JP2010017603A - Photocatalyst carrier and method of manufacturing the same - Google Patents
Photocatalyst carrier and method of manufacturing the same Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 127
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000006104 solid solution Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 101
- 239000000758 substrate Substances 0.000 claims description 49
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 30
- 238000000746 purification Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 239000011225 non-oxide ceramic Substances 0.000 claims description 5
- 229910052575 non-oxide ceramic Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000000969 carrier Substances 0.000 abstract description 19
- 239000000853 adhesive Substances 0.000 abstract description 17
- 230000001070 adhesive effect Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000004042 decolorization Methods 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、排ガス等の気体やメカニカルシール廃水等の液体を浄化処理するフィルタ等として使用される光触媒担持体であって、水処理非酸化物系セラミックス製の基体に酸化チタン（ＴｉＯ２）光触媒を担持させてなる光触媒担持体及びこれを製造する方法に関するものである。 The present invention relates to a photocatalyst carrier used as a filter or the like for purifying gas such as exhaust gas or liquid such as mechanical seal wastewater, and a titanium oxide (TiO 2 ) photocatalyst on a substrate made of water-treated non-oxide ceramics. And a method for producing the same.
ＴｉＯ２光触媒担持体としては、一般に、基体表面に有機系又は無機系の接着剤や界面活性剤を適宜にブレンドしたＴｉＯ２ゾルにディップコーティングした上、これに適宜の乾燥処理又は熱処理等を施すことにより、基体表面にＴｉＯ２光触媒層を接着固定したものが周知である。 In general, the TiO 2 photocatalyst carrier is dip-coated with a TiO 2 sol in which an organic or inorganic adhesive or surfactant is appropriately blended on the surface of the substrate, and then subjected to appropriate drying or heat treatment. Thus, a substrate in which a TiO 2 photocatalyst layer is bonded and fixed to the substrate surface is well known.
しかし、このような一般的なＴｉＯ２光触媒担持体は、基体とＴｉＯ２光触媒層との接着強度が十分でなく、耐久性に問題があった。特に、水流との接触による負荷が大きい水浄化処理用フィルタとして使用する場合には、ＴｉＯ２光触媒層が剥がれ易く、長期に亘って良好な光触媒機能を発揮，維持することができない。すなわち、光触媒層が剥がれることにより光触媒機能が短期間のうちに低下，喪失する虞れがあった。なお、ディップコーティング材であるＴｉＯ２ゾルには、上記した如く、ＴｉＯ２ゾルの安定性を高めるための界面活性剤や基体への接着性を高めるための接着剤が含まれているため、これらの界面活性剤や接着剤がＴｉＯ２光触媒層の表面に滲出して、ＴｉＯ２光触媒層による光触媒機能（浄化機能）を低下させる虞れもある。 However, such a general TiO 2 photocatalyst carrier has a problem in durability because the adhesive strength between the substrate and the TiO 2 photocatalyst layer is not sufficient. In particular, when used as a water purification treatment filter having a large load due to contact with a water stream, the TiO 2 photocatalyst layer is easily peeled off, and a good photocatalytic function cannot be exhibited and maintained over a long period of time. That is, when the photocatalyst layer is peeled off, the photocatalytic function may be reduced or lost in a short period of time. Note that, as described above, the TiO 2 sol that is a dip coating material contains a surfactant for enhancing the stability of the TiO 2 sol and an adhesive for enhancing the adhesion to the substrate. There is a possibility that the surfactant or adhesive of the TiO 2 is oozed out on the surface of the TiO 2 photocatalyst layer and the photocatalytic function (purification function) by the TiO 2 photocatalyst layer is lowered.
そこで、従来からも、ＴｉＯ２光触媒層の接着強度を向上させるべく、種々の提案がなされている。例えば、ＳｉＣ基体の表面をＳｉＯ２／Ａｌ２Ｏ３の複合酸化物であるムライトとなし、その表面上にＴｉＯ２光触媒層を一般的な方法で形成してＡｌ２Ｏ３／ＴｉＯ２の界面とすることによって、ＴｉＯ２光触媒層の接着強度を高めるようにすること（例えば、特許文献１を参照）、又は基体をアモルファル過酸化チタンゾルであるペルオキソチタン酸水溶液にアナターゼ型ＴｉＯ２粒子を分散させたコーティング液にディッピングし、これを乾燥，焼成することによって、基体との濡れ性改善とＴｉＯ２粒子間のバインダー的役割によりＴｉＯ２光触媒層の密着性向上を図るようにすること（例えば、特許文献２を参照）が提案されている。 Therefore, various proposals have been made so far in order to improve the adhesive strength of the TiO 2 photocatalyst layer. For example, the surface of the SiC substrate is made of mullite which is a composite oxide of SiO 2 / Al 2 O 3 , and a TiO 2 photocatalyst layer is formed on the surface by a general method to obtain an interface of Al 2 O 3 / TiO 2 . By increasing the adhesion strength of the TiO 2 photocatalyst layer (see, for example, Patent Document 1), or dispersing the anatase-type TiO 2 particles in a peroxotitanate aqueous solution that is an amorphal titanium peroxide sol. The coating solution is dipped, dried and fired to improve the wettability with the substrate and to improve the adhesion of the TiO 2 photocatalyst layer by the binder role between the TiO 2 particles (for example, patents) Reference 2) has been proposed.
