JP4118063B2 - Surface-modified titanium oxide and selective photolysis catalyst with selective photolysis reactivity - Google Patents
Surface-modified titanium oxide and selective photolysis catalyst with selective photolysis reactivity Download PDFInfo
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- JP4118063B2 JP4118063B2 JP2002031444A JP2002031444A JP4118063B2 JP 4118063 B2 JP4118063 B2 JP 4118063B2 JP 2002031444 A JP2002031444 A JP 2002031444A JP 2002031444 A JP2002031444 A JP 2002031444A JP 4118063 B2 JP4118063 B2 JP 4118063B2
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- titanium oxide
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- 239000003054 catalyst Substances 0.000 title claims description 21
- 238000006303 photolysis reaction Methods 0.000 title claims description 18
- 230000009257 reactivity Effects 0.000 title claims description 10
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 73
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- -1 sulfate group-modified titanium oxide Chemical class 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 13
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- 230000001699 photocatalysis Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
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- 238000001782 photodegradation Methods 0.000 description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 1
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- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
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- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- AKMXMQQXGXKHAN-UHFFFAOYSA-N titanium;hydrate Chemical compound O.[Ti] AKMXMQQXGXKHAN-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、特定の有機化合物に対して選択的な光分解反応性を示す表面修飾酸化チタン及び選択的光分解触媒にかかり、特にアルデヒド類やアルコール類等の極性有機化合物に対して優れた選択的光分解反応性を示す表面修飾酸化チタンやトルエン等の芳香族炭化水素化合物に対して優れた選択的光分解反応性を示す表面修飾酸化チタンからなる表面修飾酸化チタン及び選択的光分解触媒に関する。
【０００２】
【従来の技術】
３eV以上のバンドギャップを有する二酸化チタン（TiO2；以下、単に「酸化チタン」という）等の金属酸化物は、そのバンドギャップ以上のエネルギーの光が照射されると、価電子帯の電子が伝導帯に励起されて価電子帯に正孔が、また、伝導帯に電子が生じ、正孔は酸化反応に寄与し、また、電子は還元反応に寄与することから、この金属酸化物に接触する有害な化学物質や悪臭を有する化学物質を分解する。そして、このような金属酸化物のうち、特に酸化チタンについては、人体に対して無害で化学的安定性が高いことから、多くの分野あるいは用途、例えば大気浄化、室内空気浄化、脱臭、防汚・防曇、浄水等の分野あるいは用途において、光分解反応を触媒する物質（いわゆる光分解触媒）として盛んにその研究開発が進められている。
【０００３】
ところで、酸化チタンが光分解触媒としての作用を発揮するためには、通常５００℃以上で焼成されて結晶化していることが必要であるとされており、また一般に、その結晶構造についてはアナターゼ型結晶の方がルチル型結晶よりも高い光触媒活性を示すと考えられており、従来においても、主としてこのような観点から酸化チタンからなる光分解触媒の開発が進められている。
