JP2004050101A - Manufacturing method for photocatalyst body - Google Patents
Manufacturing method for photocatalyst body Download PDFInfo
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- JP2004050101A JP2004050101A JP2002213010A JP2002213010A JP2004050101A JP 2004050101 A JP2004050101 A JP 2004050101A JP 2002213010 A JP2002213010 A JP 2002213010A JP 2002213010 A JP2002213010 A JP 2002213010A JP 2004050101 A JP2004050101 A JP 2004050101A
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- JP
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- Prior art keywords
- photocatalyst
- coating film
- metal
- coating
- honeycomb
- 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.)
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 239000011810 insulating material Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- 235000019645 odor Nutrition 0.000 description 2
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- 235000021317 phosphate Nutrition 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
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- -1 superoxide ions Chemical class 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
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- 229910018464 Al—Mg—Si Inorganic materials 0.000 description 1
- 229910018569 Al—Zn—Mg—Cu Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910020816 Sn Pb Inorganic materials 0.000 description 1
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- 239000004115 Sodium Silicate Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は光触媒体の製造方法に関する。
【０００２】
【従来の技術】
いわゆる半導体光触媒による光反応は、その１つの機構である酸化還元反応により、脱臭、抗菌、防汚作用を生じさせる。この光触媒の作用を利用して種々の製品が検討され、実用化されている。代表的な半導体光触媒である酸化チタンのバンドギャップは約３ｅＶであり、波長に直すと４００ｎｍ程度である。したがって、４００ｎｍ以下の紫外線を照射すると半導体内部に電子（ｅ−）と正孔（ｈ＋）が生じる。この電子は酸素と反応してきわめて大きい酸化力を示すスーパーオキサイドイオン〔Ｏ２ −〕を生成し、一方の正孔は水と反応してヒドロキシラジカル〔・ＯＨ〕を生成する。この２つの活性酸素が酸化還元反応を発現させ、臭気もしくは汚れ物質の分解、さらには有機系塩素化合物等の他の難分解性化合物が酸化分解されることになる。
【０００３】