しかし、前者においては、数十ｎｍ程度と思われるＳｉＣの自然酸化膜であるＳｉＯ２とＡｌ２Ｏ３膜とで基体界面が構成され、その上面に５０〜１５０μｍのＡｌ２Ｏ３膜があり、更にその上面に酸化物とはいえ異物質であるＴｉＯ２膜があるため、水浄化処理用フィルタのように負荷の大きな用途においてはＴｉＯ２光触媒層の接着強度が十分であるとはいい難い。また、後者の場合には、ＴｉＯ２膜のクラック対策としては有効であると思われるが、ＳｉＣのような非酸化系セラミックスの基体に対してはＴｉＯ２光触媒層の接着強度が十分ではない。このように、何れの場合にも、ＳｉＣ等の非酸化系セラミックスからなる基体とＴｉＯ２光触媒層との接着強度を、水浄化処理用フィルタのような負荷抵抗の大きな用途においては十分に確保することができない。 However, in the former, substrate interface between the SiO 2 and Al 2 O 3 film is a natural oxide film of SiC appears to several tens of nm is formed, there is an Al 2 O 3 film of 50~150μm on its upper surface In addition, since there is a TiO 2 film which is a different substance although it is an oxide on its upper surface, it is difficult to say that the adhesive strength of the TiO 2 photocatalyst layer is sufficient in applications with a heavy load such as a filter for water purification treatment. . In the latter case, it is considered effective as a countermeasure against cracks in the TiO 2 film, but the adhesion strength of the TiO 2 photocatalyst layer is not sufficient for a non-oxidized ceramic substrate such as SiC. As described above, in any case, the adhesive strength between the base made of non-oxidized ceramics such as SiC and the TiO 2 photocatalyst layer is sufficiently ensured in applications with a large load resistance such as a filter for water purification treatment. I can't.
本発明は、非酸化系セラミックスからなる基体とＴｉＯ２光触媒層との接着強度を、水浄化処理用フィルタのような負荷抵抗の大きな用途にも十分適用できる程度にまで向上させることができる光触媒担持体を提供すると共に、これを容易に製造することができる方法を提供することを目的とするものである。 INDUSTRIAL APPLICABILITY The present invention provides a photocatalyst-supporting material capable of improving the adhesive strength between a non-oxidizing ceramic substrate and a TiO 2 photocatalyst layer to such an extent that it can be sufficiently applied to a use with a large load resistance such as a filter for water purification treatment. An object of the present invention is to provide a body and a method capable of easily manufacturing the body.
本発明は、上記の目的を達成すべく、非酸化物系セラミックスからなる基体と、これを大気中で加熱して酸化処理することによって基体表面に形成された酸化膜層と、この酸化膜層上に形成された当該酸化膜成分及びＴｉＯ２からなる固溶体層と、この固溶体層上に形成されたＴｉＯ２光触媒層とからなることを特徴とする光触媒担持体を提案する。好ましい実施の形態にあって、かかる光触媒担持体は、ＳｉＣ等のＳｉ質のセラミック基体と、基体表面に形成された酸化膜層たるＳｉＯ２層と、ＳｉＯ２層上に形成されたＳｉＯ２及びＴｉＯ２の拡散層である固溶体層と、固溶体層上に形成されたＴｉＯ２光触媒層とからなる。基体の形態は、当該光触媒担持体の用途に応じて適宜であり、水浄化処理用フィルタ等として使用する場合においては一般に多孔質体が好適する。酸化膜層の厚みは１〜１０μｍであることが好ましく、固溶体層の厚みは１〜１０μｍであることが好ましい。また、ＴｉＯ２光触媒層の厚みは１〜１０μｍであることが好ましい。かかる光触媒担持体は、負荷の大きな水浄化処理用フィルタ（例えば、メカニカルシールからの廃水（フラッシング水，クエンチング水等）の浄化処理装置用フィルタ）として、特に好適に使用することができる。 In order to achieve the above object, the present invention provides a substrate made of non-oxide ceramics, an oxide film layer formed on the surface of the substrate by heating the substrate in the atmosphere, and the oxide film layer. A photocatalyst carrier comprising a solid solution layer made of the oxide film component and TiO 2 formed thereon and a TiO 2 photocatalyst layer formed on the solid solution layer is proposed. In the preferred embodiment, such photocatalyst carrier includes a ceramic substrate Si quality such as SiC, and the SiO 2 layer serving as oxide film layer formed on the substrate surface, SiO 2 and formed on the SiO 2 layer a solid solution layer is a diffusion layer of TiO 2, consisting of a TiO 2 photocatalyst layer formed on the solid solution layer. The form of the substrate is appropriate depending on the use of the photocatalyst carrier, and a porous body is generally preferred when used as a water purification treatment filter or the like. The thickness of the oxide film layer is preferably 1 to 10 μm, and the thickness of the solid solution layer is preferably 1 to 10 μm. Further, it is preferable that the thickness of the TiO 2 photocatalyst layer is 1 to 10 [mu] m. Such a photocatalyst carrier can be particularly suitably used as a water purification treatment filter with a large load (for example, a purification treatment device filter for waste water (flushing water, quenching water, etc.) from a mechanical seal).
