JP2009209029A - Method for producing perovskite compound oxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a compound oxide expressed by general formula A<SB>1-x</SB>B<SB>x</SB>MO<SB>3+</SB>δ (wherein: A denotes a rare earth element; B denotes calcium, strontium or barium; M denotes manganese, iron, cobalt, nickel or the like, respectively, and 0<x≤1.0, and -0.5≤δ≤0.5), and to provide a method for producing a crystalline compound oxide in which a noble metal(s) is solid-dissolved into the M site in the general formula A<SB>1-x</SB>B<SB>x</SB>MO<SB>3+</SB>δ. <P>SOLUTION: Raw materials comprising components such as the oxide or the like of elements occupying an A site, the oxides or the like of elements occupying a B site and the oxides or the like of elements occupying an M site are subjected to wet mixing and pulverization treatment in a water-base medium, so as to prepare the precursor of the above compound oxide (compound hydroxide or compound hydroxide oxide), and this is subjected to heating treatment, thus the above compound oxide can be obtained. Further, the precursor of the above compound oxide and a noble metal salt are mixed and stirred in a solvent, and the product is heat-treated at 500 to 1,300°C, so as to obtain the noble metal solid-dissolved crystalline compound oxide. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention provides an A _1-x B _x MO ₃₊ δ-type composite oxide useful as a magnetic material, a catalyst material, an electrode material of a solid oxide fuel cell, etc. (wherein A is at least one selected from rare earth elements) B is occupied by at least one element of calcium, strontium, and barium, M is occupied by at least one element of manganese, iron, cobalt, and nickel, and 0 <x ≦ 1 0.0, −0.5 ≦ δ ≦ 0.5), and a manufacturing method in which a noble metal is dissolved in the A _1-x B _x MO ₃₊ δ-type composite oxide.

  As a method for producing a composite oxide having a perovskite structure, there has been known a “solid phase method” in which raw materials composed of oxides and carbonates of elements occupying each site are mixed and pulverized and reacted by heating at high temperature. However, in the solid phase method that requires heat treatment at a high temperature (1000 ° C. or higher) for a long time, the specific surface area of the perovskite-type composite oxide is reduced, and the obtained perovskite-type composite oxide includes other than the perovskite phase. When using complex oxide powders prepared by such a solid-phase method, the mechanical and electrical characteristics of the product (sintered body) There is a risk that the catalyst characteristics and the like are inferior.

  As an improvement method of the above solid phase method, raw materials such as metal oxides are dry-mixed and pulverized by a ball mill, and the crystallization to the perovskite phase is promoted by the action of mechanical stress of the ball mill, and crystallized without heat treatment. A solid phase method for obtaining a perovskite phase (Japanese Patent Laid-Open No. 2002-284531: Patent Document 1) has been proposed. However, the perovskite complex oxide obtained by such a method has already been crystallized. On the other hand, it is difficult to substitute and dissolve other component elements later.

  On the other hand, perovskite complex oxides (so-called “precursors”) that are not crystallized in the perovskite phase are prepared by the “liquid phase method” (coprecipitation method, sol-gel method, alkoxide method, etc.) using the solution as a raw material. Also known is a method for producing a crystallized perovskite complex oxide by heat-treating this precursor at a temperature lower than that of the solid phase method (eg, 800 ° C. or lower). However, these liquid phase methods require a step of removing by-products (for example, ammonium nitrate in the case of a coprecipitation method), and raw materials (for example, metal alkoxides used in the alkoxide method) are expensive. There is an industrial disadvantage in terms of cost.

In contrast to such conventional techniques, in recent years, the following manufacturing method has been proposed, which has a processing step of wet-mixing and pulverizing the raw material of the perovskite complex oxide.
Japanese Patent Application Laid-Open No. 2002-246216 (Patent Document 2) discloses a composition formula (1-x) AO. (X /
2) R ₂ O ₃ .nFe ₂ O ₃ [In the formula, A is at least one selected from the group consisting of Sr, Ba, Pb and Ca, R is La as an essential component, and other And at least one selected from the group consisting of rare earth elements and Bi, 0.05 ≦ x ≦ 0.35, and 5.0 ≦ n ≦ 6.7. Represented by, As a method for producing an oxide magnetic material as a main phase of ferrite with a M-type magnetoplumbite structure hexagonal, carbonates of the constituent elements of A such as (SrCO _3, etc.), the structure of R Elemental oxides (La ₂ O ₃ etc.);
Raw material mixed powder (prepared by a wet ball mill or the like) containing ferric oxide (Fe ₂ O ₃ ) is calcined at 1100 to 1450 ° C., and the obtained ferrite calcined body is oxidized with Mn (and Co) oxide Is added, mixed, pulverized, and re-sintered at 900 to 1450 ° C. (see claims, examples, etc.).

JP 2001-0664019 A (Patent Document 3) discloses a composition formula La _1-xy Eu _y Sr _x.
MnO ₃ [wherein x <0.15 and y + x> 0.15. Mn represented by
As a method for producing a perovskite oxide, La ₂ O ₃ , Eu ₂ O ₃ , SrCO ₃ and M
The raw material consisting of nO is mixed and pulverized by a wet ball mill, the resulting slurry is dried, temporarily calcined in air at 1000 ° C. for several hours, this powder is mixed and pulverized again by a wet ball mill, dried, and then gold A production method is disclosed in which a mold is formed and fired at 1200 ° C. for 10 to 20 hours in an oxygen stream (see Example 1).

Japanese Patent Laid-Open No. 04-34259 (Patent Document 4) discloses a composition formula (Pb _{1- (3/2) x} A _x ) (Ti _{1- y By} ) O ₃ [wherein A is La, Sm, One or more selected from Nd, Sr, and Ca, B is one or more selected from Mn, Ni, and Cr, 0.02 ≦ x ≦ 0.06, 0.001 ≦ y ≦ 0 .007. As a manufacturing method of the lead titanate-based piezoelectric ceramic material represented by the formula, oxide raw materials such as La ₂ O ₃ are wet-mixed in a pot mill for 48 hours, mixed and dehydrated and dried at 700 to 950 ° C. for 2 hours. A manufacturing method is disclosed in which after baking, the mixture is again wet-mixed in a pot mill for 48 hours, and the dehydrated and dried product is granulated, shaped and fired (see [0009] and Examples [0012]).

