JPH07315847A - Production of lanthanum-based perovskite-type multiple oxide - Google Patents

Abstract

PURPOSE:To obtain the subject homogeneous and highly active multiple oxide by homogeneously mixing a lanthanum alkoxyalcoholate and specific metal alkoxyalcoholate(s) with an organic solvent followed by heating and baking. CONSTITUTION:This lanthanum-based perovskite-type multiple oxide of formula IV (0<(x)<=1) is obtained, without generating any offensive odor, by heating and baking a mixed solution, a mixture of (A) a lanthanum alkoxyalcoholate of formula I [IR<1> is H or a lower alkyl; R<2> is a lower alkyl; (a) is 1-3], (B) at least one kind of metal alkoxyalcoholate of formula II (B is Mg, Cr, Mn, Fe, Co, Ni, Cu or Zn), (C) an organic solvent, and, optionally, (D) another metal alkoxyalcoholate of formula III [A is Sc, Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr or Ba; (s) is 2-3]}.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a lanthanum-based perovskite complex oxide, and more specifically, as an electrode material for a high temperature solid electrolyte fuel cell, a separator for the battery, an interconnector for the battery, and the like. Alternatively, the present invention relates to a method for producing a lanthanum-based perovskite complex oxide that can be widely used as a catalyst for purifying exhaust gas such as NOx, a high-temperature combustion catalyst, or a ceramics sensor.

[0002]

BACKGROUND OF THE INVENTION Conventionally, several methods for producing a composite oxide powder are known as shown below. (1) The most general method is to mix the oxides of the constituent components of the composite oxide in a predetermined amount ratio, or to mix the precursor of the composite oxide in a predetermined amount ratio, A method (solid-phase reaction method) in which pulverization is repeated after heat treatment is performed is described. This method is excellent in versatility, but this method can only obtain a powder having a small specific surface area and low activity. (2) A method for producing a complex oxide powder having a relatively large specific surface area is as follows. After evaporating and drying a mixed solution consisting of metal acetate constituting each site of the complex oxide,
A thermal decomposition method of acetate, which is a heat treatment at a temperature of about 0 ° C., is widely used. This method is excellent in versatility, and a powder having a relatively large specific surface area is obtained by this method.

In addition, a method of using a hydroxyl group-containing organic acid such as citric acid or malic acid in the production of a composite oxide has been proposed, and it is said that a powder having a considerably large specific surface area can be obtained by this method. ing.

However, in the method for producing a composite oxide using an organic acid such as acetic acid, citric acid, malic acid, etc., however, an offensive odor or a corrosive gas is generated due to the thermal decomposition of the acetate salt at a high temperature. Occurs and there is a problem in the work environment. (3) Japanese Patent Application Laid-Open No. 4-254419 discloses that "at least one element if A site is selected from La, Ce, and Gd,
The precursor of the complex perovskite type oxide represented by the general formula ABO _{3 in} which the B site is occupied by at least one element selected from Mn, Fe, Co, Ni and Cu, or the complex perovskite type oxide, In the method for producing a precursor of an Sr-substituted complex perovskite type oxide in which half or less of the metal elements of Sr are replaced with Sr, one or more of the elements constituting the both type oxides are mixed in the form of a metal salt. A method for producing a complex oxide precursor, which comprises mixing with one or more kinds selected from a polyhydric alcohol and a polyhydric alcohol derivative, or mixing in the presence of a solvent capable of dissolving the same.

In this method, unlike the above method (2),
No offensive odors or corrosive gases are generated and the working environment is not polluted. However, according to this method (3), when the La-based perovskite-type composite oxide is produced, the general formula: AB
Mn, Co, Ni, Cu, etc., which are the constituent elements of the B site in the complex oxide represented by O ₃ , are dissolved in an organic solvent in the presence of a polyhydric alcohol in the form of a metal alkoxide. The metal alkoxide obtained from the polyhydric alcohol is generally hardly soluble in an organic solvent, and a uniform mixed solution of these metal alkoxides has not been obtained. (4) Japanese Patent Laid-Open No. 3-285827 discloses that "containing two or more kinds of metal components, at least one of which is Mg, Sr,
In producing a composite oxide of Zn or La,
General formula: M (OC _m H _2m OC _n H _{2n + 1} ) _x [where M is M
represents one selected from the group consisting of g, Sr, Zn and La, m and n are each an integer of 1 or more and 5 or less, and x is x = 2 (when M = Mg, Sr or Zn). ,
It is an integer that satisfies X = 3 (when M = La). ] Preparing a raw material solution containing a metal alkoxide and another metal component, and subjecting a gelled product of the raw material solution to a heat treatment to form the complex oxide. Method for producing oxide ”. (5) Further, JP-A-5-80404 discloses that "at least one rare earth metal alkoxide, alkaline earth metal alkoxide, and transition metal alkoxide excluding rare earth elements are treated with ethanolamine and / or an organic solvent in an organic solvent. A method for producing a complex oxide precursor, which comprises reacting with an amide and then hydrolyzing each alkoxide by reaction with water to produce a complex oxide precursor ”.

However, there is a problem in that a complex oxide having sufficiently excellent uniformity has not been obtained by any of the methods described in (1) to (5) above.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has excellent uniformity.
It is an object of the present invention to provide a method for producing a lanthanum-based perovskite-type composite oxide that can obtain an La-based perovskite-type composite oxide having a single crystal phase with almost no offensive odor during production.

[0008]

SUMMARY OF THE INVENTION A first method for producing a lanthanum-based composite perovskite type oxide according to the present invention is represented by (i) a lanthanum alkoxy alcoholate represented by the following general formula [I] and a general formula [III] below. One or more metal alkoxy alcoholates and an organic solvent, or (ii) a lanthanum alkoxy alcoholate represented by the following general formula [I] and a metal alkoxy alcoholate represented by the following general formula [II], One or more kinds of metal alkoxy alcoholates represented by the following general formula [III] and an organic solvent are uniformly mixed, and the obtained alkoxy alcoholate mixed solution is heated and calcined. A lanthanum-based perovskite complex oxide represented by the following general formula [IV] is obtained. (a) General formula [I]:

[0009]

[Chemical 5]

[In the formula, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and a is 1 to 3
Indicates an integer. ] (B) General formula [II]:

[0011]

[Chemical 6]

[Wherein A is Sc, Y, Ce, Pr, N
d, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
The metal of any one of m, Yb, Lu, Ca, Sr, and Ba is shown, and R ¹ , R ^2, and a are the same as above. s is 2
Indicates an integer of 3. ] (C) General formula [III]:

[0013]

[Chemical 7]

[In the formula, B is Mg, Cr, Mn, Fe, C
O, Ni, Cu, or Zn, and R
¹ , R ² and a are the same as above. s shows the integer of 2-3. ] (D) General formula [IV]:

[0015]

[Chemical 8]

[Where A is Sc, Y, Ce, Pr, N
d, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
m, Yb, Lu, Ca, Sr, or Ba is a metal, and B is Mg, Cr, Mn, Fe, Co, Ni,
One or more metals selected from Cu and Zn are shown, and x is a number of 0 <x ≦ 1. The second method for producing a lanthanum-based perovskite-type composite oxide according to the present invention is (i) the lanthanum alkoxy alcoholate represented by the general formula [I] and the general formula [II]
[I] represented by one or more kinds of metal alkoxy alcoholates and an organic solvent, or (ii) the lanthanum alkoxy alcohol represented by the general formula [I] and the general formula [II]. The metal alkoxy alcoholate, one or more metal alkoxy alcoholates represented by the general formula [III], and an organic solvent are uniformly mixed to prepare an alkoxy alcoholate mixed solution, and then the obtained mixture is mixed. The method is characterized in that the alkoxy alcoholate in the solution is hydrolyzed and then heated and calcined, whereby a lanthanum-based perovskite complex oxide represented by the above general formula [IV] is obtained.

