JP2000288407A - Production of immobilized photocatalytic material and immobilized photocatalytic material - Google Patents
Production of immobilized photocatalytic material and immobilized photocatalytic materialInfo
- Publication number
- JP2000288407A JP2000288407A JP2000026246A JP2000026246A JP2000288407A JP 2000288407 A JP2000288407 A JP 2000288407A JP 2000026246 A JP2000026246 A JP 2000026246A JP 2000026246 A JP2000026246 A JP 2000026246A JP 2000288407 A JP2000288407 A JP 2000288407A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- binder
- solution
- film
- immobilized
- 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
- 239000000463 material Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 230000001699 photocatalysis Effects 0.000 title abstract description 14
- 239000011941 photocatalyst Substances 0.000 claims abstract description 63
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000004408 titanium dioxide Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 6
- 239000004111 Potassium silicate Substances 0.000 abstract description 5
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052913 potassium silicate Inorganic materials 0.000 abstract description 5
- 235000019353 potassium silicate Nutrition 0.000 abstract description 5
- 239000004115 Sodium Silicate Substances 0.000 abstract description 3
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 27
- 239000011521 glass Substances 0.000 description 10
- 238000007654 immersion Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有害有機化合物の
分解などに用いられる、支持体上に光触媒を固定化した
光触媒材の製造方法とこの方法により得られる固定化光
触媒材に関する。The present invention relates to a method for producing a photocatalyst material having a photocatalyst immobilized on a support, which is used for decomposing harmful organic compounds, and to an immobilized photocatalyst material obtained by this method.
【０００２】[0002]
【従来の技術】従来、粉末状の光触媒は、無機接着剤と
混合して支持体に塗布し、乾燥することにより固定化さ
れている。しかしこの方法では、接着剤と光触媒との割
合や、乾燥時の環境の湿度、温度により光触媒機能にば
らつきが生じるという問題があり、この方法で固定化し
た触媒を用いて反応を行うと再現性の良い結果が得られ
ない。また、光触媒粒子の表面が接着剤で被覆されてい
るため、触媒機能が十分に発現しにくいという問題もあ
る。これに対し、固定化において接着剤の使用量を少な
くする試みがなされているが、接着剤の使用量を低減す
ると光触媒を含む膜の物理的強度が損なわれ、十分に固
定化されたものは得られていない。2. Description of the Related Art Conventionally, a powdery photocatalyst has been fixed by mixing with an inorganic adhesive, applying the mixture to a support, and drying the mixture. However, this method has the problem that the photocatalytic function varies depending on the ratio between the adhesive and the photocatalyst, and the humidity and temperature of the drying environment, and if the reaction is performed using the catalyst immobilized by this method, the reproducibility will be high. Does not give good results. Further, since the surface of the photocatalyst particles is coated with the adhesive, there is also a problem that the catalyst function is not sufficiently exhibited. On the other hand, attempts have been made to reduce the amount of adhesive used in fixing, but if the amount of adhesive used is reduced, the physical strength of the film containing the photocatalyst is impaired. Not obtained.
