JPH01167232A - Compound having cubic spinel-type structure expressed by incrmn2o5 and production thereof - Google Patents
Compound having cubic spinel-type structure expressed by incrmn2o5 and production thereofInfo
- Publication number
- JPH01167232A JPH01167232A JP32795487A JP32795487A JPH01167232A JP H01167232 A JPH01167232 A JP H01167232A JP 32795487 A JP32795487 A JP 32795487A JP 32795487 A JP32795487 A JP 32795487A JP H01167232 A JPH01167232 A JP H01167232A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- incrmn2o5
- cubic spinel
- heated
- atmosphere
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 10
- 239000011029 spinel Substances 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- -1 manganese metals Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 7
- 239000004020 conductor Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BLBNEWYCYZMDEK-UHFFFAOYSA-N $l^{1}-indiganyloxyindium Chemical compound [In]O[In] BLBNEWYCYZMDEK-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規化合物であるＩｎＣｒＭｎ２Ｏ５で示され
る立方晶系のスピネル型構造を有する化合物およびその
製造法に関する。この新規化合物は半導体材料、陰イオ
ン導電体および触媒材料として使用し得られるものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel compound, InCrMn2O5, having a cubic spinel structure, and a method for producing the same. The new compounds can be used as semiconductor materials, anionic conductors and catalytic materials.
従来技術
従来立方晶系のスピネル型構造を有する化合物としては
、（１）一般式ＡＢ２Ｏｎ （Ａは２価陽イオン。Prior Art Conventional compounds having a cubic spinel structure include (1) the general formula AB2On (A is a divalent cation);
Ｂは３価陽イオンを表わす）で示される走化組成の化合
物、（２）７ Ｆｅ２Ｏ３、ＴｘｉＣｏ２Ｏｅ、 Ｔ
１４ＣＯ４０＋ｚで示される陽イオン欠陥を持つ化合物
が知られている。B represents a trivalent cation), (2) 7 Fe2O3, TxiCo2Oe, T
A compound having a cation defect represented by 14CO40+z is known.
これらの化合物は、陽イオン数と陰イオン数との割合が
３対４，２対３あるいは５対８のものであった。In these compounds, the ratio of the number of cations to the number of anions was 3:4, 2:3, or 5:8.
発明の目的
本発明は従来の立方晶系のスピネル型構造を有する化合
物の陽イオン数と陰イオン数の割合とは異なった４対５
の割合である陰イオン欠陥（酸素イオン欠陥）を有する
新規な立方晶系のスピネル型構造を有する化合物を提供
するにある。Purpose of the Invention The present invention aims to improve the ratio of the number of cations to the number of anions, which is different from the conventional compound having a cubic spinel structure, from 4 to 5.
An object of the present invention is to provide a compound having a novel cubic spinel structure having anion defects (oxygen ion defects) in a proportion of .
発明の構成
本発明の新規化合物はＩｎＣｒＭｎ２Ｏｓで示される立
方晶系のスピネル型構造を有する化合物である。Constitution of the Invention The novel compound of the present invention is a compound having a cubic spinel structure represented by InCrMn2Os.
この化合物は陽イオン数と陰イオン数の割合が４対５で
陰イオン欠陥（酸素イオン欠陥）を有するものであり、
その格子定数はａ ＝８．６２７±０．００１（入）で
ある。この化合物が陰イオン欠陥であるる密度（５，５
４ｇ／ｃ＋ｎ３）とアルキメデス法による実測値（５，
５３ｇ／ｃｍ ３）とがよく一致していることがら結論
づけられる。This compound has anion defects (oxygen ion defects) with a ratio of cations to anions of 4:5,
Its lattice constant is a=8.627±0.001 (in). The density at which this compound is an anion defect (5,5
4g/c+n3) and the actual value measured by Archimedes method (5,
It can be concluded from the fact that the results are in good agreement with 53g/cm3).
この化合物の面指数（ｈｋＪ２）、面間隔（ｄ（人））
〔ｄｏ（人）は実測値、ｄＣ（入）は計算値を示す）、
およびＸ線に対する相対反射強度Ｉ（％）を示すと表−
１の通りである。この化合物は陰イオン導電体、半導体
材料、および触媒材料として使用し得られる。Planar index (hkJ2), planar spacing (d (person)) of this compound
[do (person) indicates the measured value, dC (in) indicates the calculated value),
The table shows the relative reflection intensity I (%) for and X-rays.
As per 1. This compound can be used as anionic conductor, semiconductor material, and catalytic material.