The alkoxy alcoholate mixed solution for producing the lanthanum-based perovskite complex oxide according to the present invention comprises (i) a lanthanum alkoxy alcoholate represented by the general formula [I] and a general formula [III]. One or more kinds of metal alkoxy alcoholates and an organic solvent, or (ii) a lanthanum alkoxy alcoholate represented by the general formula [I] and a metal alkoxy alcoholate represented by the general formula [II]. , One or more metal alkoxy alcoholates represented by the above general formula [III], and an organic solvent.

In the above first and second production methods and the above alkoxy alcoholate mixed solution according to the present invention, A in the above formulas [II] and [IV] is Y, Ce, S.
It is preferable to indicate any metal of m, Ca, Sr and Ba. Also, the above formulas [I], [II] and [III]
In the above, R ¹ is particularly preferably a hydrogen atom or a methyl group, R ² is particularly preferably a chain alkyl group having about 1 to 6 carbon atoms, and a is particularly preferably 1.

According to the method for producing a lanthanum-based perovskite-type composite oxide according to the present invention as described above, a La-type perovskite-type composite oxide having excellent uniformity and having a single crystal phase produces an offensive odor during production. It can be obtained with almost no occurrence.

The alkoxy alcoholate mixed solution for producing the above lanthanum-based perovskite type complex oxide is uniform and stable for a long period of time. By using this mixed solution as a raw material, the method as described above is obtained. Thus, it is possible to produce a lanthanum-based perovskite-type composite oxide having excellent uniformity and a single crystal phase.

The lanthanum-based perovskite-type composite oxide obtained by such a method is also used as a raw material for producing thin films, fibers, coating materials and the like. Thin films, fibers, coating materials, etc. obtained from this lanthanum-based perovskite-type composite oxide include phosphors, catalysts (eg, exhaust gas purification catalysts such as NOx, high-temperature combustion catalysts), ceramics (eg, ceramics sensors),
It can be expected to be used in a wide range of fields as an optical glass, an abrasive, a magnet, a functional electronic material (eg, electrode material for high temperature solid electrolyte fuel cell, separator for the battery, interconnector for the battery) and the like.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The method for producing the lanthanum-based perovskite complex oxide according to the present invention will be specifically described below. In the description below, for example, a compound represented by the formula [I] may be represented as “compound [I]”. [First Method for Producing Lanthanum-based Perovskite Complex Oxide] In the present invention, (i) a lanthanum alkoxy alcoholate represented by a specific formula as described below [I]
And one or more kinds of metal alkoxy alcoholates [III] represented by a specific formula and an organic solvent are uniformly mixed, and the resulting alkoxy alcoholate mixed solution is heated and calcined, or (ii) ) A lanthanum alkoxy alcoholate [I] represented by a specific formula, a metal alkoxy alcoholate [II] represented by a specific formula, and one or two compounds represented by a specific formula as described below.
A lanthanum-based perovskite complex oxidation represented by a specific formula as described below is obtained by uniformly mixing one or more kinds of metal alkoxy alcoholates [III] and an organic solvent, and heating and baking the resulting alkoxy alcoholate mixed solution. Manufacture thing [IV].

The first method for producing the lanthanum-based perovskite complex oxide will be described below in detail. Lanthanum Alkoxy Alcoholate The lanthanum alkoxy alcoholate used in the present invention is represented by the following general formula [I]. (a) General formula [I]:

[0024]

[Chemical 9]

In the formula [I], R ¹ represents a hydrogen atom or a lower alkyl group. As the lower alkyl group, specifically,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. Examples thereof include chain-like or branched-chain alkyl groups. Of these, R
¹ is particularly preferably a hydrogen atom or a methyl group.

R ² represents a lower alkyl group similar to R ¹ ,
It may be the same as or different from R ¹ . a is 1 to 3
Is particularly preferable and 1 is particularly preferable. As the lanthanum alkoxy alcoholate represented by the formula [I], specifically, for example, R ¹ is hydrogen,
La (OC ₂ H ₄ O in which R ² is an ethyl group and a is 1
C ₂ H ₅ ) ₃ , R ¹ is hydrogen, R ² is a methyl group,
In addition to La (OC ₂ H ₄ OCH ₃ ) ₃ in which a is 1, La [O
_{CH (CH 3) CH 2 OCH} 3] 3, La [OCH (C
_{H 3) CH 2 OC 2 H} 5] 3, La (OC 4 H 8 OCH 3) 3,
La [OC ₂ H ₄ On-C ₄ H ₉ ] ₃ , La [OCH (C
₄ H ₉ ) CH ₂ OC ₅ H ₁₁ ] ₃ , La [OCH (C ₆ H ₁₃ ) C
Such as _{H 2 OC 6 H 13] 3} , La [OC 2 H 4 On-C 6 H 13] 3 and the like. Metal Alkoxy Alcoholate [II] The metal alkoxy alcoholate [II] optionally used in the present invention is represented by the following general formula. (b) General formula [II]:

[0027]

[Chemical 10]

In the formula [II], A is a rare earth metal scandium (Sc), yttrium (Y), cerium (C).
e), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (D)
y), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), alkaline earth metal calcium (Ca), strontium (Sr) and barium (Ba) Indicates either metal. Among these, A represents any one of yttrium (Y), cerium (Ce), samarium (Sm), alkaline earth metal calcium (Ca), strontium (Sr), and barium (Ba). It is preferable.

R¹, R²And a are the same as above. s
Represents an integer of 2 to 3. This is represented by the formula [II]
Specific examples of the metal alkoxy alcoholate
Is, for example, A is Sr and R¹Is hydrogen and R²But
A methyl group, a is 1 and s is 2 Sr (O
C₂H_FourOCH₃)₂In addition to Sr (OC₂H_FourOC ₂H_Five)₂,
Sr [OCH (CH₃) -CH₂OCH₃]₂Etc.
It

Metal Alkoxy Alcohol wherein A is Ca
As [II], Ca (OC₂H_FourOCH₃)₂, Ca
(OC₂H_FourOC₂H_Five)₂, Ca [OCH (CH₃) -CH₂
OCH ₃]₂Etc., and a metal alkoxide in which A is Ba
As the sialcholate [II], Ba (OC₂H_FourOCH
₃)₂, Ba (OC₂H_FourOC₂H_Five)₂Etc., A is
As a metal alkoxy alcoholate [II] that is Ce
Is Ce (OC₂H_FourOCH₃)₃, Ce [OCH₂CH₂O
C₂H_Five]₃, Ce [OCHCH₃CH₂OCH₃]₃Etc.
The metal alkoxy alcoholate [I
I] is Y (OC₂H_FourOCH₃)₃, Y (OC₂H_Four
OC₂H_Five)₃Etc., and metal alcohol in which A is Sm
As the xyl alcoholate [II], Sm (OC₂H_FourOC
₂H_Five)₃, Sm [OCH (CH₃) -CH₂OCH₃]₃Etc.
Can be mentioned.

