JPS59121120A - Reducing treatment of titanium dioxide - Google Patents
Reducing treatment of titanium dioxideInfo
- Publication number
- JPS59121120A JPS59121120A JP57232916A JP23291682A JPS59121120A JP S59121120 A JPS59121120 A JP S59121120A JP 57232916 A JP57232916 A JP 57232916A JP 23291682 A JP23291682 A JP 23291682A JP S59121120 A JPS59121120 A JP S59121120A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- reduction treatment
- vacuum
- photo
- stage
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 29
- 238000011282 treatment Methods 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000011941 photocatalyst Substances 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- -1 100 μm Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、光触媒反応や光電気化学反応の触媒もしくは
電極として利用される二酸化チタンの還元処理方法に関
するものであるＯ
〔発明の技術的背景とその問題点〕
近年、半導体−溶液界面における光電子移動反応は、新
しい光エネルギー変換システムとして注目されている。Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a method for reducing titanium dioxide used as a catalyst or electrode for photocatalytic reactions and photoelectrochemical reactions. Problems] In recent years, photoelectron transfer reactions at semiconductor-solution interfaces have attracted attention as a new optical energy conversion system.
この光電子移動反応を利用した光化学反応の例としては
、半導体電極として二酸化チタン板、対極として白金板
を使い光電池全構成することによって水の光分解が可能
であることが知られている（［ネイブユア（Ｎａｔｕｒ
ｅ（Ｌｏｎｄｏｎ）） Ｊ 。As an example of a photochemical reaction that utilizes this photoelectron transfer reaction, it is known that water can be photolyzed by constructing a photovoltaic cell using a titanium dioxide plate as a semiconductor electrode and a platinum plate as a counter electrode. (Natur
e(London)) J.
第２８８巻、第３７頁（１９７２年）〕。Volume 288, page 37 (1972)].
また、二酸化チタン粉末の懸濁液に光を照射することに
よって水の光分解が進行し、更にこノ系に祭素ガヌ全通
気することによってアンモニアの光生成も可能であるこ
とが知られている（ 「Ｊｏｕｎａｌ ｏｆ Ａｍｅｒ
ｉｃａｎ Ｃｈｅｍｉｃａｌ ５ｏｃｅｉｔｙ Ｊ 。It is also known that photodecomposition of water progresses by irradiating a suspension of titanium dioxide powder with light, and that photogeneration of ammonia is also possible by fully aerating the system with the fertilized element. ( ``Journal of Amer
ican Chemical 5ociety J.
第９９巻、第７１８９頁（１９７７年））。Volume 99, page 7189 (1977)).
このような反応方法においては、光照射によって半導体
内に生成した電子と正孔を夫々還元サイトと、酸化反応
サイトへ伝達する過程が含まれるために、半導体の電導
度が反応効率に大きく影響する。半導体として二酸化ブ
タン全周いる場合、その反応効率を改善する方法として
は従来、■二酸化チタンを真空中で還元処理する方法あ
るいは■二酸化チタンを水素雰囲気中で還元処理する方
法等が提案されている。しかしながら、これらの方法で
は未還元処理のものに比べて電導度は向上するが、依然
として反応効率が低く、充分に満足できるものではなか
ったＯ
〔発明の目的〕
本発明は、かかる従来方法の問題点に鑑み種々研究を行
なった結果、二段階の還元処理と、その温度条件を規定
することにより、光触媒あるいは光電極として反応効率
を大幅に向上させることができる二酸化チタンの還元処
理方法を提供すること全目的とするものである。This reaction method involves the process of transmitting electrons and holes generated in the semiconductor by light irradiation to reduction sites and oxidation reaction sites, respectively, so the conductivity of the semiconductor has a large effect on reaction efficiency. . When butane dioxide is present all around the semiconductor, methods to improve the reaction efficiency have been proposed, such as (1) reducing titanium dioxide in a vacuum, or (2) reducing titanium dioxide in a hydrogen atmosphere. . However, although these methods improve the conductivity compared to non-reduced methods, the reaction efficiency is still low and the results are not fully satisfactory. As a result of conducting various studies in view of this point, we have provided a method for reducing titanium dioxide that can significantly improve reaction efficiency as a photocatalyst or photoelectrode by performing a two-step reduction treatment and specifying the temperature conditions. This is the entire purpose.