また、本発明は、このような光触媒担持体を好適に製造する方法を提案する。すなわち、本発明は、非酸化物系セラミックスからなる基体を大気中で加熱して酸化処理することによって基体表面に酸化膜層を形成する一次前処理工程と、酸化膜層が形成された基体を、酸化膜層上にＴｉＯ２スラリをコーティングした上で、大気中で熱処理することにより、酸化膜層上に当該酸化膜成分及びＴｉＯ２の固溶体層を形成する二次前処理工程と、固溶体層が形成された基体を、固溶体層上にＴｉＯ２粉末の水スラリ（光触媒活性を低下させる虞れのある接着剤，分散剤等の添加剤を一切含まないもの）をコーティングした上で、熱処理することにより、固溶体層上にＴｉＯ２光触媒層を形成する触媒担持処理工程とからなることを特徴とする光触媒担持体の製造方法を提案する。好ましい実施の形態にあって、かかる製造方法は、ＳｉＣ等のＳｉ質のセラミック基体（好ましくは多孔質体）を大気中において８００〜１２００℃（最適には１０００℃）で加熱して酸化することによって、基体表面に酸化膜層であるＳｉＯ２層を形成する一次前処理工程と、ＳｉＯ２層が形成された基体を、ＳｉＯ２層上にＴｉＯ２濃度を０．５〜５％とするＴｉＯ２ゾル（接着剤，分散剤等の添加剤を含む市販のＴｉＯ２ゾルを希釈したものが使用できる）をコーティングした上で大気中において８００〜１２００℃（最適には１０００℃）で熱処理することにより、ＳｉＯ２層上にＳｉＯ２及びＴｉＯ２の拡散層である固溶体層を形成する二次前処理工程と、固溶体層が形成された基体を、固溶体層上にＴｉＯ２粉末を純水に分散させてなるＴｉＯ２スラリをコーティングした上で、ＴｉＯ２の結晶形態がルチル型に転移しない条件（より好ましくは、ＴｉＯ２の結晶形態がルチル型に転移せず且つＴｉＯ２結晶粒が肥大化することなく光触媒活性を最大限発揮されうる条件）で熱処理することにより、固溶体層上にＴｉＯ２光触媒層を形成する触媒担持処理工程とからなる。触媒担持処理工程において使用するＴｉＯ２スラリとしては、純水１００部にＴｉＯ２粉末５〜１５部を分散させたものを使用することが好ましい。ＴｉＯ２粉末としては、例えば、一次粒子径２１ｎｍ，比表面積５０ｍ２／ｇのアナターゼ型を主成分とするものを使用することが好ましい。触媒担持処理工程における熱処理温度は、ＴｉＯ２の結晶形態がルチル型に転移する直前の温度（一般に、４００〜７００℃）に設定することが好ましく、最適には、ＴｉＯ２の結晶形態がルチル型に転移せず且つＴｉＯ２結晶粒が肥大化することなく光触媒活性を最大限発揮されうる温度条件である６００℃に設定しておくことが好ましい。
The present invention also proposes a method for suitably producing such a photocatalyst carrier. That is, the present invention provides a primary pretreatment step of forming an oxide film layer on the surface of the substrate by heating and oxidizing the substrate made of non-oxide ceramics in the atmosphere, and a substrate on which the oxide film layer is formed. A secondary pretreatment step of forming a solid solution layer of the oxide film component and TiO 2 on the oxide film layer by coating a TiO 2 slurry on the oxide film layer and then heat-treating in the air; and a solid solution layer The substrate on which is formed is coated on a solid solution layer with a water slurry of TiO 2 powder (which does not contain any additives such as adhesives and dispersants that may reduce the photocatalytic activity) and then heat-treated. Thus, a method for producing a photocatalyst carrier comprising a catalyst carrying treatment step of forming a TiO 2 photocatalyst layer on a solid solution layer is proposed. In a preferred embodiment, such a production method includes oxidizing a Si ceramic substrate (preferably a porous body) such as SiC at 800 to 1200 ° C. (optimally 1000 ° C.) in the atmosphere. TiO 2 having a TiO 2 concentration of 0.5 to 5% on the SiO 2 layer by a primary pretreatment step of forming an SiO 2 layer as an oxide film layer on the surface of the substrate and a substrate on which the SiO 2 layer is formed 2
本発明の光触媒担持体によれば、基体とＴｉＯ２光触媒層とを酸化膜層及び固溶体層を介して接着させており、これらの層相互の界面が一種の傾斜材組成となっているため、ＴｉＯ２光触媒層の接着強度を大幅に向上させ得て、大きな負荷がかかる水浄化処理用フィルタ等の用途においても、長期に亘ってＴｉＯ２光触媒層の剥離を防止しつつ良好な光触媒機能を発揮させることができる。しかも、ＴｉＯ２光触媒層が接着剤，分散剤の添加剤を含有しないことから、ＴｉＯ２光触媒層形成時の熱処理温度を適正に設定することにより、優れた光触媒活性を発揮することができる。また、本発明の方法によれば、このような光触媒担持体を容易且つ良好に製造することができる。 According to the photocatalyst carrier of the present invention, the substrate and the TiO 2 photocatalyst layer are bonded via the oxide film layer and the solid solution layer, and the interface between these layers is a kind of gradient material composition. The adhesive strength of the TiO 2 photocatalyst layer can be greatly improved, and even in applications such as filters for water purification treatment that require a large load, the TiO 2 photocatalyst layer exhibits a good photocatalytic function over a long period of time while preventing the TiO 2 photocatalyst layer from peeling off. Can be made. Moreover, TiO 2 photocatalyst layer is adhesive, since it does not contain additives dispersing agents, by setting the heat treatment temperature for TiO 2 photocatalyst layer formed properly, it is possible to exhibit excellent photocatalytic activity. Moreover, according to the method of the present invention, such a photocatalyst carrier can be manufactured easily and satisfactorily.