【０００４】
しかしながら、これまで開発された光分解触媒としての酸化チタンは、低濃度の化学物質を長期に亘って安定的に分解・除去できる可能性を有すると考えられているにもかかわらず、この酸化チタンを触媒担体に担持させるとその光触媒活性が大幅に低下し、また、化学物質との接触確率が充分でないことから、この光分解触媒の光触媒活性を充分に活用できず、必ずしも満足できる性能が得られているとはいえない。
【０００５】
【発明が解決しようとする課題】
そこで、本発明者らは、より優れた光触媒活性を有する光分解触媒の開発について鋭意検討した結果、酸化チタンの表面を硫酸基や塩素化アルミナで修飾することにより、それぞれ特定の化合物に対して選択的にかつ高い光触媒活性を示すことを見出し、本発明を完成した。
【０００６】
従って、本発明の目的は、特定の化合物に対して選択的にかつ高い触媒活性を示す表面修飾酸化チタンを提供することにある。また、本発明の他の目的は、このような表面修飾酸化チタンからなり、特定の化合物に対して選択的にかつ高い触媒活性を示す光分解触媒を提供することにある。
【０００７】
【課題を解決するための手段】
すなわち、本発明は、酸化チタンを濃度１〜０．１Ｎの硫酸水溶液に浸漬し、次いで温度５００〜５５０℃で加熱処理し、得られた硫酸基修飾酸化チタンをアルミニウムアルコキシドの有機溶媒溶液に浸漬して酸化チタンの表面に部分的にアルミナを形成させたのち、これを塩素化物中に浸漬し、次いで温度３００℃以上で加熱処理して得られた塩素化アルミナ修飾酸化チタンであることを特徴とする選択的光分解反応性を有する表面修飾酸化チタンである。
【０００８】
更に、本発明は、上記塩素化アルミナ修飾酸化チタンからなり、芳香族炭化水素化合物に対して選択的光分解反応性を有する選択的光分解触媒である。
【０００９】
本発明において、原料として用いる酸化チタンについては、特に限定されるものではないが、好ましくは硫酸基による表面修飾をより正確に制御するために硫酸根含有量が可及的に低いものがよく、また、加熱処理されて結晶化する前のアモルファス酸化チタンであるのがよい。
【００１０】
ところで、結晶化した酸化チタンを製造する方法については、主として、ルチル鉱（TiO2）を１，０００℃程度の高温炉で塩素化して四塩化チタン（TiCl4）とし、次いで酸素の存在下で高温酸化する方法（塩素法）、イルメナイト鉱（FeTiO3）を熱分解してＴｉＯＳＯ4とし、これを加水分解してＴｉＯ（ＯＨ）2とし、次いで酸素の存在下で高温酸化する方法（硫酸法）、チタンアルコキシド｛Ti(i-PrO)4｝を加水分解触媒の存在下に室温で加水分解し、次いで縮重合させてアモルファス酸化チタンとし、このアモルファス酸化チタンを４００℃以上で加熱処理して結晶化させる方法（ゾルゲル法）が存在するが、本発明で使用する酸化チタンとしては、特にゾルゲル法で得られたアモルファス酸化チタンを用いるのが好ましい。
【００１１】
そして、本発明において、塩素化アルミナ修飾酸化チタンを調製する際に用いる硫酸水溶液の濃度については、通常５〜０．０５Ｎ、好ましくは１〜０．１Ｎである。この際の硫酸水溶液の濃度が５Ｎより高いと、光触媒活性が大きく低化するという問題があり、反対に、０．０５Ｎより低くなると、塩素化アルミナ修飾の均一制御が難しくなるという問題が生じる。
【００１２】
この塩素化アルミナ修飾酸化チタンを調製する際においては、硫酸水溶液に浸漬した後、必要により常圧又は減圧下で常温又は加温下に乾燥してから、上記の硫酸基修飾酸化チタンを調製する場合と同様に加熱処理し、次いで得られた硫酸基修飾酸化チタンをアルミニウムアルコキシドの有機溶媒溶液に浸漬して酸化チタンの表面に部分的にアルミナを形成せしめる。
【００１３】
ここで用いるアルミニウムアルコキシドとしては、アルミニウムのトリアルコキシドであれば特に制限はないが、好ましくはアルミニウムトリメトキシド、アルミニウムトリエトキシド、アルミニウムトリイソプロポキシド、アルミニウムトリイソプロポキシド等を挙げることができ、より好ましくはアルミニウムトリイソプロポキシド等である。
【００１４】
また、このアルミニウムアルコキシドの有機溶媒溶液を調製する際に用いる有機溶媒についても、炭素、水素、酸素原子から構成される有機溶媒であれば特に制限はないが、好ましくはアルコール類、ケトン類、炭化水素等を挙げることができ、より好ましくはメタノール、エタノール、イソプロパノール、シクロヘキサン等である。
【００１５】
更に、アルミニウムアルコキシドの有機溶媒溶液におけるアルミニウムアルコキシドの濃度については、アルミニウムアルコキシドと有機溶媒とのモル比（アルミニウムアルコキシド／有機溶媒）が通常１／１０〜１／１０００、好ましくは１／５０〜１／５００であるのがよい。このモル比（アルミニウムアルコキシド：有機溶媒）が１／１０００より小さいと、酸化チタン表面に担持されるアルミナの量が少なすぎるという問題があり、反対に、１／１０より大きいと、酸化チタン表面に担持されるアルミナの量が多すぎて全面が被覆されてしまうという問題が生じる。
【００１６】
また、表面に部分的にアルミナが形成された酸化チタンについては、次に塩素化物中に浸漬される。この目的で使用される塩素化物としては、酸化チタンの表面に部分的に形成されたアルミナを塩素化できるものであればよく、例えば、モノクロロメタン、ジクロロメタン、クロロホルム、四塩化炭素等の塩素化炭化水素類や、濃度１〜０．００１Ｎの塩酸水溶液、塩化アンモニウム等の塩化物類等を例示することができ、加熱時に発生するガスの毒性等の観点から、好ましくは、濃度１〜０．００１Ｎの塩酸水溶液、塩化アンモニウム等の塩化物類等である。この塩素化物への浸漬は、通常１〜２時間の範囲で行われる。