本発明方法は、種々の方法で作成された二酸化チタンを
還匹処理するにあたＩハ予め真空中４００〜５００℃で
第１段の還元処理を行なった後、水素気流中７００〜８
００℃で第２段の還元処理を行なうことを特徴とするも
のである。In the method of the present invention, titanium dioxide produced by various methods is subjected to a first reduction treatment at 400 to 500°C in vacuum, and then reduced to 700 to 800°C in a hydrogen stream.
This method is characterized by performing the second stage reduction treatment at 00°C.
本発明において用いる二酸化チタンとしては、通常、光
電極や光触媒として用いられでいる二酸化チタン単結晶
や二酸化チタン粉末の他、熱酸化被膜、スパッタ膜等２
種々の方法で作成されたものに適用することができる。The titanium dioxide used in the present invention includes titanium dioxide single crystals and titanium dioxide powders that are usually used as photoelectrodes and photocatalysts, as well as thermal oxide films, sputtered films, etc.
It can be applied to items created using various methods.
第１段の還元処理は真空中４００〜５００℃で加熱、還
元することにより反応効率が向上する。In the first stage reduction treatment, reaction efficiency is improved by heating and reducing at 400 to 500° C. in vacuum.
反応効率改善効果のピークは４００〜５００℃の範囲に
存在し、この範囲２外れる温度条件では充分な反応効率
の改善は得られない。The peak of the reaction efficiency improvement effect exists in the range of 400 to 500°C, and under temperature conditions outside this range 2, sufficient improvement in reaction efficiency cannot be obtained.
第２段の還元処理は水素気流中７００〜８００℃で加熱
、還元することにエリ反応効率全向上させることができ
る。この場合、反応効率改善効果のピークは７００〜８
００℃の範囲に存在し、この範囲を外れる温度条件では
充分な反応効率の改善は得られない。In the second stage reduction treatment, the reaction efficiency can be completely improved by heating and reducing at 700 to 800° C. in a hydrogen stream. In this case, the peak of the reaction efficiency improvement effect is 700-8
It exists in the range of 00° C., and a sufficient improvement in reaction efficiency cannot be obtained under temperature conditions outside this range.
また本発明では、第１段の還元処理を真空中で行なった
後、第２段の還元処理を水素気流中で行なう二段階の還
元処理の組み合せにエリ、これらを別個に行なっていた
従来方法お工ひ第１段と第２段の還元処理を逆に行なう
方法に比べて、反応効率が大幅に向上する。In addition, the present invention combines a two-stage reduction process in which the first stage reduction process is performed in a vacuum, and then the second stage reduction process is performed in a hydrogen stream, whereas the conventional method in which these steps were performed separately Compared to a method in which the first and second stage reduction treatments are performed in reverse, the reaction efficiency is greatly improved.
（実施例１）
純度９９９９％の二酸化チタン板をターゲフトとして高
周波ツバツタ法により石英基板上に二酸化チタン薄膜全
堆積した０これ全試料として、電気炉を用いて石英反応
管内において真空中４５０℃で１時間、還元処理した後
、７５０℃に昇温してｌｏｍｌ／ｍｉｎの水素気流中で
２時間３０分遣元した。(Example 1) A titanium dioxide thin film was completely deposited on a quartz substrate using a titanium dioxide plate with a purity of 9999% as a target by the high-frequency splatter method.The entire sample was deposited at 450°C in vacuum in a quartz reaction tube using an electric furnace. After reduction treatment for 1 hour, the temperature was raised to 750° C. and the mixture was placed in a hydrogen flow of 1 mL/min for 2 hours and 30 minutes.