A is Sc, Pr, Nd, Eu, Gd, T
b, Dy, Ho, Er, Tm, Yb, Lu
As rucoxy alcoholate [II], Pr [OCH₂
CH₂OC₂H_Five]₃, Nd [OCH₂CH₂OC₂H_Five]₃,
Eu [OCH₂CH₂OiC₃H₇] ₃, Gd [OCH₂CH
₂OC₂H_Five]₃, Tb [OCH₂CH₂OC₂H_Five]₃, Dy
[OCH₂CH₂OC₂H_Five]₃, Ho [OCH₂CH₂OC₂
H_Five]₃, Tm [OCH₂CH₂OC₂H_Five]₃, Yb [OC
H₂CH₂OC₂H_Five]₃, Lu [OCH₂CH₂OC
₂H _Five]₃, Er (OC₂H_FourOCH₃)₃, Sc (OC₂H_Four
OC₂H_Five)₂Etc.Metal alkoxy alcoholate [III] Metal alkoxy alcoholates used in the present invention
[III] is represented by the following general formula. (c) General formula [III]:

[0032]

[Chemical 11]

In the formula [III], B is magnesium (M
g), chromium (Cr), manganese (Mn), iron (F
e), cobalt (Co), nickel (Ni), copper (C
u) and zinc (Zn),
R ¹ , R ² , a and s are the same as above, and the preferable ones are also the same as above.

Specific examples of the metal alkoxy alcoholate represented by the formula [III] include, for example,
B is magnesium (Mg), R ¹ is hydrogen,
R ² is a normal butyl group, a is 1 and s is 2
In addition to Mg (OC ₂ H ₄ On-C ₄ H ₉ ) _{2 which} is
₂ H ₄ OC ₂ H ₅ ) _{2 and the} like.

The metal alkoxy alcoholate [III] in which B is Co (cobalt) includes Co (OC ₂ H ₄ OC
_{H 3) 2, Co [OCH} (CH 3) -CH 2 OCH 3] 2 _{other, Co (OC 2 H 4 OC} 2 H 5) 2, Co (OC 2 H 4 On
-C ₄ H _{9) 2} and the like.

The metal alkoxy alcoholate [III] in which B is Mn includes Mn (OC ₂ H ₄ OCH ₃ ) ₂ and M.
n (OC ₂ H ₄ OC ₂ H ₅ ) ₂ , Mn [OCH (CH ₃ ) -C
H ₂ OCH ₃ ] _{2 and the} like, and the metal alkoxy alcoholate [III] in which B is chromium (Cr) includes Cr.
(OC ₂ H ₄ OC ₂ H ₅ ) ₃ , Cr [OCH (CH ₃ ) -CH _{2
OCH 3] 3, Cr (OC} 2 H 4 On-C 4 H 9) 3 and the like, B as a copper (Cu) metal alkoxy alcoholate [III] _{is, Cu (OC 2 H 4 On} -C ₄ H ₉ ) ₂ ,
Cu [OCH (CH ₃ ) -CH ₂ OCH ₃ ] _{2 and the} like can be mentioned, and as the metal alkoxy alcoholate [III] in which B is zinc (Zn), Zn (OC ₂ H ₄ OCH ₃ ) ₂ , Z
n (OC ₂ H ₄ OC ₂ H ₅ ) _{2 and the} like. Examples of the metal alkoxy alcoholate [III] in which B is nickel (Ni) include Ni (OC ₂ H ₄ OC ₂ H ₅ ) ₂ and Ni [OCH
(CH ₃ ) -CH ₂ OCH ₃ ] _{2 and the} like, and B is iron (F
Examples of the metal alkoxy alcoholate [III] which is e) include Fe (OC ₂ H ₄ OC ₂ H ₅ ) ₃ and Fe [OCH (C
_{H 3) -CH 2 OCH 3]} 3 and the like. Preparation of Alkoxy Alcoholate Mixed Solution In the present invention, (i) whether the lanthanum alkoxy alcoholate [I] as described above, one or more metal alkoxy alcoholates [III], and an organic solvent are uniformly mixed Or (ii) the lanthanum alkoxy alcoholate [I] and the metal alkoxy alcoholate [I]
I] and one or more kinds of metal alkoxy alcoholates [III] (in the present specification, [I] and [III] or [I], [II] and [III] are collectively referred to as “alkoxy alcoholate”. Also referred to as "class") and an organic solvent are uniformly mixed to prepare an alkoxy alcoholate mixed solution.

When the alkoxy alcoholate solution is prepared as described above, these alkoxy alcoholates and the organic solvent may be stirred together, or the organic solvent may be added to the previously mixed alkoxy alcoholates and further stirred. Alternatively, the alcoholate [I], [III] and, if necessary, [II] may be added to the organic solvent in any order, and the mixture may be stirred, and the mixing method is not particularly limited.

In preparing the alkoxy alcoholate mixed solution as described above, the alkoxy alcoholates are used in an amount corresponding to the desired metal composition ratio (molar ratio) in the lanthanum-based perovskite complex oxide.

That is, when lanthanum alkoxy alcoholate [I] and metal alkoxy alcoholate [III] are used as the alkoxy alcoholates, [I]
When [III] is used in an equimolar ratio to lanthanum, and when lanthanum alkoxy alcoholate [I], metal alkoxy alcoholate [II] and metal alkoxy alcoholate [III] are used as alkoxy alcoholates,
[III] is used in an equimolar amount to the total number of moles of [I] and [II].

The metal alkoxy alcoholate [II
When two or more kinds of metal alkoxy alcoholates are used as [I], the metal alkoxy alcoholates [II
It is used in such an amount that the total number of moles of [I] is equal to the total number of moles of lanthanum alkoxy alcoholate [I] and metal alkoxy alcoholate [II].

For example, La _0.7 Ca _0.3 Cr _0.8 Mn _0.2 O
_{In 3} , the metal composition ratio (molar ratio) is La (0.7 mol) / Ca
(0.3 mol) / Cr (0.8 mol) / Mn (0.2 mol), but as shown in the corresponding Example 18, La (OC _{2
H 4 OC 2 H 5) 3} / Ca (OC 2 H 4 OC 2 H 5) 2 / Cr
(OC ₂ H ₄ OC ₂ H ₅ ) ₃ / Mn (OC ₂ H ₄ OC ₂ H ₅ ) ₂ =
0.042 / 0.018 / 0.048 / 0.012 =
Used in an amount of 0.7 / 0.3 / 0.8 / 0.2 (molar ratio). Also, La ^[I] (0.7 mol) + Ca ^[II] (0.3 mol) =
It is Cr ^[III] (0.8 mol) + Mn ^[III] (0.2 mol).