【００１７】
上記塩素化物への浸漬後に行う加熱処理は、通常３００℃以上、好ましくは３００〜５００℃で１〜２時間の条件で行われ、目的の塩素化アルミナ修飾酸化チタンが得られる。この加熱処理の際の温度が３００℃より低いと、塩素化アルミナが形成されないという問題が生じる。
【００１８】
本発明の塩素化アルミナ修飾酸化チタンは、そのままか、あるいは、ポリ四フッ化エチレン等のフッ素樹脂・シリカゾル等のバインダーと合わせて、適当な触媒担持体に担持されて、特定の化合物、例えばトルエン、ベンゼン、キシレン等の芳香族炭化水素化合物に対して選択的な光分解反応性を有し、このような芳香族炭化水素化合物をターゲットとする光分解触媒として好適に用いられる。
【００１９】
【発明の実施の形態】
以下、実施例及び比較例並びに試験例に基いて、本発明の好適な実施の形態を具体的に説明する。
【００２０】
〔アモルファス酸化チタンの調製〕
反応容器内にイソプロパノール(IPA)５１００gとチタンテトライソプロポキシド(TTIP)４００gとを仕込み、良く攪拌した後、水２５０gとＩＰＡ３４００gとを予め混合して得られた混合溶液を滴下し、滴下終了後室温下に１時間反応させ、次いで生成したチタン水和物をろ過等により分離し、更に２００℃で１時間加熱乾燥し、その後に粉砕して原料のアモルファス酸化チタン約１５０gを得た。
【００２１】
実施例１：塩素化アルミナ修飾酸化チタンの調製
このようにして得られたアモルファス酸化チタン約１５０gを１Ｎ硫酸水溶液中に、室温下に攪拌しながら１時間浸漬し、次いでろ過して得られた浸漬処理後のアモルファス酸化チタンを５２５℃、１時間の条件で加熱処理し、硫酸基修飾酸化チタン約１００gを得た。
【００２２】
次いで、得られた硫酸基修飾酸化チタン約１００gを、アルミニウムトリイソプロポキシド(ATIP)のシクロヘキサン(CyH)溶液｛ATIPとCyHとのモル比(ATIP：CyH)1:100｝５００ml中に浸漬し、室温で１時間攪拌しながら酸化チタンの表面に部分的にアルミナ水和物を生成させ、次いでろ過して固液分離した後、得られた固体物を２００℃、１時間の条件で加熱乾燥し、更に細かく粉砕した後、５００℃、１時間の条件で加熱処理し、アルミナにより表面が部分的にコートされたアルミナ部分コート酸化チタン約１００gを得た。
【００２３】
更に、このようにして得られたアルミナ部分コート酸化チタン約１００gを１Ｎ塩酸水溶液５００ml中に浸漬し、室温で１時間攪拌して反応させた後、ろ過して得られた固体物を３００℃、１時間の条件で加熱処理し、その後粉砕して実施例２の塩素化アルミナ修飾酸化チタン約１００gを得た。この実施例２の塩素化アルミナ修飾酸化チタンにおける硫酸基及びアルミナの存在は硫黄2p電子とアルミ2p電子のＸＰＳ(X ray photoelectoron spectroscopy)スペクトルで確認し、また、塩素の存在は蛍光Ｘ線分析装置で確認した。
【００２４】
比較例１
比較例１の未修飾酸化チタンとして、現在市販の光分解触媒として最も光触媒活性に優れているものの１つとされている酸化チタン（石原産業（株）製 商品名：ST-01）を用いた。
【００２５】
比較例２：未修飾酸化チタンの調製
上記と同様にして得られたアモルファス酸化チタンを５２５℃、１時間の条件で加熱処理し、アナターゼ型に結晶化した比較例２の未修飾酸化チタンとした。
【００２６】
試験例１：アセトアルデヒド及びトルエンの経時的分解率の測定
光分解触媒の光触媒活性を測定するための測定装置としては、図１に示すように、試料ホルダー、紫外線光源、及び図示外の攪拌ファンをセットしたＳＵＳ３０４製の光触媒反応容器と、光路長１０mのガスセルとをＳＵＳ３１６製フレキシブルチューブで繋いでガス流路を形成し、このガス流路にガス循環ポンプを介在させてガスを循環させるように構成し、測定機器として日本電子（株）製のフーリエ変換赤外吸収分光分析装置（FTIR）を使用した。
【００２７】
また、実施例１の塩素化アルミナ修飾酸化チタン、比較例１の未修飾酸化チタン又は比較例２の未修飾酸化チタンからなる試料粉末を一旦エタノール中に分散させた後、６７mm×１００mmの大きさのステンレス鋼繊維不織布上に超音波を印加して約０．２〜０．３gの範囲で担持させ、次いで３００℃、３０分の条件で乾燥させ、上記測定装置の試料ホルダーにセットした。
【００２８】
測定条件は、ガス循環量２．６×１０-4m3/sec、測定時の圧力は大気圧で、測定時の温度は２４±１℃、湿度が４０±１%、FTIRの測定条件は、分解能０．５cm-1、積分回数５０回、測定波数域７００〜４０００cm-1で、紫外線光源（ブラックライト）の中心波長が３６５nm、紫外線光源の中心付近での強度が１．５mW/cm2、紫外線光源の試料端部での強度が１．０mW/cm2とした。測定初期の吸着平衡に達するまでの待機時間は１時間とし、紫外線を照射しながら経時的に赤外吸収スペクトルを測定した。
【００２９】
また、測定に際しては、アルデヒドの場合は、初期濃度を１５０ppmとし、吸光度２６００〜２９００cm-1のアセトアルデヒド（CH3CHO）のＣ−Ｈ伸縮に帰属する赤外吸収スペクトルに着目し、また、トルエンの場合は、初期濃度を１５０ppmとし、吸光度３０４１cm-1のＣ−Ｈ伸縮に帰属する赤外吸収スペクトルに着目して定量した。