実施例として、図１に示す如く、ＳｉＣ多孔質材からなる基体Ａと、その表面に形成された酸化膜層であるＳｉＯ２層Ｂと、ＳｉＯ２層Ｂ上に形成されたＳｉＯ２及びＴｉＯ２の拡散層である固溶体層Ｃと、固溶体層Ｃ上に形成されたＴｉＯ２光触媒層Ｄとからなる光触媒担持体Ｅ１〜Ｅ３を製作した。 As an example, as shown in FIG. 1, a substrate A made of a SiC porous material, an SiO 2 layer B which is an oxide film layer formed on the surface thereof, and SiO 2 and TiO formed on the SiO 2 layer B Photocatalyst carriers E1 to E3 comprising a solid solution layer C as a diffusion layer 2 and a TiO 2 photocatalyst layer D formed on the solid solution layer C were produced.
すなわち、実施例１として、次のような前処理工程及び光触媒担持工程により光触媒担持体Ｅ１を製作した。 That is, as Example 1, the photocatalyst carrier E1 was manufactured by the following pretreatment process and photocatalyst support process.
（一次前処理工程）
基体Ａを大気中で１０００℃，１時間の条件で加熱して酸化することにより、基体Ａの表面にＳｉＯ２層を形成した。基体ＡとＳｉＯ２層Ｂとの境界にはＳｉＣ酸化拡散層ａが形成されており、ＳｉＯ２層Ｂは自然酸化膜に比して強固なものとなっている。
(Primary pretreatment process)
The substrate A was heated and oxidized in the atmosphere at 1000 ° C. for 1 hour to form a SiO 2 layer on the surface of the substrate A. A SiC oxide diffusion layer a is formed at the boundary between the substrate A and the SiO 2 layer B, and the SiO 2 layer B is stronger than the natural oxide film.
（二次前処理工程）
上記のように酸化処理された基体Ａを、ＳｉＯ２層Ｂ上にＴｉＯ２スラリをディップコーティング，乾燥した上で、大気中で１０００℃，１時間の条件で熱処理して、ＳｉＯ２層Ｂ上にＳｉＯ２及びＴｉＯ２が拡散する固溶体層Ｃを形成した。ＴｉＯ２スラリとしては、ＴｉＯ２濃度１０％の市販ＴｉＯ２ゾル（テイカ株式会社製「ＴＫＣ−３０３」）をＴｉＯ２濃度が２％となるように希釈したものを使用した。
(Secondary pretreatment process)
The substrate A oxidized as described above is dip-coated with TiO 2 slurry on the SiO 2 layer B, dried, and then heat-treated in the atmosphere at 1000 ° C. for 1 hour to form the SiO 2 layer B on the SiO 2 layer B. A solid solution layer C in which SiO 2 and TiO 2 diffuse was formed. As the TiO 2 slurry, a commercially available TiO 2 sol having a TiO 2 concentration of 10% (“TKC-303” manufactured by Teika Co., Ltd.) diluted to a TiO 2 concentration of 2% was used.