【０００３】[0003]
【発明が解決しようとする課題】したがって本発明は、
十分な膜強度を維持しつつ触媒機能が高く、かつ、その
機能にばらつきがなく再現性の良い光触媒膜を有する固
定化光触媒材とその製造方法を提供することを目的とす
る。Accordingly, the present invention provides
It is an object of the present invention to provide an immobilized photocatalyst material having a photocatalyst film having a high catalytic function while maintaining sufficient film strength, and having good reproducibility without variation in the function, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意研究を重ねた結果、光触媒膜を支持体上
に形成したのちに、光触媒膜に含まれる結合剤の一部を
除去することにより、触媒機能とその再現性が高く、膜
強度も十分な光触媒膜が形成できることを見出し、この
知見に基づき本発明をなすに至った。すなわち本発明
は、（１）支持体に粉末状の光触媒をケイ酸アルカリ金
属塩からなる結合剤とともに塗布し、硬化させて光触媒
膜を形成したのち、前記光触媒膜の結合剤の一部を２〜
１０重量％のフッ化水素酸水溶液処理により除去するこ
とを特徴とする固定化光触媒材の製造方法、（２）粉末
状の光触媒が二酸化チタンである（１）項記載の製造方
法、（３）支持体上に粉末状の光触媒とケイ酸アルカリ
金属塩からなる結合剤を含んでなる光触媒膜を形成し、
２〜１０重量％のフッ化水素酸水溶液処理によって前記
光触媒膜中の光触媒粒子を露出させてなることを特徴と
する固定化光触媒材、（４）粉末状の光触媒が二酸化チ
タンである（３）項記載の固定化光触媒材を提供するも
のである。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have formed a photocatalyst film on a support and then removed a part of the binder contained in the photocatalyst film. It has been found that by removing, a photocatalytic film having a high catalytic function and its reproducibility and sufficient film strength can be formed, and based on this finding, the present invention has been accomplished. That is, the present invention provides (1) applying a powdered photocatalyst to a support together with a binder composed of an alkali metal silicate and curing it to form a photocatalyst film; ~
A process for producing an immobilized photocatalyst material, wherein the photocatalyst is removed by treatment with a 10% by weight aqueous solution of hydrofluoric acid; (2) the process according to (1), wherein the photocatalyst in powder form is titanium dioxide; (3) Forming a photocatalyst film comprising a binder made of a powdery photocatalyst and an alkali metal silicate on a support,
An immobilized photocatalyst material wherein the photocatalyst particles in the photocatalyst film are exposed by treatment with a 2 to 10% by weight aqueous hydrofluoric acid solution. (4) The powdery photocatalyst is titanium dioxide. (3) The present invention provides an immobilized photocatalyst material described in the above item.
【０００５】[0005]
【発明の実施の形態】本発明で用いる粉末状の光触媒
は、通常光触媒として用いることができるものであれば
特に制限はなく、具体的には例えば、二酸化チタン、酸
化亜鉛、酸化ジルコニウム、酸化タングステン等があげ
られ、好ましくは二酸化チタンである。粉末の粒径は特
に制限はないが、好ましくは０．０１〜１μｍである。
本発明の固定化光触媒材は、支持体上にこの光触媒の粒
子と結合剤を含んでなる光触媒膜を有し、光触媒膜表面
の、光触媒粒子を被覆する結合剤の一部を酸処理により
除去してなることを特徴とする。DESCRIPTION OF THE PREFERRED EMBODIMENTS The powdery photocatalyst used in the present invention is not particularly limited as long as it can be usually used as a photocatalyst, and specific examples thereof include titanium dioxide, zinc oxide, zirconium oxide, and tungsten oxide. And the like, preferably titanium dioxide. The particle size of the powder is not particularly limited, but is preferably 0.01 to 1 μm.
The immobilized photocatalyst material of the present invention has a photocatalyst film comprising the photocatalyst particles and a binder on a support, and a part of the binder covering the photocatalyst particles on the surface of the photocatalyst film is removed by acid treatment. It is characterized by becoming.
【０００６】本発明においては、上記の粉末状光触媒
を、結合剤とともに支持体上に塗布して光触媒膜を形成
する。結合剤としては、ケイ酸ナトリウム、ケイ酸カリ
ウム等のケイ酸アルカリ金属塩を使用するが、特にその
水溶液が好ましい。この水溶液の濃度は５〜３０重量％
が好ましく、１０〜２５重量％がさらに好ましい。ま
た、結合剤の使用量は、粉末状の光触媒１ｇに対し、
０．５〜３ｍｌが好ましい。In the present invention, the above-mentioned powdery photocatalyst is coated on a support together with a binder to form a photocatalyst film. As the binder, an alkali metal silicate such as sodium silicate or potassium silicate is used, and an aqueous solution thereof is particularly preferable. The concentration of this aqueous solution is 5 to 30% by weight.