【００３０】
実施例１の塩素化アルミナ修飾酸化チタン（表面修飾Ｂ）を試料粉末とした場合の結果を図２に、また、比較例１の未修飾酸化チタン（ST-01）を試料粉末とした場合の結果を図２中に、更に、比較例２の未修飾酸化チタンを試料粉末とした場合の結果を図３にそれぞれ示す。
【００３１】
上記図２〜図３に示す結果から明らかなように、実施例１の塩素化アルミナ修飾酸化チタンの場合には、トルエンに対して極めて優れた光触媒活性を示しているのに対し、アセトアルデヒドに対しては比較例１や比較例２の未修飾酸化チタンと比較してむしろ低下している。このことから、実施例１の表面修飾酸化チタンは、特定の化合物に対して選択的に高い光触媒活性を示すことが判明した。
【００３２】
【発明の効果】
本発明の表面修飾酸化チタンは、特定の化合物に対して選択的にかつ高い光触媒活性を示し、特定の化合物をターゲットとして選択的にかつ効率良く分解・除去することができ、光分解触媒として極めて有用である。
【図面の簡単な説明】
【図１】 図１は、光分解触媒の光触媒活性を測定するための測定装置を示す説明図である。
【図２】 図２は、実施例１の塩素化アルミナ修飾酸化チタン及び比較例１の未修飾酸化チタンを試料粉末とした場合の結果を示すグラフ図である。
【図３】 図３は、比較例２の未修飾酸化チタンを試料粉末とした場合の結果を示すグラフ図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a surface-modified titanium oxide and a selective photodegradation catalyst that exhibit selective photodegradation reactivity with respect to a specific organic compound, and particularly excellent selection for polar organic compounds such as aldehydes and alcohols. Modified surface-modified titanium oxide and selective photolysis catalyst comprising surface-modified titanium oxide exhibiting excellent selective photodegradation reactivity with respect to aromatic hydrocarbon compounds such as surface-modified titanium oxide and toluene exhibiting selective photodegradation reactivity .
[0002]
[Prior art]
When a metal oxide such as titanium dioxide (TiO 2 ; hereinafter simply referred to as “titanium oxide”) having a band gap of 3 eV or more is irradiated with light having energy higher than the band gap, electrons in the valence band are conducted. Excited by the band, holes are generated in the valence band, and electrons are generated in the conduction band. The holes contribute to the oxidation reaction, and the electrons contribute to the reduction reaction. Decomposes harmful chemicals and odorous chemicals. Among such metal oxides, particularly titanium oxide is harmless to the human body and has high chemical stability, so it can be used in many fields or applications such as air purification, indoor air purification, deodorization, and antifouling.・ In fields such as anti-fogging, water purification, etc., research and development are actively promoted as substances that catalyze photodecomposition reactions (so-called photodecomposition catalysts).
[0003]