The organic solvent is not particularly limited as long as it can dissolve the alkoxy alcoholates. Specific examples of such an organic solvent include hydrocarbons, alcohols,
Examples thereof include ketones and esters. Considering solubility and operability, aromatic hydrocarbons such as xylene, toluene and benzene are preferably used. In consideration of economy and the like, such an organic solvent is usually used in an amount of about 0.5 to 2 liters (about 5 to 20 moles) per 1 mole of the total alkoxy alcoholates used. In the present invention, a lanthanum-based perovskite-type composite oxide is produced by heating (heating) an alkoxy alcoholate mixed solution obtained by mixing the alkoxy alcoholates and the organic solvent as described above. . The heating and firing conditions differ depending on the type of the target lanthanum-based perovskite-type composite oxide and are not unconditionally determined, but are usually 500 to 1000 ° C., preferably 600 to 1000.
It is heated and baked at a temperature of about C for about 1 to 5 hours. The heating and firing of such an alkoxy alcoholate mixed solution is
For example, it can be performed in air or in an oxygen atmosphere.

In the present invention, it is preferable that the alkoxy alcoholate mixed solution is dried by a dryer or the like to remove the organic solvent in advance and then heated and baked. When the organic solvent is removed from the alkoxy alcoholate mixed solution in this manner, the alkoxy alcoholate mixed solution usually becomes a black gel-like viscous material.

When heated and baked in this way, it is crystallized and
A complex oxide having a perovskite structure (lanthanum-based perovskite complex oxide) represented by the general formula [IV] can be obtained. (d) General formula [IV]:

[0045]

[Chemical 12]

In the formula [IV], A is Sc, Y, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
m, Yb, Lu, Ca, Sr, or Ba is a metal, and A is Y, preferably corresponding to the above formula [II].
Ce, Sm, Ca of alkaline earth metals, Sr and Ba
It is desirable to indicate any of these metals.

B is Mg, Cr, Mn, Fe, Co, N
i represents one or more metals selected from Cu, Zn, and x represents a number of 0 <x ≦ 1. In addition,
In the formula [IV], "A site" means "La
_x A _1-x ”, and the term“ B site ”refers to the“ B ”part of formula [IV]. LaBO ₃ type complex oxide In the lanthanum-based perovskite type complex oxide represented by the general formula [IV] as described above, particularly when x is 1, the following formula [IV-a]: LaBO ₃ ... -[IV-a] [In formula, B is Mg, Cr, Mn, Fe, Co, Ni, C.
One or more metals selected from u and Zn are shown. ]] Is represented.

Such a lanthanum-based perovskite-type composite oxide [IV-a] is represented by (i) a lanthanum alkoxy alcoholate represented by the general formula [I] and the general formula [III]. It can be obtained by using one or more metal alkoxy alcoholates described above.

Specific examples of the lanthanum-based perovskite complex oxide [IV-a] obtained by using one kind of metal alkoxy alcoholate as the metal alkoxy alcoholate [III] are, for example, LaCoO ₃ and LaCr.
_{O 3, LaMnO 3, LaFeO 3} , LaNiO 3 , and the like.

Further, metal alkoxy alcoholate [II
As the lanthanum-based perovskite-type composite oxide [IV-a] using two or more kinds of metal alkoxy alcoholates [III] as I], specifically, for example, La
_{Cr 0.8 Mg 0.2 O 3, LaCu} 0 .4 Co 0.6 O 3, LaCr
_0.9 Zn _0.1 O _{3 and the} like can be mentioned. La _x A _1-x BO ₃ (0 <x <1) type composite oxide Also, in the lanthanum-based perovskite type composite oxide represented by the above general formula [IV], x is particularly 0 <x <1. In this case, such a lanthanum-based perovskite complex oxide [IV] is represented by the following formula (ii): the lanthanum alkoxy alcoholate represented by the general formula [I] and the general formula [II]. It can be obtained by using a metal alkoxy alcoholate and one or more metal alkoxy alcoholates represented by the general formula [III].

As the metal alkoxy alcoholate [III], a lanthanum-based perovskite complex oxide [IV] using one kind of metal alkoxy alcoholate [III]
Specifically, for example, La _0.9 Sr _0.1 MnO
₃ , La _0.8 Sm _0.2 CoO ₃ , La _0.4 Sr _0.6 CoO ₃ ,
La _0.8 Ca _0.2 MnO ₃ , La _0.8 Ba _0.2 CoO ₃ , La
_0.9 Ce _0.1 CoO ₃ , La _0.8 Y _0.2 CoO _{3 and the} like can be mentioned.

Further, metal alkoxy alcoholate [II
Examples of the lanthanum-based perovskite-type composite oxide [IV] formed by using two or more kinds of metal alkoxy alcoholates [III] as I] include, for example, La _0.8 Ca _0.2 Cr _0.8 Co _0.2. O ₃ , La _0.7 Ca
_0.3 Cr _0.8 Mn _0.2 O _{3 and the} like. [Second Method for Producing Lanthanum-based Perovskite Complex Oxide] In the present invention, (i) a lanthanum alkoxy alcoholate represented by the general formula [I] and one or two represented by the general formula [III]. At least one metal alkoxy alcoholate and an organic solvent, or (ii) a lanthanum alkoxy alcoholate represented by the above general formula [I], a metal alkoxy alcoholate represented by the above general formula [II], and the above general formula [III] One or more kinds of metal alkoxy alcoholates represented by the formula and an organic solvent are uniformly mixed to prepare an alkoxy alcoholate mixed solution, and the alkoxy alcoholate in the obtained mixed solution is hydrolyzed and then heated and baked. , The above general formula [IV]
The lanthanum-based perovskite complex oxide represented by

That is, in the second manufacturing method, the first
Water is added to the alkoxy alcoholate mixed solution obtained in the production method of Example 1 to temporarily hydrolyze the alkoxy alcoholates in the mixed solution, and then the mixture is heated and calcined in the same manner as in the first method to produce a lanthanum-based perovskite complex oxide. Are manufactured.

This hydrolysis step will be described in detail. When the "alkoxy alcoholate mixed solution" obtained as described above is hydrolyzed, water is added in a theoretical amount of 4 to 60.
It is used in the range of about double mole. When the alkoxy alcoholates in the alkoxy alcoholate mixed solution are hydrolyzed with such an amount of water, the alkoxy alcoholate mixed solution may be poured into a large amount of water at once, or the alkoxy alcoholate mixed solution may be added in a large amount. To 1
Water may be gradually added dropwise over a period of about 0 to 120 minutes. When the alkoxy alcoholates are brought into contact with water in this way, the hydrolysis reaction of the alkoxy alcoholates usually proceeds instantaneously and a large amount of gel-like precipitate is produced.
The reaction system after the completion of such a hydrolysis reaction contains an organic solvent and water together with a gel-like precipitate, but the reaction solution thus obtained is directly filtered to form a cake (precipitation in the reaction solution). Substance) may be collected, and in some cases, one of water and an organic solvent is distilled off to form a mixture of a precipitate and water or a mixture of a precipitate and an organic solvent, and the cake is filtered to form a cake. The cake may be collected or the cake may be collected using an existing solid-liquid separator.

The cake thus separated is composed of extremely fine particles, and a large amount of water or an organic solvent is usually attached to the surface of the particles. In the present invention, it is preferable to sufficiently volatilize and remove the attached water or the attached organic solvent from the cake, and a dryer or the like may be used at this time.

By removing the adhering water or the adhering organic solvent from the cake in this manner, an amorphous, fairly bulky powder is obtained. By heating (baking) this powder in the same manner as in the first method, the desired lanthanum-based perovskite complex oxide [IV] can be obtained.

The lanthanum-based perovskite type complex oxide [IV] obtained by the above-mentioned first and second methods is
It is in powder form, has excellent homogeneity, high purity and excellent activity, and its specific surface area is usually 2 to 4 although it depends on the type of complex oxide.
It is about 0 m ² / g.

As the above-mentioned alkoxy alcoholates, when the alkoxy alcoholates and the organic solvent are mixed, the alkoxy alcohol residue of each alcoholate [I], [II] and [III]:

[0059]

[Chemical 13]

Although there is no problem in terms of solubility, it is possible to use alkoxyalcoholates having different values from each other, but an alkoxyalcohol produced as a by-product when water is added to the alkoxyalcoholate mixed solution to hydrolyze the alkoxyalcoholates. In order to recover and reuse the above, it is preferable to use alkoxy alcoholates in which the alkoxy alcohol moieties constituting the alkoxy alcoholate of each metal are the same. Preparation of Raw Material Alkoxy Alcoholates The method for preparing the above-mentioned alkoxy alcoholates used in the present invention will be described below. First, the lanthanum alkoxy alcoholate [I] and optionally the metal alkoxy alcoholate [II] can be obtained by the following method proposed by the present inventors in Japanese Patent Application No. 6-7731. Some of them can be obtained by a conventionally known method. [First production method of rare earth metal alkoxy alcoholate]
In the first production method, a rare earth metal carboxylate represented by the following general formula (Q) is reacted with an alkali metal alkoxy alcoholate represented by the following general formula (R) to give the following general formula: A rare earth metal alkoxy alcoholate represented by (P) can be produced.

[0061]

[Chemical 14]

[Wherein M ¹ represents a rare earth metal, X represents a carboxylic acid residue, and A ¹ represents an alkali metal (Li, Na, K, etc.)
And R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a lower alkyl group, a represents an integer of 1 to 3, and b represents 1 or 2. However, when b is 1, X represents a monovalent carboxylic acid residue, and when b is 2, X represents a divalent carboxylic acid residue. ] That is, in a mixed liquid comprising a rare earth metal carboxylate represented by the above formula (Q) and an organic solvent described below,
The alkali metal alkoxy alcoholate solution represented by the formula (R) is gradually added dropwise over, for example, about 10 minutes.
Then, the obtained mixed solution containing the rare earth metal carboxylate (Q) and the alkali metal alkoxy alcoholate (R) is heated from room temperature to 80 to 180 ° C. which is the reflux temperature of the organic solvent used, and this solvent is heated. Usually, the mixture is stirred at the reflux temperature of 2 to 4 hours. By stirring the mixed solution under the above conditions, an organic solvent solution (reaction solution) containing a rare earth metal alkoxy alcoholate (P) and a by-product alkali metal carboxylate (XA ¹ _b ) is obtained. To be

The reaction solution obtained is filtered to obtain a by-product.
Alkali metal carboxylate (XA ¹ _b) Is removed,
Dissolution of rare earth metal alkoxy alcoholate (P) in organic solvent
A liquid is obtained. Then, this rare earth metal alkoxy al
Evaporate the organic solvent from the organic solvent solution of cholate (P)
Rare earth metal alkoxy alcoholate (P) dried and solidified
The desired rare earth metal alkoxy alcoholate
(P) is obtained.

As the rare earth metal carboxylic acid salt represented by the above formula (Q), conventionally known ones are used. The rare earth metal element (M ¹ ) includes Sc, Y, La, C
e, Pr, Nd, Sm, Eu, Gd, Tb, Dy, H
and o, Er, Tm, Yb, and Lu.

Such a rare earth metal carboxylate (Q)
Specifically, for example, Sc (OCOC
_{H 3) 3, Y (OCOCH} 3) 3, La (OCOCH 3) 3,
La (OCOH) ₃ , La (OCOC ₂ H ₅ ) ₃ , La (O
COC ₆ H ₅ ) ₃ , Ce (OCOCH ₃ ) ₃ , Pr (OCO
CH ₃ ) ₃ , Nd (OCOCH ₃ ) ₃ , Sm (OCOC
H ₃ ) ₃ , Eu (OCOCH ₃ ) ₃ , Gd (OCOC
H ₃ ) ₃ , Tb (OCOCH ₃ ) ₃ , Dy (OCOC
_{H 3) 3, Ho (OCOCH} 3) 3, Er (OCOC
H ₃ ) ₃ , Tm (OCOCH ₃ ) ₃ , Yb (OCOC
A compound in which X is a monovalent carboxylic acid residue in formula (Q), such as H ₃ ) ₃ or Lu (OCOCH ₃ ) ₃ ;
Examples thereof include compounds in which X is a divalent carboxylic acid residue in the formula (Q), such as ₂ (C ₂ O ₄ ) ₃ .

The alkali metal alkoxy alcoholate represented by the above formula (R) is described in, for example, JP-A-63-270688 and can be obtained by a conventionally known synthesis method. Specific examples of the alkali metal alkoxy alcoholate (R) include lithium ethoxyethylate, sodium ethoxyethylate, sodium methoxyethylate, sodium 1-methoxy-2-propylate and sodium 4-methoxy-1-butyrate. , Sodium n-butoxy-2-ethylate, sodium 3-ethoxy-1-propylate, sodium 2-i-propoxyethylate, potassium ethoxyethylate and the like.

In the above reaction, the alkali metal alkoxy alcoholate (R) is 3.0 mol per 1 mol of the monovalent rare earth metal carboxylate (Q) and the divalent rare earth metal carboxylate (Q) 1 is. It is used in an amount of 6.0 mol per mol, and the organic solvent is used in an amount of about 0.6 to 7 liters.

As the organic solvent, benzene, toluene,
Aromatic hydrocarbons such as xylene are used. Above
First production method of una rare earth metal alkoxy alcoholate
According to, the rare earth metal alkoxy represented by the formula (P)
Alcoholates, for example La (OC₂H _FourOC₂H_Five)₃,
La (OC₂H_FourOCH₃)₃, La [OCH (CH₃) C
H₂OC₂H_Five]₃, La (OC_FourH₈OCH₃)₃, La (O
C₂H_FourOn-C_FourH₉)₃, Sc (OC₂H_FourOC₂H_Five)₃,
Nd (OC₂H_FourOC₂H_Five)₃, Er (OC₂H_FourOC
₂H_Five)₃, Eu (OC₂H_FourOC₂H_Five)₃, Y (OC₂H_FourO
C₂H_Five)₃Of course, the following new rare earths
Metal alkoxy alcoholates can also be obtained in high yield and high purity.
Be done.

With a novel rare earth metal alkoxy alcoholate
Then, for example, Ce [OCH₂CH₂-OC₂H_Five]₃,
Ce [OCHCH₃CH₂OCH₃]₃, Pr [OCH₂C
H₂OC₂H_Five]₃, Sm [OCH₂CH₂OC₂H_Five]₃, S
m [OCH₂CH₂OiC₃H₇] ₃, Gd [OCH₂CH₂
OC₂H_Five]₃, Tb [OCH₂CH₂OC₂H_Five]₃, Dy
[OCH₂CH₂OC₂H_Five]₃, Ho [OCH₂CH₂OC₂
H_Five]₃, Tm [OCH₂CH₂OC₂H_Five]₃, Yb [OC
H₂CH₂OC₂H_Five]₃, Lu [OCH₂CH₂OC₂H _Five]₃
Etc. [Second production method of rare earth metal alkoxy alcoholate]
The above rare earth metal alkoxy alcoholate (P) is
Rare earth metal carboxylate (Q) and the following general formula (S)
Alkoxy alcohol represented by
Potassium metal (A¹) Produced by reacting in the presence of
You can also do it.

[0070]

[Chemical 15]

(Wherein M ¹ , X, A ¹ , R ¹ , R ² , a, b
Is the same as above. ) That is, the rare earth metal carboxylate represented by the formula (Q), the alkoxy alcohol represented by the formula (S), and the same organic solvent as described above are put into the reactor. While stirring the obtained reactor contents, the alkali metal (A ¹ ) is gradually added to the reactor contents over 30 minutes to 2 hours.

The alkali metal (A
^The mixed solution containing ¹ ) is heated from room temperature to 80 to 180 ° C., which is the reflux temperature of the organic solvent, and stirred at this temperature for 2 to 6 hours.

As described above, when the solvent is refluxed at the reflux temperature for the above time, hydrogen is generated as the reaction progresses, and the rare earth metal alkoxy alcoholate represented by the above formula (P) and the by-product alkali metal are formed. An organic solvent solution (reaction solution) containing the carboxylate (XA ¹ _b ) is obtained.

The reaction solution thus obtained is filtered in the same manner as in the above-mentioned first production method to remove the alkali metal carboxylate (XA ¹ _b ), whereby the rare earth metal alkoxy alcoholate (P) is obtained. An organic solvent solution of is obtained. Then, the organic solvent solution is evaporated to dryness to obtain the desired rare earth metal alkoxy alcoholate (P).

In this second production method, the alkoxy alcohol (S) is usually used in an amount of 0.1 to 2 liters per 1 mol of the rare earth metal carboxylate (Q).
The alkali metal (A ¹ ) is usually used in an amount of about 3.0 to 6.0 mol, and the organic solvent is used in an amount of about 0.5 to 5 liters.

There are also alkoxy alcoholates which can be obtained by utilizing a conventionally known method.
For example, the lanthanum alkoxy alcoholate [I] and the metal alkoxy alcoholate [II] are described in JP-A-62-62.
As shown in the following reaction formula described in JP-A-281835, it can be obtained by directly reacting an alkoxy alcohol containing an alcohol reactant with lanthanum, scandium, or yttrium (M ³ ) which is a rare earth metal.

[0077]

[Chemical 16]

(In the formula, M ³ represents a metal selected from scandium, yttrium and lanthanum, n, m and p may be the same or different and each is a positive integer of 1 to 12). Z is (R ¹ 0)-or (R ¹ )-, and R ¹ and R ² are the same or different alkyl groups containing 1 to 20 carbon atoms. II], A is C of alkaline earth metal
Alkaline earth metal alkoxylates represented by a or Ba and alkaline earth metal alkoxy alcoholates represented by the general formula [III] where B is Mg are as described in JP-A-62-281835. It can be produced by a direct reaction of alkali metal Ca, Ba or Mg with an alkoxy alcohol.

In the general formula [III], the metal alkoxy alcoholate in which B is Cu is disclosed in JP-A-63-2706.
As shown in the following reaction formula described in Japanese Patent No. 88,
It can be produced by reacting an organic copper carboxylate with an alkoxy alcohol in the presence of an alkali metal A ¹ .

[0080]

[Chemical 17]

[In the formula, R ¹ and R ³ represent a hydrogen atom or a lower alkyl group, R ² represents a lower alkyl group, and n is 1
Alternatively, it represents an integer of 2, and A ¹ represents an alkali metal. ] In the general formula [III], the metal alkoxy alcoholate [III] in which B is Co, Ni, or Cr is Zh, Obshch K
It can be obtained by the following reaction described in him (Zoo Obsuk Kim) Vol. 60, pages 1333-1336.

[0082]

[Chemical 18]

[In the formula, M represents Co, Ni, and Cr, and n
Represents an integer of 2 to 3. In the general formula [III], the metal alkoxy alcoholate [III] in which B is Zn is obtained by the following reaction described in Inorg, Chem (Inorganic Chemistry) Vol. 29 (23), pages 4646-4652. To be

[0084]

[Chemical 19]

In the general formula [III], the metal alkoxy alcoholate [III] in which B is Mn is Mn (OC ₂ H ₄ described in "Chemical Abstracts 12th Collective Index Formulas".
OC ₂ H ₅ ) ₂ or the like can be used.

[0086]

EFFECTS OF THE INVENTION According to the present invention, a La-based perovskite-type composite oxide having a single crystal phase having a large specific surface area, which is excellent in uniformity (homogeneity) and activity, causes almost no off-odor during production. You can get without.

In particular, in the second method, the substance by-produced by hydrolysis is only an alkoxy alcohol that can be recovered and reused, and the lanthanum-based perovskite complex oxide can be industrially used without contaminating the working environment. Can be mass-produced.

The lanthanum-based perovskite-type composite oxide obtained by such a method is also used as a raw material for producing thin films, fibers, coating materials and the like. Thin films, fibers, coating materials, etc. made using this lanthanum-based perovskite complex oxide are phosphors, catalysts, ceramics, optical glass, abrasives, magnets,
It is expected to be used in a wide range of fields as functional electronic materials.

[0089]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

[0090]

Example 1 Synthesis of La _0.8 Sm _0.2 CoO ₃ (First Production Method) La (OC ₂ H ₄ OC ) was added to an alumina crucible having a capacity of 50 ml.
₂ H ₅ ) ₃ : 1.9 g (0.0048 mol), Sm (OC _{2
H 4 OC 2 H 5) 3} : 0.5g (0.0012 mol), Co
(OC ₂ H ₄ OC ₂ H ₅ ) ₂ : 1.4 g (0.006 mol)
I put it in considerably. 10 ml of toluene was added to this crucible and stirred to form a uniform mixed alkoxide solution. The crucible was placed in a ventilation dryer and dried at 60 ° C. for one day to obtain a black gel-like viscous substance (composite oxide precursor). Further, this viscous material was placed in an electric furnace and heated and baked at 700 ° C. for 1 hour.
The powder obtained was a single crystalline phase of La _0.8 Sm _0.2 CoO ₃ and had a specific surface area of 5.6 m ² / g.

A powder X-ray diffraction chart is shown in FIG.

[0092]

Example 2 Synthesis of LaCr _0.9 Zn _0.1 0 ₃ (First Production Method) Table 1 shows a composite oxide obtained in the same manner as in Example 1.

The various composite oxides described in Examples 3 to 13 and 15 to 18 can be produced according to the method described in Example 1.