この化合物は次の方法によって製造し得られる。This compound can be produced by the following method.
インジウム、クロムおよびマンガンの金属あるいは金属
酸化物もしくは加熱により金属酸化物となる化合物を、
インジウム、クロムおよびマンガンの割合が原子比で１
対１対２になるように混合し、該混合物を１２００℃以
上の温度で、インジウムおよびクロムが各々３価イオン
状態、マンガンが２価イオン状態を維持する雰囲気中で
加熱することによって得られる。Indium, chromium, and manganese metals or metal oxides, or compounds that become metal oxides when heated,
The proportion of indium, chromium and manganese is 1 in atomic ratio
It is obtained by mixing them in a ratio of 1:2 and heating the mixture at a temperature of 1200° C. or higher in an atmosphere in which indium and chromium are each maintained in a trivalent ion state and manganese is maintained in a divalent ion state.
本発明に用いる出発物質は市販のものをそのまま使用し
てもよいが、出発物質相互間の化学反応を速やかに進行
させるためには粒径が小さい程よく、特に１０μｍ以下
であることが望ましい。また、陰イオン導電体、半導体
材料、触媒材料等として用いる場合には不純物の混入を
きらうので、出発物質の純度は高いほど好ましい。加熱
により金属酸化物となる化合物としては、それぞれの金
属の水酸化物、炭酸塩、硝酸塩等が挙げられる。これら
の原料をそのままあるいはアルコールまたはアセトンと
共に充分混合する。混合割合はＩｎ、 Ｃｒ。Commercially available starting materials for use in the present invention may be used as they are, but in order to speed up the chemical reaction between the starting materials, the smaller the particle size, the better, and it is particularly desirable that the particle size is 10 μm or less. Further, when used as an anion conductor, a semiconductor material, a catalyst material, etc., the higher the purity of the starting material, the better, since contamination with impurities is avoided. Compounds that become metal oxides when heated include hydroxides, carbonates, nitrates, etc. of the respective metals. These raw materials are thoroughly mixed as is or with alcohol or acetone. The mixing ratio is In and Cr.
Ｍｎが原子比で１対１対２の割合である。この割合をは
ずすと目的とする化合物の単一相を得ることができない
。この混合物をＩｎおよびＣｒが各々３価イオンの状態
、Ｍｎが２価イオン状態を維持する雰囲気の下で１２０
０″Ｃ以上に加熱する。加熱時間は数時間もしくはそれ
以上である。加熱後はｏ′ｃに急冷するか、あるいは大
気中に象、速に引き出せばよい。The atomic ratio of Mn is 1:1:2. If this ratio is exceeded, a single phase of the target compound cannot be obtained. This mixture was heated at 120° C. in an atmosphere where In and Cr each maintained a trivalent ion state, and Mn maintained a divalent ion state.
The material is heated to 0"C or above. The heating time is several hours or more. After heating, it may be rapidly cooled to 0"C or quickly drawn out into the atmosphere.
得られるＩｎＣｒＭｎｘＯｓ化合物の色は黒色であり、
粉末Ｘ−線回折法により結晶構造を有することが分かっ
た。その結晶構造はスピネル型であり、通常のスピネル
型化合物が示す陽イオン数と陰イオン数との比である３
対４がら著しくずれた４対５のものであった。The color of the obtained InCrMnxOs compound is black,
It was found to have a crystal structure by powder X-ray diffraction. Its crystal structure is spinel type, and the ratio of the number of cations to the number of anions shown in normal spinel type compounds is 3.
It was 4 to 5, which was a significant deviation from 4 to 4.
実施例
純度９９．９９％以上の酸化インジウム（Ｉｎ２Ｏ＋）
粉末、純度９９．９％以上の酸化クロム（Ｃｒ２Ｏｉ）
粉末および純度９９．９％以上の酸化マンガン（ＭｎＯ
）粉末をモル比で１対１対４の割合に秤量し、めのう乳
ばち内でエタノールを加えて約３０分間混合し、平均粒
径数μｍの微粒子状混合物を得た。該混合物を白金管内
に封入し、１４５０℃に設定された管状シリコニット炉
内に入れ、４日間加熱し、その後試料を炉外で室温まで
象、速に冷却した。得られた試料は．ＩｎＣｒＭｎ２Ｏ
５単一相試料であり、粉末Ｘ−線回折法によって、面指
数（ｈｋｊ２）、各反射の面間隔（ｄ（入））および相
対反射強度■（％）を測定した。Example Indium oxide (In2O+) with a purity of 99.99% or more
Powder, chromium oxide (Cr2Oi) with a purity of 99.9% or more
Powder and manganese oxide (MnO) with a purity of 99.9% or more
) The powder was weighed in a molar ratio of 1:1:4, ethanol was added in an agate mortar, and the mixture was mixed for about 30 minutes to obtain a fine particulate mixture with an average particle size of several μm. The mixture was sealed in a platinum tube and placed in a tubular siliconite furnace set at 1450°C and heated for 4 days, after which the sample was rapidly cooled to room temperature outside the furnace. The obtained sample is. InCrMn2O
The surface index (hkj2), the interplanar spacing of each reflection (d (on)), and the relative reflection intensity (%) were measured using a powder X-ray diffraction method.