Japanese Patent Application Laid-Open No. 05-249072 (Patent Document 5) discloses a composition formula La _(1-x) M _x MnO ₃ used for a cathode material of a limiting current type oxygen sensor, wherein M = Sr, Ca; 0 < As a method for producing a perovskite complex oxide represented by x <1], oxide raw materials such as La ₂ O ₃ are mixed, calcined in air at 1500 ° C. for 10 hours, and then wet pulverized by a ball mill. Is made 0.5 to 1 μm, and a paste-like mixture of the obtained perovskite complex oxide powder and turpentine oil is applied to the cathode surface and baked in air at 1100 ° C. for 1 hour. (See [0006]).

  However, in the production methods described in Patent Documents 2, 3, and 5, it is not clear whether the target single composition can be produced by the first heat treatment at a relatively high temperature, and the remaining heat treatment is not performed. The process of extinguishing the impurity phase that is being performed and simultaneously producing a sintered body is necessary. The production method described in Patent Document 4 is also complicated because it requires a wet mixing and pulverization treatment and firing again after firing (calcination) the raw material mixture in order to synthesize a uniform powder.

Further, palladium (Pd), rhodium (R) is included in the crystal lattice of the perovskite complex oxide.
h) “Precious metal solid solution perovskite type complex oxide” in which a precious metal such as platinum (Pt) is dissolved.
For example, carbon monoxide (CO), hydrocarbon (HC) and nitrogen oxide (N
It is important as a catalyst material because it can be used as a three-way catalyst capable of simultaneously purifying Ox).

  As a method for producing such a noble metal solid solution perovskite complex oxide, a method using a precursor obtained by the liquid phase method described above, for example, an organic solvent solution of a metal alkoxide (alkoxy alcoholate) of an element other than a noble metal and a noble metal An “alkoxide method” (JP-A-8-217461: Patent Document 6) in which a precursor is produced by mixing and stirring with an aqueous salt solution and calcined at about 500 to 800 ° C., mineral acids of elements other than noble metals A “coprecipitation method” in which a precipitant is added to a mixed aqueous solution of salt to form a precursor precipitate, a noble metal salt is further added to the precipitate, and a solid obtained by drying is heat-treated at 400 to 700 ° C. (Japanese Patent Laid-Open No. 2005-179168: Patent Document 7) Or, sodium hydroxide is added to a chloride of an element containing a noble metal, and a precursor is produced by dry grinding. So, the method of the precursor after heat treatment at 500 to 600 ° C.-product sodium chloride are removed by washing with water: and the like are known (JP 2005-298251 JP Patent Document 8).

However, even in the production of the above-mentioned noble metal solid solution perovskite type complex oxide by the alkoxide method and coprecipitation method, the same by-products and raw materials as in the production of the perovskite type complex oxide not containing noble metal by the alkoxide method and coprecipitation method are used. However, the method using the dry pulverization treatment still has a problem that a step of removing by-products such as sodium chloride is required.

The present applicants have a general formula ABO ₃ [wherein A is occupied by at least one element selected from rare earth elements, and B is at least one element selected from the group consisting of manganese, iron, and cobalt. Occupied by. And a raw material containing at least one of oxides, hydroxides, oxide hydroxides and simple metals occupying the A site, and a precursor of a perovskite complex oxide represented by A perovskite-type composite oxide, characterized by mixing and grinding a raw material containing at least one of oxides, hydroxides, oxide hydroxides, and simple metals occupying the B site in an aqueous solvent And a method for producing a perovskite-type composite oxide containing a crystalline perovskite phase, characterized by heat-treating the precursor obtained by this production method. No. 2008-007394: Patent Document 9).
Japanese Patent Laid-Open No. 2002-284531 JP 2002-246216 A JP 2001-0664019 A Japanese Patent Laid-Open No. 04-342459 Japanese Patent Laid-Open No. 05-249072 JP-A-8-217461 JP 2005-179168 A JP-A-2005-298251 JP 2008-007394 A

The present invention provides an inexpensive and efficient method for producing an A _1-x B _x MO ₃₊ δ-type composite oxide containing a crystalline perovskite phase, and a method for producing a noble metal solid solution of the perovskite-type composite oxide. The purpose is to do.

As a result of diligent studies to solve such problems, the present inventors have found that at least one of oxides, hydroxides and oxide hydroxides of elements occupying the A site and elements occupying the B site. A raw material comprising at least one of oxides and hydroxides of the above and at least one of oxides, hydroxides, oxide hydroxides and simple metals of elements occupying M sites, By performing wet mixing and pulverizing treatment in a solvent, composite water that does not generate by-products other than water, and that is inexpensive and efficient, can be a precursor of A _1-x B _x MO ₃₊ δ-type composite oxide. An oxide or a composite oxide hydroxide (hereinafter sometimes referred to as a “hydrated precursor”) can be obtained, and the precursor can be heat treated to contain an A _1-x B _x MO containing a crystalline perovskite phase. The inventors found that ₃₊ δ-type complex oxides can be produced and completed the present invention. It came to make it.

  The aqueous solvent used in the present invention is preferably composed only of water. The manufacturing method of the present invention is particularly effective when a complex oxide in which the element occupying the A site is at least one element of Y, La, Ce, Pr, Sm, Gd, Dy, and Yb is targeted. It is suitable for a complex oxide in which the element occupying the site is La, the element occupying the B site is strontium, and the element occupying the M site is manganese. When wet mixed pulverization is performed in an aqueous solvent, if an elemental metal or a low oxidation number oxide, hydroxide or oxide hydroxide is used as a raw material, an oxidizing agent such as hydrogen peroxide is used. It is preferable to do.

In addition, in order to produce an A _1-x B _x MO ₃₊ δ-type composite oxide containing a crystalline perovskite phase, the temperature at which the precursor obtained by the wet mixed pulverization treatment is heat-treated is 500 to 1200 degreeC is preferable and 600-1000 degreeC is more preferable.

  Further, a crystalline perovskite phase obtained in a wet pulverization process for obtaining the precursor, or a precursor obtained by a wet pulverization process, or a heat treatment of this precursor at a relatively low temperature of 500 ° C. or less. Noble metal solid solution perovskite-type composite oxidation by adding a precious metal salt to a precursor low-temperature heat-treated product containing an amorphous phase in which no metal has yet been formed, followed by heat treatment at a temperature of 500 to 1300 ° C. in an oxidizing atmosphere. Can be manufactured. As the noble metal salt, it is preferable to use an organic carboxylate of a noble metal and / or a diketone complex such as palladium acetylacetonate.

