normal conditions, so these reactions are carried out in non-aqueous solvents) (c) anodic oxidation of the parent metal in a chalconide-containing aqueous electrolyte. 

The method nearest to electronic device fabrication is the nanoscale processing based on the anodic oxidation of semiconductors and metals. The following electrochemical reactions proceed after applying voltage between the probe and the substrate in the column of adsorbed water generated at the region between them in the air as shown in Fig. 17. 

The electronic absorption spectrum of the cation-radical of thiophene itself has been observed following low-temperature y-radiolysis of the heterocycle in a Freon matrix.The radical has also been implicated in the oxidation of thiophene by dibenzoyl peroxide it is believed to be formed at the contact of certain transition metal layer-silicates with thiophene.The anodic oxidation of 2,5-dimethylthiophene has been studied by Japanese workers who found strong evidence for the formation of the cation-radical as the primary oxidation product.In the presence of strong nucleophiles such as cyanide ion, the cation-radical undergoes nucleophilic attack before further oxidation. In the presence of more basic species such as acetate ion, the cation-radical is deprotonated to give a thienylmethyl radical which undergoes further reaction. The results were compared with similar observations for the oxidation of 2,5-dimethylfuran. Czech workers have also studied the anodic oxidation of substituted thiophenes. This work has focused on the preparative value of anodic oxidations in acidified methanol. Cation-radical formation is implied for the primary step, but the value of the method lies in the fact that sulfur is ultimately eliminated from the substrate and functionalized y-dicarbonyl compounds result. 

In contrast to the processes described above, the electrooxidation of metals and alloys still cannot be considered as an accepted electrosynthetic method as yet only its principal possibilities have been demonstrated. At the same time, the anodic oxidation of transition metals, which forms the basis for a number of semiconductor technologies, is extremely effective and convenient for varying and controlling the thickness, morphology, and stoichiometry of oxide films [233]. It therefore cannot be mled out that, as the concepts concerning the anodic behavior of metal components of HTSCs in various media are developed, new approaches will be found. The development of combined methods that include anodic oxidation can also be expected, by analogy with hydrothermal-electrochemical methods used for obtaining perovskites based on titanium [234,235], even at room temperature [236]. 

Oxyfluorocuprates of rare-earth metals with low concentrations of fluorine exhibit tht properties of HTSCs [364], By slightly fluorinating certain HTSC materials, one car enhance Tc, and the content of the superconducting phase [365], and reduce AT] [366,367]. Apparently, attempts are being made to synthesize the simplest HTSC oxyfluorides of the Sr2Cu03 xFx type [368] using the simpler method of anodic oxidation of copper in certain solutions. 

Electrochemical reactions serve as efficient and convenient methods for the synthesis of organoelemental compounds. There are four major methods for the formation of element (metal)-carbon bonds. The first method utilizes the anodic oxidation of organometallic compounds using reactive metal anodes. In the second method, the organic compounds are reduced using reactive metal cathodes. The third method involves the cathodic reduction of organic compounds in the presence of metal halides. The fourth one utilizes both the cathodic and the anodic processes. 

To avoid high-pressure drop and clogging problems in randomly packed micro-structured reactors, multichannel reactors with catalytically active walls were proposed. The main problem is how to deposit a uniform catalyst layer in the microchannels. The thickness and porosity of the catalyst layer should also be enough to guarantee an adequate surface area. It is also possible to use methods of in situ growth of an oxide layer (e.g., by anodic oxidation of a metal substrate [169]) to form a washcoat of sufficient thickness to deposit an active component (metal particles). Suzuki et al. [170] have used this method to prepare Pt supported on nanoporous alumina obtained by anodic oxidation and integrate it into a microcatalytic combustor. Zeolite-coated microchannel reactors could be also prepared and they demonstrate higher productivity per mass of catalyst than conventional packed beds [171]. Also, a MSR where the microchannels are coated by a carbon layer, could be prepared [172]. 

The anodic oxidation of carboxylic acids has also been carried out using a solid-supported base in methanol. Non-Kolbe-type electrolysis takes place to give the corresponding methoxylated product (Equation 12.7). The acid-base reaction between a carboxylic acid and a solid-supported base seems to reduce the cell voltage and makes the electrochemical reaction possible. Kolbe-type carbon-carbon coupling using aliphatic and benzylic carboxylic acids has also been accomplished using this method [26]. Based on a similar concept, anodic fluorination by an alkali metal... 

The application of photocurrent spectroscopy is not restricted to bulk semiconductors and insulator electrodes. The anodic oxidation of many metal electrodes produces surface films that are insulators or semiconductors, and in spite of the fact that these surface films are often very thin, their characterisation by photocurrent spectroscopy poses few experimental difficulties since photocurrents as small as 10 10 A can be measured by conventional lock-in methods. The instrumentation required for photocurrent spectroscopy is relatively modest and the technique is undemanding in terms of the degree of optical perfection of the electrode surface. Consequently, there seems to be considerable scope for the application of this type of spectroscopy to electrochemical problems such as corrosion, for example, where surface roughening may rule out methods that require an optically flat surface. 

Other methods, among which thermolysis or photolysis of tetrazene [59], photolysis of nitrosoamines in acidic solution [60], photolysis of nitrosoamides in neutral medium [61], anodic oxidation of lithium amides [62], tributylstannane-mediated homolysis of O-benzoyl hydroxamic derivatives [63, 64], and spontaneous homolysis of a transient hydroxamic acid sulfinate ester [65] could have specific advantages. The redox reaction of hydroxylamine with titanium trichloride in aqueous acidic solution results in the formation of the simplest protonated aminyl radical [66] similarly, oxaziridines react with various metals, notably iron and copper, to generate a nitrogen-centered radical/oxygen-centered anion pair [67, 68]. The development of thiocarbazone derivatives by Zard [5, 69] has provided complementary useful method able to sustain, under favorable conditions, a chain reaction where stannyl radicals act simply as initiators and allow transfer of a sulfur-containing... 

While the anodic oxidation of the zinc coating gives some protection to steel structures, the problems arising from the rusting of steel which is in prolonged contact with seawater are serious. A successful protective measure is to attach metal blocks to, for example, undersea pipelines, the metal being chosen so as to function as an anode in an electrochemical cell in which the seawater is the electrolyte and the Fe of the pipeline is forced to be the cathode. This method of protection (known as cathodic protection) is... 

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