JP2005254085A - Surface-modified titanium oxide photocatalyst and organic compound oxidation method using the photocatalyst - Google Patents
Surface-modified titanium oxide photocatalyst and organic compound oxidation method using the photocatalyst Download PDFInfo
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- JP2005254085A JP2005254085A JP2004066916A JP2004066916A JP2005254085A JP 2005254085 A JP2005254085 A JP 2005254085A JP 2004066916 A JP2004066916 A JP 2004066916A JP 2004066916 A JP2004066916 A JP 2004066916A JP 2005254085 A JP2005254085 A JP 2005254085A
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- Prior art keywords
- titanium oxide
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- photocatalyst
- modified
- ceramic film
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 78
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 24
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000919 ceramic Substances 0.000 claims abstract description 47
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
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Abstract
【課題】 高い光触媒活性を発現する表面修飾酸化チタン光触媒、及び該光触媒を用いた有機化合物の酸化方法を提供する。
【解決手段】 表面修飾された多孔質セラミックス膜被覆酸化チタンで構成されている表面修飾酸化チタン光触媒。この光触媒において、多孔質セラミックス膜被覆酸化チタンが親油性基、金属化合物又は分子認識基により表面修飾されているのが好ましい。好ましい親油性基には炭素数１〜３０の炭化水素基を含む基が含まれ、好ましい金属化合物には金属錯体が含まれる。分子認識基としては、クラウンエーテル、シクロデキストリン、カリックスアレーンに対応する基等が好ましい。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide a surface-modified titanium oxide photocatalyst exhibiting high photocatalytic activity and an organic compound oxidation method using the photocatalyst.
A surface-modified titanium oxide photocatalyst composed of titanium oxide coated with a surface-modified porous ceramic film. In this photocatalyst, the porous ceramic film-coated titanium oxide is preferably surface-modified with a lipophilic group, a metal compound, or a molecular recognition group. Preferred lipophilic groups include groups containing a hydrocarbon group having 1 to 30 carbon atoms, and preferred metal compounds include metal complexes. As the molecular recognition group, a group corresponding to crown ether, cyclodextrin, calixarene and the like are preferable.
[Selection figure] None
Description
本発明は、酸化、消臭、空気浄化、水質浄化、有害物質や汚れの分解、抗菌、抗カビ等の機能を発現する表面修飾酸化チタン光触媒、及び該光触媒を用いた有機化合物の酸化方法に関する。 The present invention relates to a surface-modified titanium oxide photocatalyst that exhibits functions such as oxidation, deodorization, air purification, water purification, decomposition of harmful substances and dirt, antibacterial, antifungal, and the like, and an organic compound oxidation method using the photocatalyst .
酸化チタン光触媒は、光を照射することで強力な酸化還元力を発揮し、消臭、空気浄化、水質浄化、有害物質や汚れの分解、抗菌・抗カビ等の機能を発現することから、環境浄化素材として使用されている。また、繊維、塗料、合成樹脂等の有機素材に含有させたり、光酸化反応触媒として用いる等の用途が検討されている。しかし、この光触媒をそのまま有機素材に適用すると、有機素材が分解するという問題があった。そこで、酸化チタン光触媒の表面を多孔質セラミックスからなる被膜で被覆した多孔質セラミックス膜被覆酸化チタンが提案されている（例えば、特許文献１参照）。このような多孔質セラミックス膜被覆酸化チタンはマスクメロン型光触媒とも称されている。この光触媒は、光触媒表面が多孔質膜で被覆されているため、有機素材の分解等が抑制される一方、有害物質等は孔を通じて光触媒と接触し分解等の作用を受けるので、有機素材に添加する等、適用分野を拡大できるという利点を有する。しかしながら、このような多孔質セラミックス膜被覆酸化チタンは、光触媒が被膜で被覆され見かけの表面積が小さくなるため、光触媒活性が低下しやすい。また、セラミックス被膜が高い親水性を有するため、有機物質が光触媒に接近しにくくなり、反応速度が低下するという問題がある。 