JP2005263598A - Anatase / Brookite Titanium Dioxide, Use and Manufacturing Method - Google Patents
Anatase / Brookite Titanium Dioxide, Use and Manufacturing Method Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000006552 photochemical reaction Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 19
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 235000010746 mayonnaise Nutrition 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
【課題】 粉体の形のアナタース形二酸化チタンに比較して光触媒活性が高く、大量生産に適した光触媒用二酸化チタンを提供する。
【解決手段】 アナタース／ブルッカイト比が３５／６５ないし４５／５５であり、アナタース形およびブルッカイト形結晶それぞれの粒子径が２０ｎｍ未満であるアナタース／ブルッカイト接合型二酸化チタン。
【選択図】 なしPROBLEM TO BE SOLVED: To provide a titanium dioxide for photocatalyst having high photocatalytic activity and suitable for mass production as compared with anatase type titanium dioxide in a powder form.
An anatase / brookite junction type titanium dioxide having an anatase / brookite ratio of 35/65 to 45/55, and anatase and brookite crystals each having a particle diameter of less than 20 nm.
[Selection figure] None
Description
本発明は、高い光触媒活性を有するアナタース／ブルッカイト接合型二酸化チタン、その使用および製造方法に関する。 The present invention relates to anatase / brookite-bonded titanium dioxide having high photocatalytic activity, its use and production method.
二酸化チタンは、そのバンドキャップ以上のエネルギーを持った光の照射により、伝導帯に電子を、価電子帯に正孔を生じ、生成した電子及び正孔が水と酸素の存在下で酸化還元反応を起こす光触媒機能を果し、主として酸化反応によって接触する汚染物を分解したり、微生物を殺菌する作用を発揮する。 Titanium dioxide generates electrons in the conduction band and holes in the valence band by irradiation with light with energy higher than its band cap, and the generated electrons and holes undergo a redox reaction in the presence of water and oxygen. It functions as a photocatalyst that causes the degradation of contaminants that are contacted mainly by oxidation reactions and sterilizes microorganisms.
二酸化チタンには、無定形に加え、主な結晶形としてアナタース形、ルチル形およびブルッカイト形が存在し、光触媒活性は結晶形によって異なる。現在粉体として光触媒に使用されている二酸化チタンの結晶形は安定で合成が容易なアナタース形およびルチル形である。ブルッカイト形は合成が容易でないため利用されていない。 In addition to amorphous, titanium dioxide has anatase, rutile, and brookite forms as main crystal forms, and the photocatalytic activity varies depending on the crystal form. The crystal forms of titanium dioxide currently used as photocatalysts as powders are anatase and rutile forms that are stable and easy to synthesize. The brookite form is not used because it is not easy to synthesize.
特開２０００−９５５２１号公報は、非晶質二酸化チタンを水酸化ナトリウム水溶液中で水熱処理することにより他の多形が共存することなくブルッカイト形二酸化チタンを製造する方法を開示し、その光触媒活性はアナタース形二酸化チタンより高いと述べている。 Japanese Patent Application Laid-Open No. 2000-95521 discloses a method for producing brookite-type titanium dioxide by hydrothermally treating amorphous titanium dioxide in an aqueous sodium hydroxide solution without coexisting other polymorphs, and its photocatalytic activity. States that it is higher than anatase titanium dioxide.
しかしながら水熱処理はオートクレーブ中の反応であり、１回の処理量がオートクレーブの容量によって限られるなど大量生産には不向である。そこで大量生産に適し、アナタース形に比較して高い光触媒活性を有する新しいタイプの二酸化チタンの提供が望まれる。 However, hydrothermal treatment is a reaction in an autoclave and is unsuitable for mass production because the amount of one treatment is limited by the capacity of the autoclave. Therefore, it is desired to provide a new type of titanium dioxide that is suitable for mass production and has a higher photocatalytic activity than the anatase type.
本発明は、アナタース／ブルッカイト比が３５／６５ないし４５／５５であり、アナタース形およびブルッカイト形結晶それぞれの粒子径が２０ｎｍ未満であるアナタース／ブルッカイト接合型二酸化チタンを提供する。 The present invention provides an anatase / brookite-bonded titanium dioxide having an anatase / brookite ratio of 35/65 to 45/55, and each anatase-type and brookite-type crystal having a particle diameter of less than 20 nm.
