JP2000226259A - Electroconductive material consisting of cerium vanadium oxide compound - Google Patents
Electroconductive material consisting of cerium vanadium oxide compoundInfo
- Publication number
- JP2000226259A JP2000226259A JP11024863A JP2486399A JP2000226259A JP 2000226259 A JP2000226259 A JP 2000226259A JP 11024863 A JP11024863 A JP 11024863A JP 2486399 A JP2486399 A JP 2486399A JP 2000226259 A JP2000226259 A JP 2000226259A
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- Japan
- Prior art keywords
- oxide compound
- vanadium oxide
- cerium
- heated
- cevo
- 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.)
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- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Conductive Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、正方晶系の構造を
有する一般式ＣｅＶＯ4 で示されるセリウム・バナジウ
ム酸化物化合物からなる電気伝導材料に関する。The present invention relates to relates to electrically conductive material consisting of the general formula cerium-vanadium oxide compounds represented by the CEVO 4 having the structure of tetragonal.
【０００２】[0002]
【従来の技術】従来、セリウム・バナジウム酸化物化合
物（ＣｅＶＯ4 ）は、セリウムの酸化状態が＋３である
ことから、合成原料である酸化物のセリア（ＣｅＯ2 ）
を還元する必要があり、真空中または水素気流中での五
酸化バナジウム（Ｖ2 Ｏ5 ）との固相反応法、あるいは
酸化状態が＋３のセリウムを含む化合物（ＣｅＣｌ
3 等）を溶解した液相からの沈澱法で合成されたものが
知られている。また、セリアと五酸化バナジウムをモル
比で２：１に混合した出発原料を、空気中で固相反応さ
せたＣｅＶＯ4 も知られている。Conventionally, cerium vanadium oxide compounds (CEVO 4) are ceria from the oxidation state of cerium is +3, oxide is a synthetic raw material (CeO 2)
And a solid-phase reaction method with vanadium pentoxide (V 2 O 5 ) in a vacuum or a hydrogen stream, or a compound containing cerium having an oxidation state of +3 (CeCl 2).
3 ) are known which have been synthesized by precipitation from a liquid phase in which is dissolved. CeVO 4 is also known in which a starting material obtained by mixing ceria and vanadium pentoxide at a molar ratio of 2: 1 is subjected to a solid-phase reaction in air.
【０００３】しかし、セリウム・バナジウム酸化物化合
物（ＣｅＶＯ4 ）は、図４に示されるようなジルコン
（ＺｒＳｉＯ4 ，ａ＝６．６１６４オングストローム，
ｃ＝６．０１５０オングストローム）型と称される正方
晶系の結晶構造を有するものであり、これと同一の構造
をもつ希土類・バナジウム酸化物化合物（ＬｎＶＯ4 、
ここで、Ｌｎは、Ｐｒ〜Ｌｕ，Ｙ）は、電気絶縁体であ
り、ＣｅＶＯ4 もこれらと類似の物性を有するものと従
来考えられていた。However, a cerium-vanadium oxide compound (CeVO 4 ) has a zircon (ZrSiO 4 , a = 6.6164 Å, as shown in FIG. 4).
It has a tetragonal crystal structure called c = 6.0150 angstrom type, and has a rare earth / vanadium oxide compound (LnVO 4 ,
Here, Ln is Pr to Lu, Y) is an electric insulator, and CeVO 4 has been conventionally considered to have similar physical properties.
【０００４】[0004]
【発明の構成】本発明者は、従来のセリウム・バナジウ
ム酸化物化合物の種々の合成法について再検討し、適正
な合成条件により得られた正方晶系の結晶構造を有する
ＣｅＶＯ4 の物性について検討するなかで、意外にも、
一般式ＣｅＶＯ4 で示されるＣｅＶＯ4 酸化物化合物
が、同一の結晶構造を有するＬｎＶＯ4 と異なって、良
好な電気伝導性を有することを発見した。The present inventors reexamined various methods for synthesizing conventional cerium-vanadium oxide compounds, and examined the physical properties of CeVO 4 having a tetragonal crystal structure obtained under appropriate synthesis conditions. In doing so, surprisingly,
It has been discovered that the CeVO 4 oxide compound represented by the general formula CeVO 4 has good electrical conductivity, unlike LnVO 4 having the same crystal structure.