Is preferable, and 10 to 25% by weight is more preferable. The amount of the binder used was 1 g of the powdery photocatalyst.
0.5 to 3 ml is preferred.
【０００７】本発明においては、上記のような結合剤と
粉末状の光触媒を混合したのち、支持体に塗布し、乾
燥、硬化させる。乾燥は好ましくは室温〜１００℃で行
い、その後、好ましくは３００〜５００℃で３０分〜１
時間焼成することにより、光触媒膜を硬化させ、光触媒
を支持体に強く固定させることができる。支持体上に塗
布する光触媒と結合剤の混合物の量は特に制限はない
が、好ましくは硬化後の膜厚が１００〜５５０μｍとな
るようにする。In the present invention, the above-mentioned binder and a powdery photocatalyst are mixed, then applied to a support, dried and cured. Drying is preferably performed at room temperature to 100 ° C., and then preferably at 300 to 500 ° C. for 30 minutes to 1 hour.
By baking for a time, the photocatalyst film is cured, and the photocatalyst can be strongly fixed to the support. The amount of the mixture of the photocatalyst and the binder applied on the support is not particularly limited, but is preferably adjusted so that the film thickness after curing is 100 to 550 µm.
【０００８】次に本発明においては、２〜１０重量％の
フッ化水素酸水溶液処理によって、この光触媒膜に含ま
れる結合剤の一部を取り除く。フッ化水素酸水溶液の濃
度は２〜１０重量％とするが、４〜６重量％がさらに好
ましい。結合剤の除去は、この水溶液に浸漬して行うの
が好ましく、浸漬時間は水溶液の濃度により異なるが、
例えば４〜５重量％水溶液を用いた場合には、５〜１０
分の浸漬が好ましい。水溶液の濃度が２重量％よりも低
い場合には、浸漬時間が長くなり結合剤の除去に時間が
かかる。また、水溶液の濃度が１０重量％を超えた場合
には、結合剤の除去反応が急速に進行し、結合剤の除去
量の調節が困難となり、安定した性状を有する光触媒膜
が得られない。この酸処理により除去される結合剤の量
は、好ましくは酸処理前の光触媒膜に含まれていた結合
剤の２０〜４０重量％である。本発明においては酸処理
により結合剤の除去を行うため、比較的複雑な形状の支
持体に形成した光触媒膜の処理も可能であり、例えば円
筒状の支持体の内面に光触媒粒子を露出させた光触媒膜
を有する固定化光触媒材を製造することなども可能であ
る。本発明で用いることのできる支持体の形状は特に制
限はなく、板状、円筒状、球状、ファイバー状のものな
どが使用できる。また、支持体の材質も特に制限はな
く、ガラス、金属、セラミクス、高分子など、通常用い
られるものを使用することができる。Next, in the present invention, a part of the binder contained in the photocatalyst film is removed by treating with a 2 to 10% by weight aqueous solution of hydrofluoric acid. The concentration of the aqueous solution of hydrofluoric acid is 2 to 10% by weight, and more preferably 4 to 6% by weight. Removal of the binder is preferably performed by immersion in this aqueous solution, and the immersion time varies depending on the concentration of the aqueous solution.
For example, when using a 4 to 5% by weight aqueous solution, 5 to 10%
Minutes immersion is preferred. If the concentration of the aqueous solution is lower than 2% by weight, the immersion time becomes longer, and it takes time to remove the binder. On the other hand, if the concentration of the aqueous solution exceeds 10% by weight, the removal reaction of the binder proceeds rapidly, and it becomes difficult to adjust the amount of the binder removed, so that a photocatalytic film having stable properties cannot be obtained. The amount of the binder removed by the acid treatment is preferably 20 to 40% by weight of the binder contained in the photocatalytic film before the acid treatment. In the present invention, since the binder is removed by acid treatment, it is possible to treat a photocatalyst film formed on a support having a relatively complicated shape. It is also possible to manufacture an immobilized photocatalyst material having a photocatalyst film. The shape of the support that can be used in the present invention is not particularly limited, and a plate, a cylinder, a sphere, a fiber, and the like can be used. The material of the support is not particularly limited, and a commonly used material such as glass, metal, ceramics, and polymer can be used.