この二段階の還元処理をした二酸化チタンを光触媒とし
て、水５ｒＩＬｌ、メタノール５罰の混合溶液金入れた
フラスコ内に浸漬して真空脱気した後、５００Ｗキセノ
ンランプを用いて１ｏａｙ間光照射した０この結果、フ
ラスコ内にｌＯμｍｏｌの水素が発生した。The two-stage reduction treated titanium dioxide was used as a photocatalyst and immersed in a flask containing a mixed solution of 5 parts of water and 5 parts of methanol, vacuum degassed, and then irradiated with light for 1 oay using a 500 W xenon lamp. As a result, 10 μmol of hydrogen was generated in the flask.
また、上記実施例において、第２段の水素還元を７５０
℃で行ない、第１段の真空還元処理温度全変化させた場
合について、夫々の温度条件における水素発生量全測定
し、これを第１図のグラフに示した。このグラフから明
らかなように、第１段の真空還元処理は４５０℃でピー
クを示し、４００〜５００℃の範囲で充分な水素発生ｄ
Ｋ認められた○
また上記実施例において、第１段の真空還元を４５０℃
とし、第２段の水素還元温度全変化させた場合について
、夫々の温度条件における水素発生量を測定し、これ全
第２図のグラフに示した。このグラフから明らかなよう
に、第２段の水素還元処理は７５０℃でピークを示し、
７００〜８００℃の範囲で充分な水素発生量が認められ
た。In addition, in the above example, the second stage hydrogen reduction was carried out at 750
℃, and the first stage vacuum reduction treatment temperature was completely changed, the total amount of hydrogen generated under each temperature condition was measured, and the results are shown in the graph of FIG. As is clear from this graph, the first stage vacuum reduction treatment shows a peak at 450°C, and sufficient hydrogen generation d occurs in the range of 400 to 500°C.
○ In the above example, the first stage vacuum reduction was carried out at 450°C.
When the hydrogen reduction temperature of the second stage was completely changed, the amount of hydrogen generated under each temperature condition was measured, and the results are all shown in the graph of FIG. As is clear from this graph, the second stage hydrogen reduction treatment showed a peak at 750°C,
A sufficient amount of hydrogen generation was observed in the range of 700 to 800°C.
（比較例１）
上記実施例１において真空中４５０℃で第１段の還元処
理だけを行なった二酸化チタンを光触媒として、同様に
光照射を行なったととる、水素発生量は０．１ ｌｚｍ
ｏｌ であったＯ（比較例２）
上記実施例１において、第１段の真空還元処理を省き、
水素気流中７５０℃で第２段の還元処理だけを行なった
二酸化チタンを光触媒として、同様に光照射を行なった
ところ、水素発生量かま０．０２μｍ０１であった０
（比較例３）
上記実施例１において、本発明における第２段の水素還
元処理全７５０℃で先に行なった後、第１段の真空還元
処理を４５０’Ｃで行なった二酸化チタンを光触媒とし
て、同様に光照射を行なったところ水素は全く発生しな
かった。(Comparative Example 1) Light irradiation was performed in the same manner as in Example 1 using titanium dioxide, which was subjected to only the first stage reduction treatment at 450° C. in vacuum as a photocatalyst, and the amount of hydrogen generated was 0.1 lzm.
ol (Comparative Example 2) In the above Example 1, the first stage vacuum reduction treatment was omitted,
When light irradiation was performed in the same manner using titanium dioxide which had undergone only the second stage reduction treatment at 750°C in a hydrogen stream as a photocatalyst, the amount of hydrogen generated was 0.02 μm0 (Comparative Example 3) The above example In 1, after the second stage hydrogen reduction treatment of the present invention was performed at a total temperature of 750°C, light irradiation was performed in the same manner using titanium dioxide, which had been subjected to the first stage vacuum reduction treatment at 450'C, as a photocatalyst. However, no hydrogen was generated.