本発明のアナタース／ブルッカイト接合型二酸化チタンは、これまでの二酸化チタン光触媒と同様に、酸素および水の存在下紫外線へ曝露することにより、二酸化チタンと接触する有害汚染物を破壊し、除去するための光触媒として使用することができる。そしてその光触媒活性は、これまで高いとされて来たアナタース形二酸化チタンに比較してさらに高いことが確認された。そのため本発明のアナタース／ブルッカイト接合型二酸化チタンは、光触媒による酸化還元反応に耐えることができる媒体に担持させることにより、有害汚染物を除去するための組成物を提供することができる。 The anatase / brookite-bonded titanium dioxide of the present invention is used to destroy and remove harmful contaminants that come into contact with titanium dioxide by exposure to ultraviolet rays in the presence of oxygen and water, as with conventional titanium dioxide photocatalysts. It can be used as a photocatalyst. And it was confirmed that the photocatalytic activity is higher than that of anatase-type titanium dioxide, which has been considered to be high. Therefore, the anatase / brookite-bonded titanium dioxide of the present invention can be provided on a medium capable of withstanding a redox reaction by a photocatalyst to provide a composition for removing harmful contaminants.
本発明はまた、無定形二酸化チタンをアナタース／ブルッカイト接合型結晶が生成するように０．０５Ｍないし０．３Ｍ濃度の塩酸中で沸点以下の温度で処理し、乾燥することよりなるアナタース／ブルッカイト接合型二酸化チタンの製造法を提供する。 The present invention also provides an anatase / brookite junction comprising treating amorphous titanium dioxide in a 0.05M to 0.3M hydrochloric acid at a temperature below the boiling point and drying so that anatase / brookite junction type crystals are formed. A method for producing type titanium dioxide is provided.
この方法は、例えば無定形二酸化チタン粒子を前記濃度範囲の塩酸水溶液に懸濁し、室温で無定形二酸化チタンがアナタース／ブルッカイト接合型結晶に転移するまで攪拌を続け、濾過、洗浄、乾燥することによって実行される。このように入手し易い原料を使用し、操作も簡単なため、この方法は光触媒用二酸化チタンの大量生産に適している。 In this method, for example, amorphous titanium dioxide particles are suspended in an aqueous hydrochloric acid solution having the above-mentioned concentration range, and stirring is continued at room temperature until the amorphous titanium dioxide is transferred to anatase / brookite-bonded crystals, followed by filtration, washing, and drying. Executed. Since such readily available raw materials are used and the operation is simple, this method is suitable for mass production of titanium dioxide for photocatalysts.
ここでいう「アナタース／ブルッカイト接合型二酸化チタン」とは、アナタース形およびブルッカイト形の二酸化チタン結晶の個々の粒子が独立して存在する混合物ではなく、両結晶間で電子のやり取りでできるように強固に接合している状態を意味する。 The “anatase / brookite-bonded titanium dioxide” here is not a mixture in which individual particles of anatase and brookite-type titanium dioxide crystals exist independently, but is strong so that electrons can be exchanged between the two crystals. It means the state where it is joined.
アナタース／ブルッカイト接合型二酸化チタンは、アナタース形二酸化チタンに比較して高い光触媒活性を有する。これは両相間の光誘導界面電子移動による電荷分離効率の向上によるものと推定される。 The anatase / brookite bonded titanium dioxide has a higher photocatalytic activity than the anatase titanium dioxide. This is presumably due to the improvement in charge separation efficiency due to photoinduced interfacial electron transfer between both phases.
また、ブルッカイト形のフラットバンドポテンシャルは−０．０３Ｖ（ｖｓ．ＳＨＥ）と見積もられており、アナタース形のそれよりも約０．０９Ｖポジティブであることから、熱力学的にアナタース形からブルッカイト形への電子移動が起こり、その結果電荷分離効率が向上し、アナタース形に比較してアナタース／ブルッカイト接合型二酸化チタンの光触媒活性が向上するものと推定される。 The flat band potential of the brookite form is estimated to be -0.03V (vs. SHE), and is about 0.09V positive than that of the anatase form. Therefore, from the anatase form to the brookite form thermodynamically. As a result, the charge separation efficiency is improved, and the photocatalytic activity of the anatase / brookite junction type titanium dioxide is estimated to be improved as compared with the anatase type.