【０００９】本発明の固定化光触媒材は、例えばフェノ
ールやエタノールの酸化反応など、用いた粉末状光触媒
が触媒活性を有する反応として知られている有機化合物
の分解反応を触媒する。したがって、本発明の固定化光
触媒材を用いて、空気中や水中などに含まれる有害有機
化合物を分解処理することができる。この分解処理は、
処理対象の水や空気を固定化光触媒材の光触媒膜と接触
させつつ、近紫外光を照射することにより行うことがで
きる。照射光源としては、好ましくは３８０ｎｍより短
波長の光を含む光源を用い、このようなものとしては例
えば、低圧又は高圧水銀灯、キセノンランプ、ブラック
ライト、ハロゲンランプ、太陽光などがあげられる。[0009] The immobilized photocatalyst material of the present invention catalyzes a decomposition reaction of an organic compound known as a reaction in which the used powdery photocatalyst has catalytic activity, such as an oxidation reaction of phenol or ethanol. Therefore, harmful organic compounds contained in air, water and the like can be decomposed using the immobilized photocatalyst material of the present invention. This decomposition process
The irradiation can be performed by irradiating near ultraviolet light while bringing the water or air to be treated into contact with the photocatalytic film of the immobilized photocatalytic material. As the irradiation light source, a light source containing light having a wavelength shorter than 380 nm is preferably used, and examples thereof include a low-pressure or high-pressure mercury lamp, a xenon lamp, a black light, a halogen lamp, and sunlight.
【００１０】[0010]
【実施例】次に、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は以下の実施例に限定されるもの
ではない。 実施例１ ０．５ｇの二酸化チタン（平均粒径０．１５μｍの粉
末）にケイ酸カリウムの１８〜２１重量％水溶液１ｍｌ
を加え、よく混合し、これを４０ｍｍ×４０ｍｍのガラ
ス板に塗布した。これを室温で乾燥した後、４００℃で
１時間焼成した（膜厚５００μｍ）。これをフッ化水素
酸水溶液（４６〜４８重量％溶液を１０倍に希釈）に５
分間浸漬した後に、十分に水洗した。こうして得られた
二酸化チタン固定ガラス板を、縦５０ｍｍ、横５０ｍｍ
で奥行１０ｍｍのガラスセルに入れて、１０−４Ｍのフ
ェノール水溶液１５ｍｌを加え、５００Ｗ超高圧水銀灯
を３０分照射した。この処理により、フェノールの３７
％（モル）が分解した。さらに３０分水銀灯を照射した
ところ、フェノールの７１％（モル）が分解した。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Example 1 0.5 ml of titanium dioxide (powder having an average particle diameter of 0.15 μm) and 1 ml of an 18-21% by weight aqueous solution of potassium silicate were added.
Was added and mixed well, and this was applied to a 40 mm × 40 mm glass plate. After drying at room temperature, it was baked at 400 ° C. for 1 hour (film thickness 500 μm). This is added to an aqueous solution of hydrofluoric acid (dilute a 46-48% by weight solution 10 times).
After immersion for a minute, it was thoroughly washed with water. Titanium dioxide fixed glass plate obtained in this way, 50mm in length, 50mm in width
And placed in a glass cell having a depth of 10 mm, 15 ml of a 10 -4 M aqueous phenol solution was added, and irradiation was performed with a 500 W ultrahigh pressure mercury lamp for 30 minutes. By this treatment, 37 of phenol
% (Mol) decomposed. Further irradiation with a mercury lamp for 30 minutes decomposed 71% (mol) of phenol.