The wet mixing and pulverizing treatment used in the production method of the present invention can be carried out without the need for special equipment or expensive raw materials, and no by-product other than water is generated, and therefore no by-product removal step is required. . Impurities (unreacted substances such as chloride raw materials, by-products, Cl, etc.) that deteriorate performance in various applications by heat treating the precursor obtained by such wet mixing and grinding treatment once at a relatively low temperature. High-quality A _1-x B _x MO ₃₊ δ-type composite oxide that does not contain any of these elements can be produced at low cost and efficiently. Such a method for producing a precursor of A _1-x B _x MO ₃₊ δ-type composite oxide is also useful in that it can be applied to a method for producing a noble metal solid solution perovskite-type composite oxide.

  Hereinafter, raw materials used in the production method of the present invention, methods and conditions for wet mixing and pulverizing treatment, and heat treatment will be described in detail.

A _1-x B _x MO ₃₊ δ Type Composite Oxide A composite oxide which is an object of the present invention is represented by the general formula A _1-x B _x MO ₃₊ δ. In the formula, A is occupied by at least one element selected from rare earth elements, B is occupied by at least one element selected from calcium, strontium, and barium, and M is selected from manganese, iron, cobalt, and nickel. Occupied with at least one element. x is a number satisfying 0 <x ≦ 1.0. Further, δ represents an excess amount of oxygen or an oxygen deficiency that varies depending on the composition (B site addition amount, M valence change, etc.) and heat treatment conditions (temperature, atmosphere, etc.). It is a number that satisfies 5 ≦ δ ≦ 0.5.

  In the production method of the present invention, the element occupying the A site is at least one element of Y, La, Ce, Pr, Sm, Gd, Dy, and Yb, and in particular, the element occupying the A site is La. And suitable for industrially useful composite oxides such as those in which the element occupying the B site is strontium and the element occupying the M site is manganese.

The A site, B site, and M site of the A _1-x B _x MO ₃₊ δ-type composite oxide may be substituted with an element other than the above-described elements by substitution solid solution after the preparation of the precursor. it can. That is, the application target of the manufacturing method of the present invention is A in which the molar ratio [(A + B) / M] of “the above-mentioned element contained in the A site and B site” and “the above-mentioned element contained in the M site” is 1. It is not limited to the _1-x B _x MO ₃₊ δ-type complex oxide.

The rare earth elements occupying the raw material A site [Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu] Oxides [A ₂ O ₃ , AO ₂ ], hydroxides [A (OH) ₃ , A (OH) ₄ ], oxide hydroxides [AO (
OH), AOOH]. In addition, the above compounds include those containing crystal water [A ₂ O ₃ · nH ₂ O, AO ₂ · nH ₂ O, A (OH) ₃ · nH ₂ O, A (OH) ₄ · nH ₂ O, n is a positive number], and for rare earth hydroxides and rare earth oxide hydroxides, non-stoichiometric rare earth oxide hydrates [A ₂ O ₃ .XH ₂ O, AO ₂ .XH ₂ O and X are arbitrary positive numbers]. These substances may be crystalline or amorphous. Any one of the rare earth element occupying the A site may be used alone, or two or more may be used in combination.

Examples of raw material components of elements occupying the B site [calcium (Ca), strontium (Sr), barium (Ba)] include oxides [BO] and hydroxides [B (OH) ₂ ] of these elements. . The above-mentioned compounds include those containing crystal water [BO.nH ₂ O, B (OH) ₂ .nH ₂ O, n is a positive number]. Hydrate of product [
BO · XH ₂ O, X is an arbitrary positive number]. These substances may be crystalline or amorphous. As the raw material component of the element occupying the B site, any one kind may be used alone, or two or more kinds may be used in combination.

As raw material components of elements occupying M sites [manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni)], oxides of these elements [M ₂ O ₃ , MO, MnO ₂ , M ₃ O ₄ ], hydroxide [M (OH) ₂ , M (OH) ₃ , M (OH) ₄ ], oxidized hydroxide [MO (OH)], and simple metal. The above compound contains water of crystallization [M ₂ O ₃ .nH ₂ O,
MO ₂ · nH ₂ O, M ₃ O ₄ · nH ₂ O, M (OH) ₂ · nH ₂ O, M (OH) ₃ · nH ₂ O, M (OH) ₄ · nH ₂ O, n is positive Number], and for hydroxides and oxide hydroxides, non-stoichiometric oxide hydrates [MO · XH ₂ O, M ₂ O ₃ · XH ₂ O, MO ₂ · XH ₂ O, X is an arbitrary positive number]. These substances may be crystalline or amorphous. Any one of the raw material components of the element occupying the M site may be used alone, or two or more may be used in combination.

The raw material whose M element is divalent or zero valent (metal simple substance) reacts with water in an aqueous solvent to form an oxide, hydroxide or oxide hydroxide. In the case of using these raw materials, an oxidizing agent (for example, a 30% aqueous hydrogen peroxide (H ₂ O ₂ ) solution is preferably used), an oxide, a hydroxide or an oxyhydroxide in order to accelerate the reaction. It is preferable to add about 10 equivalents or less of the stoichiometric amount necessary for forming the product.

The particle size of the material used as the raw material is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 10 μm or less. For metals and oxides, hydration or hydroxide formation occurs during the mixing and grinding process, and the particle size becomes small. Therefore, there is no problem even if the initial particle size of these raw materials is large.
Moreover, the compounding amount of each component of the raw material should be such that the amount ratio of each element occupying the A site, B site and M site in the raw material is comparable to the amount ratio in the target composite oxide. .

Wet mixing and pulverization treatment The raw material wet mixing and pulverization treatment in the present invention is generally carried out in an aqueous solvent using a mixing and pulverizing machine.

  The aqueous solvent in the present invention is a solvent (grinding medium) that is put into a grinding container together with raw materials when preparing a hydrated precursor (composite hydroxide or composite oxide hydroxide) by mixing and grinding. Industrially, it is preferable to use only inexpensive water, but a mixed solvent containing water and an organic solvent compatible with water may be used.

This aqueous solvent is usually prepared in advance and supplied into the pulverization container before the start of the mixing and pulverizing treatment. The raw material is an oxide, hydroxide or oxide hydroxide containing crystal water. In this case, only an organic solvent compatible with water is supplied into the pulverization vessel, and the treatment is performed in an aqueous solvent composed of crystal water and organic solvent released after the start of mixed pulverization. Also good.

