Heterometallic neodymium (iii) and iron (iii) malate and a method for preparation thereof

FIELD: inorganic synthesis.

SUBSTANCE: invention provides heterometallic neodymium (III) and iron (III) malate having formula I:

appropriate for synthesis of mixed oxides with perovskite structure, which are used as catalysts in oxidative catalysis of unsaturated acyclic hydrocarbons and as materials used in microwave frequency technology and in computer memory materials. Preparation consists in electrolysis of concentrated aqueous solution of neodymium (III) chloride and malic acid at 1:3 ratio in presence of pyridine with pressed reduced iron anode and inert cathode at anode current density 1 A/cm2, followed by separating precipitate and washing it with organic solvent before drying.

EFFECT: enlarged assortment of oxidation catalysts.

2 cl, 1 dwg, 2 tbl

 

The invention relates to coordination chemistry, more specifically to obtaining heterometallic malate neodymium(III) and iron(III) formula 1

used to obtain mixed oxides with perovskite structure, widely used as catalysts in the oxidation catalysis of unsaturated acyclic hydrocarbons, and as materials in the technique of ultra-high frequencies and storage devices of the computer.

Known heteronuclear containing d-elements salicylideneaniline rare earth elements [Samus NM, Capcom VI, Khoroshun I., Petrenko P.A., ghoul A.P.// Coord. chemistry. 2000, t, No. 4, S-304], the General formula LnL3·M(NO3)2·nH2O, where Ln is a lanthanide ion (III), M is Co(II), Ni(II), L - ion salicilidentiosemicarbazido obtained by adding to a suspension containing 10 mmol of salicylideneaniline rare earth element 50 ml of purified chloroform, with constant stirring on a magnetic stirrer with 10 mmol of nitrate of cobalt(II) or nitrate Nickel(II), dissolved in minimum quantity of methanol, followed by heating at 50-55° With under reflux for 1.5-2.0 hours, cooling, filtering, washing with chloroform, drying in the vacuum over silica gel. Dedicated connections are used to obtain the mixed oxide is about a perovskite structure, however, due to the high cost of the original organic reagent obtain the specified product unprofitable.

Known basically heteronuclear acetate Fe(III) and Mg(II) [Fe2Mao(CH3Soo)6(H2O)3]· 2H2O [Antony C. Blake, Ahmad Yavari, William E. Hatfield, Sethulekshmi C.N.// J. Chem. Soc. Dalton trans 1985]obtained by adding to the solution of three-hydrate sodium acetate (11 g in 8 ml of water) solution of magnesium chloride (II) (0.01 mol and nitrate iron (III) 0.02 mol in 9 ml of water, Department of the red-brown precipitate in a day, by filtration, washing with alcohol and drying in air.

The closest analogue to the claimed connection are bridged sorption complexes of Ln(III)-Cr(III) General formula [Ln2(μ -Oh){SG(Di)(μ -Oh)(Oh)}4(H2O)6]· 13 H2O where Oh-oxalate-dianion, Ln=Pr,Gd, obtained by the interaction of the complex species [Cr(Dipy)(Ox)2]-ions Ln(III) in the presence of piperidine. [Zhang Xing, Cni Youg, Zhend Fakun, Huang Jinshun // Chem. Letl, 1999, No. 10, S-1112].

The above compounds are used to obtain mixed oxides with spinel structure, which, in contrast to mixed oxides with perovskite structure are not widely used in optoelectronics.

A method of obtaining heterometallic complex compounds with organic ligands, opisannym [garnovsky A.D., Vasilchenko, I.S., garnovsky D.A. Modern aspects of the synthesis of metallocomplexes. The main ligands and methods. Rostov-on-don, Lapo, 2000], which includes ion exchange reactions between the original reagents. The disadvantage is the impossibility of obtaining heterometallic malate iron(III) and neodymium(III) with malic acid as described above.

The closest analogue to the present method of production is a method of obtaining complex compounds with REE [U.S. Pat. 2191190 of the Russian Federation, IPC(7) C 07 F 5/00, C 07 C 49/92. The method of obtaining acetylacetonates of rare earth elements/ Vuepro, Wetpussy, Whiteleaf. No. 2001102640/04; Claimed 29.01.2001; Publ. 20.10.2002; Priority 29.01.2001 //BIPM. No. 29. - 4 S.], according to which the acetylacetonates REE General formula Ln(AA)3where Ln is a lanthanide ion and AA - acetylacetone, was obtained by electrolysis of acetylacetone and lithium chloride in acetonitrile, taken in the ratio 1:1:500) with rare earth metal anode and an inert cathode at a potential of the anode in the range of 0,5-1, using a single semiconductor diode, connected in series with the cell to create an asymmetric alternating current. The resulting electrolysis precipitate was separated, washed with absolute alcohol and dried.

The disadvantages of the prototype can be attributed to the impossibility of obtaining in the described conditions the heterometallic malate iron(III) and neodymium(III), besides the use of expensive solvent acetonitrile.

None of the proposed methods, the inventive compound of formula 1 has not been received.

An object of the invention is the obtaining of malate iron(III) and neodymium(III), the pyrolysis of which are formed mixed oxides with perovskite structure, a simple, one-step method.