（実施例２）
純度９９．９９％の二酸化チタン粉末（３００メツシユ
）を電気炉を用いて石英反応管内において真空中４５０
℃で１時間、第１段の還元処理を行なった後、７５０℃
に昇温して１０ｍｅ／ ｍｉｎの水素気流中で２時間３
０分、第２段の還元処理を行なった。(Example 2) Titanium dioxide powder (300 mesh) with a purity of 99.99% was heated in a quartz reaction tube using an electric furnace for 450 min in vacuum.
After performing the first stage reduction treatment at ℃ for 1 hour, 750℃
The temperature was raised to 2 hours in a 10 me/min hydrogen flow.
The second stage reduction treatment was performed for 0 minutes.
この二段階の還元処理’ｘ−１，た二酸化チタンを光触
媒として、１００■を、水５ ｍｌ 、メタノール５
ｔｎｌの混合溶液を人ｉｔたフラスコ内に混合し、真空
脱気した後、５００Ｗキセノンランプ１１いて３時間光
照射を行なった０
この結果３０μｍｏｌの水素が発生した。これは何ら還
元処理を施さない二酸化チタン粉末音用いた場合に比べ
て約４倍の水素発生量であった。In this two-stage reduction treatment 'x-1, using titanium dioxide as a photocatalyst, 100 μm, water 5 ml, methanol 5
A mixed solution of tnl was mixed in a flask, vacuum degassed, and then irradiated with light for 3 hours using a 500W xenon lamp 11. As a result, 30 μmol of hydrogen was generated. This was about 4 times the amount of hydrogen generated compared to the case where titanium dioxide powder without any reduction treatment was used.
以上説明した如く、本発明に係わる二酸化チタンの還元
処理方法に工れば、真空と水素の二段階の還元処理と、
その温度条件全規定すること、にエリ、光触媒あるいは
光電極としての反応効率金入幅に向上させることかでき
る○゛まだ、従来エリ知られている二酸化テタ／に白金
や二酸化ルテニウムを担持させた光触媒においても、二
酸化チタンに本発明の還元処理を施すことにより更に反
応効率全向上さぜることかできる。As explained above, if the titanium dioxide reduction treatment method according to the present invention is applied, a two-step reduction treatment of vacuum and hydrogen can be performed.
By fully specifying the temperature conditions, it is possible to greatly improve the reaction efficiency as a photocatalyst or photoelectrode. In photocatalysts as well, the reaction efficiency can be further improved by subjecting titanium dioxide to the reduction treatment of the present invention.
Claims (1)
あたり、予め真空中４００〜５００℃で、第１段の還元
処理を行なった後、水素気流中７００〜８００℃で第２
段の還元処理を行なうことを特徴とする二酸化チタンの
還元処理方法０When titanium dioxide produced by various methods is subjected to reduction treatment, the first reduction treatment is performed in advance at 400 to 500°C in a vacuum, and then the second reduction treatment is performed at 700 to 800°C in a hydrogen stream.
Titanium dioxide reduction treatment method 0 characterized by performing a stage reduction treatment
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57232916A JPS59121120A (en) | 1982-12-24 | 1982-12-24 | Reducing treatment of titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57232916A JPS59121120A (en) | 1982-12-24 | 1982-12-24 | Reducing treatment of titanium dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59121120A true JPS59121120A (en) | 1984-07-13 |
Family
ID=16946843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57232916A Pending JPS59121120A (en) | 1982-12-24 | 1982-12-24 | Reducing treatment of titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59121120A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1125636A1 (en) * | 1998-08-21 | 2001-08-22 | Ecodevice Laboratory Co., Ltd | Visible radiation type photocatalyst and production method thereof |
-
1982
- 1982-12-24 JP JP57232916A patent/JPS59121120A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1125636A1 (en) * | 1998-08-21 | 2001-08-22 | Ecodevice Laboratory Co., Ltd | Visible radiation type photocatalyst and production method thereof |
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