  The organic solvent compatible with water is not particularly limited, but alcohols (methanol, ethanol, propanol, butanol, etc.), ethers (diethyl ether, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, diethyl) Ketones), polyhydric alcohols (ethylene glycol, etc.), sulfoxides (dimethyl sulfoxide, etc.) and the like. Any one of these organic solvents may be used alone, or two or more thereof may be used in combination.

  As the organic solvent compatible with water, it is desirable to employ an organic solvent having an appropriate relative dielectric constant and viscosity according to the raw material and the wet mixing and pulverization processing conditions. If the relative permittivity of the organic solvent is in an appropriate range, the dispersibility of the pulverized product in the aqueous solvent is not too high, and the formation of particle aggregates (aggregated particles) is sufficient, and the perovskite type obtained by heat treatment The crystallinity of the composite oxide is improved. Further, if the viscosity of the organic solvent is in an appropriate range, a sedimentary particle aggregate is formed, and the pulverization stress effectively acts on the particle aggregate, so that the crystallinity is further improved.

  If an organic solvent (benzene, toluene, xylene, etc.) that is not compatible with water is mixed with water and used as a grinding fluid, the raw material powder will adhere to the inside of the mixing and grinding machine, and mixing and grinding treatment Although the efficiency may be greatly reduced, such an organic solvent incompatible with water can be used by mixing with an organic solvent (and water) compatible with water.

  The amount of water in the aqueous solvent is not particularly limited, but it is more than the amount that the composite hydroxide or composite oxide hydroxide hydrate produced by the wet mixing and pulverization process satisfies the stoichiometric composition. Is desirable. In this case, the development of the precursor particle aggregate is improved, and the crystallization to the perovskite phase by heat treatment can be further promoted. In the case where crystallization water is included in the material used as the precursor raw material, the amount of water initially added to the aqueous solvent can be adjusted in consideration of the amount of crystallization water.

  The mixing pulverizer may be any material that can mechanically pulverize and grind the raw material. For example, the raw material and a pulverizing medium (rod, cylinder, ball, bead, etc.) are placed in a pulverization container. A ball mill such as a rolling ball mill, a vibration ball mill, a stirring ball mill, or a planetary ball mill that pulverizes the raw material by stirring is suitable. Crushers with such a continuous ball mill (for example, “SC Mill” manufactured by Mitsui Mining Co., Ltd., “Dyno Mill” manufactured by Shinmaru Enterprises Co., Ltd.), or very small balls (beads) having a diameter of 1 mm or less. A ball mill that can be used is also recommended.

As a ball (bead) which is a typical grinding medium, a diameter of about 0.1 to 10 mm, Z
Materials made of materials such as rO ₂ (zirconia), Si ₃ N ₄ (silicon nitride), SiC (silicon carbide), WC (tungsten carbide), and steel can be used. For example, zirconia balls manufactured by Tosoh Corporation “YTZ” (registered trademark) is preferred.

What is necessary is just to adjust the process conditions of wet-mixing grinding suitably according to the kind of mixing-grinding machine. For example, when a planetary ball mill is used, the filling amount of balls (beads) as a grinding medium is 15 to 60 mL, the total filling amount of the aqueous solvent and the raw material is 10 to 30 mL per 100 mL of the container volume, and the aqueous solvent It is preferable that the concentration of the raw material in the mixture of the raw material is 2 to 30% by volume. The revolution speed of the planetary ball mill is usually 1 to 10 Hz, preferably 4 to 6 H.
z, and the processing time for mixing and grinding is preferably 1 to 10 hours.

Heat treatment The above-mentioned wet mixed pulverization product is filtered off and dried, whereby a powdery hydrated precursor of the A _1-x B _x MO ₃₊ δ-type composite oxide (composite hydroxide or composite oxidation hydroxide) Product) is obtained.

  The filtration method may be appropriately selected from general methods such as pressure filtration, suction filtration, and centrifugal separation. The drying method may be any method such as normal ventilation drying and vacuum drying. In the wet mixing and pulverizing treatment of the present invention, by-products other than water (such as salts) are not generated, and drying methods such as evaporation to dryness and spray drying can also be employed. Although drying temperature is not specifically limited, 50-300 degreeC is preferable.

The hydrated precursor thus obtained was crystallized by heat treatment (calcination) (all are crystalline perovskite phases, or partly amorphous phases, other crystalline phases or their Both are mixed or both cases are included.) A _1-x B _x MO ₃₊ δ-type composite oxide is obtained.

The heat treatment conditions (temperature, time, etc.) can be appropriately adjusted according to the target A _1-x B _x MO ₃₊ δ type complex oxide (crystallization rate, etc.). For example, the temperature of the heat treatment is preferably 500 to 1200 ° C, more preferably 600 to 1000 ° C. The heat treatment may be performed in the air or in an inert gas atmosphere such as argon or nitrogen.

The crystallinity of the A _1-x B _x MO ₃₊ δ-type composite oxide can be confirmed by an X-ray diffraction pattern. When a crystalline perovskite phase is formed in the obtained A _1-x B _x MO ₃₊ δ-type composite oxide, a sharp peak appears in the X-ray diffraction pattern. On the other hand, the A _1-x B _x MO ₃₊ δ-type composite oxide in which the crystalline perovskite phase is not yet formed (is amorphous) and is obtained when heat-treated at a relatively low temperature is a crystalline perovskite phase. No clear peak is shown.

Method for producing noble metal solid solution perovskite type complex oxide In the present invention, a precursor obtained by wet pulverization treatment for obtaining a perovskite type complex oxide precursor as described above, or by wet pulverization treatment, or this precursor A noble metal salt is added to a precursor low-temperature heat-treated product containing an amorphous phase in which a crystalline perovskite phase is not yet formed, which is obtained by a relatively low-temperature heat treatment at 500 ° C. or lower, and then heat-treated. A solid solution perovskite complex oxide can be produced.

  Addition and mixing of the noble metal salt to the precursor or the low-temperature processed precursor containing an amorphous phase can be carried out by using a dry pulverizer or the like, but the noble metal salt is mixed in a wet manner. The method is preferred. For example, it is more preferable to stir and mix in a solvent in which a noble metal salt is dissolved.

