JPH0725556B2 - Bismuth-palladium-copper oxide having tetragonal structure and its production method - Google Patents
Bismuth-palladium-copper oxide having tetragonal structure and its production methodInfo
- Publication number
- JPH0725556B2 JPH0725556B2 JP3256983A JP25698391A JPH0725556B2 JP H0725556 B2 JPH0725556 B2 JP H0725556B2 JP 3256983 A JP3256983 A JP 3256983A JP 25698391 A JP25698391 A JP 25698391A JP H0725556 B2 JPH0725556 B2 JP H0725556B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- palladium
- bismuth
- copper oxide
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000005751 Copper oxide Substances 0.000 title claims description 24
- 229910000431 copper oxide Inorganic materials 0.000 title claims description 24
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 20
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 10
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 239000006104 solid solution Substances 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- KGYVPEZNLFNUKA-UHFFFAOYSA-N bismuth palladium Chemical compound [Pd].[Bi] KGYVPEZNLFNUKA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 copper oxide compound Chemical class 0.000 description 1
- UTDFEXXDUZZCQQ-UHFFFAOYSA-N copper;oxobismuth Chemical class [Cu].[Bi]=O UTDFEXXDUZZCQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 229910000953 kanthal Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、正方晶系の構造を有す
る新規なビスマス・パラジウム・銅酸化物とその製造法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel bismuth-palladium-copper oxide having a tetragonal structure and a process for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
２成分系のビスマス・パラジウム酸化物化合物(Ｂi2Ｐd
Ｏ4)や、ビスマス・銅酸化物化合物(Ｂi2ＣuＯ4)の存在
は知られており、いずれも、空間群Ｐ４／nncに属する
正方晶系の同一構造を有している。これら公知の両化合
物の結晶学的データと熱特性とを2. Description of the Related Art Conventionally, the problems to be solved by the invention
Binary bismuth-palladium oxide compound (Bi 2 Pd
O 4 ) and bismuth / copper oxide compound (Bi 2 CuO 4 ) are known to exist, and both have the same tetragonal structure belonging to the space group P4 / nnc. The crystallographic data and thermal properties of both these known compounds are
【表１】 に示す。また、ビスマス・パラジウム酸化物化合物に関
しては、室温でも良好な電気伝導性を示す半導体である
ことが知られている。[Table 1] Shown in. Further, it is known that the bismuth-palladium oxide compound is a semiconductor showing good electric conductivity even at room temperature.
【０００３】本発明は、上記の２つの酸化物化合物の存
在に鑑みて、正方晶系に属する同一構造を有する新規な
ビスマス・パラジウム・銅酸化物を提供し、またその製
造法を提供することを目的とするものである。In view of the existence of the above-mentioned two oxide compounds, the present invention provides a novel bismuth-palladium-copper oxide having the same structure belonging to the tetragonal system, and a method for producing the same. The purpose is.
【０００４】[0004]
【課題を解決するための手段】前記課題を解決するた
め、本発明者は、従来の正方晶系の構造を有するビスマ
ス・パラジウム酸化物化合物とビスマス・銅酸化物化合
物について分析検討し、酸化ビスマス・酸化パラジウム
・酸化銅の３成分系において、新規な複酸化物を見い出
すべく鋭意研究した結果、ここに新規な酸化物固溶体を
発見したものである。In order to solve the above-mentioned problems, the present inventor analyzed and examined bismuth-palladium oxide compounds and bismuth-copper oxide compounds having a conventional tetragonal structure, -In a three-component system of palladium oxide and copper oxide, as a result of intensive research to find a new complex oxide, a new oxide solid solution was discovered here.
【０００５】すなわち、本発明に係る酸化物固溶体は、
一般式That is, the oxide solid solution according to the present invention is
General formula
【化３】 Ｂｉ２Ｐｄ１−ｘＣｕｘＯ４ （０＜ｘ＜１） で示される正方晶系の構造を有することを特徴とするビ
スマス・パラジウム・銅酸化物である。Embedded image Bi 2 Pd 1-x Cu x O 4 (0 <x <1) is a bismuth-palladium-copper oxide having a tetragonal structure.