Titanium oxide photocatalyst exhibits strong redox power when irradiated with light, and exhibits functions such as deodorization, air purification, water purification, decomposition of harmful substances and dirt, antibacterial and antifungal functions, etc. Used as a purification material. In addition, applications such as inclusion in organic materials such as fibers, paints, and synthetic resins, and use as a photooxidation reaction catalyst have been studied. However, when this photocatalyst is applied to an organic material as it is, there is a problem that the organic material is decomposed. Therefore, a porous ceramic film-coated titanium oxide in which the surface of the titanium oxide photocatalyst is coated with a coating made of porous ceramics has been proposed (see, for example, Patent Document 1). Such a porous ceramic film-coated titanium oxide is also called a mask melon type photocatalyst. Since this photocatalyst is coated with a porous membrane on the photocatalyst surface, decomposition of the organic material is suppressed, while harmful substances come into contact with the photocatalyst through the pores and are subject to decomposition and the like. For example, the application field can be expanded. However, in such a porous ceramic film-coated titanium oxide, the photocatalyst activity is easily lowered because the photocatalyst is coated with a coating and the apparent surface area becomes small. Further, since the ceramic coating has high hydrophilicity, there is a problem that the organic substance is difficult to approach the photocatalyst and the reaction rate is lowered.
本発明の目的は、高い光触媒活性を発現する表面修飾酸化チタン光触媒、及び該光触媒を用いた有機化合物の酸化方法を提供することにある。
本発明の他の目的は、有機物質を効率よく酸化できる表面修飾酸化チタン光触媒、及び該光触媒を用いた有機化合物の酸化方法を提供することにある。
An object of the present invention is to provide a surface-modified titanium oxide photocatalyst exhibiting high photocatalytic activity and an organic compound oxidation method using the photocatalyst.
Another object of the present invention is to provide a surface-modified titanium oxide photocatalyst capable of efficiently oxidizing an organic substance and an organic compound oxidation method using the photocatalyst.
本発明者らは、上記目的を達成するため鋭意検討した結果、多孔質セラミックス膜被覆酸化チタンを表面修飾すると、光触媒活性を著しく向上できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have found that photocatalytic activity can be remarkably improved when the surface of the porous ceramic film-coated titanium oxide is modified, and the present invention has been completed.
すなわち、本発明は、表面修飾された多孔質セラミックス膜被覆酸化チタンで構成されている表面修飾酸化チタン光触媒を提供する。 That is, the present invention provides a surface-modified titanium oxide photocatalyst composed of a surface-modified porous ceramic film-coated titanium oxide.
この光触媒において、多孔質セラミックス膜被覆酸化チタンが親油性基、金属化合物又は分子認識基により表面修飾されているのが好ましい。好ましい親油性基には炭素数１〜３０の炭化水素基を含む基が含まれ、好ましい金属化合物には金属錯体が含まれる。分子認識基としては、クラウンエーテル、シクロデキストリン、カリックスアレーンに対応する基等が好ましい。 In this photocatalyst, the porous ceramic film-coated titanium oxide is preferably surface-modified with a lipophilic group, a metal compound, or a molecular recognition group. Preferred lipophilic groups include groups containing a hydrocarbon group having 1 to 30 carbon atoms, and preferred metal compounds include metal complexes. As the molecular recognition group, a group corresponding to crown ether, cyclodextrin, calixarene and the like are preferable.
本発明の表面修飾酸化チタン光触媒によれば、高い光触媒活性が発現し、有機物質を効率よく酸化することができる。また、反応の選択性を向上できる。 According to the surface-modified titanium oxide photocatalyst of the present invention, high photocatalytic activity is exhibited, and an organic substance can be oxidized efficiently. Moreover, the selectivity of the reaction can be improved.
本発明の表面修飾酸化チタン光触媒は、表面修飾された多孔質セラミックス膜被覆酸化チタンで構成されている。 The surface-modified titanium oxide photocatalyst of the present invention is composed of a surface-modified porous ceramic film-coated titanium oxide.