（光触媒担持工程）
固溶体層Ｃが形成された基体Ａを、固溶体層Ｃ上にＴｉＯ２スラリをディップコーティング，乾燥した上で、６００℃，１時間の条件で熱処理して、固溶体層Ｃ上にＴｉＯ２光触媒層Ｄが形成された光触媒担持体Ｅ１を得た。ＴｉＯ２スラリは、一次粒子径２１ｎｍ，比表面積５０ｍ２／ｇのルチル型を含みアナターゼ型を主成分とするＴｉＯ２粉末を純水に分散させた水スラリであり、ＴｉＯ２粉末３０ｇを純水２７０ｇに添加してボールミル（又はビーズミル）により１６時間攪拌することによって得られたものである。なお、ＴｉＯ２粉末についてＸ線回折パターン(Ｘ線：Ｃｕ／３０ｋＶ／３０ｍＡ，ゴニオメータ：ＲＩＮＴ２０００広角ゴニオメータ，アタッチメント：標準試料ボルダー，フィルタ：不使用，インシデントノモクロ：不使用，カウンタモノクロメータ：固定モノクロメータ，発散スリット：１°，発散縦制限スリット：１０．００ｍｍ，散乱スリット：１°，受光スリット：０．１５ｍｍ，モノクロ受光スリット：なし，カウンタ：シンチレーションカウンタ，走査モード：連続，スキャンスピード：２．０００°／ｍｉｎ，サンプリング幅：０．０２０°，走査軸：２θ／θ，走査範囲：１０．０００〜９０．０００°，θオフセット：０．０００°)を測定したところ、図２に示す如く、熱処理後のＸ線回折パターン（同図(Ａ)）と熱処理前のＸ線回折パターン（同図(Ｂ)）とは殆ど変化がなく、上記温度(６００℃)の熱処理によってはＴｉＯ２結晶子が増大しないことが確認されている。
(Photocatalyst loading process)
The substrate A on which the solid solution layer C is formed is dip-coated with TiO 2 slurry on the solid solution layer C, dried, and then heat-treated at 600 ° C. for 1 hour, so that the TiO 2 photocatalyst layer D is formed on the solid solution layer C. A photocatalyst carrier E1 was obtained. TiO 2 slurry, the primary particle diameter of 21 nm, a water slurry of TiO 2 powder was dispersed in pure water as a main component an anatase type include rutile specific surface area 50 m 2 / g, pure water of TiO 2 powder 30g It was obtained by adding to 270 g and stirring for 16 hours with a ball mill (or bead mill). TiO 2 powder X-ray diffraction pattern (X-ray: Cu / 30 kV / 30 mA, goniometer: RINT2000 wide-angle goniometer, attachment: standard sample boulder, filter: not used, incident nomograph: not used, counter monochromator: fixed monochrome Meter, divergence slit: 1 °, divergence length limiting slit: 10.00 mm, scattering slit: 1 °, light receiving slit: 0.15 mm, monochrome light receiving slit: none, counter: scintillation counter, scanning mode: continuous, scan speed: 2 .000 ° / min, sampling width: 0.020 °, scanning axis: 2θ / θ, scanning range: 10.000 to 90.000 °, θ offset: 0.000 °) are measured and shown in FIG. As shown above, the X-ray diffraction pattern after heat treatment ((A) in the figure) and before heat treatment X-ray diffraction pattern (FIG. (B)) hardly changes and, in the heat treatment of the above temperature (600 ° C.) has been confirmed that the TiO 2 crystallites does not increase.
実施例２として、光触媒担持工程における熱処理条件を４００℃，１時間とした点を除いて実施例１と同一の工程により、光触媒担持体Ｅ２を得た。 As Example 2, a photocatalyst carrier E2 was obtained by the same process as Example 1 except that the heat treatment conditions in the photocatalyst carrying process were 400 ° C. and 1 hour.
実施例３として、光触媒担持工程における熱処理条件を７００℃，１時間とした点を除いて実施例１と同一の工程により、光触媒担持体Ｅ３を得た。 As Example 3, a photocatalyst carrier E3 was obtained by the same process as Example 1 except that the heat treatment condition in the photocatalyst carrying process was 700 ° C. and 1 hour.
また、比較例として、次のような光触媒担持体Ｅ４〜Ｅ９を製作した。なお、各光触媒担持体Ｅ４〜Ｅ９における基体は実施例１〜３と同一のものが使用されている。 Moreover, the following photocatalyst carriers E4 to E9 were manufactured as comparative examples. In addition, the same thing as Examples 1-3 is used for the base | substrate in each photocatalyst carrier E4-E9.
すなわち、比較例１として、基体をＴｉＯ２ゾルにディッピング，乾燥した上、４００℃，１時間の条件で熱処理することによって、基体表面にＴｉＯ２光触媒層が形成された光触媒担持体Ｅ４を得た。ＴｉＯ２ゾルとしては、ＴｉＯ２濃度１０％の市販ＴｉＯ２ゾル（テイカ株式会社製「ＴＫＣ−３０３」）を使用した。 That is, as Comparative Example 1, the substrate was dipped in TiO 2 sol, dried, and then heat-treated at 400 ° C. for 1 hour to obtain a photocatalyst carrier E4 having a TiO 2 photocatalyst layer formed on the surface of the substrate. . As the TiO 2 sol, a commercially available TiO 2 sol having a TiO 2 concentration of 10% (“TKC-303” manufactured by Teika Co., Ltd.) was used.
比較例２として、基体表面にＴｉＯ２ゾルをディップコーティングする前に基体を大気中４００℃で酸化処理した点を除いて、比較例１と同一工程により光触媒担持体Ｅ５を得た。 As Comparative Example 2, a photocatalyst carrier E5 was obtained by the same process as Comparative Example 1, except that the substrate was oxidized at 400 ° C. in the atmosphere before dip coating of the TiO 2 sol on the substrate surface.
比較例３として、一次前処理及び二次前処理を行わない点を除いて実施例１と同一の工程（光触媒担持工程）により光触媒担持体Ｅ６を得た。 As Comparative Example 3, a photocatalyst carrier E6 was obtained by the same process (photocatalyst carrying process) as Example 1 except that the primary pretreatment and the secondary pretreatment were not performed.
比較例４として、二次前処理を行わない点を除いて実施例２と同一の工程（二次前処理工程及び光触媒担持工程）により光触媒担持体Ｅ７を得た。 As Comparative Example 4, a photocatalyst carrier E7 was obtained by the same steps (secondary pretreatment step and photocatalyst carrying step) as Example 2 except that the secondary pretreatment was not performed.
比較例５として、二次前処理を行わない点を除いて実施例１と同一の工程（二次前処理工程及び光触媒担持工程）により光触媒担持体Ｅ８を得た。 As Comparative Example 5, a photocatalyst carrier E8 was obtained by the same steps (secondary pretreatment step and photocatalyst carrying step) as Example 1 except that the secondary pretreatment was not performed.