【０００６】また、該ビスマス・パラジウム・銅酸化物
の製造法は、酸化ビスマス(Ｂi2Ｏ3)若しくは加熱され
ることにより酸化ビスマスに分解される化合物と、酸化
パラジウム(ＰdＯ)若しくは加熱されることにより酸化
パラジウムに分解される化合物又は酸化されて酸化パラ
ジウムとなる金属パラジウムと、酸化銅(ＣuＯ)若しく
は加熱分解により酸化銅を生ずる化合物とを、酸化ビス
マス、酸化パラジウム、酸化銅の割合がそれぞれ５０モ
ル％、５０(１−ｘ)モル％、５０ｘモル％(ここで、ｘ
は１を超えない正の数である)となるように混合して、
８００℃以下の温度で大気中で加熱することにより、一
般式In the method for producing bismuth-palladium-copper oxide, bismuth oxide (Bi 2 O 3 ) or a compound decomposed into bismuth oxide by heating and palladium oxide (PdO) or heating are used. A compound that is decomposed into palladium oxide or metallic palladium that is oxidized to form palladium oxide, and copper oxide (CuO) or a compound that produces copper oxide by thermal decomposition are respectively mixed in the proportions of bismuth oxide, palladium oxide, and copper oxide. 50 mol%, 50 (1-x) mol%, 50x mol% (where x
Is a positive number that does not exceed 1),
By heating in air at a temperature of 800 ° C or less, the general formula
【化４】 Ｂｉ２Ｐｄ１−ｘＣｕｘＯ４ で示される正方晶系の構造を有するビスマス・パラジウ
ム・銅酸化物を得ることを特徴とするものである。Embedded image A bismuth-palladium-copper oxide having a tetragonal system structure represented by Bi 2 Pd 1-x Cu x O 4 is obtained.
【０００７】以下に本発明について詳述する。The present invention will be described in detail below.
【０００８】[0008]
【０００９】前述の公知の正方晶系の構造を有する酸化
物化合物のうち、代表例とみなされるビスマス・パラジ
ウム酸化物化合物(Ｂi2ＰdＯ4)の場合について粉末Ｘ線
回折の結果を、面間隔実測値、相対強度、面指数(ｈｋ
ｌ)の順にAmong the above-mentioned known oxide compounds having a tetragonal system structure, a powder X-ray diffraction result of a bismuth-palladium oxide compound (Bi 2 PdO 4 ) which is regarded as a typical example is shown by the interplanar spacing. Measured value, relative intensity, surface index (hk
in order of l)
【表２】 に示す。[Table 2] Shown in.
【００１０】一方、本発明に係るビスマス・パラジウム
・銅酸化物固溶体のうち、ｘ＝０.５の場合の一般式Ｂi
2Ｐd0.5Ｃu0.5Ｏ4で示される化合物について、その粉末
Ｘ線回折パターンを同様にOn the other hand, of the bismuth / palladium / copper oxide solid solutions according to the present invention, the general formula Bi in the case of x = 0.5
2 Pd 0. For 5 Cu 0. 5 a compound represented by O 4, similarly to the powder X-ray diffraction pattern
【表３】 に示す。[Table 3] Shown in.
【００１１】表２及び表３を比較対照することから明ら
かなように、本発明に係るこの化合物Ｂi2Ｐd0.5Ｃu0.5
Ｏ4は、上記の公知の化合物Ｂi2ＰdＯ4と同様な正方晶
系の構造を有することがわかる。[0011] Table 2 and as is apparent from a comparison of Table 3, the compound Bi 2 Pd 0 according to the present invention. 5 Cu 0. 5
It can be seen that O 4 has the same tetragonal structure as the known compound Bi 2 PdO 4 described above.
【００１２】なお、図１及び図２は、一般式1 and 2 are represented by the general formula
【化５】 Ｂｉ２Ｐｄ１−ｘＣｕｘＯ４ （０＜ｘ＜１） 、ｘ＝０.１、０.２５、０.５、０.７５、０.９の組成
を有する化合物の格子定数を、組成に対してプロットし
たものである。Embedded image Bi 2 Pd 1-x Cu x O 4 (0 <x <1), x = 0.1, 0.25, 0.5, 0.75, 0.9 lattice of compounds The constants are plotted against composition.
【００１３】以上の分析結果より、本発明に係るビスマ
ス・パラジウム・銅酸化物は、正方晶系の構造を有する
と共に、公知の化合物であるＢi2ＰdＯ4とＢi2ＣuＯ4と
の間で完全固溶体を形成していることが認められる。From the above analysis results, the bismuth-palladium-copper oxide according to the present invention has a tetragonal structure and is completely formed between known compounds Bi 2 PdO 4 and Bi 2 CuO 4. It is recognized that a solid solution is formed.