前記多孔質セラミックス膜被覆酸化チタンとしては、酸化チタンが多孔質のセラミックス膜で被覆されたものであれば特に限定されず、公知の方法により製造できる。また、市販品を使用できる。このような多孔質セラミックス膜被覆酸化チタンは、例えば、有機溶媒にセラミックスの前駆体を溶解し、これに界面活性剤を添加し、次いで酸化チタン（光触媒）を加えて均一に分散させ、得られた分散液に酸又はアルカリを含む水溶液を添加し、固体を濾別、乾燥、加熱焼成することにより調製することができる。また、多孔質セラミックス膜被覆酸化チタンは、セラミックスの前駆体である金属アルコキシド（例えば、テトラアルキルオルトシリケート等のケイ素、アルミニウム、ジルコニウム、マグネシウム、カルシウム、チタン等のアルコキシド又はそれらの混合物など）を多価アルコール（例えば、エチレングリコール、ジエチレングリコールなど）を用いた親水化反応により親水化して膜材を調製し、この膜材に対して水と酸化チタン（光触媒）又は水に酸化チタンを分散させたスラリーを添加して混合スラリーを調製し、この混合スラリーを乾燥、加熱焼成することにより製造することもできる（特開２００１−２８６７２８号公報参照）。 The porous ceramic film-coated titanium oxide is not particularly limited as long as titanium oxide is coated with a porous ceramic film, and can be produced by a known method. Moreover, a commercial item can be used. Such a porous ceramic film-coated titanium oxide is obtained by, for example, dissolving a ceramic precursor in an organic solvent, adding a surfactant to this, and then adding titanium oxide (photocatalyst) to uniformly disperse it. An aqueous solution containing an acid or an alkali is added to the obtained dispersion, and the solid is separated by filtration, dried, and calcined. In addition, the porous ceramic film-coated titanium oxide contains many metal alkoxides (for example, silicon such as tetraalkylorthosilicate, alkoxide such as tetraalkylorthosilicate, alkoxide such as zirconium, magnesium, calcium, and titanium, or a mixture thereof). A film material is prepared by hydrophilization using a monohydric alcohol (for example, ethylene glycol, diethylene glycol, etc.) and water and titanium oxide (photocatalyst) or slurry in which titanium oxide is dispersed in water are prepared. It is also possible to prepare a mixed slurry by adding and drying and heating and firing the mixed slurry (see Japanese Patent Application Laid-Open No. 2001-286728).
前記酸化チタンとしては特に限定されず、ルチル型結晶構造を有する二酸化チタン（ルチル型二酸化チタン）、アナターゼ型結晶構造を有する二酸化チタン（アナターゼ型二酸化チタン）、それらの混合物（アナターゼ型−ルチル型混合二酸化チタン）等の何れの二酸化チタン（結晶性二酸化チタン）であってもよい。 The titanium oxide is not particularly limited, and titanium dioxide having a rutile type crystal structure (rutile type titanium dioxide), titanium dioxide having an anatase type crystal structure (anatase type titanium dioxide), and a mixture thereof (anatase type-rutile type mixture). Any titanium dioxide (crystalline titanium dioxide) such as titanium dioxide) may be used.
前記多孔質セラミックス膜被覆酸化チタンは、ほぼ球状をなす酸化チタン（光触媒）と、この酸化チタンを被覆する被膜とから構成されている。前記被膜は全面に多数の細孔（貫通孔）を有しており、この細孔により酸化チタンの一部が外部に露出した状態にある。このため、前記細孔の孔径以下の物質は細孔を通過して被膜内にある酸化チタンに吸着され、光が照射されると、該酸化チタンの酸化還元作用を受けることになる。 The porous ceramic film-coated titanium oxide is composed of titanium oxide (photocatalyst) having a substantially spherical shape and a film covering the titanium oxide. The coating has a large number of pores (through holes) on the entire surface, and a part of the titanium oxide is exposed to the outside through the pores. For this reason, a substance having a diameter smaller than that of the pores passes through the pores and is adsorbed by titanium oxide in the coating, and when irradiated with light, the titanium oxide undergoes a redox action.