By the way, in order for titanium oxide to exhibit an action as a photodegradation catalyst, it is usually necessary to be baked and crystallized at 500 ° C. or more, and generally its crystal structure is anatase type. The crystal is considered to exhibit higher photocatalytic activity than the rutile crystal, and the development of a photodecomposition catalyst mainly composed of titanium oxide has been promoted mainly from such a viewpoint.
[0004]
However, although titanium oxide as a photodecomposition catalyst developed so far is considered to have the possibility of being able to stably decompose and remove low-concentration chemical substances over a long period of time, this titanium oxide When the catalyst is supported on the catalyst carrier, its photocatalytic activity is greatly reduced, and the probability of contact with chemical substances is not sufficient, so that the photocatalytic activity of this photodegradation catalyst cannot be fully utilized, and satisfactory performance is not always obtained. It cannot be said that it is done.
[0005]
[Problems to be solved by the invention]
Therefore, as a result of intensive investigations on the development of a photodegradation catalyst having superior photocatalytic activity, the present inventors have modified the surface of titanium oxide with a sulfate group or chlorinated alumina to give specific compounds. The inventors have found that the photocatalytic activity is high selectively and completed the present invention.
[0006]
Accordingly, an object of the present invention is to provide a surface-modified titanium oxide that selectively shows high catalytic activity for a specific compound. Another object of the present invention is to provide a photodegradation catalyst comprising such surface-modified titanium oxide and selectively exhibiting high catalytic activity for a specific compound.
[0007]
[Means for Solving the Problems]
That is, in the present invention, titanium oxide is immersed in an aqueous sulfuric acid solution having a concentration of 1 to 0.1 N, then heat-treated at a temperature of 500 to 550 ° C., and the resulting sulfate group-modified titanium oxide is immersed in an organic solvent solution of aluminum alkoxide. It is characterized by being a chlorinated alumina modified titanium oxide obtained by partially forming alumina on the surface of titanium oxide and then immersing it in a chlorinated product and then heat-treating at a temperature of 300 ° C. or higher. Is a surface-modified titanium oxide having selective photolytic reactivity.