【００１４】この新規な正方晶系の構造を有するビスマ
ス・パラジウム・銅酸化物は、センサー、触媒等への応
用が期待される。The bismuth / palladium / copper oxide having the novel tetragonal structure is expected to be applied to sensors, catalysts and the like.
【００１５】本発明に係る新規な酸化物は、次の方法に
よって製造される。The novel oxide according to the present invention is produced by the following method.
【００１６】すなわち、酸化ビスマス(Ｂi2Ｏ3)若しく
は加熱されることにより酸化ビスマスに分解される化合
物と、酸化パラジウム(ＰdＯ)若しくは加熱されること
により酸化パラジウムに分解される化合物又は酸化され
て酸化パラジウムとなる金属パラジウムと、酸化銅(Ｃu
Ｏ)若しくは加熱分解により酸化銅を生ずる化合物と
を、酸化ビスマス、酸化パラジウム、酸化銅の割合がそ
れぞれ５０モル％、５０(１−ｘ)モル％、５０ｘモル％
(ここで、ｘは１を超えない正の数である)となるように
混合して、８００℃以下の温度で大気中で加熱すること
により、製造することができる。That is, bismuth oxide (Bi 2 O 3 ) or a compound which is decomposed to bismuth oxide when heated, and palladium oxide (PdO) or a compound which is decomposed to palladium oxide when heated or is oxidized. Metallic palladium that becomes palladium oxide and copper oxide (Cu
O) or a compound that produces copper oxide by thermal decomposition, the proportions of bismuth oxide, palladium oxide, and copper oxide being 50 mol%, 50 (1-x) mol%, and 50x mol%, respectively.
(Where x is a positive number not exceeding 1), and the mixture is heated in the air at a temperature of 800 ° C. or less, whereby the product can be produced.
【００１７】なお、表１に示すように、Ｂi2ＰdＯ4は８
３５℃でＢi2Ｏ3とＰdに分解してしまい、Ｂi2ＣuＯ4は
８４０℃で分解溶融してしまうため、ビスマス・パラジ
ウム・銅酸化物の製造においては、８００℃以下の温度
で加熱する必要がある。As shown in Table 1, Bi 2 PdO 4 is 8
Since it is decomposed into Bi 2 O 3 and Pd at 35 ° C and Bi 2 CuO 4 is decomposed and melted at 840 ° C, it is heated at a temperature of 800 ° C or lower in the production of bismuth / palladium / copper oxide. There is a need.
【００１８】次に本発明の実施例を示す。Next, examples of the present invention will be described.
【００１９】[0019]
【実施例】いずれも純度が９９.９％以上の酸化ビスマ
ス(Ｂi2Ｏ3)と酸化パラジウム(ＰdＯ)と酸化銅(ＣuＯ)
の粉末を、それぞれの割合が５０モル％、２５モル％、
２５モル％となるように秤量し、メノウ乳鉢中で十分に
混合した。この混合物をアルミナルツボに充填し、カン
タル線発熱体電気炉に移し、室温から加熱し始め、７０
０℃で８０時間保った後、ルツボを当該電気炉から取り
出した。生成物はメノウ乳鉢中で再度混合し、同様な手
順で電気炉中で８００℃で６０時間反応させた後、取り
出した。これを分析した結果、表３に示すように正方晶
系に属するビスマス・パラジウム・銅酸化物であった。[Embodiments] All of which have a purity of 99.9% or more, bismuth oxide (Bi 2 O 3 ), palladium oxide (PdO) and copper oxide (CuO).
Powder of 50 mol%, 25 mol%,
Weighed to be 25 mol% and thoroughly mixed in an agate mortar. This mixture was filled in an alumina crucible, transferred to a Kanthal wire heating element electric furnace, and started heating from room temperature.
After maintaining at 0 ° C. for 80 hours, the crucible was taken out of the electric furnace. The product was mixed again in an agate mortar, reacted in the electric furnace at 800 ° C. for 60 hours in the same procedure, and then taken out. As a result of analysis of this, as shown in Table 3, it was bismuth / palladium / copper oxide belonging to the tetragonal system.