  As the noble metal salt, inorganic salts such as nitrates, chlorides, dinitrodiammine nitrates, hexaammine chlorides and hexachloro acid hydrates, or organic salts such as carboxylates and diketone complexes of the noble metals to be dissolved are used. be able to. These noble metal salts of Pd, Rh, and Pt may be used in combination of two or more.

  When heat treatment is performed at 500 to 1300 ° C. with a mixture of a precursor or a low temperature precursor containing an amorphous phase and a precious metal salt, the organic salts are decomposed milder than the inorganic salts, and the inorganic salts Since no harmful corrosive gas such as nitric acid is generated during use, and production under clean conditions is possible, in the present invention, a carboxylate and / or diketone complex is used as a noble metal salt. preferable.

Examples of the carboxylate include acetate and propionate. The diketone complex may be represented by the general formula R ¹ COCH ₂ COR ² [wherein R ¹ and R ² may be the same or different, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , S-butyl group, t-butyl group and the like, and an alkyl group having 1 to 4 carbon atoms. ] The metal chelate complex of Pd, Rh, and Pt formed from the diketone compound shown by these is mentioned. Specifically, palladium acetylacetonate [Pd (CH ₃ COCHCOCH ₃ ) ₂ ], rhodium acetylacetonate [Rh (CH ₃ COCHCOCH ₃ ) ₃ ], platinum acetylacetonate [Pt (
CH ₃ COCHCOCH ₃ ) ₂ ] and the like.

  The method for producing a noble metal solid solution perovskite complex oxide of the present invention can be suitably used when palladium acetylacetonate is used as a noble metal salt to produce a palladium solid solution perovskite complex oxide.

The addition amount of the noble metal salt can be appropriately adjusted according to the ratio of substitutional solid solution at the M site.
Further, the solvent for dissolving the noble metal salt is not particularly limited, but when the noble metal salt is an inorganic salt, water, methanol, ethanol, isopropyl alcohol, etc., and in the case of an organic salt, acetone, methanol, ethanol, isopropyl alcohol, benzene, toluene, An organic solvent such as xylene is suitable, and an appropriate amount may be used. These solvents may be used in combination.

  In the wet pulverization process for obtaining the perovskite complex oxide precursor as described above, or the precursor obtained by the wet pulverization process or the low-temperature heat-treated product of this precursor at 500 ° C. or less, a noble metal salt is added. The wet mixture obtained by addition is freed from the solvent, further dried and solidified to obtain a mixture powder, and then heat treated at a temperature of 500 to 1300 ° C. in an oxidizing atmosphere to solidify the noble metal into the crystal lattice. A dissolved noble metal solid solution perovskite complex oxide is produced.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

[Example 1] La _0.5 Sr _0.5 MnO ₃₊ δ
To a planetary ball mill (stainless steel pot, capacity 420 mL) manufactured by Kurimoto Seiko Co., Ltd., 5.65 g of raw powder La ₂ O _3, 9.22 g of Sr (OH) ₂ .8H ₂ O, 6.03 g of electrolytic MnO ₂ , ₂ mmφYTZ ^(R) Ball (manufactured by Tosoh Corp.) 168 mL, acetone 67 mL, and water 1.88 mL were filled, and subjected to revolution and rotation at 6 Hz for 3 hours. The treated product was filtered and vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of La _0.5 Sr _0.5 MnO ₃₊ δ.

The La _0.5 Sr _0.5 MnO ₃₊ δ composite oxide hydrate precursor is heat-treated at 700 ° C. for 1 hour in the air to obtain a single phase of crystalline La _0.5 Sr _0.5 MnO ₃₊ δ composite oxide. was gotten. The specific surface area value was 19 m ² / g. FIG. 1 shows the X-ray diffraction pattern.

[Example 2] La _0.5 Sr _0.5 MnO ₃₊ δ
Raw material powder La _{2 in a} planetary ball mill (stainless steel pot, capacity 420 mL) manufactured by Kurimoto Steel Works
Filled with 5.65 g of O _3, 9.22 g of Sr (OH) ₂ .8H ₂ O, 5.48 g of Mn ₂ O ₃ , 168 mL of ₂ mmφYTZ ^(R) balls, 67 mL of acetone, and 1.88 mL of water, the revolution and rotation speed The treatment was performed for 3 hours at 6 Hz. The treated product was filtered and vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of La _0.5 Sr _0.5 MnO ₃₊ δ.

The La _0.5 Sr _0.5 MnO ₃₊ δ composite oxide hydrated precursor is heat-treated at 800 ° C. for 1 hour in the air to obtain a single phase of crystalline La _0.5 Sr _0.5 MnO ₃₊ δ composite oxide. was gotten. The specific surface area value was 15 m ² / g. FIG. 2 shows the X-ray diffraction pattern.

[Example 3] La _0.5 Sr _0.5 CoO ₃₊ δ
Raw material powder La _{2 in a} planetary ball mill (stainless steel pot, capacity 420 mL) manufactured by Kurimoto Steel Works
5.53 g of O _{3 and} 9.05 g of Sr (OH) ₂ .8H ₂ O and 6.33 g of Co (OH) ₂ , ₂ mmφ
Filled with 168 mL YTZ ^(R) balls, 67 mL acetone, 1.84 mL water,
Treatment for 3 hours was performed at revolution and rotation speed 6 Hz. The treated product was filtered and then vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of La _0.5 Sr _0.5 CoO ₃₊ δ.

The La _0.5 Sr _0.5 CoO ₃₊ δ composite oxide hydrated precursor is heat-treated at 800 ° C. for 1 hour in the air to obtain a single phase of crystalline La _0.5 Sr _0.5 CoO ₃₊ δ composite oxide. was gotten. The specific surface area value was 8 m ² / g. FIG. 3 shows the X-ray diffraction pattern.

Example 4 La _0.5 Sr _0.5 FeO ₃₊ δ
Raw material powder La _{2 in a} planetary ball mill (stainless steel pot, capacity 420 mL) manufactured by Kurimoto Steel Works
O ₃ 5.63 g and _{Sr (OH) 2 · 8H 2} O 9.18g and Fe ₂ O ₃ 5.52g, filled 2mmφYTZ ^(R) ball 168 mL, acetone 67 mL, water 1.87 mL, revolution and rotation rpm The treatment was performed for 3 hours at 6 Hz. The treated product was filtered and vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of La _0.5 Sr _0.5 FeO ₃₊ δ.