[0008]
Furthermore, the present invention is a selective photolysis catalyst comprising the above chlorinated alumina-modified titanium oxide and having selective photolysis reactivity with respect to an aromatic hydrocarbon compound.
[0009]
In the present invention, titanium oxide used as a raw material is not particularly limited, but preferably has a sulfate group content as low as possible in order to more accurately control the surface modification with sulfate groups, Moreover, it is good that it is an amorphous titanium oxide before heat-processing and crystallizing.
[0010]
By the way, as for the method of producing crystallized titanium oxide, mainly rutile ore (TiO 2 ) is chlorinated in a high temperature furnace of about 1,000 ° C. to titanium tetrachloride (TiCl 4 ), and then in the presence of oxygen. High temperature oxidation method (chlorine method), ilmenite ore (FeTiO 3 ) thermally decomposed to TiOSO 4 , hydrolyzed to TiO (OH) 2 , then high temperature oxidation in the presence of oxygen (sulfuric acid method) ), The titanium alkoxide {Ti (i-PrO) 4 } is hydrolyzed at room temperature in the presence of a hydrolysis catalyst, then subjected to condensation polymerization to form amorphous titanium oxide, and the amorphous titanium oxide is heated at 400 ° C. or higher. There is a method of crystallization (sol-gel method), but as the titanium oxide used in the present invention, it is particularly preferable to use amorphous titanium oxide obtained by the sol-gel method.
[0011]
And in this invention, about the density | concentration of the sulfuric acid aqueous solution used when preparing a chlorinated alumina modification titanium oxide, it is 5-0.05N normally, Preferably it is 1-0.1N. If the concentration of the sulfuric acid aqueous solution at this time is higher than 5N, there is a problem that the photocatalytic activity is greatly reduced. On the other hand, if the concentration is lower than 0.05N, it is difficult to uniformly control the chlorinated alumina modification.
[0012]
When preparing this chlorinated alumina-modified titanium oxide, after immersing it in a sulfuric acid aqueous solution, if necessary, drying at normal pressure or reduced pressure at room temperature or under heating, and then preparing the above sulfate group-modified titanium oxide Heat treatment is performed as in the case, and the obtained sulfate group-modified titanium oxide is then immersed in an organic solvent solution of aluminum alkoxide to partially form alumina on the surface of the titanium oxide.
[0013]
The aluminum alkoxide used herein is not particularly limited as long as it is an aluminum trialkoxide, but preferably aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum triisopropoxide, and the like can be mentioned. More preferred is aluminum triisopropoxide.
[0014]
The organic solvent used in preparing the organic solvent solution of aluminum alkoxide is not particularly limited as long as it is an organic solvent composed of carbon, hydrogen, and oxygen atoms, but is preferably alcohols, ketones, carbonized. Hydrogen etc. can be mentioned, More preferably, they are methanol, ethanol, isopropanol, cyclohexane, etc.
[0015]
Furthermore, regarding the concentration of aluminum alkoxide in the organic solvent solution of aluminum alkoxide, the molar ratio of aluminum alkoxide to organic solvent (aluminum alkoxide / organic solvent) is usually 1/10 to 1/1000, preferably 1/50 to 1 /. It should be 500. If this molar ratio (aluminum alkoxide: organic solvent) is smaller than 1/1000, there is a problem that the amount of alumina supported on the titanium oxide surface is too small. There is a problem that the amount of alumina supported is too large and the entire surface is covered.