[0094]

[Table 1]

[0095]

Example 3 Synthesis of LaCoO ₃ (Second Production Method) La (OC ₂ H ₄ OC _{2 was} added to a 500 ml round bottom flask.
H _{5) 3:} 24.4g (0.060 mole), Co (OC ₂ H
₄ OC ₂ H ₅ ) ₂ : 14.2 g (0.060 mol) equivalent was added and 200 ml of toluene was added and stirred to obtain a uniform mixed alkoxide solution. On the other hand, water in a beaker of 1 liter capacity
Then, 00 ml was placed therein, and the above mixed alkoxide solution of La and Co was injected into the mixture with stirring to cause hydrolysis, and immediately green crystals were formed and became viscous. After stirring for 1 hour, the organic solvent was distilled off to give an aqueous slurry, and the crystals were filtered off,
Washed with water. After that, the crystals were placed in a petri dish, dried by ventilation at 60 ° C. for 24 hours, transferred to an electric furnace, and baked (heat-treated) at 800 ° C. for 1 hour. The obtained powder was a single crystal phase of LaCoO ₃ and had a specific surface area of 4 m ² / g.

A powder X-ray diffraction chart of the obtained crystal is shown in FIG.

[0097]

Examples 4 to 7 In the same manner as in Example 3, lanthanum-based perovskite complex oxides shown in Table 2 were produced.

Table 2 shows the obtained complex oxides. In Examples 3 to 7, when “A site (La _x A _1-x part)” is La and “B site” is 1 mol, B site is M
It may be g, Cu or Zn.

[0099]

[Table 2]

[0100]

Example 8 La _0.9 Sr _0.1 Mn _1.0 0 ₃ Synthesis (second manufacturing method) La round bottom flask 500ml capacity (OC ₂ H ₄ OCH
₃ ) ₃ : 19.7 g (0.054 mol), Sr (OC ₂ H ₄
OCH ₃ ) ₂ : 1.4 g (0.006 mol), Mn (OC
_{2 H 4 OCH 3) 2:} 12.3g (0.060 mole) equivalent placed and uniformly dissolved by adding xylene 200 ml. With vigorous stirring, 20.8 g of water was gradually added dropwise thereto over 30 minutes. Immediately after the addition of water, hydrolysis started and a blackish brown gel precipitate was formed. After stirring for 1 hour, water was distilled off from the system to give a slurry of an organic solvent. The precipitate was filtered and taken out, put in a petri dish, and dried by ventilation at 60 ° C. for 24 hours, and the obtained amorphous powder was heated and calcined at 600 ° C. for 1 hour. The obtained powder is La _0.9 Sr _0.1 M
In n _1.0 0 ₃ crystalline single phase, its specific surface area 38.2m
It was ² / g.

A powder X-ray diffraction chart is shown in FIG.

[0102]

Examples 9 to 13 In the same manner as in Example 8, lanthanum-based perovskite type complex oxides shown in Table 3 were produced.

Table 3 shows the obtained complex oxides. In addition, in Examples 8 to 13 and the above Example 1,
When the "A site" consists of La and one other element and the "B site" consists of one element, the A site is La
Other than, Sc, Pr, Nd, Eu, Gd, Tb, Dy,
It may be any of Ho, Er, Tm, Yb and Lu, and the B site is Mg, Cr, Fe, Ni, C.
It may be u or Zn.

[0104]

[Table 3]

[0105]

Example 14 Synthesis of LaCr _0.9 Zn _0.1 0 ₃ (Second Production Method) La (OC ₂ H ₄ O · n) was added to a 500 ml round bottom flask.
_{-C 4 H 9) 3: 29.4g} (0.060 mol), Cr
_{(OC 2 H 4 O · n} -C 4 H 9) 3: 21.8g (0.054
_{Mol), Zn (OC 2 H 4} O · n-C 4 H 9) 2: 1.2g
(0.006 mol) equivalent addition, benzene 200m
1 was added and dissolved uniformly. On the other hand, the above-mentioned alkoxide solution was added dropwise to the round-bottomed flask having a capacity of 1 liter containing 200 ml of water with stirring for about 10 minutes, and the contents of the flask were hydrolyzed to immediately produce a viscous black precipitate. After continuing stirring for 1 hour, the organic solvent was distilled off to give an aqueous slurry. Thereafter, the precipitate was taken out by filtration, washed with water, placed in a petri dish, and dried by ventilation at 60 ° C. for 24 hours. Then, the obtained dried product was placed in an electric furnace and heated and baked at 800 ° C. for 1 hour. The obtained powder was a single crystal phase of LaCr _0.9 Zn _{0.10 3} and had a specific surface area of 10.6 m ² / g.

The powder X-ray diffraction chart is shown in FIG.

[0107]

Examples 15 to 16 In the same manner as in Example 14, lanthanum-based perovskite type complex oxides shown in Table 4 were produced.

Table 4 shows the obtained complex oxides. In Examples 14 to 16, when the A site is La and the B site is composed of two kinds of elements, B (B site) may be Mn, Fe or Ni.

[0109]

[Table 4]

[0110]

Example 17 Synthesis of _{La 0.8 Ca 0.2 Cr 0.8 Co 0.2} 0 3 ( second manufacturing
Method) La (OCHCH ₃ C was added to a 500 ml round bottom flask.
H ₂ OCH ₃ ) ₃ : 19.5 g (0.048 mol), Ca
(OCHCH ₃ CH ₂ OCH ₃ ) ₂ : 2.2 g (0.012
_{Mol), Cr (OCHCH 3 CH 2} OCH 3) 3: 15.3
g (0.048 mol), Co (OCHCH ₃ CH ₂ OCH
₃ ) ₂ : Equivalent to 2.8 g (0.012 mol) was added, and 200 ml of toluene was added and uniformly dissolved. While vigorously stirring, 36.3 g of water was gradually added dropwise to this flask over about 5 minutes. Immediately after the addition, hydrolysis started and a black gel-like precipitate started to form. After stirring the contents of the flask for 1 hour, water was distilled off from the reaction system to obtain a slurry of an organic solvent. The precipitate in the flask was taken out by filtration, put in a petri dish, and air-dried at 60 ° C for 24 hours, and the obtained powder was heated and calcined at 1000 ° C for 1 hour. When heat-baked (heat-treated) in this way, La _0.8 Ca _0.2 Cr _0.8
Co _0.2 0 ₃ powder was obtained as a crystalline single phase, its specific surface area was 3.1m ² / g.

The powder X-ray diffraction chart is shown in FIG.

[0112]

Example 18Synthesis of _{La 0.7 Ca 0.3 Cr 0.8 Mn 0.2} 0 3 ( second manufacturing
Method) La (OC₂H_FourOC₂H_Five)₃: 17.1 g (0.042
Mol), Ca (OC₂H _FourOC₂H_Five)₂: 3.9 g (0.
018 mol), Cr (OC₂H_FourOC₂H_Five)₃: 15.3
g (0.048 mol), Mn (OC₂H_FourOC₂H_Five)₂:
Toluene solution containing 2.8 g (0.012 mol) equivalent
Prepared and hydrolyzed and vented dry as in Example 14.
Which treatment was performed to obtain an amorphous powder. 1 of this amorphous powder
La when heated and baked at 000 ° C for 1 hour_0.7Ca_0.3Cr
_0.8Mn_0.20₃Was obtained as a crystalline single phase. That conclusion
The specific surface area of the crystal is 5.0m²/ G.