【００１１】実施例２ 実施例１で塗布したのと同じ二酸化チタンとケイ酸カリ
ウム水溶液の混合物を、直径５８ｍｍ、高さ１１０ｍｍ
のガラス製円筒管の内側に塗布した。１００℃で乾燥し
た後に、実施例１と全く同様にして焼成（膜厚５００μ
ｍ）、フッ化水素酸水溶液浸漬処理を行った。得られた
二酸化チタン固定ガラス円筒管を、直径６５ｍｍ、高さ
１１５ｍｍの円筒型反応セルに入れ、１０−４Ｍのアゾ
色素（商品名 オレンジＧ）２００ｍｌを加えた。これ
に、反応セルの中央に設置したランプ保護管付きの６Ｗ
低圧水銀灯を照射した。４０分の照射で色素の１００％
が分解した。Example 2 The same mixture of titanium dioxide and potassium silicate aqueous solution as applied in Example 1 was applied to a sample having a diameter of 58 mm and a height of 110 mm.
Was applied to the inside of a glass cylindrical tube. After drying at 100 ° C., baking was performed in exactly the same manner as in Example 1 (film thickness 500 μm).
m), a hydrofluoric acid aqueous solution immersion treatment was performed. The obtained titanium dioxide fixed glass cylindrical tube was placed in a cylindrical reaction cell having a diameter of 65 mm and a height of 115 mm, and 200 ml of a 10 -4 M azo dye (trade name: Orange G) was added. 6W with lamp protection tube installed in the center of the reaction cell
Irradiated with a low pressure mercury lamp. 100% of dye in 40 minutes irradiation
Decomposed.
【００１２】比較例１ チタン酸イソプロポシドのアルコール溶液（１５重量
％）から、ゾルゲル法により二酸化チタン薄膜（膜厚
１．５μｍ）を調製した。これを用い、実施例２と全く
同様にしてアゾ色素の分解を行ったところ、色素が１０
０％分解されるまでに９０分を要した。Comparative Example 1 A titanium dioxide thin film (1.5 μm thick) was prepared from an alcohol solution of isoproposide titanate (15% by weight) by a sol-gel method. When azo dye was decomposed in exactly the same manner as in Example 2,
It took 90 minutes for 0% decomposition.
【００１３】実施例３ ケイ酸カリウムに代えてケイ酸ナトリウムを用いた以外
は、実施例２と全く同様にして二酸化チタン固定ガラス
円筒管を得た。これを実施例２で用いたのと同じ反応セ
ルに入れ、１０−４Ｍのフェノール水溶液２００ｍｌを
加え、実施例２と同様にして低圧水銀灯を照射した。３
０分の照射でフェノールの９０％が分解した。Example 3 A titanium dioxide fixed glass cylindrical tube was obtained in exactly the same manner as in Example 2 except that sodium silicate was used instead of potassium silicate. This was placed in the same reaction cell as used in Example 2, and 200 ml of a 10 −4 M phenol aqueous solution was added, and the mixture was irradiated with a low-pressure mercury lamp in the same manner as in Example 2. 3
90 minutes of irradiation decomposed 90% of the phenol.
【００１４】比較例２ フッ化水素酸水溶液として、実施例１で使用したものの
４分の１の濃度を有する水溶液（４６〜４８重量％溶液
を４０倍に希釈）を使用したところ、実施例１とほぼ同
様の性状を有する二酸化チタン固定ガラス板を得るため
には、浸漬時間を４０分間とする必要があった。Comparative Example 2 An aqueous solution having a concentration one-fourth of that used in Example 1 (diluted 46 to 48% by weight of a 40-fold solution) was used as an aqueous solution of hydrofluoric acid. In order to obtain a titanium dioxide fixed glass plate having almost the same properties as those described above, the immersion time had to be set to 40 minutes.