[0016]
Moreover, about the titanium oxide in which the alumina was partially formed in the surface, it is immersed in a chlorination thing next. The chlorinated material used for this purpose may be any material that can chlorinate alumina partially formed on the surface of titanium oxide. For example, chlorinated carbonization such as monochloromethane, dichloromethane, chloroform, carbon tetrachloride, etc. Examples thereof include hydrogens, hydrochloric acid aqueous solutions having a concentration of 1 to 0.001 N, chlorides such as ammonium chloride, and the like, preferably from a concentration of 1 to 0.001 N from the viewpoint of toxicity of gas generated during heating. Hydrochloric acid aqueous solution, chlorides such as ammonium chloride, and the like. The immersion in the chlorinated product is usually performed in a range of 1 to 2 hours.
[0017]
The heat treatment performed after immersion in the chlorinated product is usually performed at 300 ° C. or higher, preferably at 300 to 500 ° C. for 1 to 2 hours to obtain the target chlorinated alumina modified titanium oxide. When the temperature during the heat treatment is lower than 300 ° C., there arises a problem that chlorinated alumina is not formed.
[0018]
Chlorinated alumina modified titanium oxide of the present invention, or directly or, in conjunction with a binder such as a fluorine resin, silica sol, such as polytetrafluoroethylene, is supported on a suitable catalyst support, the specific compound, such as toluene It has selective photodecomposition reactivity with respect to aromatic hydrocarbon compounds such as benzene and xylene, and is suitably used as a photodecomposition catalyst targeting such aromatic hydrocarbon compounds.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described in detail based on examples, comparative examples, and test examples.
[0020]
[Preparation of amorphous titanium oxide]
After charging 5100 g of isopropanol (IPA) and 400 g of titanium tetraisopropoxide (TTIP) into the reaction vessel and stirring well, a mixed solution obtained by previously mixing 250 g of water and 3400 g of IPA was added dropwise, and after completion of the addition The reaction was carried out at room temperature for 1 hour, and then the produced titanium hydrate was separated by filtration or the like, further dried by heating at 200 ° C. for 1 hour, and then pulverized to obtain about 150 g of raw material amorphous titanium oxide.
[0021]
Example 1: Preparation of chlorinated alumina modified titanium oxide
The thus amorphous titanium oxide about 150g obtained in 1N sulfuric acid aqueous solution, and immersed for 1 hour with stirring at room temperature, then 525 ° C. The amorphous titanium oxide after the immersion treatment obtained by filtration, 1 About 100 g of sulfate group-modified titanium oxide was obtained by heat treatment under time conditions.
[0022]
Next, about 100 g of the resulting sulfate group-modified titanium oxide was immersed in 500 ml of a solution of aluminum triisopropoxide (ATIP) in cyclohexane (CyH) {molar ratio of ATIP to CyH (ATIP: CyH) 1: 100}. Then, alumina hydrate is partially formed on the surface of titanium oxide while stirring at room temperature for 1 hour, and then filtered and solid-liquid separated, and then the obtained solid is heated and dried at 200 ° C. for 1 hour. After further finely pulverizing, heat treatment was performed at 500 ° C. for 1 hour to obtain about 100 g of alumina partially coated titanium oxide whose surface was partially coated with alumina.
[0023]
Further, about 100 g of the alumina partially coated titanium oxide thus obtained was immersed in 500 ml of 1N hydrochloric acid aqueous solution, stirred and reacted at room temperature for 1 hour, and then filtered to obtain a solid material obtained at 300 ° C. Heat treatment was performed for 1 hour, and then pulverized to obtain about 100 g of chlorinated alumina modified titanium oxide of Example 2. The presence of sulfate groups and alumina in the chlorinated alumina modified titanium oxide of Example 2 was confirmed by XPS (X ray photoelectoron spectroscopy) spectra of sulfur 2p electrons and aluminum 2p electrons, and the presence of chlorine was measured by a fluorescent X-ray analyzer. Confirmed with.
[0024]
Comparative Example 1
As the unmodified titanium oxide of Comparative Example 1, titanium oxide (trade name: ST-01, manufactured by Ishihara Sangyo Co., Ltd.), which is one of the most commercially available photodecomposition catalysts with the most excellent photocatalytic activity, was used.