【０００５】すなわち、本発明は、一般式ＣｅＶＯ4 で
示される正方晶系の構造を有するセリウム・バナジウム
酸化物化合物からなることを特徴とする電気伝導材料で
ある。本発明のセリウム・バナジウム酸化物化合物から
なる電気伝導材料は、１６０℃における電気伝導度が１
０-5Ｓｃｍ-1であり、図１に示されるように半導体特性
を有している。本発明のセリウム・バナジウム酸化物化
合物からなる電気伝導材料は、良好な電気伝導性を示す
ことから、電極、センサー、触媒等の材料としての用途
を有する。That is, the present invention is an electric conductive material comprising a cerium-vanadium oxide compound having a tetragonal structure represented by the general formula CeVO 4 . The electric conductive material comprising the cerium-vanadium oxide compound of the present invention has an electric conductivity of 1 at 160 ° C.
0 -5 Scm -1 and has semiconductor characteristics as shown in FIG. The electric conductive material comprising the cerium-vanadium oxide compound of the present invention has good electric conductivity and therefore has application as a material for electrodes, sensors, catalysts and the like.
【０００６】本発明のセリウム・バナジウム酸化物化合
物からなる電気伝導材料は、従来公知の方法によって製
造することができ、例えば、セリア（ＣｅＯ2 ）と五酸
化バナジウム（Ｖ2 Ｏ5 ）のモル比２：１の混合物を５
００℃以上の温度で固相反応させることにより得られ
る。The electric conductive material comprising the cerium-vanadium oxide compound of the present invention can be produced by a conventionally known method, for example, a molar ratio of ceria (CeO 2 ) to vanadium pentoxide (V 2 O 5 ). 5: 1 2: 1 mixture
It is obtained by performing a solid phase reaction at a temperature of 00 ° C. or higher.
【０００７】均一な組成のＣｅＶＯ4 セラミックス粉末
を合成するためには、上記の混合物を空気中で６５０℃
で加熱した後、再度粉砕・混合し、８００〜１０００℃
で再加熱することが望ましい。In order to synthesize CeVO 4 ceramic powder having a uniform composition, the above mixture is heated at 650 ° C. in air.
, Then pulverize and mix again, 800-1000 ° C
It is desirable to re-heat.
【０００８】上記のＣｅＶＯ4セラミックス合成粉末を
圧粉成形し、空気中で８５０℃〜１０００℃程度で加熱
することにより多結晶焼結体を製造することができる
他、単結晶、厚膜、薄膜などとしても製造し得る。単結
晶を製造する場合は、例えば、Ｖ2 Ｏ5 を融液としたフ
ラックス法で育成できる。厚膜は、例えばドクターブレ
ード法により、薄膜は例えば、スパッタリング法で製造
することができる。The above-mentioned CeVO 4 ceramic synthetic powder is compacted and heated in air at about 850 ° C. to 1000 ° C. to produce a polycrystalline sintered body. It can also be manufactured as such. When a single crystal is produced, for example, it can be grown by a flux method using V 2 O 5 as a melt. The thick film can be manufactured by, for example, a doctor blade method, and the thin film can be manufactured by, for example, a sputtering method.
【０００９】[0009]
【発明の実施の形態】以下に、一般式ＣｅＶＯ4で示さ
れる正方晶系の構造を有するセリウム・バナジウム酸化
物化合物を得るための空気中での固相反応の条件と反応
生成物の物性の測定結果について説明する。BEST MODE FOR CARRYING OUT THE INVENTION The solid-state reaction conditions in air for obtaining a cerium-vanadium oxide compound having a tetragonal structure represented by the general formula CeVO 4 and the physical properties of the reaction product are described below. The measurement result will be described.