従来、光触媒体として種々の基材、形状のものが知られている。たとえば、空気清浄機等の脱臭に光触媒体が用いられる場合、通気性がよく、軽量で、表面積が大きい等の点から、ダンボール紙もしくは不織布を基材として酸化チタンを塗布することが多いが、紙の場合には照射される紫外線によりパルプ繊維が劣化されやすく、また紙も不織布も紫外線のあたらない内側部分での光触媒活性に難があり、有効な触媒活性を得るのは困難であった。
【０００４】
そこで、基材として金属を使用すると低波長の紫外線による劣化がないので有利であり、たとえば金属基材をハニカム形状とし、チタンのアルコシドを塗布した後に加熱して酸化チタンを形成させることも行われている。しかし、このような場合、加熱によりハニカム形成に用いられた接着剤が失活ないしは強度低下してしまうことが避けづらく、ハニカムの機械的強度が著しく低下する恐れがある。
【０００５】
【発明が解決しようとする課題】
本発明は、上記のような難点を解決し、光の当たる表面積を大きくし、紫外線を効率的に照射することにより優れた光触媒活性を有し、しかも紫外線による劣化を少なくし得、機械的強度にも優れた光触媒体を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明の要旨は、金属基板上に光触媒のコーティング膜を形成させ、ついでこのコーティング膜形成金属基板を加工して立体構造体とすることにより、立体構造を有する光触媒体を得ることを特徴とする光触媒体の製造方法にある。
【０００７】
【発明の実施の形態】
本発明の光触媒体において、上記の金属は好適にはアルミニウム、チタン、マグネシウム、鋼もしくはステンレス鋼から選択されるが、特に好適にはアルミニウムである。アルミニウム、チタンもしくはマグネシウムは合金であってもよい。たとえばアルミニウム合金としては、Ａｌ−Ｍｇ、Ａｌ−Ｍｇ−Ｓｉ、Ａｌ−Ｃｕ−Ｍｇ−Ｍｎ、Ａｌ−Ｚｎ−Ｍｇ−Ｃｕ等、マグネシウム合金としては、Ｍｇ−Ａｌ、Ｍｇ−Ａｌ−Ｚｎ、Ｍｇ−Ｍｎ等が挙げられる。本発明においてはこれらの金属の基板上に、光触媒のコーティング膜が形成されるが、この形成前に、金属表面は絶縁被覆されるのが好ましい。この絶縁被覆により、光触媒上の電子が金属側に流れることなく、電子の授受を十分に行ないうるので、光分解活性を格段に高めることができる。
【０００８】
この絶縁被覆処理は、好適には陽極酸化、化成処理もしくはガラスコーティング処理から選ばれる。たとえば、アルミニウム、チタンの場合には、それらを電解質水溶液中に浸漬してアノード分極することにより、金属の表面に酸化物皮膜を形成する、いわゆる陽極酸化皮膜が一般的である。また、鋼板の場合には電気めっき、もしくは溶融めっき、さらにはリン酸、およびリン酸塩による化成処理が一般的である。さらにアルミニウムの場合には、陽極酸化に代えて化学薬品による化学的皮膜化成法（化成処理）を採用しうる。この化成処理としてはクロム酸またはクロム酸−リン酸を主体とするもの、すなわちクロメート処理皮膜が好適である。マグネシウムの場合にも、陽極酸化，化成処理が適用されうる。
【０００９】
またアルミニウム等の表面に珪酸ソーダ（水ガラス）を塗布して焼結させるガラスコーティング法を採用することもできる。
【００１０】
ステンレス鋼の場合、表面を酸化させ不働態化を目的とする酸（好適には重クロム酸ソーダ）処理（化成処理）も採用しうる。
【００１１】
絶縁被覆の膜厚は特に制限されないが、通常約０．１〜１μｍ程度から選択される。
【００１２】
本発明における光触媒としては、酸化ジルコニウム、酸化チタン、酸化亜鉛、酸化タングステン、酸化カドミウム、酸化マンガン、酸化銅等の金属酸化物；硫化カドミウム、硫化亜鉛、硫化インジウム、硫化鉛、硫化タングステン等の金属硫化物；ポリパラフェニレン、ポリアニリン、ポリチオフェン等の有機高分子；チタン酸ストロンチウムに各種の金属酸化物を添加した層間化合物、等が挙げられるが、酸化ジルコニウムおよび酸化チタンが好適である。そして最も好適には、酸化ジルコニウムを選択することにより、比較的短波長の紫外光を利用しうるので向上した光触媒活性が得られ易い。酸化チタンとしてはアナタ−ゼ、ルチルもしくはブロッカイト型のいずれでもよいが、触媒活性および入手し易さの点からアナタ−ゼ型が最適である。
【００１３】