本発明のアナタース／ブルッカイト接合型二酸化チタンは、無定形二酸化チタンをアナタース／ブルッカイト接合型結晶が生成するように０．０５Ｍないし０．３Ｍ濃度の塩酸中沸点以下の温度で処理し、乾燥することによって製造される。塩酸による処理は、無定形二酸化チタンの粉体を上記濃度の塩酸中に懸濁し、例えば室温で攪拌することによってアナタース／ブルッカイト接合型二酸化チタンへ転移させ、濾過、洗浄および乾燥することによって実施することができる。この時の塩酸濃度の範囲は、アナタース／ブルッカイト接合型への相転移が起こるには十分であるが、ルチル形への相転移が実質上起こらない範囲である。処理時間は例えば室温の場合、１５分ないし６０分が適当である。 The anatase / brookite-bonded titanium dioxide of the present invention is processed by drying amorphous titanium dioxide at a temperature below the boiling point of hydrochloric acid in a concentration of 0.05M to 0.3M so that anatase / brookite-bonded crystals are formed. Manufactured by. The treatment with hydrochloric acid is carried out by suspending the powder of amorphous titanium dioxide in hydrochloric acid having the above concentration and transferring it to anatase / brookite-bonded titanium dioxide, for example, by stirring at room temperature, filtering, washing and drying. be able to. The range of the hydrochloric acid concentration at this time is sufficient for the phase transition to the anatase / brookite junction type to occur, but the phase transition to the rutile form does not substantially occur. The treatment time is, for example, 15 minutes to 60 minutes at room temperature.
上の処理により無定形二酸化チタンは、アナタース／ブルッカイト比が３５／６５ないし４５／５５のアナタース／ブルッカイト接合型二酸化チタンへ転移する。光触媒にとってその粒子径、従って比表面積が高いことが触媒活性を示す上で重要である。本発明の場合、接合したアナタースおよびブルッカイト形のそれぞれの粒子径は２０ｎｍ未満、特に１０ｎｍ未満である。両者の接合型の比表面積は１００ｍ2 ／ｇ以上、特にと１２０ないし１５０ｍ2 ／ｇの範囲内にあることが望ましい。 By the above treatment, amorphous titanium dioxide is transferred to anatase / brookite junction type titanium dioxide having an anatase / brookite ratio of 35/65 to 45/55. It is important for the photocatalyst to exhibit catalytic activity that its particle size, and hence its specific surface area, is high. In the case of the present invention, the particle size of each of the joined anatase and brookite forms is less than 20 nm, in particular less than 10 nm. It is desirable that the specific surface area of both the joining molds be 100 m 2 / g or more, particularly in the range of 120 to 150 m 2 / g.
所望により乾燥後接合型二酸化チタンをルチル型への転移が実質上起こらない温度、例えば６００℃で焼成することができる。焼成により粒子径が大きくなり、比表面積が小さくなるが、接合したアナタース形およびブルッカイト形それぞれの粒子径は２０ｎｍ未満にとどまる。しかしながら両相が一層強固に結合し、両相間の光誘導界面電子移動が活発化するため光触媒活性は焼成前に比較してさらに高まる。 If desired, after drying, the bonded titanium dioxide can be fired at a temperature at which substantially no transition to the rutile type occurs, for example, 600 ° C. Although the particle size is increased by firing and the specific surface area is decreased, the particle size of each of the bonded anatase type and brookite type is less than 20 nm. However, the photocatalytic activity is further increased as compared to before the calcination because the two phases are bonded more firmly and the photoinduced interfacial electron transfer between the two phases is activated.