【００１０】まず、セリア（ＣｅＯ2 ）と五酸化バナジ
ウム（Ｖ2 Ｏ5 ）を２：１のモル比で秤量し、混合した
出発原料を、空気中で加熱し、昇温した。固相反応過程
の測定には、示差熱・熱天秤同時測定法を用いた。図２
は、測定の結果を示すグラフである。点線は、示差熱曲
線を、実線は、熱天秤曲線を示す。First, ceria (CeO 2 ) and vanadium pentoxide (V 2 O 5 ) were weighed at a molar ratio of 2: 1 and the mixed starting materials were heated in air to raise the temperature. For the measurement of the solid phase reaction process, a simultaneous measurement method of differential heat and thermobalance was used. FIG.
Is a graph showing measurement results. The dotted line shows the differential heat curve, and the solid line shows the thermobalance curve.
【００１１】その結果は、図２に示すように、混合原料
は、加熱されると、示差熱分析では５１８℃で、熱天秤
では５４０℃で変化が生じている。さらに、示差熱分析
の６６６℃の吸熱ピークは、五酸化バナジウムの融点
（文献値、６９０℃）に対応している。また、この吸熱
ピーク終了と共に、混合原料の熱変化も終了しているこ
とが、熱天秤曲線の結果から明瞭である。As a result, as shown in FIG. 2, when the mixed raw material is heated, a change occurs at 518 ° C. in the differential thermal analysis and at 540 ° C. in the thermal balance. Further, the endothermic peak at 666 ° C. in the differential thermal analysis corresponds to the melting point of vanadium pentoxide (literature value, 690 ° C.). Further, it is clear from the result of the thermobalance curve that the heat change of the mixed raw material has ended along with the end of the endothermic peak.
【００１２】測定終了後の試料を粉末Ｘ線回折で検討し
た結果は、図３に示すようなパターンを呈し、これは、
ジルコン型の正方晶系の結晶構造に由来するものであ
り、目的のＣｅＶＯ4 が生成されたことを表している。The result of examining the sample after the measurement by powder X-ray diffraction shows a pattern as shown in FIG.
It is derived from a zircon-type tetragonal crystal structure, and indicates that the desired CeVO 4 was produced.
【００１３】図２に示された熱天秤曲線から得られる混
合原料の重量減量率３．０９％は、下記の化学反応式で
の酸素の放出（計算値、３．０４％）に対応している。 ２ＣｅＯ2 ＋Ｖ2 Ｏ5 →２ＣｅＶＯ4 ＋（１／２）Ｏ2 したがって、一般式ＣｅＶＯ4 で示される正方晶系の構
造を有するセリウム・バナジウム酸化物化合物は、セリ
ア（ＣｅＯ2 ）と五酸化バナジウム（Ｖ2 Ｏ5）を２：
１のモル比で秤量し、混合した出発原料を、空気中で固
相反応させることにより合成できる。The weight loss of 3.09% of the mixed raw material obtained from the thermobalance curve shown in FIG. 2 corresponds to the release of oxygen (calculated value: 3.04%) in the following chemical reaction formula. I have. 2CeO 2 + V 2 O 5 → 2CeVO 4 + (１ ／) O 2 Therefore, the cerium-vanadium oxide compound having a tetragonal structure represented by the general formula CeVO 4 is composed of ceria (CeO 2 ) and vanadium pentoxide. (V 2 O 5 ) is 2:
The starting materials weighed and mixed at a molar ratio of 1 can be synthesized by a solid-phase reaction in air.
【００１４】得られたＣｅＶＯ4 酸化物化合物の電気伝
導度を測定するために、円盤状の圧粉焼結体を形成し
て、直流２端子法で１６０℃から８００℃まで昇温し、
測定したところ、図１に示すとおりの電気伝導度の温度
変化が見られた。この結果から、このＣｅＶＯ4 酸化物
化合物は、半導体であることが判り、１６０℃の低温度
でも電気伝導度が１０-5Ｓｃｍ-1で、実用に値する良好
な電気伝導性材料であることが確認された。In order to measure the electrical conductivity of the obtained CeVO 4 oxide compound, a disk-shaped sintered compact was formed, and the temperature was raised from 160 ° C. to 800 ° C. by a DC two-terminal method.
As a result of the measurement, a temperature change of the electric conductivity as shown in FIG. 1 was observed. From this result, it can be seen that this CeVO 4 oxide compound is a semiconductor, and has an electric conductivity of 10 −5 Scm −1 even at a low temperature of 160 ° C., indicating that it is a good electric conductive material that is worthy of practical use. confirmed.
【００１５】[0015]
【実施例】次に本発明の実施例を示す。純度が９９．９
％以上の酸化セリウム（ＣｅＯ2 ）と純度が９９．９％
以上の五酸化バナジウム（Ｖ2 Ｏ5 ）の粉末を、モル比
でＣｅＯ2 ：Ｖ2 Ｏ5 が２：１となるように秤量し、メ
ノウ乳鉢中で十分に混合した。この混合物を白金ルツボ
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、６５５℃で１５６時間保った後、ルツボを当
該電気炉から取り出した。Next, examples of the present invention will be described. 99.9 purity
% Or more of cerium oxide (CeO 2 ) and purity of 99.9%
The above-mentioned powder of vanadium pentoxide (V 2 O 5 ) was weighed so that the molar ratio of CeO 2 : V 2 O 5 was 2: 1 and mixed well in an agate mortar. This mixture was filled in a platinum crucible, transferred to a Kanthal wire heating element electric furnace, heated from room temperature, kept at 655 ° C. for 156 hours, and then taken out of the electric furnace.
【００１６】生成物は、メノウ乳鉢中で再度粉砕、混合
した後、８００℃で５７時間、同様に白金ルツボ中で再
加熱し、均一な組成のＣｅＶＯ4 セラミックス粉末を得
た。その粉末Ｘ線回折パターンは、図３と同一であり、
ピーク回折角度から求めた正方晶系の格子定数は、ａ＝
７．４０１６オングストローム、ｃ＝６．４９８０オン
グトロームであった。The product was again ground and mixed in an agate mortar, and then heated again at 800 ° C. for 57 hours in a platinum crucible to obtain a CeVO 4 ceramic powder having a uniform composition. The powder X-ray diffraction pattern is the same as FIG.
The tetragonal lattice constant obtained from the peak diffraction angle is a =
It was 7.4016 angstroms and c = 6.4980 angstroms.
【００１７】電気伝導度測定用試料として、合成された
ＣｅＶＯ4 セラミックス粉末を直径１６ｍｍの金型を使
用して厚さ３ｍｍの圧粉円盤体を作製し、その圧粉体を
さらに９０ＭＰａの静水圧で等方的に圧縮した後、電気
炉中で８５０℃で１２時間加熱焼結した。この焼結体の
両面に白金ペーストを塗布して電極とし、直流２端子法
の電気伝導度測定用試料とした。電気炉中に設置した試
料の電気抵抗を１６０℃から８００℃まで測定した。そ
の結果は、図１に示すように良好な半導性電気伝導度を
示した。As a sample for measuring electric conductivity, a 3 mm-thick compact disk was prepared from the synthesized CeVO 4 ceramic powder using a mold having a diameter of 16 mm, and the compact was further subjected to a hydrostatic pressure of 90 MPa. Then, it was sintered by heating at 850 ° C. for 12 hours in an electric furnace. Platinum paste was applied to both surfaces of this sintered body to form electrodes, which were used as samples for measuring the electrical conductivity by the DC two-terminal method. The electric resistance of the sample placed in the electric furnace was measured from 160 ° C to 800 ° C. The results showed good semiconductive electrical conductivity as shown in FIG.
【００１８】一般式ＣｅＶＯ4 で示される正方晶系の構
造を有するセリウム・バナジウム酸化物化合物は、実施
例に一例を示したような製造方法により製造して電気伝
導材料として各種の用途に使用できる。A cerium-vanadium oxide compound having a tetragonal structure represented by the general formula CeVO 4 can be produced by a production method as exemplified in the examples, and can be used for various uses as an electrically conductive material. .
【図１】本発明セリウム・バナジウム酸化物化合物から
なる電気伝導材料の電気伝導度の温度変化を示すグラ
フ。FIG. 1 is a graph showing the temperature change of the electric conductivity of an electric conductive material comprising a cerium-vanadium oxide compound of the present invention.
【図２】ＣｅＶＯ4 の固相反応合成中の示差熱・熱天秤
同時測定の結果を示すグラフ。FIG. 2 is a graph showing the results of simultaneous measurement of differential heat and thermobalance during solid-phase reaction synthesis of CeVO 4 .
【図３】本発明のセリウム・バナジウム酸化物化合物か
らなる電気伝導材料の粉末Ｘ線回折結果を示すグラフ。FIG. 3 is a graph showing the results of powder X-ray diffraction of an electric conductive material comprising a cerium-vanadium oxide compound of the present invention.
【図４】ジルコンの結晶構造を示す模式図。FIG. 4 is a schematic view showing a crystal structure of zircon.
Claims (1)
構造を有するセリウム・バナジウム酸化物化合物からな
ることを特徴とする電気伝導材料。1. An electrically conductive material comprising a cerium-vanadium oxide compound having a tetragonal structure represented by the general formula CeVO 4 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11024863A JP2000226259A (en) | 1999-02-02 | 1999-02-02 | Electroconductive material consisting of cerium vanadium oxide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11024863A JP2000226259A (en) | 1999-02-02 | 1999-02-02 | Electroconductive material consisting of cerium vanadium oxide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000226259A true JP2000226259A (en) | 2000-08-15 |
Family
ID=12150065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11024863A Pending JP2000226259A (en) | 1999-02-02 | 1999-02-02 | Electroconductive material consisting of cerium vanadium oxide compound |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445399A (en) * | 2014-11-30 | 2015-03-25 | 湘潭大学 | Preparation method of hexagonal cerium vanadate nanodisk and use thereof |
| CN105126814A (en) * | 2013-12-31 | 2015-12-09 | 淮南师范学院 | Preparation method for CeVO4 micro-sphere photocatalyst |
| CN108585040A (en) * | 2018-01-25 | 2018-09-28 | 淮北师范大学 | A kind of CeVO4The fast preparation method of functional material |
| CN110026181A (en) * | 2019-05-13 | 2019-07-19 | 辽宁大学 | A kind of novel Z-type photochemical catalyst CeO2/CeVO4/V2O5And its preparation method and application |
-
1999
- 1999-02-02 JP JP11024863A patent/JP2000226259A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126814A (en) * | 2013-12-31 | 2015-12-09 | 淮南师范学院 | Preparation method for CeVO4 micro-sphere photocatalyst |
| CN105126814B (en) * | 2013-12-31 | 2017-09-15 | 淮南师范学院 | A kind of CeVO4The preparation method of micron ball photocatalyst |
| CN104445399A (en) * | 2014-11-30 | 2015-03-25 | 湘潭大学 | Preparation method of hexagonal cerium vanadate nanodisk and use thereof |
| CN108585040A (en) * | 2018-01-25 | 2018-09-28 | 淮北师范大学 | A kind of CeVO4The fast preparation method of functional material |
| CN110026181A (en) * | 2019-05-13 | 2019-07-19 | 辽宁大学 | A kind of novel Z-type photochemical catalyst CeO2/CeVO4/V2O5And its preparation method and application |
| CN110026181B (en) * | 2019-05-13 | 2022-04-05 | 辽宁大学 | Novel Z-shaped photocatalyst CeO2/CeVO4/V2O5And preparation method and application thereof |
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