The La _0.5 Sr _0.5 FeO ₃₊ δ composite oxide hydrate precursor is heat-treated in the atmosphere at 600 ° C. for 1 hour, whereby a single phase of crystalline La _0.5 Sr _0.5 FeO ₃₊ δ composite oxide is obtained. was gotten. The specific surface area value was 24 m ² / g. FIG. 4 shows the X-ray diffraction pattern.

Example 5 La _0.8 Sr _0.2 MnO ₃₊ δ
Raw material powder La _{2 in a} planetary ball mill (stainless steel pot, capacity 420 mL) manufactured by Kurimoto Steel Works
8.44 g of O _3, 3.44 g of Sr (OH) ₂ .8H ₂ O, 5.63 g of electrolytic MnO ₂ , ₂ mmφ
A YTZ ^(R) ball ⁽ 168 mL ⁾ , acetone ⁽ 67 mL ⁾ , and water (4.90 mL ⁾ were filled, and a revolution and a rotational speed of 6 Hz were performed for 3 hours. The treated product was filtered and then vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of La _0.8 Sr _0.2 MnO ₃₊ δ.

The La _0.8 Sr _0.2 MnO ₃₊ δ complex oxide hydrate precursor is heat-treated in the atmosphere at 700 ° C. for 1 hour to obtain a crystalline La _0.8 Sr _0.2 MnO ₃₊ δ complex oxide single phase. was gotten. The specific surface area value was 14 m ² / g. FIG. 5 shows how the X-ray diffraction pattern changes with temperature when a La _0.8 Sr _0.2 MnO ₃₊ δ complex oxide hydrate precursor is heat-treated in the atmosphere.

Example 6 Pr _0.2 Sr _0.8 MnO ₃₊ δ
Raw material powder Pr _{6 in a} planetary ball mill (stainless steel pot, volume 420 mL) manufactured by Kurimoto Steel Works
Filled with 2.54 g of O ₁₁ , 15.85 g of Sr (OH) ₂ .8H ₂ O, 6.48 g of electrolytic MnO ₂ , 168 mL of ₂ mmφYTZ ^(R) balls and 76 mL of acetone, and revolution and rotational speed 6 Hz
For 3 hours. The treated product was filtered and then vacuum-dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of Pr _0.2 Sr _0.8 MnO ₃₊ δ.

The hydrated precursor of a composite oxide of the Pr _0.2 Sr _0.8 MnO ₃₊ δ by the heat treatment for 1 hour at 1000 ° C. in air, single phase crystalline Pr _0.2 Sr _0.8 MnO ₃₊ δ complex oxide was gotten. The specific surface area value was 12 m ² / g. FIG. 6 shows the X-ray diffraction pattern.

Example 7 La _0.8 Ca _0.2 MnO ₃₊ δ
Raw material powder La _{2 in a} planetary ball mill (stainless steel pot, capacity 420 mL) manufactured by Kurimoto Steel Works
8.80 g of O ₃ , 0.76 g of CaO, 5.87 g of electrolytic MnO ₂ , 168 mL of ₂ mmφYTZ ^(R) balls, 77 mL of acetone, and 7.30 mL of water were charged, and the treatment was performed for 3 hours at revolution and rotation speed of 6 Hz. . The treated product was filtered and vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of La _0.8 Ca _0.2 MnO ₃₊ δ.

The hydrated precursor of a composite oxide of the La _0.8 Ca _0.2 MnO ₃₊ δ by the heat treatment for 1 hour at 700 ° C. in air, single phase crystalline La _0.8 Ca _0.2 MnO ₃₊ δ complex oxide was gotten. The specific surface area value was 10 m ² / g. FIG. 7 shows the X-ray diffraction pattern.

Example 8 SrMO ₃₊ δ (M = Fe, Mn, Co)
A planetary ball mill (stainless steel pot, 420 mL capacity) made by Kurimoto Steel Works was filled with raw material powder, 168 mL of ² mmφYTZ ^(R) balls, acetone and water at the ratios shown in Table 1, respectively, and 3 hours at 6 Hz revolution and rotation speed. Processing was performed. The treated product was filtered and then vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of SrFeO ₃₊ δ, SrMnO ₃₊ δ and SrCoO ₃₊ δ.

The above hydrated precursors of the composite oxides of SrFeO ₃₊ δ, SrMnO ₃₊ δ and SrCoO ₃₊ δ, SrFeO ₃₊ δ is 600 ° C., SrMnO ₃₊ δ and SrCoO ₃₊ δ are 700 ° C. in the atmosphere. 1 hour heat treatment was performed. In any case, a single phase of a composite oxide of crystalline SrFeO ₃₊ δ, SrMnO ₃₊ δ and SrCoO ₃₊ δ was obtained. The specific surface area value of SrFeO ₃₊ [delta] was 6.1 m ² / g at 13m ² / g, 800 ℃ at 24m ² / g, 700 ℃ at 600 ° C.. The specific surface area values of SrMnO ₃₊ δ were 13 m ² / g at 700 ° C. and 9.0 m ² / g at 800 ° C. The specific surface area values of SrCoO ₃₊ δ were 6.5 m ² / g at 700 ° C. and 3.5 m ² / g at 800 ° C. FIG. 8 shows an X-ray diffraction pattern when heat-treated at 800 ° C. for 1 hour.

Example 9 La _0.5 Sr _0.5 Mn _0.8 Ni _0.2 O ₃₊ δ
Raw material powder La _{2 in a} planetary ball mill (stainless steel pot, capacity 420 mL) manufactured by Kurimoto Steel Works
O ₃ 5.63 g and _{Sr (OH) 2 · 8H 2} O9.19g an electrolytic MnO ₂ 4.81 g and _{Ni (OH) 2 1.28g, 2mmφYTZ} (R) ball 168 mL, acetone 67 mL, water 1.62mL filling And the process for 3 hours was performed at the revolution and rotation speed 6Hz. The treated product was filtered and vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of La _0.5 Sr _0.5 Mn _0.8 Ni _0.2 O ₃₊ δ.

The La _0.5 Sr _0.5 Mn _0.8 Ni _0.2 O ₃₊ δ precursor is subjected to a heat treatment in the atmosphere at 600 ° C. for 1 hour to obtain crystalline La _0.5 Sr _0.5 Mn _0.8 Ni _0.2 O _3+. A single phase of δ complex oxide was obtained. The specific surface area value was 17m ² / g at 19m ² / g, 800 at 19m ² / g, 700 ℃ at 600 ° C.. FIG. 9 shows an X-ray diffraction pattern when heat-treated at 800 ° C. for 1 hour.