本発明のアナタース／ブルッカイト接合型二酸化チタンは、光化学反応による有害汚染物の分解および除去を含む二酸化チタン光触媒の既知の用途に使用することができる。粉体のまま使用することもできるが、飛散を防止するため結合剤を使用して固定化するのが好ましい。多くの有機結合剤、例えば塗料用ビヒクル樹脂は光触媒の光化学反応によって分解を受けるので、これに耐えられる無機質の結合剤、例えばシリカゾルおよびその前駆体であるテトラアルコキシシランの部分加水分解物を用いるのが好ましい。光触媒をこのような結合剤に分散し、建造物の表面に塗膜を形成することにより、ＮＯx ，ＳＯx ，アルデヒド類、アンモニア、アミン類、メルカプタン類などの悪臭物質の除去、タール、タバコのヤニ、油などの汚れの除去、細菌、かびなどの微生物の殺菌、藻類の付着防止および除去など有害汚染物の分解および除去に役立たせることができる。屋外建造物に適用した場合、超親水化現象により降雨によるセルフクリーニング作用も期待できる。またガラス繊維のような無機質の繊維に抄き込み、大気中の有害汚染物を分解、除去するためのフィルターとして利用することもできる。 The anatase / brookite bonded titanium dioxide of the present invention can be used in the known applications of titanium dioxide photocatalysts, including decomposition and removal of harmful contaminants by photochemical reactions. Although it can be used as a powder, it is preferably immobilized using a binder in order to prevent scattering. Many organic binders, such as paint vehicle resins, are subject to degradation by photocatalytic photochemical reactions, so that they can withstand inorganic binders such as silica sol and its precursor, tetraalkoxysilane partial hydrolysates. Is preferred. By dispersing the photocatalyst in such a binder and forming a coating film on the surface of the building, removal of malodorous substances such as NO x , SO x , aldehydes, ammonia, amines, mercaptans, tar, tobacco It can be used for decomposing and removing harmful pollutants such as removal of dirt such as spider and oil, sterilization of microorganisms such as bacteria and fungi, prevention and removal of algae. When applied to outdoor buildings, self-cleaning action due to rainfall can be expected due to the superhydrophilic phenomenon. In addition, it can be used as a filter for decomposing and removing harmful pollutants in the air by embedding in inorganic fibers such as glass fibers.
以下に実施例、比較例によって本発明を例証する。これらにおいて「％」は特記しない限り重量基準により表わされ、結晶形はＸ線回折により同定し、アナタース率およびブルッカイト率の測定方法、アナタース形およびブルッカイト形の結晶粒子径、比表面積、光触媒活性の測定方法は以下のとおりである。 The present invention is illustrated by the following examples and comparative examples. In these, “%” is expressed on a weight basis unless otherwise specified, crystal form is identified by X-ray diffraction, anatase ratio and brookite ratio measurement method, anatase form and brookite form crystal particle diameter, specific surface area, photocatalytic activity The measuring method is as follows.
１．アナタース率およびブルッカイト率
理学電機社製Ｘ線回折装置ＲＩＮＴ２５００を使用し、Ｘ線源としてＣｕ−Ｋα線、フィラメントの管電圧４００ｋＶ、管電流８０ｍＡ、測定範囲２θ＝２０〜６０°の条件で測定した。アナタース率およびブルッカイト率は、それぞれアナタース（１０１）面（２θ＝２５．４°）、ブルッカイト（１２１）面（２θ＝３０．８°）の回折ピーク強度から計算し、百分率（％）で表わした。
1. Anatase rate and brookite rate Using an X-ray diffractometer RINT2500 manufactured by Rigaku Corporation, measurement was performed under the conditions of an X-ray source of Cu-Kα ray, filament tube voltage 400 kV, tube current 80 mA, measurement range 2θ = 20 to 60 °. . The anatase rate and brookite rate were calculated from the diffraction peak intensities of the anatase (101) plane (2θ = 25.4 °) and the brookite (121) plane (2θ = 30.8 °), respectively, and expressed as a percentage (%). .
２．アナタース形およびブルッカイト形の結晶粒子径
上の１と同じ装置および同じ条件で測定したアナタース（１０１）面（２θ＝２５．４°）、ブルッカイト（１２１）面（２θ＝３０．８°）の回折ピーク半価からＳｃｈｅｒｒｅｒの式を用いて算出した。
2. Anatase-type and brookite-type crystal particle sizes Diffraction of anatase (101) plane (2θ = 25.4 °) and brookite (121) plane (2θ = 30.8 °) measured using the same apparatus and conditions as above 1. The peak half value was calculated using the Scherrer equation.
３．比表面積
ＢＥＴ法による。
3. Specific surface area According to BET method.
４．光触媒活性（粉体）
（１）試料２５ｍｇを７ｃｍ2 の試料台に乗せ、内容積６４０ｍＬのパイレックスガラス反応容器に入れる。
（２）反応容器内を減圧し、アセトアルデヒド標準ガス（５０６ｐｐｍ、Ｎ2 バランス、太陽東洋酸素社製）を加えて常圧に戻してアセトアルデヒド濃度を４００ｐｐｍに調整する。
（３）約１８時間放置して吸着平衡に到達したことを確認した後、アセトアルデヒドの初期濃度をガスクロマトグラフで測定する。
（４）３００Ｗキセノンランプ（ＨＸ−５００、Ｗａｃｏｍ社製）により試料を上方から光照射し、１５分毎に容器内の気体を０．５ｍＬづつサンプリングし、アセトアルデヒドの濃度をガスクロマトグラフにより測定する。
（５）アセトアルデヒドの見掛け分解定数（ｋ）／ｈ-1を次式により計算し、試料重量ｇ（０．０２５ｇ）で除去し、試料単位重量あたりの分解定数（ｋ）／ｈ-1・ｇ-1を求める。
4). Photocatalytic activity (powder)
(1) Place 25 mg of sample on a 7 cm 2 sample stage and place in a Pyrex glass reaction vessel with an internal volume of 640 mL.