To solve the technical problem is proposed by electrolysis of concentrated aqueous solution of neodymium chloride(III) and malic acid, taken in the ratio 1:3 in the presence of pyridine to the anode pressed from the restored iron, and an inert cathode and anode current density of 1 A/cm2, followed by separation of the precipitate, washing with an organic solvent and drying to obtain malate iron(III) and neodymium(III), General formula 1 NdFe(C4H4O5)3·5H2O.

The proposed method of obtaining differs from the closest analogue that allows you to isolate the compound described by formula 1, the electrolysis of a chloride solution of neodymium(III) and malic acid in a ratio of 1:3 in water instead of acetonitrile, in the presence of pyridine, with the anode pressed from the restored iron brand “hç : ” instead of the anode of the rare earth metal, the resulting solid product is separated, washed with ethyl alcohol and diethyl ether in the seat of absolute alcohol.

The drawing shows the circuit used to implement the inventive method.

The electrosynthesis of heterometallic malate neodymium(III) and iron(III) are as follows:

make the circuit (shown in the drawing)containing as a current source adjustable step-down transformer 1 at 220 V, the cell 2 is connected in series to the rectifier diode 3 series KD 226, ammeter 4 100 mA, the voltmeter 5 100 Century

The electrolyzer 2 composed of a glass vessel (thermostatted chemical glass (298 K), in which are placed two electrodes - one pressed from the restored iron, the other of platinum or graphite (not illustrated), is filled with electrolyte consisting of an aqueous solution of neodymium chloride(III) and malic acid, taken in the ratio 1:3, in the presence of pyridine.

The transformer 1 is set to the minimum output voltage, is included in the circuit AC 220 V 50 Hz and adjust so that the voltmeter 5 showed the voltage between the electrodes 1-20 In passing through the electrolytic cell 2 current should correspond to the anodic current density of 1 A/cm2calculated according to the indications of the ammeter 4. The use of a diode 3 allows you to simplify the procedure for obtaining an asymmetric current, which reduces the adhesion poluchaemoj the connection to the anode. The resulting electrolysis product was separated, washed with alcohol and diethyl ether and dried.

Specific example

The electrolyzer 2, provided with two electrodes - one pressed from the restored iron brand “hç : ” another of smooth platinum, filled with an electrolyte consisting of an aqueous solution of neodymium chloride(III) 0.3 M and malic acid 0.9 M in the presence of pyridine, was connected through the diode 3 to the transformer 1, set the voltage on the voltmeter 5 so that the density of the anode current, which is regulated by the readings of the ammeter 4, was 1 A/cm2, which was separated from the electrolysis precipitate was washed with ethyl alcohol and diethyl ether and air-dried to constant weight.

The metal content in the obtained compound was identified complexometrically: joint titration of iron(III) and neodymium(III) EDTA indicator selenology orange in urotropine buffer, in the presence of ascorbic acid; and the titration of iron(III) EDTA with sulfosalicylic acid to pH=2-3 with 70° s; content of neodymium(III) found by difference. For the determination of malate ions used ion exchange reaction between the compound and the cation exchange resin KU-2-8 followed by titration of malic acid and alkali with phenolphthalein. The ratio of the components in the connection SOS is avilo Fe:Nd: (C 4H4O5)=1:1:3. In addition, the complex compound contains 5 molecules of water. The individuality of the obtained compounds was confirmed by IR spectroscopy (see tab. 1) and by thermal method of analysis (see table 2).

The formula of the compound: NdFe(C4H4O5)3·5H2O

IR spectroscopic analysis method. The sample for recording the IR spectra of the prepared by pressing the investigated substances with KBR (10 mg to 200 mg total weight pill)

From the data of table 1 it follows that the absorption bands in the region 1700-1750 cm-1no, and in the field 1630-1500 cm-1appear, which indicates the formation of secondary salt.

Thermal analysis method. The heating rate of 10 deg/min, temperature range 20-1000° C.

Table 2
The data of thermal analysis NdFe(C4H4O5)3·5H2O
Δ T, °Ts°Δ m %Δ N
65-230 13.8 
230-2552455.3>0
255-325 6.4  
325-38534020.2>0
385-4504205.3>0
450-60056012.73>0
65-1000 63.78 

Thermal analysis showed that in the field 65-230° With NdFe(C4H4O5)3·5H2O loses water of crystallization, and at a temperature of about 300° goes into a mixed carbonate, at temperatures above 325° begins to decompose and 600° goes into the oxide.

Proposed one-step, simple electrochemical method for the synthesis of heterometallic malate iron(III) and neodymium(III). The proposed method offers the possibility of obtaining high purity of the desired product of formula 1 in one stage using more available and inexpensive reagents: pyridine instead of dipyridine, water instead of acetonitrile, chloride, neodymium(III) instead of metal neodymium, security, further method to obtain the desired product in the industry.

1. Heterometallic malate neodymium (III) and iron (III) formula 1

used to obtain the mixed oxide with structure the perovskite.

2. The method of obtaining the compounds described by formula 1, including the electrolysis of a solution of the initial components in specific proportions, with an inert cathode, anode current density of 1 A/cm2, sedimentation, washing and drying, characterized in that as starting components taken concentrated aqueous chloride solutions of neodymium (III) and malic acid in a ratio of 1:3 in the presence of pyridine to the anode pressed from the restored iron, washing was carried out with alcohol with diethyl ether.



 

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