Example 10 La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co)
A planetary ball mill (stainless steel pot, volume 420 mL) manufactured by Kurimoto Steel Works was filled with raw material powder, 168 mL of 2 mmφYTZ ^(R) balls, acetone, and water at the ratios shown in Table 2, respectively, and the revolution and rotational speed of 6 Hz were 3 hours. Processing was performed. Thereafter, palladium acetylacetonate [Pd (CH ₃ COCHCOCH ₃ ) ₂ ] was added to the planetary ball mill at the ratios shown in Table 2, respectively, and further subjected to a revolution and a rotation speed of 6 Hz for 20 minutes. The treated product was evaporated to obtain a powder. The obtained powder was vacuum dried at 85 ° C. for 15 hours, and La _0.6 Sr _0.4 Fe _0.95 Pd _0.05 O ₃₊ δ, La _0.6 Sr _0.4 Mn _0.95 Pd _0.05 O ₃₊ δ, La _0.6 Sr _0.4 Co
_A hydrated precursor of a complex oxide of _0.95 Pd _0.05 O ₃₊ δ was obtained.

The La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co) composite oxide hydrated precursor is heat-treated at 800 ° C. for 1 hour in the atmosphere to obtain crystalline La _0.6 A single phase of a composite oxide of Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co) was obtained. Specific surface area values are La _0.6 Sr _0.4 Fe _0.95 Pd _0.05 O ₃₊ δ 13 m ² / g, La _0.6 Sr _0.4 Mn _0.95 Pd _0.05 O ₃₊ δ 17 m ² / g, La _0.6 Sr _0.4 Co _0.95 Pd _0.05 O _{3 +} δ was 14 m ² / g. FIG. 10 shows the X-ray diffraction pattern.

Example 11 La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co)
A planetary ball mill (stainless steel pot, volume 420 mL) manufactured by Kurimoto Steel Works was filled with raw material powder, 168 mL of 2 mmφYTZ ^(R) balls, acetone, and water at the ratios shown in Table 2, respectively, and the revolution and rotational speed of 6 Hz were 3 hours. Processing was performed. After filtering the treated product, vacuum drying was performed at 85 ° C. for 15 hours, La _0.6 Sr _0.4 Fe _0.95 O ₃₊ δ, La _0.6 Sr _0.4 Mn _0.95 O ₃₊ δ, La _0.6 Sr _0.4 Co _0.95 O ₃₊ δ, A hydrated precursor of the composite oxide was obtained. Next, palladium acetylacetonate [Pd (CH ₃ COCHCOCH ₃ ) ₂ ] is added to Table 2 as a hydration precursor of a composite oxide of La _0.6 Sr _0.4 M _0.95 O ₃₊ δ (M = Fe, Mn, Co). The indicated ratio and 300 g of toluene were placed in a round bottom flask, stirred and mixed for 1 hour under heating and reflux, and then the solvent was distilled off to obtain a powder. The obtained powder was air-dried at 80 ° C. for 12 hours and then heat-treated in the air at 800 ° C. for 1 hour to obtain crystalline La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co). A single phase of composite oxide was obtained. Specific surface area values are La _0.6 Sr _0.4 Fe _0.95 Pd _0.05 O ₃₊ δ 13 m ² / g, La _0.6 Sr _0.4 Mn _0.95 Pd _0.05 O ₃₊ δ 16 m ² / g, La _0.6 Sr _0.4 Co _0.95 Pd _0.05 O _{3 +} δ was 15 m ² / g. FIG. 11 shows the X-ray diffraction pattern.

Example 12 La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co)
A planetary ball mill (stainless steel pot, volume 420 mL) manufactured by Kurimoto Steel Works was filled with raw material powder, 168 mL of 2 mmφYTZ ^(R) balls, acetone, and water at the ratios shown in Table 2, respectively, and the revolution and rotational speed of 6 Hz were 3 hours. Processing was performed. After filtering the treated product, vacuum drying was performed at 85 ° C. for 15 hours, La _0.6 Sr _0.4 Fe _0.95 O ₃₊ δ, La _0.6 Sr _0.4 Mn _0.95 O ₃₊ δ, La _0.6 Sr _0.4 Co _0.95 O ₃₊ δ, A hydrated precursor of the composite oxide was obtained. This La _0.6 Sr _0.4 M _0.95 O ₃₊ δ (M = Fe, Mn, Co) composite oxide hydrated precursor is subjected to heat treatment at 400 ° C. for 1 hour in the atmosphere to produce La _0.6 Sr _0.4 M _0.95 O. A powder containing an amorphous phase of a composite oxide of ₃₊ δ (M = Fe, Mn, Co) was obtained. Next, palladium acetylacetonate [Pd (CH ₃ COCHCOCH ₃ ) ₂ ] in the ratio shown in Table 2 and 300 g of toluene are placed in a round bottom flask and stirred for 1 hour with heating under reflux. Distilled to obtain a powder. The obtained powder was air-dried at 80 ° C. for 12 hours and then heat-treated in the air at 800 ° C. for 1 hour to obtain crystalline La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co). A single phase of composite oxide was obtained. Specific surface area values are La _0.6 Sr _0.4 Fe _0.95 Pd _0.05 O ₃₊ δ 13 m ² / g, La _0.6 Sr _0.4 Mn _0.95 Pd _0.05 O ₃₊ δ 17 m ² / g, La _0.6 Sr _0.4 Co _0.95 Pd _0.05 O _{3 +} δ was 15 m ² / g. FIG. 12 shows the X-ray diffraction pattern.