(2) The inside of the reaction vessel is depressurized, acetaldehyde standard gas (506 ppm, N 2 balance, manufactured by Taiyo Toyo Oxygen Co., Ltd.) is added to return to normal pressure, and the acetaldehyde concentration is adjusted to 400 ppm.
(3) After standing for about 18 hours and confirming that the adsorption equilibrium has been reached, the initial concentration of acetaldehyde is measured with a gas chromatograph.
(4) The sample is irradiated with light from above with a 300 W xenon lamp (HX-500, manufactured by Wacom), and 0.5 mL of gas in the container is sampled every 15 minutes, and the concentration of acetaldehyde is measured by a gas chromatograph.
(5) Apparent decomposition constant (k) / h −1 of acetaldehyde is calculated by the following formula, removed by sample weight g (0.025 g), and decomposition constant per sample unit weight (k) / h −1 · g Find -1 .
ｋｔx ＝１ｎ（ｔo ／ｔx ） kt x = 1n (t o / t x )
ここでｔx は照射時間（ｈ）、Ｃo はアセトアルデヒド濃度の初期値、Ｃx は光照射後のアセトアルデヒド濃度である。 Here, t x is the irradiation time (h), Co is the initial value of the acetaldehyde concentration, and C x is the acetaldehyde concentration after light irradiation.
５．光触媒活性（塗膜）
試料として下記操作により調製した塗膜を用い、上の粉体についての光触媒活性測定方法と同じ方法を用いてアセトアルデヒドの見掛け分解定数（ｋ）ｈ-1を求めた。
5). Photocatalytic activity (coating)
Using a coating film prepared by the following operation as a sample, the apparent decomposition constant (k) h −1 of acetaldehyde was determined using the same method as the photocatalytic activity measurement method for the above powder.
試料塗膜の調製：
４００ｍＬのマヨネーズ瓶に粉体試料５．０ｇと、バインダーとしてＫＰ−８５４（信越化学社製シリカ系バインダー、固形分２２．８％）２０．８ｇと、メタノール７４．２ｇ、およびガラスビーズ（直径１．５ｍｍ）３００ｇを入れる。
Sample coating preparation:
In a 400 mL mayonnaise bottle, 5.0 g of powder sample, 20.8 g of KP-854 (silica binder manufactured by Shin-Etsu Chemical Co., Ltd., solid content 22.8%), 74.2 g of methanol, and glass beads (diameter 1) .5mm) Add 300g.
ペイントコンディショナー（レッドビル社製、Ｍｏｄｅｌ Ｎｏ．５４００）により７００ｒｐｍで１時間分散する。 Disperse with a paint conditioner (Redville, Model No. 5400) at 700 rpm for 1 hour.
ガラスプレート（５２ｍｍ×７６ｍｍ）に自動バーコーター（安田精機製作所製、オートマチックフィルムアプリケーターＮｏ．５４２−ＡＢ型）により、塗布量が約４０ｍｇ／１００ｃｍ2 となるように塗布し、１２０℃で１時間乾燥する。 It is applied to a glass plate (52 mm × 76 mm) with an automatic bar coater (manufactured by Yasuda Seiki Seisakusho, automatic film applicator No. 542-AB type) so that the applied amount is about 40 mg / 100 cm 2 and dried at 120 ° C. for 1 hour. To do.