その結果は表−１に示す通りであった。The results were as shown in Table-1.
立方晶系としての格子定数は、以下のとおりであった。The lattice constants as a cubic system were as follows.
ａ ＝８．６２７±０．００１ （人）上記の格子定数
および表−１の各反射、ｈｋＩ！。a = 8.627±0.001 (person) The above lattice constant and each reflection in Table 1, hkI! .
より算出した面間隔（ｄ（人））は実測の面間隔（ｄ（
入））と極めてよく一致した。また原料重量を加熱前後
で精密に秤量し、得られた化合物の化学量輸Ｉ矢が上記
のようであることが分かった。The calculated surface distance (d (person)) is the actually measured surface distance (d (
The results were in excellent agreement with the results. In addition, the weight of the raw materials was precisely weighed before and after heating, and it was found that the stoichiometric flux of the obtained compound was as shown above.
発明の効果
本発明は半導体材料、陰イオン導電体、触媒材料として
有用な陰イオン欠陥を有する新規な立方晶系のスピネル
型構造を有する化合物（ＩｎＣｒＭｎ２Ｏｓ）を提供し
得たものである。Effects of the Invention The present invention has provided a novel compound (InCrMn2Os) having an anion defect and a cubic spinel structure that is useful as a semiconductor material, an anion conductor, and a catalyst material.
Claims (2)
ネル型構造を有する化合物。1. A compound having a cubic spinel structure represented by InCrMn_2O_5.
金属酸化物もしくは加熱により金属酸化物となる化合物
を、インジウム，クロムおよびマンガンの割合が原子比
で１対１対２になるように混合し、該混合物を１２００
℃以上の温度で、インジウムおよびクロムが各々３価イ
オン状態、マンガンが２価イオン状態を維持する雰囲気
中で加熱することを特徴とするＩｎＣｒＭｎ＿２Ｏ＿５
で示される立方晶系のスピネル型構造を有する化合物の
製造法。2. Indium, chromium, and manganese metals or metal oxides or compounds that become metal oxides by heating are mixed so that the atomic ratio of indium, chromium, and manganese is 1:1:2, and the mixture is heated to 1200
InCrMn_2O_5, which is heated at a temperature of ℃ or higher in an atmosphere where indium and chromium each maintain a trivalent ion state and manganese maintain a divalent ion state.
A method for producing a compound having a cubic spinel structure represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32795487A JPH0248491B2 (en) | 1987-12-24 | 1987-12-24 | INCRMN2O5DESHIMESARERURITSUHOSHOKEINOSUPINERUGATAKOZOOJUSURUKAGOBUTSUOYOBISONOSEIZOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32795487A JPH0248491B2 (en) | 1987-12-24 | 1987-12-24 | INCRMN2O5DESHIMESARERURITSUHOSHOKEINOSUPINERUGATAKOZOOJUSURUKAGOBUTSUOYOBISONOSEIZOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01167232A true JPH01167232A (en) | 1989-06-30 |
| JPH0248491B2 JPH0248491B2 (en) | 1990-10-25 |
Family
ID=18204868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32795487A Expired - Lifetime JPH0248491B2 (en) | 1987-12-24 | 1987-12-24 | INCRMN2O5DESHIMESARERURITSUHOSHOKEINOSUPINERUGATAKOZOOJUSURUKAGOBUTSUOYOBISONOSEIZOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0248491B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6800400B2 (en) | 2001-04-19 | 2004-10-05 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
-
1987
- 1987-12-24 JP JP32795487A patent/JPH0248491B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6800400B2 (en) | 2001-04-19 | 2004-10-05 | Sanyo Electric Co., Ltd. | Lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0248491B2 (en) | 1990-10-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |