JPH10167729A - Plate molybdenum oxide containing alkali metal and its production - Google Patents
Plate molybdenum oxide containing alkali metal and its productionInfo
- Publication number
- JPH10167729A JPH10167729A JP8353665A JP35366596A JPH10167729A JP H10167729 A JPH10167729 A JP H10167729A JP 8353665 A JP8353665 A JP 8353665A JP 35366596 A JP35366596 A JP 35366596A JP H10167729 A JPH10167729 A JP H10167729A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- molybdenum oxide
- oxide containing
- plate
- surface area
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、例えば触媒などに
使用されるモリブデン酸化物に関し、特に特異な形状を
有するアルカリ金属含有モリブデン酸化物及びその製造
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molybdenum oxide used for, for example, a catalyst, and more particularly to an alkali metal-containing molybdenum oxide having a specific shape and a method for producing the same.
【０００２】[0002]
【従来の技術】モリブデン酸化物は、例えば石油系触
媒、反応試薬、潤滑材などとして粉末状のものが使用さ
れている。その電子顕微鏡下での形状は、例えば図４乃
至図７に示したような、球状の一次粒子が塊状に集合し
た形状又は角状の集合体である。2. Description of the Related Art Molybdenum oxides are used in powder form, for example, as petroleum catalysts, reaction reagents, lubricants and the like. The shape under the electron microscope is, for example, a shape in which spherical primary particles are aggregated in a lump or an angular aggregate as shown in FIGS.
【０００３】[0003]
【発明が解決しようとする課題】粉末状のモリブデン酸
化物は、上述のように反応試薬、触媒等に使用される
が、常に粉末であるということを意識した使用方法が取
られてきた。例えば微視的に塊状である粉末は、個々の
みかけの表面積は大きいが使用時には多量集合した粉末
として存在するので、本来の微視的な表面積を生かすた
め、他の物質（高分子、セラミックス等）中に分散して
使用するか、又は粉末そのものを少量ずつ反応場に間欠
的に投与する方法で用いられる。As described above, molybdenum oxide in powder form is used for a reaction reagent, a catalyst and the like as described above, but a method of use has always been taken in consideration of the fact that it is a powder. For example, powders that are microscopically lump have a large apparent surface area, but exist as a large amount of powder when used. Therefore, in order to make use of the original microscopic surface area, other substances (polymers, ceramics, etc.) are used. ), Or used in such a manner that the powder itself is intermittently administered to the reaction field in small quantities.
【０００４】[0004]
【課題を解決するための手段】エレクトロクロミック現
象を示す酸化物の一つとしてモリブデン酸化物が注目さ
れ、例えば特開昭６０−２２８６９８号にモリブデンの
酸化物被覆の製造方法が開示されている。それによれ
ば、導電性を有する基板をモリブデン酸水溶液中に浸漬
し、この基板をカソードとして電解析出を行ない、基板
表面にモリブデンの酸化物被膜を形成させている。Attention has been paid to molybdenum oxide as one of the oxides exhibiting the electrochromic phenomenon. For example, Japanese Patent Application Laid-Open No. 60-228698 discloses a method for producing an oxide coating of molybdenum. According to this method, a conductive substrate is immersed in a molybdic acid aqueous solution, and electrolytic deposition is performed using the substrate as a cathode to form a molybdenum oxide film on the substrate surface.
【０００５】本願の発明者は、この酸化物被膜を剥離す
ることにより形状が微小な板状即ちフレーク状のモリブ
デン酸化物が得られることを見出し、本願発明を完成し
た。The inventor of the present application has found that by removing this oxide film, a plate-like or flake-like molybdenum oxide having a minute shape can be obtained, and the present invention has been completed.
【０００６】本発明においては、形状が板状即ちフレー
ク状であるアルカリ金属含有モリブデン酸化物、好まし
くは厚さが１〜３０μｍ、最大幅が５０〜５００μｍの
板状のアルカリ金属含有モリブデン酸化物である。そし
て、モリブデン酸の金属塩の水溶液を電解液として電解
し、電極上に電着物を析出させた後、該電極を加熱して
電着物を剥離させることによる板状であるアルカリ金属
含有モリブデン酸化物の製造法を提供する。この形状で
は使用時の物質のみかけの嵩密度が小さくなるため、本
来の表面積を生かすことができる。In the present invention, an alkali metal-containing molybdenum oxide having a plate-like or flake shape, preferably a plate-like alkali metal-containing molybdenum oxide having a thickness of 1 to 30 μm and a maximum width of 50 to 500 μm, is used. is there. Then, after electrolyzing an aqueous solution of a metal salt of molybdic acid as an electrolytic solution to deposit an electrodeposit on the electrode, the electrode is heated to peel off the electrodeposit, thereby forming a plate-like alkali metal-containing molybdenum oxide. And a method for producing the same. In this shape, the apparent bulk density of the substance at the time of use is reduced, so that the original surface area can be utilized.
【０００７】[0007]
【発明の実施の形態】本発明のアルカリ金属含有モリブ
デン酸化物のモリブデンの価数は６価乃至４価の混合物
であり、又含有するアルカリ金属は、リチウム、ナトリ
ウム、カリウム、ルビジウム等、各金属のものが得られ
る。さらに複数のアルカリ金属を含有させることも可能
である。該モリブデンの価数、含有アルカリ金属量は、
例えば当業界で手法が公知であるＥＳＣＡ分析により求
めることができる。一般に含有アルカリ金属量は数重量
％乃至２０重量％である。又、本発明のアルカリ金属含
有モリブデン酸化物を電極として適当に充放電すること
により、含有アルカリ金属量を増減させることが可能で
あり、必要に応じて含有量を０重量％にすることもでき
る。BEST MODE FOR CARRYING OUT THE INVENTION The molybdenum in the alkali metal-containing molybdenum oxide of the present invention is a mixture of hexavalent to tetravalent molybdenum, and the contained alkali metal is lithium, sodium, potassium, rubidium or other metal Is obtained. Further, a plurality of alkali metals can be contained. The valence of the molybdenum, the amount of alkali metal contained,
For example, it can be determined by an ESCA analysis whose method is known in the art. Generally, the content of the alkali metal is from several weight% to 20 weight%. Also, by appropriately charging and discharging the alkali metal-containing molybdenum oxide of the present invention as an electrode, the content of the alkali metal can be increased or decreased, and the content can be reduced to 0% by weight, if necessary. .
【０００８】本発明のアルカリ金属含有モリブデン酸化
物の形状は厚さ１〜３０μｍ、幅５０〜５００μｍの板
状であり、この形状のためみかけの嵩密度が従来のもの
より小さくなり、実質的な表面積が増大する。The shape of the alkali metal-containing molybdenum oxide of the present invention is a plate having a thickness of 1 to 30 μm and a width of 50 to 500 μm. The surface area increases.
【０００９】本発明の形状が板状であるアルカリ金属含
有モリブデン酸化物は、モリブデン酸のアルカリ金属塩
の水溶液を電解し、電極上の析出物を加熱することによ
って製造できる。この時の電解時間および加熱温度によ
って、各々該板状酸化物の厚さおよび幅が決定される。
尚該板状酸化物の長さの最大のものは、使用した電極の
電解液中の長さと同一になる。又、使用するモリブデン
酸のアルカリ金属塩のアルカリ金属種を複数個用いる
と、複数のアルカリ金属を含有したモリブデン酸化物が
得られる。The plate-shaped alkali metal-containing molybdenum oxide of the present invention can be produced by electrolyzing an aqueous solution of an alkali metal salt of molybdic acid and heating the deposit on the electrode. At this time, the thickness and width of the plate-like oxide are determined by the electrolysis time and the heating temperature.
The maximum length of the plate-like oxide is the same as the length of the electrode used in the electrolytic solution. When a plurality of alkali metal species of an alkali metal salt of molybdic acid is used, a molybdenum oxide containing a plurality of alkali metals can be obtained.
【００１０】上述した電解法で得られる本発明のアルカ
リ金属含有モリブデン酸化物は、濃茶色から黒色を示
し、１０5 乃至１０8 Ωｃｍの半導体であった。[0010] alkali metal-containing molybdenum oxide of the present invention obtained by the above-described electrolysis showed black from dark brown was semiconductors 10 5 to 10 8 [Omega] cm.
【００１１】[0011]
【実施例】以下、本発明を実施例によりさらに詳細に説
明する。 実施例１〜６ モリブデン酸ナトリウムを表１に示した量を水に溶か
し、硫酸でｐＨを６〜７にし、体積１００ｍｌの電解液
を得た。次いで鉄ニッケル合金を電極として表１で記載
した時間電解した。次に電極上に析出した電着物を充分
水洗した後、表１に列記した温度の加熱炉に２時間放置
し、目的とする板状アルカリ金属含有モリブデン酸化物
を得た。形状値およびアルカリ金属含有量を表２に示し
た。The present invention will be described in more detail with reference to the following examples. Examples 1 to 6 The amounts of sodium molybdate shown in Table 1 were dissolved in water, the pH was adjusted to 6 to 7 with sulfuric acid, and a 100 ml volume electrolytic solution was obtained. Then, electrolysis was performed for the time shown in Table 1 using an iron-nickel alloy as an electrode. Next, the electrodeposits deposited on the electrodes were sufficiently washed with water, and then left in a heating furnace at a temperature listed in Table 1 for 2 hours to obtain a target plate-like alkali metal-containing molybdenum oxide. Table 2 shows the shape values and alkali metal contents.
【００１２】実施例７〜１０ 実施例４でモリブデン酸ナトリウムの代わりにモリブデ
ン酸リチウム、モリブデン酸カリウム、モリブデン酸リ
チウムとモリブデン酸ナトリウム、モリブデン酸アンモ
ニウムとモリブデン酸ナトリウムを使用した以外は、実
施例４と同様にして板状アルカリ金属含有モリブデン酸
化物を得た。各実験で得た板状アルカリ金属含有モリブ
デン酸化物の形状値およびアルカリ金属含有量を表３に
示した。Examples 7 to 10 Example 4 is the same as Example 4 except that lithium molybdate, potassium molybdate, lithium molybdate and sodium molybdate, and ammonium molybdate and sodium molybdate were used in place of sodium molybdate. In the same manner as in Example 1, a plate-like alkali metal-containing molybdenum oxide was obtained. Table 3 shows the shape value and alkali metal content of the plate-like alkali metal-containing molybdenum oxide obtained in each experiment.
【００１３】尚、実施例４で得た板状アルカリ金属含有
モリブデン酸化物の電子顕微鏡写真を図１乃至図３に示
した。又該実施例で得た板状アルカリ金属含有モリブデ
ン酸化物のみかけの嵩密度は、従来のモリブデン酸化物
の嵩密度を１とすると、おおよそ０．０１〜０．３であ
った。An electron micrograph of the plate-like alkali metal-containing molybdenum oxide obtained in Example 4 is shown in FIGS. The apparent bulk density of the plate-like alkali metal-containing molybdenum oxide obtained in the example was about 0.01 to 0.3, where the bulk density of the conventional molybdenum oxide was 1.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【表２】 [Table 2]
【００１６】[0016]
【表３】 [Table 3]
【００１７】[0017]
【発明の効果】本発明の板状アルカリ金属含有モリブデ
ン酸化物は、従来の粉末状のモリブデン酸化物に比較し
てみかけの嵩密度が小さく表面積が大きいためより有効
な反応試薬、触媒となりうる。又板状高表面積を利用し
た各種フィラーとして、或いは含有アルカリ金属の出し
入れを利用した電池等の各種デバイスに利用できる。The plate-like alkali metal-containing molybdenum oxide of the present invention has a smaller apparent bulk density and a larger surface area than the conventional powdery molybdenum oxide, and thus can be a more effective reaction reagent and catalyst. Further, it can be used as various fillers utilizing a plate-like high surface area, or various devices such as batteries utilizing the taking in and out of an alkali metal contained therein.
【図１】本願発明の板状のアルカリ金属含有モリブデン
酸化物の全体を示す顕微鏡写真（倍率：５０倍）であ
る。FIG. 1 is a photomicrograph (magnification: 50 times) of the entire plate-like alkali metal-containing molybdenum oxide of the present invention.
【図２】本願発明の板状のアルカリ金属含有モリブデン
酸化物の厚さを示す顕微鏡写真（倍率：１０００倍）で
ある。FIG. 2 is a micrograph (magnification: 1000 times) showing the thickness of a plate-like alkali metal-containing molybdenum oxide of the present invention.