比較例６として、二次前処理を行わない点を除いて実施例３と同一の工程（二次前処理工程及び光触媒担持工程）により光触媒担持体Ｅ９を得た。 As Comparative Example 6, a photocatalyst carrier E9 was obtained by the same steps (secondary pretreatment step and photocatalyst carrying step) as Example 3 except that the secondary pretreatment was not performed.
上記のようにして得られた各光触媒担持体Ｅ１〜Ｅ９について、ＴｉＯ２光触媒層の接着強度ないし光触媒性能を比較，確認すべく、次のような超音波試験及び脱色試験を行った。 For each of the photocatalyst carriers E1 to E9 obtained as described above, the following ultrasonic test and decoloration test were performed in order to compare and confirm the adhesive strength or photocatalytic performance of the TiO 2 photocatalyst layer.
すなわち、超音波試験においては、各光触媒担持体Ｅ１〜Ｅ９から縦横６０ｍｍ，厚み３０ｍの正方形試験片を採取して、これをビーカ(容量５００ｍＬ)内の水（４００ｍＬ）にいれ、このビーカに超音波洗浄機を使用して３０分間超音波（周波数２８ｋＨｚ）を印加し、各試験片におけるＴｉＯ２光触媒層の剥離量を測定した。剥離量は、超音波試験前後の試験片重量差から剥離重量（＝試験前の試験片重量−試験後の試験片重量）を求めて、試験前の試験片重量に対する比率（＝（剥離重量／試験前の試験片重量）×１００％）で示したものである。その結果は、表１に示す通りであった。 That is, in the ultrasonic test, a square test piece having a length and width of 60 mm and a thickness of 30 m is collected from each of the photocatalyst carriers E1 to E9 and placed in water (400 mL) in a beaker (capacity 500 mL). An ultrasonic wave (frequency 28 kHz) was applied for 30 minutes using a sonic cleaner, and the amount of TiO 2 photocatalyst layer peeled from each test piece was measured. The peel amount is obtained by calculating the peel weight (= test piece weight before test−test piece weight after test) from the difference in test piece weight before and after the ultrasonic test, and the ratio to the test piece weight before the test (= (peel weight / Test piece weight before test) × 100%). The results were as shown in Table 1.
表１に示す超音波試験結果から理解されるように、実施例の光触媒担持体Ｅ１〜Ｅ３は、比較例の光触媒担持体Ｅ４〜Ｅ９の何れに比しても、剥離量が極めて少なく、特に光触媒担持工程における熱処理温度を６００℃とした実施例１の光触媒担持体Ｅ１においては光触媒層Ｄの剥離は認められなかった。また、比較例１〜３の光触媒担持体Ｅ４〜Ｅ６と比較例４〜６の光触媒担持体Ｅ７〜Ｅ９との比較及び比較例４〜６の光触媒担持体Ｅ７〜Ｅ９と実施例１〜３の光触媒担持体Ｅ１〜Ｅ３との比較から、前処理工程が光触媒層の接着強度向上に極めて有効であることが理解される。 As can be understood from the ultrasonic test results shown in Table 1, the photocatalyst carrier E1 to E3 of the example has an extremely small amount of peeling compared to any of the photocatalyst carrier E4 to E9 of the comparative example. In the photocatalyst carrier E1 of Example 1 in which the heat treatment temperature in the photocatalyst carrying step was 600 ° C., no peeling of the photocatalyst layer D was observed. Further, the comparison between the photocatalyst carriers E4 to E6 of Comparative Examples 1 to 3 and the photocatalyst carriers E7 to E9 of Comparative Examples 4 to 6 and the photocatalyst carriers E7 to E9 of Comparative Examples 4 to 6 and Examples 1 to 3 From comparison with the photocatalyst carriers E1 to E3, it is understood that the pretreatment process is extremely effective for improving the adhesive strength of the photocatalyst layer.
また、走査型電子顕微鏡（ＳＥＭ）により超音波試験後の各試験片について観察したところ、比較例の光触媒担持体Ｅ４〜Ｅ９では、程度の差はあるものの、何れもＴｉＯ２光触媒層表面にクラックが生じており、ＴｉＯ２光触媒層が剥離して基体骨格が露出している部分が認められたが、実施例１〜３の光触媒担持体Ｅ１〜Ｅ３では、このようなクラックや基体骨格の露出は認められなかった。 In addition, when the specimens after the ultrasonic test were observed with a scanning electron microscope (SEM), the photocatalyst carriers E4 to E9 of the comparative examples had cracks on the surface of the TiO 2 photocatalyst layer, although there were some differences. has occurred, but the portion is TiO 2 photocatalyst layer has to the base skeleton is exposed peeling was observed, the photocatalyst carrier E1~E3 of examples 1 to 3, exposure of such cracks and the substrate skeleton Was not recognized.