これらの光触媒の金属基板へのコーティング膜の形成法自体は、常法によることができるが、液相から析出させる方法、気相から蒸着させる方法が好ましい。たとえば、液相法としてはゾル−ゲル法等、気相法としてはスパッタリング、真空蒸着等の物理蒸着法（ＰＶＤ）または気相化学反応法（ＣＶＤ）等の化学的方法が挙げられるが、得られる被覆の均一性、コスト等の点からゾル−ゲル法が最適である。そしてゾル−ゲル法における出発物質としては、たとえば金属アルコキシド、金属アセチルアセトネート、金属カルボキシレート等の金属有機化合物、たとえばオキシ塩化物、塩化物、硝酸塩等の金属無機化合物が一般的に用いられる。これらの中で、金属アルコキシドが反応性等の点から好適であり、ブトキシド、エトキシド、プロポキシド等の金属（たとえばジルコニウムもしくはチタン）アルコキシドをブタノール、プロパノール等の溶媒を用いて溶液として、これを金属基板に塗布することにより目的とするコーティング膜が形成されうる。塗布は、はけ塗り、ロール塗り、浸漬法、スプレー、スピン等を適宜選択しうる。コーティング膜の厚さは通常３〜５００μｍ、好ましくは５〜２０μｍ程度から選ばれる。たとえば、ゾル−ゲル法を用いて金属アルコキシド溶液に基板を浸漬し、引き上げることによりによりーティング膜を得る。このコーティング膜は常法により、たとえば室温で乾燥され、ついで３００〜５５０℃程度に加熱され基板に固着される。上記のＣＶＤ法としてはプラズマＣＶＤ法が４００〜５００℃程度までの比較的低い温度範囲の気相化学反応で成膜しうるので、基材に制限がなく好適である。
【００１４】
得られたコーティング膜形成基板はついで立体構造体に加工される。この構造体はハニカム、波板および／平板より構成される。ハニカムは六角形のコアに限定されず、いかなる形状であってもよい。波板は、平板と組合わせて（波付け）、平行に配置して使用してもよいが、巻き上げてハニカムを形成することもできる。平板は、平行に配置して、いわゆるパラレルパッセージ形として使用するのが好適である。本発明の構造体は通気抵抗が極めて小さいので効率的な光触媒反応を可能にする。上記の立体構造体を形成するための加工は、接着、切削もしくは切断であり、常法によることができる。接着に際しては、有機接着剤は光触媒により劣化するおそれがあるので、無機接着剤が使用されるのが好ましい。そのような無機接着剤としては、低融点ガラス等のガラス系；Ｓｎ−Ｉｎ，Ｂｉ−Ｐｂ，Ｓｎ−Ｐｂ，Ｐｂ−Ｓｂ等の軟ろう等の金属系；ケイ酸アルカリ（特に水ガラス）、リン酸塩系等、のその他の無機系、等が挙げられるが、接着温度が１００〜５００℃、好ましくは１２０〜２００℃のものが特に好ましい。これらの無機接着剤のうち、最も好適なのは水ガラスである。
【００１５】
本発明による光触媒体は、その表面粗さが５０ｎｍＲａ（中心線粗さ）以下であるのが好適であり、このように鏡面を形成し、コーティング膜も透明であると、光の反射率が著しく高くなり、たとえばハニカム光触媒体の内部まで紫外線を乱反射して照射することができ、触媒活性を著しく向上しうる。
【００１６】
本発明の光触媒体に近接して紫外線源を適宜配置することにより、脱臭装置、殺菌装置、空気清浄化器、水純化装置等に使用しうる。この場合、従来の活性炭等の吸着剤層等を併置することもできる。
【００１７】
脱臭は悪臭物質を拡散現象により光触媒表面に接触させて酸化分解することにより行なわれる。悪臭物質としては硫化水素、メルカプタン、アミン、アンモニア、アルデヒド等が挙げられる。空気中に離散した揮発性有機ハロゲン化合物、例えばトリクロロエタン、トリクロロエチレン等も光触媒反応により分解しうる。
【００１８】
照射に利用される紫外線としてはたとえば波長が１８５ｎｍ、２５４ｎｍ、３００〜４００ｎｍの紫外線が挙げられる。光触媒を光励起する波長は光触媒の種類により異なるが、たとえば二酸化チタンの場合、アナタ−ゼ型で３８０ｎｍ以下、ルチル型で４１５ｎｍ以下であり、さらに酸化ジルコニウムの場合、２５４ｎｍ以下である。このような光線を放射するランプとしては、ブラックライト、低圧、中圧もしくは高圧の水銀ランプ等の放電ランプが好適である。
【００１９】
【実施例】
以下、実施例によりさらに本発明を詳細に説明する。
実施例１ Ａｌ板−陽極酸化／ＺｒＯ２／ゾル−ゲル／ハニカム（波板巻き上げ）
アルミニウム（Ａｌ）基板（平板および波板）を次の条件で陽極酸化した。
【００２０】
・ 浴組成 硫酸 １３．７％
・ 処理条件 約２２℃、０．５Ａ／ｄｍ２、ＤＣ，５分間、陰極：カーボン
得られた陽極酸化アルミニウム基板（酸化皮膜厚さ：約０．５μｍ）をジルコニウムブトキシドのエタノール溶液（ジルコニウムブトキシド２０ｇ、エタノール４５ｇ、水２０ｇ、塩酸０．３ｇ）に浸漬し、引き上げ、乾燥（室温）を繰り返して、ついで焼成（約５００℃）し、厚さ約１０μｍのＺｒＯ２コーティング膜（５０ｎｍＲａ以下）を作製した。ついで得られた陽極酸化膜／ＺｒＯ２コーティング膜／アルミニウム基板から水ガラス接着剤を用いて、平板および波板を組合わせて波付けし、これをハニカム状に巻き上げることによりハニカム光触媒体を得た。
実施例２ Ａｌ板−陽極酸化／ＴｉＯ２／ゾル−ゲル／ハニカム（波板巻き上げ）
実施例１において、ＺｒＯ２コーティング膜に代えてＴｉＯ２コーティング膜（厚さ約１０μｍ）を作製する以外は同様にしてハニカム光触媒体を得た。チタンイソプロポキシドのエタノール溶液（チタンイソプロポキシド２５ｇ、エタノール４０ｇ、水２５ｇ、塩酸０．３ｇ）を用いた。
実施例３ Ａｌ板−化成処理／ＺｒＯ２／ゾル−ゲル／ＰＰＲ
実施例１において、Ａｌ基板の陽極酸化に代えて化成処理を採用した以外は同様にしてＺｒＯ２コーティング膜を作製した。化成処理はクロム酸−リン酸法により、処理方法：浸漬、濃度：４．５％、温度：４０〜５０℃、時間：３０秒で行った（膜厚：０．２μｍ）。ついで得られた化成皮膜／ＺｒＯ２コーティング膜／アルミニウム基板から、平板もしくは波板を間隔約０．５ｃｍで常法により平行に配置することによりＰＰＲ光触媒体を得た。
実施例４ 鋼板−めっき／ＴｉＯ２／ＣＶＤ／ハニカム（波板巻き上げ）
鋼基板を次の条件でめっきして亜鉛めっき皮膜（厚さ０．３μｍ）を形成させた。
【００２１】
【００２２】
反応装置：対向電極型プラズマＣＶＤ装置
反応ガス：ＴｉＣｌ４
雰囲気：Ａｒ＋Ｏ２
温度：３００〜４００℃
圧力：１．０Ｔｏｒｒ
実施例５ Ｍｇ板−陽極酸化／ＴｉＯ２／ゾル−ゲル／ハニカム（波板巻き上げ）
マグネシウム合金（Ｍｇ−Ａｌ−Ｚｎ）基板を次の条件で陽極酸化した。
【００２３】
参考例
実施例１で得られた光触媒体（１）を用いて、図１に示す脱臭装置を作製した。（２）は低圧水銀ランプ（３０Ｗ）であり、さらに光の反射効率を上げるために反射鏡（３）を設けてなる。悪臭・細菌を含むガスは送風ファン（図示せず）により装置内に送られ、悪臭成分は光触媒により酸化分解され、細菌は紫外線によるＤＮＡ分解とともに光触媒による溶菌酸化により殺菌される。
【図面の簡単な説明】
【図１】本発明の光触媒体を用いた脱臭装置の１態様を示す概略図。
【符号の説明】
１…光触媒体
２…低圧水銀ランプ（３０Ｗ）
３…反射鏡[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a photocatalyst.
[0002]
[Prior art]
A photoreaction by a so-called semiconductor photocatalyst causes deodorization, antibacterial and antifouling actions by an oxidation-reduction reaction, which is one of the mechanisms. Various products have been studied by utilizing the action of the photocatalyst and have been put to practical use. The band gap of titanium oxide, which is a typical semiconductor photocatalyst, is about 3 eV, which is about 400 nm in terms of wavelength. Therefore, when ultraviolet light of 400 nm or less is irradiated, electrons (e − ) and holes (h + ) are generated inside the semiconductor. These electrons react with oxygen to generate superoxide ions [O 2 − ] exhibiting extremely large oxidizing power, and one hole reacts with water to generate hydroxyl radicals [.OH]. These two active oxygens cause an oxidation-reduction reaction to decompose odors or dirt substances, and further oxidatively decompose other hardly decomposable compounds such as organic chlorine compounds.
[0003]
BACKGROUND ART Conventionally, various substrates and shapes having a photocatalyst have been known. For example, when a photocatalyst is used for deodorization of an air purifier or the like, titanium oxide is often applied using corrugated cardboard or a nonwoven fabric as a base material in terms of good air permeability, light weight, and large surface area. In the case of paper, the pulp fibers are liable to be degraded by the irradiated ultraviolet light, and both the paper and the nonwoven fabric have poor photocatalytic activity in the inner part where the ultraviolet light does not reach, and it has been difficult to obtain effective catalytic activity.
[0004]
Therefore, it is advantageous to use a metal as a base material, because there is no deterioration due to low-wavelength ultraviolet rays. For example, a metal base material is formed into a honeycomb shape, and after applying an alkoxide of titanium, heating is performed to form titanium oxide. ing. However, in such a case, it is difficult to avoid that the adhesive used for forming the honeycomb is deactivated or the strength is reduced by heating, and the mechanical strength of the honeycomb may be significantly reduced.
[0005]
[Problems to be solved by the invention]
The present invention solves the above-mentioned difficulties, has a large surface area exposed to light, has excellent photocatalytic activity by efficiently irradiating ultraviolet rays, and can reduce deterioration due to ultraviolet rays, and has a mechanical strength. Another object of the present invention is to provide a photocatalyst excellent in the above.
[0006]
[Means for Solving the Problems]
The gist of the present invention is characterized in that a photocatalyst having a three-dimensional structure is obtained by forming a coating film of a photocatalyst on a metal substrate, and then processing the metal substrate on which the coating film is formed into a three-dimensional structure. A method for producing a photocatalyst.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
In the photocatalyst of the present invention, the metal is preferably selected from aluminum, titanium, magnesium, steel or stainless steel, and is particularly preferably aluminum. Aluminum, titanium or magnesium may be an alloy. For example, as an aluminum alloy, Al-Mg, Al-Mg-Si, Al-Cu-Mg-Mn, Al-Zn-Mg-Cu, etc., and as a magnesium alloy, Mg-Al, Mg-Al-Zn, Mg- Mn and the like. In the present invention, a coating film of a photocatalyst is formed on a substrate of such a metal, and it is preferable that the metal surface is coated with an insulating film before this formation. By this insulating coating, the electrons on the photocatalyst can be sufficiently exchanged without flowing to the metal side, so that the photolytic activity can be remarkably enhanced.
[0008]
This insulating coating treatment is preferably selected from anodic oxidation, chemical conversion treatment or glass coating treatment. For example, in the case of aluminum and titanium, a so-called anodic oxide film that forms an oxide film on a metal surface by immersing them in an aqueous electrolyte solution and subjecting them to anodic polarization is generally used. In the case of a steel sheet, electroplating or hot-dip plating, and furthermore, chemical conversion treatment with phosphoric acid and phosphate are common. Further, in the case of aluminum, a chemical film formation method (chemical conversion treatment) using a chemical agent may be adopted instead of anodic oxidation. As the chemical conversion treatment, a treatment mainly composed of chromic acid or chromic acid-phosphoric acid, that is, a chromate treatment film is preferable. Also in the case of magnesium, anodic oxidation and chemical conversion treatment can be applied.
[0009]
Further, a glass coating method in which sodium silicate (water glass) is applied to the surface of aluminum or the like and then sintered may be employed.
[0010]
In the case of stainless steel, an acid (preferably sodium dichromate) treatment (chemical conversion treatment) for oxidizing the surface to passivate the surface may be employed.
[0011]
The thickness of the insulating coating is not particularly limited, but is usually selected from about 0.1 to 1 μm.
[0012]
Examples of the photocatalyst in the present invention include metal oxides such as zirconium oxide, titanium oxide, zinc oxide, tungsten oxide, cadmium oxide, manganese oxide, and copper oxide; metals such as cadmium sulfide, zinc sulfide, indium sulfide, lead sulfide, and tungsten sulfide. Sulfides; organic polymers such as polyparaphenylene, polyaniline, and polythiophene; intercalation compounds obtained by adding various metal oxides to strontium titanate; and zirconium oxide and titanium oxide are preferable. Most preferably, by selecting zirconium oxide, an ultraviolet light having a relatively short wavelength can be used, so that an improved photocatalytic activity can be easily obtained. Titanium oxide may be any of an anatase, rutile or blockite type, but an anatase type is optimal from the viewpoint of catalytic activity and availability.
[0013]
The method of forming the coating film of the photocatalyst on the metal substrate itself can be a conventional method, but a method of depositing from a liquid phase and a method of depositing from a gas phase are preferable. For example, the liquid phase method includes a sol-gel method and the like, and the gas phase method includes a chemical method such as a physical vapor deposition method (PVD) such as sputtering and vacuum vapor deposition or a gas phase chemical reaction method (CVD). The sol-gel method is optimal from the viewpoint of uniformity of coating to be obtained, cost and the like. As a starting material in the sol-gel method, a metal organic compound such as a metal alkoxide, a metal acetylacetonate, or a metal carboxylate, for example, a metal inorganic compound such as an oxychloride, a chloride, or a nitrate is generally used. Among these, metal alkoxides are preferable from the viewpoint of reactivity and the like. Metal alkoxides such as butoxide, ethoxide and propoxide (for example, zirconium or titanium) are used as a solution using a solvent such as butanol or propanol, and this is converted to a metal. A desired coating film can be formed by applying the composition to a substrate. For application, brushing, roll coating, dipping, spraying, spinning, or the like can be appropriately selected. The thickness of the coating film is generally selected from the range of 3 to 500 μm, preferably about 5 to 20 μm. For example, a substrate is immersed in a metal alkoxide solution using a sol-gel method, and is lifted to obtain a coating film. The coating film is dried by a conventional method, for example, at room temperature, and then heated to about 300 to 550 ° C. and fixed to the substrate. As the above-mentioned CVD method, a plasma CVD method can be used for forming a film by a gas phase chemical reaction in a relatively low temperature range of about 400 to 500 ° C., and thus there is no limitation on the base material, which is suitable.
[0014]
The obtained coating film forming substrate is then processed into a three-dimensional structure. This structure comprises a honeycomb, a corrugated sheet and / or a flat sheet. The honeycomb is not limited to a hexagonal core and may have any shape. The corrugated plate may be used in combination with a flat plate (corrugation) and arranged in parallel, or may be rolled up to form a honeycomb. The flat plates are preferably arranged in parallel and used as a so-called parallel passage type. The structure of the present invention enables efficient photocatalytic reaction because of extremely low airflow resistance. The processing for forming the three-dimensional structure is bonding, cutting, or cutting, and can be performed by an ordinary method. At the time of bonding, an organic adhesive is likely to be degraded by a photocatalyst, so that an inorganic adhesive is preferably used. Examples of such inorganic adhesives include glass based materials such as low melting point glass; metal based materials such as soft solder such as Sn-In, Bi-Pb, Sn-Pb and Pb-Sb; alkali silicate (particularly water glass); Other inorganic materials such as phosphates and the like can be mentioned, and those having an adhesion temperature of 100 to 500 ° C, preferably 120 to 200 ° C, are particularly preferable. Of these inorganic adhesives, the most preferred is water glass.
[0015]
The photocatalyst according to the present invention preferably has a surface roughness of 50 nmRa (center line roughness) or less. When the mirror surface is formed and the coating film is transparent, the light reflectance is remarkable. Thus, for example, the inside of the honeycomb photocatalyst body can be irradiated with ultraviolet rays with irregular reflection, and the catalytic activity can be significantly improved.
[0016]
By appropriately arranging an ultraviolet light source close to the photocatalyst of the present invention, it can be used for a deodorizer, a sterilizer, an air purifier, a water purifier and the like. In this case, a conventional adsorbent layer of activated carbon or the like may be provided.
[0017]
Deodorization is performed by bringing a malodorous substance into contact with the photocatalyst surface by a diffusion phenomenon and oxidatively decomposing it. Examples of the offensive odor include hydrogen sulfide, mercaptan, amine, ammonia, aldehyde and the like. Volatile organic halogen compounds dispersed in the air, such as trichloroethane and trichloroethylene, can also be decomposed by a photocatalytic reaction.
[0018]
Examples of the ultraviolet light used for the irradiation include ultraviolet light having a wavelength of 185 nm, 254 nm, or 300 to 400 nm. The wavelength of photoexcitation of the photocatalyst varies depending on the type of photocatalyst. For example, in the case of titanium dioxide, it is 380 nm or less for anatase type and 415 nm or less for rutile type, and further, it is 254 nm or less for zirconium oxide. As a lamp that emits such a light beam, a discharge lamp such as a black light, a low-pressure, medium-pressure or high-pressure mercury lamp is preferable.
[0019]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1 Al plate - anodic oxidation / ZrO 2 / sol - gel / honeycomb (hoisting corrugated)
An aluminum (Al) substrate (flat plate and corrugated plate) was anodized under the following conditions.
[0020]
・ Bath composition sulfuric acid 13.7%
Treatment conditions: about 22 ° C., 0.5 A / dm 2 , DC, 5 minutes, cathode: carbon An anodized aluminum oxide substrate (oxide film thickness: about 0.5 μm) was obtained and ethanol solution of zirconium butoxide (zirconium butoxide 20 g) was used. , 45 g of ethanol, 20 g of water, 0.3 g of hydrochloric acid), pulling up, drying (room temperature), repeating baking (about 500 ° C.), and producing a ZrO 2 coating film (about 50 nm Ra or less) having a thickness of about 10 μm. did. Then, a flat plate and a corrugated plate were combined and corrugated from the obtained anodic oxide film / ZrO 2 coating film / aluminum substrate using a water glass adhesive, and this was rolled up in a honeycomb shape to obtain a honeycomb photocatalyst. .
Example 2 Al plate - anodic oxidation / TiO 2 / sol - gel / honeycomb (hoisting corrugated)
A honeycomb photocatalyst was obtained in the same manner as in Example 1, except that a TiO 2 coating film (thickness: about 10 μm) was formed instead of the ZrO 2 coating film. An ethanol solution of titanium isopropoxide (25 g of titanium isopropoxide, 40 g of ethanol, 25 g of water, 0.3 g of hydrochloric acid) was used.
Example 3 Al plate - chemical treatment / ZrO 2 / sol - gel / PPR
A ZrO 2 coating film was produced in the same manner as in Example 1, except that a chemical conversion treatment was employed instead of the anodic oxidation of the Al substrate. The chemical conversion treatment was performed by a chromic acid-phosphoric acid method at a treatment method: immersion, concentration: 4.5%, temperature: 40 to 50 ° C., and time: 30 seconds (film thickness: 0.2 μm). Then, a PPR photocatalyst was obtained by arranging flat plates or corrugated plates in parallel by a conventional method at intervals of about 0.5 cm from the obtained chemical conversion film / ZrO 2 coating film / aluminum substrate.
Example 4 steel - Plating / TiO 2 / CVD / honeycomb (hoisting corrugated)
A steel substrate was plated under the following conditions to form a galvanized film (thickness 0.3 μm).