The powder X-ray diffraction chart is shown in FIG. In Examples 17 to 18, when “A site” is composed of La and one other element, and “B site” is composed of two elements, A site is La and other elements. “Be, Sr, Ba, or a rare earth other than La”, and the B site may be Mg, Fe, Ni, Cu, or Zn.

[0114]

[Reference manufacturing example]Synthesis of Fe (OC ₂ H ₄ OC ₂ H ₅ ) ₃ [in Formula (III)
(When B is Fe) In a 500 ml round bottom flask, ferric chloride (FeCl 2
₃) 32.5 g (0.20 mol), toluene 150 ml
The mixture was put and stirred under cooling. Into this, ethyl cellosolve 10
When 0 ml was gradually added dropwise, it dissolved while generating heat. on the other hand
Add 100 ml of toluene to a 300 ml round bottom flask.
And metal Na: 13.8 g (0.60 mol) are added and heated.
Since Na dissolves at about 100 ° C, ethyl acetate is dissolved at this temperature.
When 50 ml of Rosolve was dropped slowly, metallic Na
H while generating heat₂Reacts while generating gas, NaOC₂H
_FourOC₂H_FiveA clear toluene solution of was obtained. This NaO
C ₂H_FourOC₂H_FiveFerric chloride (FeCl 2)₃) Melting
When gradually injected into the liquid over about 5 minutes, an exothermic reaction
As it happens, the temperature rises from 30 ° C to 50 ° C and the brown salt (N
aCl) was produced. Further heat and 115 ° C for 4 hours
Refluxed to complete the reaction. The reaction was then cooled
After that, the salt was filtered off, and the solvent was distilled off from the filtrate. In the flask
To the remaining viscous material was added 120 ml of toluene and stirred,
After some filtration to remove some insoluble matter, Fe (OC
₂H_FourOC₂H_Five)₃As a yellow toluene solution
It was

The weight of the solution was 186.6 g, the Fe content was determined by chelate titration to be 1.059 mol / kg, the yield was 0.198 mol, and the yield was 98.
It was 8%.

From this toluene solution, toluene was concentrated to dryness, and Fe (OC ₂ H ₄ OC ₂ H ₅ ) ₃ was isolated as a brown viscous substance. The elemental analysis values are shown in Table 5.

[0117]

[Table 5]

[Brief description of drawings]

FIG. 1 is a powder X-ray diffraction chart of a lanthanum-based perovskite-type composite oxide obtained in Example 1.

FIG. 2 is a powder X-ray diffraction chart of a lanthanum-based perovskite-type composite oxide obtained in Example 2.

FIG. 3 is a powder X-ray diffraction chart of a lanthanum-based perovskite-type composite oxide obtained in Example 3.

FIG. 4 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 4.

FIG. 5 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 5.

FIG. 6 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 6.

FIG. 7 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 7.

FIG. 8 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 8.

FIG. 9 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 9.

FIG. 10 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 10.

FIG. 11 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 11.

FIG. 12 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 12.

FIG. 13 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 13.

FIG. 14 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 14.

FIG. 15 is a powder X-ray diffraction chart of a lanthanum-based perovskite-type composite oxide obtained in Example 15.

16 is a powder X-ray diffraction chart of a lanthanum-based perovskite-type composite oxide obtained in Example 16. FIG.

FIG. 17 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 17.

FIG. 18 is a powder X-ray diffraction chart of the lanthanum-based perovskite-type composite oxide obtained in Example 18.

[Explanation of symbols]

1 to 18, the left vertical axis indicates the X-ray intensity, the unit thereof is cps, the lower horizontal axis indicates the angle, and the unit thereof is 2θ.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C07C 31/28 9155-4H H01M 4/86 T // C04B 35/495 35/50 H01M 4/88 (72) Akira Nagai Yoshiyoshi 4-29-2 Orion Heights 105 Atsugi City, Kanagawa Prefecture Orion Heights 105 (72) Inventor Matsuzawa Masami 317 Yoshiura Shrine, Tamano City, Okayama Prefecture

Claims (5)

[Claims] 1. A lanthanum alkoxy alcoholate represented by the following general formula [I], one or more metal alkoxy alcoholates represented by the following general formula [III], and an organic solvent, or (ii) A lanthanum alkoxy alcoholate represented by the following general formula [I], a metal alkoxy alcoholate represented by the following general formula [II], and one or more metal alkoxy alcoholates represented by the following general formula [III]. And an organic solvent are uniformly mixed, and the resulting alkoxy alcoholate mixed solution is heated and calcined, and a method for producing a lanthanum-based perovskite complex oxide represented by the following general formula [IV]. (a) General formula [I]: [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group,
R ² represents a lower alkyl group, and a represents an integer of 1 to 3. ] (B) General formula [II]: [Wherein A is Sc, Y, Ce, Pr, Nd, Sm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u, Ca, Sr, or any of the metals Ba, R
¹ , R ² and a are the same as above. s shows the integer of 2-3. ] (C) General formula [III]: [In the formula, B is Mg, Cr, Mn, Fe, Co, Ni, C
A metal of either u or Zn is shown, and R ¹ , R ² , a and s are the same as above. ] (D) General formula [IV]: [Wherein A is Sc, Y, Ce, Pr, Nd, Sm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u, Ca, Sr, or any one of the metals Ba, B
Is Mg, Cr, Mn, Fe, Co, Ni, Cu and Z
One or more metals selected from n are shown, and x is a number of 0 <x ≦ 1. ] 2. (i) A lanthanum alkoxy alcoholate represented by the above general formula [I], one or more metal alkoxy alcoholates represented by the above general formula [III], and an organic solvent, or (ii) Lanthanum alkoxy alcoholate represented by the general formula [I], metal alkoxy alcoholate represented by the general formula [II], and one or more metal alkoxy alcoholates represented by the general formula [III]. And an organic solvent are homogeneously mixed to prepare an alkoxy alcoholate mixed solution, and then the alkoxy alcoholate in the obtained mixed solution is hydrolyzed, followed by heating and baking, and the above general formula [IV ] The manufacturing method of the lanthanum type perovskite type complex oxide represented by these. 3. A in the above formulas [II] and [IV] is Y, C
The method according to claim 1 or 2, wherein the metal is one of e, Sm, Ca, Sr and Ba. 4. (i) A lanthanum alkoxy alcoholate represented by the above general formula [I], one or more metal alkoxy alcoholates represented by the above general formula [III], and an organic solvent, or (ii) Lanthanum alkoxy alcoholate represented by the general formula [I], metal alkoxy alcoholate represented by the general formula [II], and one or more metal alkoxy alcoholates represented by the general formula [III]. And an organic solvent, and an alkoxy alcoholate mixed solution for producing a lanthanum-based perovskite complex oxide. 5. A in the above formulas [II] and [IV] is Y, C
The mixed solution according to claim 4, wherein the mixed solution shows a metal selected from the group consisting of e, Sm, Ca, Sr, and Ba.