本発明の表面修飾酸化チタン光触媒の重要な特徴は、このような多孔質セラミックス膜被覆酸化チタンが表面修飾されている点にある。多孔質セラミックス膜被覆酸化チタンを表面修飾することにより、セラミックス膜表面における極性（疎水性、親水性）、反応物質との親和性、反応物質の捕捉性、酸化チタンの触媒活性等を変化させることができるので、酸化チタン光触媒による反応の選択性や反応速度を向上できる。 An important feature of the surface-modified titanium oxide photocatalyst of the present invention is that such porous ceramic film-coated titanium oxide is surface-modified. By modifying the surface of the porous ceramic film-coated titanium oxide, the polarity (hydrophobic, hydrophilic) on the ceramic film surface, affinity with reactants, scavenging of reactants, catalytic activity of titanium oxide, etc. can be changed. Therefore, the selectivity and reaction rate of the reaction with the titanium oxide photocatalyst can be improved.
多孔質セラミックス膜被覆酸化チタンの表面修飾の態様は特に限定されないが、代表的な態様として、多孔質セラミック膜又は露出している酸化チタン表面への親油性基、金属化合物、分子認識基等の導入が挙げられる。親油性基等の導入方法は、特に限定されず、例えば、化学結合（共有結合、イオン結合、配位結合等）による方法、物理吸着による方法等の何れの方法であってもよい。化学結合による導入法としては、例えば、導入すべき分子又は基にシランカップリング剤等により反応性シリル基（ハロシリル基、アルコキシシリル基等）を導入した後、これを多孔質セラミックス膜被覆酸化チタンの多孔質セラミック膜の表面水酸基又は露出している酸化チタンの表面水酸基と反応させてシリル化する方法などが挙げられる。 The mode of surface modification of the porous ceramic film-coated titanium oxide is not particularly limited, but as a typical mode, a lipophilic group, a metal compound, a molecular recognition group, etc. on the porous ceramic film or the exposed titanium oxide surface, etc. Introduction is mentioned. The method for introducing a lipophilic group or the like is not particularly limited, and may be any method such as a method using a chemical bond (covalent bond, ionic bond, coordinate bond, etc.) or a method using physical adsorption. As an introduction method by chemical bonding, for example, a reactive silyl group (halosilyl group, alkoxysilyl group, etc.) is introduced into a molecule or group to be introduced by a silane coupling agent and the like, and then this is applied to a porous ceramic film-coated titanium oxide. And a method of reacting with the surface hydroxyl group of the porous ceramic film or the exposed surface hydroxyl group of titanium oxide to silylate.
親油性基としては、例えば、炭化水素基又は炭化水素基を含有する基などが挙げられる。該炭化水素基には、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、これらが２以上結合した基が含まれる。脂肪族炭化水素基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル、ペンチル、ヘキシル、オクチル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、ビニル、アリル、１−プロペニル、エチニル基などの炭素数１〜３０（好ましくは１〜２０）程度の直鎖状又は分岐鎖状の脂肪族炭化水素基（アルキル基、アルケニル基及びアルキニル基）などが挙げられる。 Examples of the lipophilic group include a hydrocarbon group or a group containing a hydrocarbon group. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Examples of the aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, vinyl, allyl, Examples thereof include a linear or branched aliphatic hydrocarbon group (an alkyl group, an alkenyl group, and an alkynyl group) having about 1 to 30 (preferably 1 to 20) carbon atoms such as 1-propenyl and ethynyl groups.
脂環式炭化水素基としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘキセニル、シクロオクチル、シクロデシル、シクロドデシル、アダマンチル、ノルボルナン−２−イル、デカリン−１−イル基などの炭素数３〜３０（好ましくは炭素数３〜２０）程度の脂環式炭化水素基（シクロアルキル基、シクロアルケニル基、橋架け炭素環式基等）などが挙げられる。 Examples of the alicyclic hydrocarbon group include 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantyl, norbornan-2-yl, and decalin-1-yl groups. And alicyclic hydrocarbon groups (cycloalkyl group, cycloalkenyl group, bridged carbocyclic group, etc.) of about ˜30 (preferably having 3 to 20 carbon atoms).
芳香族炭化水素基としては、例えば、フェニル、ナフチル基などの炭素数６〜３０（好ましくは６〜２０）程度の芳香族炭化水素基などが挙げられる。芳香族炭化水素基には、芳香環にシクロヘキサン環等の脂環式炭素環が縮合した基も含まれる。 Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 30 (preferably 6 to 20) carbon atoms such as phenyl and naphthyl groups. The aromatic hydrocarbon group also includes a group in which an alicyclic carbon ring such as a cyclohexane ring is condensed to an aromatic ring.
脂肪族炭化水素基と脂環式炭化水素とが結合した基としては、例えば、メチルシクロヘキシル基等のアルキル−シクロアルキル基；シクロヘキシルメチル基等のシクロアルキル−アルキル基；３，５−ジメチル−１−アダマンチル基などのアルキル基を有する橋架け環式基などが挙げられる。脂肪族炭化水素基と芳香族炭化水素基とが結合した基としては、例えば、トルイル、キシリル基等のアルキルアリール基；ベンジル、２−フェニルエチル、１−フェニルエチル、ジフェニルメチル、トリチル基等のアラルキル基などが挙げられる。 Examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon are bonded include an alkyl-cycloalkyl group such as a methylcyclohexyl group; a cycloalkyl-alkyl group such as a cyclohexylmethyl group; 3,5-dimethyl-1 -A bridged cyclic group having an alkyl group such as an adamantyl group. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include alkylaryl groups such as toluyl and xylyl groups; benzyl, 2-phenylethyl, 1-phenylethyl, diphenylmethyl, and trityl groups. And aralkyl groups.
炭化水素基の全炭素数は、例えば１〜３０程度、好ましくは１〜２０程度である。炭化水素基には、フッ素、塩素、臭素原子等のハロゲン原子等の置換基（特に非極性の置換基）が１又は２以上結合していてもよい。親油性基は単独で又は２種以上を組み合わせて導入できる。 The total carbon number of the hydrocarbon group is, for example, about 1 to 30, preferably about 1 to 20. One or more substituents (particularly nonpolar substituents) such as fluorine atoms, halogen atoms such as fluorine, chlorine and bromine atoms may be bonded to the hydrocarbon group. The lipophilic group can be introduced alone or in combination of two or more.
表面に親油性基がを導入された表面修飾酸化チタン光触媒は、例えば、メチルトリクロロシラン、ヘキシルトリクロロシラン、デシルトリクロロシラン、ドデシルトリクロロシラン、ヘキサデシルトリクロロシラン、オクタデシルトリクロロシラン、フェニルトリクロロシラン、２−フェニルエチルトリクロロシランなどのケイ素原子に炭化水素基が結合したハロシラン化合物（アルキルトリハロシラン、アリールトリハロシラン、アラルキルトリハロシラン等）等の反応性シリル基を有する化合物（シリル化剤）と、多孔質セラミックス膜被覆酸化チタンとを、トルエン等の不活性溶媒中で混合撹拌して、前記反応性シリル基と多孔質セラミックス膜被覆酸化チタンの表面水酸基とを反応させた後、デカンテーション、濾過等により固体を分離し、トルエン、エタノール等の適当な溶媒で洗浄し、乾燥することにより、或いは、前記洗浄後、必要に応じて、過剰に修飾された表面の疎水基を除去するため、水中に分散させた状態で光を照射し、水面に浮く固体を濾別し、乾燥することにより得ることができる。上記混合撹拌は室温付近で行うことができる。 Examples of the surface-modified titanium oxide photocatalyst having a lipophilic group introduced on its surface include methyltrichlorosilane, hexyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, hexadecyltrichlorosilane, octadecyltrichlorosilane, phenyltrichlorosilane, 2- Compounds having reactive silyl groups (silylating agents) such as halosilane compounds (alkyltrihalosilanes, aryltrihalosilanes, aralkyltrihalosilanes, etc.) in which hydrocarbon groups are bonded to silicon atoms, such as phenylethyltrichlorosilane, and porous ceramics The film-coated titanium oxide is mixed and stirred in an inert solvent such as toluene to react the reactive silyl group with the surface hydroxyl group of the porous ceramic film-coated titanium oxide, and then solidified by decantation, filtration, etc. The Release, washed with an appropriate solvent such as toluene, ethanol, etc., and dried, or after the washing, if necessary, in order to remove excessively modified surface hydrophobic groups, dispersed in water It can be obtained by irradiating with light, filtering off the solid floating on the water surface and drying. The mixing and stirring can be performed near room temperature.