【図３】本願発明の板状のアルカリ金属含有モリブデン
酸化物の表面を示す顕微鏡写真（倍率：５００倍）であ
る。FIG. 3 is a micrograph (magnification: 500 times) showing the surface of the plate-like alkali metal-containing molybdenum oxide of the present invention.
【図４】添川理化学株式会社販売の二酸化モリブデン粉
末の粒子構造を示す顕微鏡写真（倍率：１００００倍）
である。FIG. 4 is a micrograph (magnification: 10000 times) showing the particle structure of molybdenum dioxide powder sold by Soegawa Rikagaku Co., Ltd.
It is.
【図５】添川理化学株式会社販売の二酸化モリブデン粉
末の粒子構造を示す顕微鏡写真（倍率：５０００倍）で
ある。FIG. 5 is a photomicrograph (magnification: 5000 times) showing the particle structure of molybdenum dioxide powder sold by Soegawa Rikagaku Co., Ltd.
【図６】キシダ化学株式会社販売のモリブデン酸ナトリ
ウム３％水溶液を関東化学株式会社販売の水素化ホウ素
ナトリウム５％水溶液で還元して得た沈澱物を水洗後１
２０℃で乾燥して得た６価乃至４価のモリブデンを含有
したモリブデン酸化物の粒子構造を示す顕微鏡写真（倍
率：１００００倍）である。FIG. 6: A precipitate obtained by reducing a 3% aqueous solution of sodium molybdate sold by Kishida Chemical Co., Ltd. with a 5% aqueous solution of sodium borohydride sold by Kanto Chemical Co., Ltd.
It is a microscope photograph (magnification: 10000 times) which shows the particle structure of molybdenum oxide containing hexavalent to tetravalent molybdenum obtained by drying at 20 ° C.
【図７】キシダ化学株式会社販売のモリブデン酸ナトリ
ウム３％水溶液を関東化学株式会社販売の水素化ホウ素
ナトリウム５％水溶液で還元して得た沈澱物を水洗後１
２０℃で乾燥して得た６価乃至４価のモリブデンを含有
したモリブデン酸化物の粒子構造を示す顕微鏡写真（倍
率：５０００倍）である。FIG. 7: A precipitate obtained by reducing a 3% aqueous solution of sodium molybdate sold by Kishida Chemical Co., Ltd. with a 5% aqueous solution of sodium borohydride sold by Kanto Chemical Co., Ltd.
5 is a micrograph (magnification: 5000 times) showing the particle structure of molybdenum oxide containing hexavalent to tetravalent molybdenum obtained by drying at 20 ° C.
Claims (3)
ブデン酸化物。1. An alkali metal-containing molybdenum oxide having a plate shape.
００μｍの板状であるアルカリ金属含有モリブデン酸化
物。2. The thickness is 1 to 30 μm and the maximum width is 50 to 5.
An alkali metal-containing molybdenum oxide having a plate shape of 00 μm.
として電解し、電極上に電着物を析出させた後、該電極
を加熱して電着物を剥離させることを特徴とする請求項
１又は２記載の板状であるアルカリ金属含有モリブデン
酸化物の製造法。3. The method according to claim 1, wherein an electrolysis is performed using an aqueous solution of a metal salt of molybdic acid as an electrolytic solution to deposit an electrodeposit on the electrode, and then the electrode is heated to peel the electrodeposit. 3. The method for producing a plate-like alkali metal-containing molybdenum oxide according to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35366596A JP3663791B2 (en) | 1996-12-17 | 1996-12-17 | Alkali metal-containing plate-shaped molybdenum oxide and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35366596A JP3663791B2 (en) | 1996-12-17 | 1996-12-17 | Alkali metal-containing plate-shaped molybdenum oxide and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10167729A true JPH10167729A (en) | 1998-06-23 |
| JP3663791B2 JP3663791B2 (en) | 2005-06-22 |
Family
ID=18432393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35366596A Expired - Fee Related JP3663791B2 (en) | 1996-12-17 | 1996-12-17 | Alkali metal-containing plate-shaped molybdenum oxide and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3663791B2 (en) |
-
1996
- 1996-12-17 JP JP35366596A patent/JP3663791B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3663791B2 (en) | 2005-06-22 |
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