【００２０】[0020]
【発明の効果】以上説明したように、本発明によれば、
一般式As described above, according to the present invention,
General formula
【化６】 Ｂｉ２Ｐｄ１−ｘＣｕｘＯ４ で示される正方晶系の構造を有する新規なビスマス・パ
ラジウム・銅酸化物を提供できるので、センサー、触媒
等への利用が期待される。Embedded image Since a novel bismuth-palladium-copper oxide having a tetragonal system structure represented by Bi 2 Pd 1-x Cu x O 4 can be provided, it is expected to be used as a sensor, a catalyst and the like.
【図１】本発明に係る正方晶系に属する酸化物固溶体FIG. 1 is a tetragonal oxide solid solution according to the present invention.
【化７】 Ｂｉ２Ｐｄ１−ｘＣｕｘＯ４ の格子定数(ａ)のＣuＯ濃度による変化を示す図であ
る。FIG. 7 is a diagram showing a change in lattice constant (a) of Bi 2 Pd 1-x Cu x O 4 depending on the CuO concentration.
【図２】本発明に係る正方晶系に属する酸化物固溶体FIG. 2 is a tetragonal oxide solid solution according to the present invention.
【化８】 Ｂｉ２Ｐｄ１−ｘＣｕｘＯ４ の格子定数(ｃ)のＣuＯ濃度による変化を示す図であ
る。FIG. 8 is a diagram showing a change in lattice constant (c) of Bi 2 Pd 1-x Cu x O 4 depending on the CuO concentration.
Claims (2)
スマス・パラジウム・銅酸化物。1. A bismuth-palladium-copper oxide characterized by having a tetragonal structure represented by the general formula: Bi 2 Pd 1-x Cu x O 4 (0 <x <1). .
れることにより酸化ビスマスに分解される化合物と、酸
化パラジウム(ＰdＯ)若しくは加熱されることにより酸
化パラジウムに分解される化合物又は酸化されて酸化パ
ラジウムとなる金属パラジウムと、酸化銅(ＣuＯ)若し
くは加熱分解により酸化銅を生ずる化合物とを、酸化ビ
スマス、酸化パラジウム、酸化銅の割合がそれぞれ５０
モル％、５０(１−ｘ)モル％、５０ｘモル％(ここで、
ｘは１を超えない正の数である)となるように混合し
て、８００℃以下の温度で大気中で加熱することによ
り、一般式 【化２】 Ｂｉ２Ｐｄ１−ｘＣｕｘＯ４ で示される正方晶系の構造を有するビスマス・パラジウ
ム・銅酸化物を得ることを特徴とするビスマス・パラジ
ウム・銅酸化物の製造法。2. Bismuth oxide (Bi 2 O 3 ) or a compound that decomposes to bismuth oxide when heated, and palladium oxide (PdO) or a compound that decomposes to palladium oxide when heated or to be oxidized Metal palladium, which becomes palladium oxide, and copper oxide (CuO) or a compound which produces copper oxide by thermal decomposition, are mixed with bismuth oxide, palladium oxide, and copper oxide at a ratio of 50, respectively.
Mol%, 50 (1-x) mol%, 50x mol% (where
x is a positive number not exceeding 1) and heated in the atmosphere at a temperature of 800 ° C. or lower to give a compound represented by the general formula: Bi 2 Pd 1-x Cu x O 4 A method for producing bismuth-palladium-copper oxide, which comprises obtaining a bismuth-palladium-copper oxide having a tetragonal structure shown by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3256983A JPH0725556B2 (en) | 1991-09-09 | 1991-09-09 | Bismuth-palladium-copper oxide having tetragonal structure and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3256983A JPH0725556B2 (en) | 1991-09-09 | 1991-09-09 | Bismuth-palladium-copper oxide having tetragonal structure and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570148A JPH0570148A (en) | 1993-03-23 |
| JPH0725556B2 true JPH0725556B2 (en) | 1995-03-22 |
Family
ID=17300098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3256983A Expired - Lifetime JPH0725556B2 (en) | 1991-09-09 | 1991-09-09 | Bismuth-palladium-copper oxide having tetragonal structure and its production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725556B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113957394B (en) * | 2021-09-27 | 2023-09-26 | 山东省科学院能源研究所 | P-type semiconductor thin film bismuth copper oxide and preparation method and application thereof |
-
1991
- 1991-09-09 JP JP3256983A patent/JPH0725556B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0570148A (en) | 1993-03-23 |
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