脱色試験では、濃度７．５ｐｐｍのメチレンブルー水溶液１００Ｌを収容する原水タンクと水浄化装置とを連結する循環水路において、マクネットポンプによりメチレンブルー水溶液を循環させ、水浄化装置から原水タンクへの返戻水の透過率（メチレンブルー吸収波長６６５ｎｍでの透過率）が９０％となる（メチレンブルー水溶液が目視でほぼ透明となる）までの時間（脱色時間）を測定した。水浄化装置は、水浄化処理用フィルタである光触媒担持体を充填した９本の水路管（呼び径１インチ，長さ７１４ｍｍのＰＦＡチューブであって、ＵＶ照度計測定で波長２５４ｎｍのＵＶ光を約７０％透過するＵＶ光高透過性チューブ）を１６本のＵＶランプ(２０Ｗ)により照射するようにしたものであり、メチレンブルー水溶液が水路管内の光触媒担持体を通過する間において浄化処理(脱色処理)されるように構成されている。透過率測定器としては、セントラル化学（株）製の可視・紫外分光光度計「ＤＲ／４０００Ｕ」を使用した。 In the decolorization test, a methylene blue aqueous solution is circulated by a Macnet pump in a circulation channel connecting a raw water tank containing 100 L of a methylene blue aqueous solution having a concentration of 7.5 ppm and a water purification device, and water returned to the raw water tank from the water purification device is circulated. The time until the transmittance (transmittance at a methylene blue absorption wavelength of 665 nm) reached 90% (the methylene blue aqueous solution became almost transparent visually) (decolorization time) was measured. The water purification device is composed of nine water pipes (nominal diameter 1 inch, length 714 mm PFA tubes filled with a photocatalyst carrier which is a filter for water purification treatment, and UV light having a wavelength of 254 nm is measured by a UV illuminance meter. It is designed to irradiate 16% UV lamp (20W) with about 70% transparent UV light transmission tube), and purify treatment (decolorization treatment) while the methylene blue aqueous solution passes through the photocatalyst support in the water pipe. ). As a transmittance measuring instrument, a visible / ultraviolet spectrophotometer “DR / 4000U” manufactured by Central Chemical Co., Ltd. was used.
而して、脱色試験は、各光触媒担持体Ｅ１〜Ｅ９を上記各水路管内に充填した上、メチレンブルー水溶液の循環流量を異にして３回に分けて行い、第１回目の脱色試験ではメチレンブルー水溶液の循環流量を５Ｌ／ｍｉｎとして、第２回目の脱色試験では当該循環流量を第１回目の２倍（１０Ｌ／ｍｉｎ）として、更に第３回目の脱色試験では当該循環流量を第１回目と同一（５Ｌ／ｍｉｎ）として、夫々脱色時間を測定した。また、各脱色試験後において、水路管から光触媒担持体を取り出して重量を測定することによって、ＴｉＯ２光触媒層の累積剥離量を求めた。すなわち、累積剥離量は、第１回目の脱色試験については（(第１回目の脱色試験前の光触媒担持体重量−第１回目の脱色試験後の光触媒担持体重量)／第１回目の脱色試験前の光触媒担持体重量）×１００％）であり、第２回目の脱色試験については（(第１回目の脱色試験前の光触媒担持体重量−第２回目の脱色試験後の光触媒担持体重量)／第１回目の脱色試験前の光触媒担持体重量）×１００％）であり、第３回目の脱色試験については（(第１回目の脱色試験前の光触媒担持体重量−第３回目の脱色試験後の光触媒担持体重量)／第１回目の脱色試験前の光触媒担持体重量）×１００％）である。 Thus, the decolorization test was carried out in three times with the photocatalyst carriers E1 to E9 being filled in the above-mentioned water channel pipes, and the circulation flow rate of the methylene blue aqueous solution was different. In the first decolorization test, the methylene blue aqueous solution The circulation flow rate is 5 L / min, the circulation flow rate is doubled (10 L / min) in the second decolorization test, and the circulation flow rate is the same as in the first decoloration test. The decolorization time was measured as (5 L / min). Further, after each decolorization test, the photocatalyst carrier was taken out from the water pipe and the weight was measured, thereby obtaining the cumulative amount of TiO 2 photocatalyst layer. That is, the cumulative peeling amount is ((the weight of the photocatalyst carrier before the first decoloring test−the weight of the photocatalyst carrier after the first decoloring test)) / the first decoloring test. The weight of the previous photocatalyst carrier) × 100%), and for the second decoloration test ((photocatalyst carrier weight before the first decoloration test−photocatalyst carrier weight after the second decoloration test)) / Photocatalyst carrier weight before first decoloring test) × 100%), and for the third decoloring test ((photocatalyst carrier weight before first decoloring test−third decoloring test) The weight of the subsequent photocatalyst carrier) / the weight of the photocatalyst carrier before the first decolorization test) × 100%).