【００１５】比較例３ フッ化水素酸水溶液として、実施例１で使用したものの
約３倍の濃度を有する水溶液（４６〜４８重量％溶液を
３．３倍に希釈）を使用したところ、ケイ酸カリウムの
除去反応の進行が速く、安定な性状を有する二酸化チタ
ン固定ガラス板を得ることは困難であった。（浸漬時間
を１分間としたものは、二酸化チタン膜の接着性が悪
く、ガラス板から簡単に剥離するために、実用には不適
なものであった。）COMPARATIVE EXAMPLE 3 An aqueous solution having a concentration approximately three times that of the solution used in Example 1 (diluted 46-48 wt% solution 3.3 times) was used as a hydrofluoric acid aqueous solution. The removal reaction of potassium progressed quickly, and it was difficult to obtain a titanium dioxide fixed glass plate having stable properties. (When the immersion time was 1 minute, the adhesion of the titanium dioxide film was poor, and it was not suitable for practical use because it was easily peeled off from the glass plate.)
【００１６】[0016]
【発明の効果】本発明の固定化光触媒材は、光触媒膜表
面の、光触媒粒子を被覆する結合剤が除去されているた
め、高い触媒活性を発現し、固定化したときの温度、湿
度などによる触媒機能への影響をうけにくく、触媒機能
の再現性が高い。本発明方法においては、ケイ酸アルカ
リ金属塩からなる結合剤により粉末状の光触媒を支持体
上に固定化したのち、特定の濃度を有するフッ化水素酸
水溶液で処理することによってその表面を被覆する結合
剤の除去を行うため、膜の強度を維持したまま所定量の
結合剤を効率的に除去し、高い触媒活性を発現する光触
媒膜を形成することができる。The immobilized photocatalyst material of the present invention exhibits high catalytic activity because the binder covering the photocatalyst particles on the surface of the photocatalyst film is removed, and the immobilized photocatalyst material depends on the temperature and humidity when immobilized. It is not easily affected by the catalyst function, and the reproducibility of the catalyst function is high. In the method of the present invention, after a powdery photocatalyst is immobilized on a support with a binder comprising an alkali metal silicate, the surface is coated by treating with a hydrofluoric acid aqueous solution having a specific concentration. Since the binder is removed, a predetermined amount of the binder is efficiently removed while maintaining the strength of the film, and a photocatalytic film exhibiting high catalytic activity can be formed.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０９Ｃ 1/36 Ｂ０１Ｄ 53/36 Ｊ Ｇ Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) // C09C 1/36 B01D 53/36 J G
Claims (4)
リ金属塩からなる結合剤とともに塗布し、硬化させて光
触媒膜を形成したのち、前記光触媒膜の結合剤の一部を
２〜１０重量％のフッ化水素酸水溶液処理により除去す
ることを特徴とする固定化光触媒材の製造方法。1. A photocatalyst in the form of a powder is coated on a support together with a binder made of an alkali metal silicate, and cured to form a photocatalyst film. A method for producing an immobilized photocatalyst material, wherein the photocatalyst material is removed by treating with a hydrofluoric acid aqueous solution of 10%.
求項１記載の製造方法。2. The method according to claim 1, wherein the powdery photocatalyst is titanium dioxide.
カリ金属塩からなる結合剤を含んでなる光触媒膜を形成
し、２〜１０重量％のフッ化水素酸水溶液処理によって
前記光触媒膜中の光触媒粒子を露出させてなることを特
徴とする固定化光触媒材。3. A photocatalyst film comprising a powdery photocatalyst and a binder comprising an alkali metal silicate is formed on a support, and the photocatalyst film is treated with a 2 to 10% by weight aqueous hydrofluoric acid solution. An immobilized photocatalyst material, wherein the photocatalyst particles are exposed.