[0025]
Comparative Example 2 Preparation of Unmodified Titanium Oxide Amorphous titanium oxide obtained in the same manner as above was heat-treated at 525 ° C. for 1 hour to give an unmodified titanium oxide of Comparative Example 2 crystallized into anatase type. .
[0026]
Test Example 1: Measurement of degradation rate of acetaldehyde and toluene over time As a measuring device for measuring the photocatalytic activity of a photolysis catalyst, as shown in FIG. 1, a sample holder, an ultraviolet light source, and a stirring fan (not shown) are used. A gas flow path is formed by connecting a set SUS304 photocatalyst reaction vessel and a gas cell having an optical path length of 10 m with a SUS316 flexible tube, and a gas circulation pump is interposed in the gas flow path to circulate the gas. As a measuring instrument, a Fourier transform infrared absorption spectrometer (FTIR) manufactured by JEOL Ltd. was used.
[0027]
Further, after a sample powder made of chlorinated alumina modified titanium oxide of Example 1, unmodified titanium oxide of Comparative Example 1 or unmodified titanium oxide of Comparative Example 2 was once dispersed in ethanol, the size of 67 mm × 100 mm was obtained. On the stainless steel fiber nonwoven fabric, ultrasonic waves were applied and supported in the range of about 0.2 to 0.3 g, then dried at 300 ° C. for 30 minutes, and set in the sample holder of the measuring apparatus.
[0028]
Measurement conditions are gas circulation rate 2.6 × 10 -4 m 3 / sec, measurement pressure is atmospheric pressure, measurement temperature is 24 ± 1 ° C, humidity is 40 ± 1%, FTIR measurement condition is , resolution 0.5 cm -1, the integral number of 50 times, measured in wavenumbers 700～4000Cm -1, the ultraviolet light source (black light) the central wavelength of 365 nm, intensity 1.5 mW / cm 2 in the vicinity of the center of the ultraviolet light source The intensity at the sample end of the ultraviolet light source was 1.0 mW / cm 2 . The waiting time until reaching the initial adsorption equilibrium was 1 hour, and the infrared absorption spectrum was measured over time while irradiating with ultraviolet rays.
[0029]
At the time of measurement, in the case of aldehyde, the initial concentration is 150 ppm, and attention is paid to the infrared absorption spectrum attributed to C—H stretching of acetaldehyde (CH 3 CHO) having an absorbance of 2600-2900 cm −1 . In this case, the initial concentration was set to 150 ppm, and quantification was performed by paying attention to an infrared absorption spectrum belonging to C—H stretching having an absorbance of 3041 cm −1 .
[0030]
The result when the chlorinated alumina modified titanium oxide (surface modification B) of Example 1 is used as the sample powder is shown in FIG. 2 , and the case where the unmodified titanium oxide (ST-01) of Comparative Example 1 is used as the sample powder. The results are shown in FIG. 2, and the results when the unmodified titanium oxide of Comparative Example 2 is used as the sample powder are shown in FIG .
[0031]
As is clear from the results shown in FIGS . 2 to 3 above, the chlorinated alumina-modified titanium oxide of Example 1 showed extremely excellent photocatalytic activity against toluene, whereas As compared with the unmodified titanium oxides of Comparative Example 1 and Comparative Example 2, they are rather lowered. From this, it was found that the surface-modified titanium oxide of Example 1 showed high photocatalytic activity selectively with respect to a specific compound.
[0032]
【The invention's effect】
The surface-modified titanium oxide of the present invention exhibits selective and high photocatalytic activity for a specific compound, can be decomposed and removed selectively and efficiently using a specific compound as a target, and is extremely useful as a photodecomposition catalyst. Useful.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing a measuring apparatus for measuring the photocatalytic activity of a photolysis catalyst.
FIG. 2 is a graph showing the results when chlorinated alumina modified titanium oxide of Example 1 and unmodified titanium oxide of Comparative Example 1 were used as sample powders.
FIG . 3 is a graph showing the results when unmodified titanium oxide of Comparative Example 2 was used as a sample powder.
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