脱色試験の結果は表１に示す通りであり、実施例の光触媒担持体Ｅ１〜Ｅ３では、循環流量の変化に拘わらずＴｉＯ２光触媒層が剥離されず、脱色時間も殆ど変化がなかった。これに対して、比較例の光触媒担持体Ｅ４〜Ｅ９では、累積剥離量が脱色試験回数に応じて増加しており、脱色時間も脱色試験を重ねるに従って増大している。このことからも、超音波長試験の結果と同様に、前処理工程が光触媒機能向上に極めて有効であることが理解される。特に、実施例の光触媒担持体Ｅ１〜Ｅ３と比較例の光触媒担持体Ｅ４，Ｅ５とで第１回目の脱色時間が大きく異なるのは、光触媒担持体Ｅ４，Ｅ５においてＴｉＯ２光触媒層形成に接着剤，分散剤等の添加剤を含むＴｉＯ２ゾルを使用したことによるものであり、第２回目及び第３回目の脱色時間が実施例の光触媒担持体Ｅ１〜Ｅ３において殆ど変化がないのに対し比較例の光触媒担持体Ｅ４〜Ｅ９では脱色試験を重ねるに従って増大しているのは、ＴｉＯ２光触媒層の剥離によるものであると考えられる。なお、脱色試験後の光触媒担持体Ｅ１〜Ｅ９についてＳＥＭ観察したところ、超音波試験後のＳＥＭ観察結果と一致した。 The results of the decolorization test are as shown in Table 1. In the photocatalyst carriers E1 to E3 of the examples, the TiO 2 photocatalyst layer was not peeled regardless of the change in the circulation flow rate, and the decolorization time hardly changed. On the other hand, in the photocatalyst carriers E4 to E9 of the comparative examples, the cumulative peel amount increases according to the number of decoloring tests, and the decoloring time also increases as the decoloring tests are repeated. From this, it is understood that the pretreatment process is extremely effective for improving the photocatalytic function, similarly to the result of the ultrasonic length test. In particular, the photocatalyst carriers E1 to E3 of the example and the photocatalyst carriers E4 and E5 of the comparative example differ greatly in the first decolorization time because the adhesive for forming the TiO 2 photocatalyst layer in the photocatalyst carriers E4 and E5 is different. This is due to the use of a TiO 2 sol containing additives such as a dispersant, and the second and third decolorization times are almost unchanged in the photocatalyst carriers E1 to E3 of the examples. In the photocatalyst carriers E4 to E9 in the example, it is considered that the increase in the decoloring test is due to the peeling of the TiO 2 photocatalyst layer. In addition, when SEM observation was carried out about the photocatalyst carrier E1-E9 after a decoloring test, it corresponded with the SEM observation result after an ultrasonic test.
Ａ 基体
ａ ＳｉＣ酸化拡散層
Ｂ 酸化膜層（ＳｉＯ２層）
Ｃ 固溶体層
Ｄ ＴｉＯ２光触媒層
Ｅ１ 光触媒担持体
Ｅ２ 光触媒担持体
Ｅ３ 光触媒担持体
A substrate a SiC oxidation diffusion layer B oxide film layer (SiO 2 layer)
C solid solution layer D TiO 2 photocatalyst layer E1 photocatalyst carrier E2 photocatalyst carrier E3 photocatalyst carrier
Claims (7)
非酸化物系セラミックスからなる基体を大気中で加熱して酸化処理することによって基体表面に酸化膜層を形成する一次前処理工程と、酸化膜層が形成された基体を、酸化膜層上にＴｉＯ２スラリをコーティングした上で、大気中で熱処理することにより、酸化膜層上に当該酸化膜成分及びＴｉＯ２の固溶体層を形成する二次前処理工程と、固溶体層が形成された基体を、固溶体層上にＴｉＯ２粉末の水スラリをコーティングした上で、熱処理することにより、固溶体層上にＴｉＯ２光触媒層を形成する触媒担持処理工程とからなることを特徴とする光触媒担持体の製造方法。 A method for producing a photocatalyst carrier according to any one of claims 1 to 4,
A primary pretreatment process for forming an oxide film layer on the surface of the substrate by heating and oxidizing the substrate made of non-oxide ceramic in the atmosphere, and the substrate on which the oxide film layer is formed on the oxide film layer A secondary pretreatment step of forming a solid solution layer of the oxide film component and TiO 2 on the oxide film layer by coating with TiO 2 slurry and heat-treating in the atmosphere, and a substrate on which the solid solution layer is formed And a catalyst supporting treatment step of forming a TiO 2 photocatalyst layer on the solid solution layer by coating the solid solution layer with a water slurry of TiO 2 powder and then heat-treating it. Method.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08224445A (en) * | 1994-12-20 | 1996-09-03 | Hitachi Ltd | Catalyst-containing heat shielding member and gas turbine using the same |
| JPH1036144A (en) * | 1996-07-26 | 1998-02-10 | Murakami Corp | Antifogging element |
| JPH11342343A (en) * | 1998-03-31 | 1999-12-14 | Toshiba Lighting & Technology Corp | Photocatalyst, lamp and luminaire |
| JP2004067480A (en) * | 2002-08-09 | 2004-03-04 | Ube Ind Ltd | Material coated with ceramic thin film having gradient composition and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08224445A (en) * | 1994-12-20 | 1996-09-03 | Hitachi Ltd | Catalyst-containing heat shielding member and gas turbine using the same |
| JPH1036144A (en) * | 1996-07-26 | 1998-02-10 | Murakami Corp | Antifogging element |
| JPH11342343A (en) * | 1998-03-31 | 1999-12-14 | Toshiba Lighting & Technology Corp | Photocatalyst, lamp and luminaire |
| JP2004067480A (en) * | 2002-08-09 | 2004-03-04 | Ube Ind Ltd | Material coated with ceramic thin film having gradient composition and method for manufacturing the same |
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