Example 13 Sr _1.0 Co _0.95 Pd _0.05 O ₃₊ δ
Raw material powder Sr (stainless steel pot, capacity 420 mL) made by Kurimoto Steel Factory
OH) ₂ · 8H ₂ O 20.74 g, Co (OH) ₂ 6.73 g, ₂ mmφYTZ ^(R) ball 168 mL, acetone 75 mL are charged, and charged and subjected to revolution and rotation at 6 Hz for 3 hours. It was. The treated product was filtered and then vacuum dried at 85 ° C. for 15 hours to obtain a hydrated precursor of a composite oxide of SrCoO ₃₊ δ. Subsequently, palladium acetylacetonate [Pd (CH ₃ COCHCOCH ₃ ) ₂ ] 1.168 was added to the hydrated precursor of the composite oxide of SrCo _0.95 O ₃₊ δ.
g and 300 g of toluene were placed in a round bottom flask and stirred and mixed for 1 hour under heating and reflux, and then the solvent was distilled off to obtain a powder. The obtained powder was air-dried at 80 ° C. for 12 hours and then heat-treated at 800 ° C. for 1 hour in the atmosphere to obtain a substantially single phase of crystalline SrCo _0.95 Pd _0.05 O ₃₊ δ complex oxide. It was 6.8 m ² / g. FIG. 13 shows the X-ray diffraction pattern.

2 is an X-ray diffraction pattern of the crystalline La _0.5 Sr _0.5 MnO ₃₊ δ composite oxide obtained in Example 1. FIG. 4 is an X-ray diffraction pattern of the crystalline La _0.5 Sr _0.5 MnO ₃₊ δ composite oxide obtained in Example 2. FIG. 4 is an X-ray diffraction pattern of the crystalline La _0.5 Sr _0.5 CoO ₃₊ δ composite oxide obtained in Example 3. FIG. 4 is an X-ray diffraction pattern of the crystalline La _0.5 Sr _0.5 FeO ₃₊ δ composite oxide obtained in Example 4. FIG. X-ray diffraction pattern of crystalline La _0.8 Sr _0.2 MnO ₃₊ δ complex oxide obtained in Example 5 (heating change). 6 is an X-ray diffraction pattern of the crystalline Pr _0.2 Sr _0.8 MnO ₃₊ δ composite oxide obtained in Example 6. FIG. X-ray diffraction pattern of crystalline La _0.8 Ca _0.2 MnO ₃₊ δ complex oxide obtained in Example 7. 8 is an X-ray diffraction pattern of the crystalline SrMO ₃₊ δ (M = Fe, Mn, Co) composite oxide obtained in Example 8. FIG. X-ray diffraction pattern of the resulting crystalline _{La 0.5 Sr 0.5 Mn 0.8 Ni 0.2} O 3+ δ complex oxide in Example 9. The X-ray diffraction pattern of the crystalline La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co) composite oxide obtained in Example 10. The X-ray diffraction pattern of the crystalline La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co) composite oxide obtained in Example 11. The X-ray diffraction pattern of the crystalline La _0.6 Sr _0.4 M _0.95 Pd _0.05 O ₃₊ δ (M = Fe, Mn, Co) composite oxide obtained in Example 12. The X-ray diffraction _{pattern of the} crystalline Sr _1.0 Co _0.95 Pd _0.05 O ₃₊ δ composite oxide obtained in Example 13.

Claims (14)

General formula A _1-x B _x MO ₃₊ δ (where A is occupied by at least one element selected from rare earth elements, and B is occupied by at least one element selected from calcium, strontium, and barium) , M is occupied by at least one element selected from the group consisting of manganese, iron, cobalt, and nickel, and is a precursor of a composite oxide represented by 0 <x ≦ 1.0 and −0.5 ≦ δ ≦ 0.5) A method for manufacturing a body,
At least one of oxides, hydroxides and oxide hydroxides of elements occupying A site, at least one of oxides and hydroxides of elements occupying B site, and elements occupying M site A composite hydroxide which becomes the above precursor by subjecting a raw material containing at least one of oxides, hydroxides, oxide hydroxides, and simple metals as a component to wet mixing and pulverization in an aqueous solvent. Alternatively, a method for producing a precursor of an A _1-x B _x MO ₃₊ δ-type composite oxide, which comprises obtaining a composite oxide hydroxide. The method for producing a precursor of an A _1-x B _x MO ₃₊ δ-type complex oxide according to claim 1, wherein the aqueous solvent is only water. 2. The A _1-x B _{x according} to claim 1, wherein the element occupying the A site is at least one element of Y, La, Ce, Pr, Sm, Gd, Dy, and Yb. A method for producing a precursor of MO ₃₊ δ-type composite oxide. 2. The A _1-x B _x MO according to claim 1, wherein the element occupying the A site is La, the element occupying the B site is strontium, and the element occupying the M site is manganese. _A method for producing a precursor of ₃₊ δ-type complex oxide. 5. The A _1-x B _x MO ₃₊ δ-type composite oxide according to claim 1, wherein an oxidizing agent is used when performing wet mixing and pulverization in the aqueous solvent. A method for producing the precursor. The method for producing a precursor of an A _1-x B _x MO ₃₊ δ-type complex oxide according to claim 5, wherein the oxidizing agent is hydrogen peroxide water. Production of an A _1-x B _x MO ₃₊ δ-type composite oxide containing a crystalline perovskite phase, wherein the precursor obtained by the production method according to claim 1 is heat-treated. Method. The method for producing an A _1-x B _x MO ₃₊ δ-type composite oxide containing a crystalline perovskite phase according to claim 7, wherein the temperature of the heat treatment is 500 to 1200 ° C. The method for producing an A _1-x B _x MO ₃₊ δ-type composite oxide containing a crystalline perovskite phase according to claim 7, wherein the temperature of the heat treatment is 600 to 1000 ° C.   A noble metal, wherein a noble metal salt is added in a wet mixed pulverization process for obtaining a precursor by the production method according to any one of claims 1 to 6 and heat-treated at a temperature of 500 to 1300 ° C in an oxidizing atmosphere. A method for producing a solid solution perovskite complex oxide.   A noble metal solid solution perovskite type composite oxidation characterized by adding a noble metal salt to the precursor obtained by the production method according to any one of claims 1 to 6 and heat-treating the precursor at a temperature of 500 to 1300 ° C in an oxidizing atmosphere. Manufacturing method. A precursor obtained by the production method according to claim 1 is heat-treated at a temperature of 500 ° C. or lower, a noble metal salt is added, and the heat treatment is performed at a temperature of 500 to 1300 ° C. in an oxidizing atmosphere. A method for producing a noble metal solid solution perovskite complex oxide.   The method for producing a noble metal solid solution perovskite complex oxide according to any one of claims 10 to 12, wherein the noble metal salt is a noble metal organic carboxylate and / or diketone complex.   The method for producing a noble metal solid solution perovskite complex oxide according to claim 13, wherein the noble metal salt is palladium acetylacetonate.

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