[0021]
[0022]
Reactor: Counter electrode type plasma CVD device Reactant gas: TiCl 4
Atmosphere: Ar + O 2
Temperature: 300-400 ° C
Pressure: 1.0 Torr
Example 5 Mg plate - anodic oxidation / TiO 2 / sol - gel / honeycomb (hoisting corrugated)
A magnesium alloy (Mg-Al-Zn) substrate was anodized under the following conditions.
[0023]
Reference Example Using the photocatalyst (1) obtained in Example 1, a deodorizing apparatus shown in FIG. 1 was produced. (2) is a low-pressure mercury lamp (30 W), and further provided with a reflecting mirror (3) to increase the light reflection efficiency. The gas containing the malodor and bacteria is sent into the apparatus by a blower fan (not shown), and the malodor component is oxidatively decomposed by a photocatalyst.
[Brief description of the drawings]
FIG. 1 is a schematic view showing one embodiment of a deodorizing apparatus using a photocatalyst according to the present invention.
[Explanation of symbols]
1: Photocatalyst body 2: Low-pressure mercury lamp (30W)
3. Reflector
Claims (16)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002213010A JP2004050101A (en) | 2002-07-22 | 2002-07-22 | Manufacturing method for photocatalyst body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002213010A JP2004050101A (en) | 2002-07-22 | 2002-07-22 | Manufacturing method for photocatalyst body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004050101A true JP2004050101A (en) | 2004-02-19 |
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| JP2002213010A Pending JP2004050101A (en) | 2002-07-22 | 2002-07-22 | Manufacturing method for photocatalyst body |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006263625A (en) * | 2005-03-24 | 2006-10-05 | Univ Kinki | Production method of functional coating on aluminum based material and aluminum based material having the same |
| JP2012161711A (en) * | 2011-02-03 | 2012-08-30 | U-Vix Corp | Photocatalyst and method for producing the same |
| CN114984987A (en) * | 2022-06-29 | 2022-09-02 | 河南师范大学 | ZnIn 2 S 4 /Ti 3 C 2 /CuCo 2 S 4 Preparation and application of composite catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000093807A (en) * | 1998-09-25 | 2000-04-04 | Sharp Corp | Photocatalyst body, and heat exchanger and purifying device using the same |
| JP2000312830A (en) * | 1999-04-28 | 2000-11-14 | Sumitomo Metal Ind Ltd | Photocatalyst composite material and production thereof |
| JP2002177790A (en) * | 2000-12-13 | 2002-06-25 | Mitsubishi Alum Co Ltd | Photocatalyst precoated molding material and photocatalyst precoated molding and photocatalyst precoated fin |
-
2002
- 2002-07-22 JP JP2002213010A patent/JP2004050101A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000093807A (en) * | 1998-09-25 | 2000-04-04 | Sharp Corp | Photocatalyst body, and heat exchanger and purifying device using the same |
| JP2000312830A (en) * | 1999-04-28 | 2000-11-14 | Sumitomo Metal Ind Ltd | Photocatalyst composite material and production thereof |
| JP2002177790A (en) * | 2000-12-13 | 2002-06-25 | Mitsubishi Alum Co Ltd | Photocatalyst precoated molding material and photocatalyst precoated molding and photocatalyst precoated fin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006263625A (en) * | 2005-03-24 | 2006-10-05 | Univ Kinki | Production method of functional coating on aluminum based material and aluminum based material having the same |
| JP4719919B2 (en) * | 2005-03-24 | 2011-07-06 | 学校法人近畿大学 | Method for producing functional coating on aluminum-based material and aluminum-based material having the functional coating |
| JP2012161711A (en) * | 2011-02-03 | 2012-08-30 | U-Vix Corp | Photocatalyst and method for producing the same |
| CN114984987A (en) * | 2022-06-29 | 2022-09-02 | 河南师范大学 | ZnIn 2 S 4 /Ti 3 C 2 /CuCo 2 S 4 Preparation and application of composite catalyst |
| CN114984987B (en) * | 2022-06-29 | 2023-09-15 | 河南师范大学 | ZnIn 2 S 4 /Ti 3 C 2 /CuCo 2 S 4 Preparation and application of composite catalyst |
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