求項３記載の固定化光触媒材。4. The immobilized photocatalyst material according to claim 3, wherein the powdery photocatalyst is titanium dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000026246A JP2000288407A (en) | 1999-02-05 | 2000-02-03 | Production of immobilized photocatalytic material and immobilized photocatalytic material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-27989 | 1999-02-05 | ||
| JP2798999 | 1999-02-05 | ||
| JP2000026246A JP2000288407A (en) | 1999-02-05 | 2000-02-03 | Production of immobilized photocatalytic material and immobilized photocatalytic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000288407A true JP2000288407A (en) | 2000-10-17 |
Family
ID=26366001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000026246A Pending JP2000288407A (en) | 1999-02-05 | 2000-02-03 | Production of immobilized photocatalytic material and immobilized photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000288407A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008079865A1 (en) * | 2006-12-22 | 2008-07-03 | 3M Innovative Properties Company | Photocatalytic coating |
| WO2008079756A1 (en) | 2006-12-22 | 2008-07-03 | 3M Innovative Properties Company | Photocatalytic coating |
| WO2008079754A1 (en) * | 2006-12-22 | 2008-07-03 | 3M Innovative Properties Company | Photocatalytic coating |
-
2000
- 2000-02-03 JP JP2000026246A patent/JP2000288407A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008079865A1 (en) * | 2006-12-22 | 2008-07-03 | 3M Innovative Properties Company | Photocatalytic coating |
| WO2008079756A1 (en) | 2006-12-22 | 2008-07-03 | 3M Innovative Properties Company | Photocatalytic coating |
| WO2008079754A1 (en) * | 2006-12-22 | 2008-07-03 | 3M Innovative Properties Company | Photocatalytic coating |
| US8993471B2 (en) | 2006-12-22 | 2015-03-31 | 3M Innovative Properties Company | Photocatalytic coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6306796B1 (en) | Photocatalyst, process for producing the same and multifunctional members | |
| JP4957244B2 (en) | Titanium oxide photocatalyst, method for producing the same, and use thereof | |
| US6610135B1 (en) | Titanium-containing finely divided particulate material, aqueous sol composition and coating liquid containing same, process for producing same, and shaped article having film thereof | |
| JP3949374B2 (en) | Titanium oxide, photocatalyst and photocatalyst coating using the same | |
| JP4686536B2 (en) | Photocatalyst, method for producing the same, dispersion containing photocatalyst, and photocatalyst coating composition | |
| US5780380A (en) | Photocatalyst composition and process for its production, and photocatalyst composition-attached substrate | |
| JP2002510717A (en) | Photocatalyst composition | |
| JPH08318166A (en) | Immobilized photocatalyst and method for immobilizing photocatalyst | |
| JP2004283646A (en) | Photocatalyst and method for producing photocatalyst | |
| WO2007119489A1 (en) | Visible light response-type titanium oxide photocatalyst, method for manufacturing the visible light response-type titanium oxide photocatalyst, and use of the visible light response-type titanium oxide photocatalyst | |
| JP2002320862A (en) | Photocatalyst thin film in which metal is supported on titanium oxide thin film | |
| JPH11290692A (en) | Photocatalyst, its manufacture, and photocatalyst-containing molding and its manufacture | |
| JP2000288407A (en) | Production of immobilized photocatalytic material and immobilized photocatalytic material | |
| JP3978636B2 (en) | Coating composition for photocatalyst film formation | |
| JP2002085967A (en) | Photocatalyst membrane and method of producing the same | |
| JPH10180118A (en) | Fixed photocatalyst, preparation thereof, and method for decomposition-removing harmful substance | |
| JP4592846B2 (en) | Photocatalytic coating for removing nitrogen oxides in air and article having this coating | |
| JPH105598A (en) | Photocatalyst powder, photocatalyst body using the same and their production, and environmental cleaning method using them | |
| JP2739128B2 (en) | Decomposition method of organic chemicals by titanium ceramic membrane | |
| JPH09613A (en) | Article with silica film containing powder of functional substance | |
| RU2477257C1 (en) | Nanocrystalline titanium dioxide-based composition, method for preparation thereof and method of using said composition to obtain photocatalytic coating on glass | |
| JPH11157966A (en) | Pottery with photocataytic function and its production | |
| JP2000070728A (en) | Photocatalytic material irradiated with electron beam, its coating material and coating film | |
| JP3431301B2 (en) | Tile with photocatalytic function | |
| JPH08175887A (en) | Structural material of ceramic or pottery-based having photocatalyst function and its production |