無定形二酸化チタンの製造：
ＴｉＯ2 濃度５０ｇ／Ｌに調整した硫酸チタニル水溶液１Ｌに、液温２０℃において攪拌下２５％アンモニア水１３０ｍＬを添加し、ｐＨ７．０とし、硫酸チタニルを加水分解した。加水分解後３０分間熟成した後、ケーキを水で洗浄した。得られたケーキを１１０℃で１２時間乾燥し、卓上コーヒーミルで粉砕し、二酸化チタン粉末を得た。この粉末をＸ線回折分析したところ、そのプロファイルに明瞭なピークが確認されなかったことから、無定形二酸化チタンであることを同定した。
Production of amorphous titanium dioxide:
To 1 L of an aqueous titanyl sulfate solution adjusted to a TiO 2 concentration of 50 g / L, 130 mL of 25% aqueous ammonia was added with stirring at a liquid temperature of 20 ° C. to adjust the pH to 7.0, thereby hydrolyzing the titanyl sulfate. After aging for 30 minutes after hydrolysis, the cake was washed with water. The obtained cake was dried at 110 ° C. for 12 hours and pulverized with a desktop coffee mill to obtain titanium dioxide powder. When this powder was analyzed by X-ray diffraction, a clear peak was not confirmed in its profile, and it was identified as amorphous titanium dioxide.
アナタース／ブルッカイト接合型二酸化チタンの製造：
上で製造した無定形二酸化チタン５ｇを、０．１Ｍ塩酸２００ｍＬに懸濁し、室温で３０分間攪拌した。攪拌後、スラリーを濾過、水洗し、ケーキを５０℃で４８時間乾燥した。得られた粉体をＡとする。
Manufacture of anatase / brookite bonded titanium dioxide:
5 g of amorphous titanium dioxide produced above was suspended in 200 mL of 0.1 M hydrochloric acid and stirred at room temperature for 30 minutes. After stirring, the slurry was filtered and washed with water, and the cake was dried at 50 ° C. for 48 hours. The obtained powder is designated as A.
実施例１で製造した粉体Ａを６００℃で１時間焼成した。得られた粉体をＢとする。 The powder A produced in Example 1 was fired at 600 ° C. for 1 hour. The obtained powder is designated as B.
実施例１で製造した無定形二酸化チタンを塩酸で処理することなく直接６００℃で１時間焼成した。得られた粉体をＣとする。 The amorphous titanium dioxide produced in Example 1 was directly calcined at 600 ° C. for 1 hour without being treated with hydrochloric acid. Let the obtained powder be C.
粉体Ａ，ＢおよびＣについて前記した方法で分析を行った。結果を表１に示す。 The powders A, B and C were analyzed by the method described above. The results are shown in Table 1.
考察：
アナタース結晶形の比較例の粉体Ｃに比較して、アナタース／ブルッカイト接合型結晶の実施例１の二酸化チタン粉体Ａは、アセトアルデヒド分解速度定数によって代表される光触媒活性において明らかにすぐれている。粉体Ａを焼成することによって得た粉体Ｂ（実施例２）は、粉体Ａよりも高い光触媒活性を持っている。
Discussion:
Compared with the powder C of the comparative example of the anatase crystal form, the titanium dioxide powder A of the anatase / brookite bonded crystal of Example 1 is clearly superior in the photocatalytic activity represented by the acetaldehyde decomposition rate constant. Powder B (Example 2) obtained by firing powder A has a higher photocatalytic activity than powder A.
Claims (6)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101206489B1 (en) * | 2010-11-02 | 2012-11-30 | 충남대학교산학협력단 | Manufacturing Method of Visible Rays Active Anatase-Brookite Type Titanium Dioxide Photocatalyst |
| JPWO2011049068A1 (en) * | 2009-10-19 | 2013-03-14 | 国立大学法人 東京大学 | Method for inactivating virus and antiviral property-imparting article |
| CN105776327A (en) * | 2016-03-25 | 2016-07-20 | 武汉理工大学 | Brookite and anatase mixed-phase TiO2 micron hollow spheres assembled by nanorods and its preparation method and application |
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2004
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2011049068A1 (en) * | 2009-10-19 | 2013-03-14 | 国立大学法人 東京大学 | Method for inactivating virus and antiviral property-imparting article |
| KR101206489B1 (en) * | 2010-11-02 | 2012-11-30 | 충남대학교산학협력단 | Manufacturing Method of Visible Rays Active Anatase-Brookite Type Titanium Dioxide Photocatalyst |
| CN105776327A (en) * | 2016-03-25 | 2016-07-20 | 武汉理工大学 | Brookite and anatase mixed-phase TiO2 micron hollow spheres assembled by nanorods and its preparation method and application |
| CN105776327B (en) * | 2016-03-25 | 2017-09-29 | 武汉理工大学 | A kind of brockite and anatase mixed phase TiO of nanometer rods assembling2Micrometre hollow sphere and its preparation method and application |
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