こうして得られる親油性基が導入された表面修飾酸化チタン光触媒は、触媒表面が疎水化されているので、疎水性の有機物質を基質とする酸化反応等の反応速度を促進できるとともに、水溶液又は水分散液中で高い光触媒活性を示す。また、疎水性化され表面に捕捉される疎水性の有機物質は、脱溶媒和され反応の活性化エネルギーを低下させるとともに、均一溶液中に比べてより高濃度に濃縮されるという利点もある。 The surface-modified titanium oxide photocatalyst into which the lipophilic group thus obtained is introduced has a hydrophobized catalyst surface, so that the reaction rate of an oxidation reaction using a hydrophobic organic substance as a substrate can be accelerated, and an aqueous solution or water High photocatalytic activity in the dispersion. In addition, the hydrophobic organic substance that is hydrophobicized and trapped on the surface has the advantage that it is desolvated to lower the activation energy of the reaction and is concentrated at a higher concentration than in a homogeneous solution.
図１は親油性基が導入された本発明の表面修飾酸化チタン光触媒を示す模式図（概念図）である。この表面修飾酸化チタン光触媒は、ほぼ球状をなす酸化チタン（ＴｉＯ2）が多数の細孔（貫通孔）を有するセラミック膜［「Porus Silica」（多孔質シリカ）と表記］で被覆されているとともに、前記セラミック膜又は露出している酸化チタンの表面に親油性基［「Hydrocarbon chain」（炭化水素鎖）と表記］が結合又は吸着している。この光触媒に光（hν）が照射されると、電子（e-）と正孔（h+）という２つのキャリアが生じる。この光触媒は表面に親油性基を有しているため、親油性基と親和性の強い疎水性のゲスト分子（「Hydrophobic Guest Molecule」と表記；反応成分）が近づきやすくなり、前記正孔において効率よく酸化される。従って、従来の表面が修飾されていない多孔質セラミックス膜被覆酸化チタンと比較して、疎水性の反応成分の反応速度が速くなるとともに、疎水性の程度の異なる複数の反応成分が存在する場合には反応の選択性も向上する。また、有機溶媒中でも、酸化反応等の反応が円滑に進行する。 FIG. 1 is a schematic diagram (conceptual diagram) showing a surface-modified titanium oxide photocatalyst of the present invention in which a lipophilic group is introduced. This surface-modified titanium oxide photocatalyst is coated with a ceramic film [denoted as “Porus Silica” (porous silica)] in which titanium oxide (TiO 2 ) having a substantially spherical shape has a large number of pores (through holes). The lipophilic group [denoted as “Hydrocarbon chain”] is bonded to or adsorbed on the surface of the ceramic film or the exposed titanium oxide. When this photocatalyst is irradiated with light (hν), two carriers of electrons (e − ) and holes (h + ) are generated. Since this photocatalyst has a lipophilic group on its surface, hydrophobic guest molecules (represented as “Hydrophobic Guest Molecule”, which has a strong affinity with the lipophilic group; the reaction component) can be easily approached, and the holes are efficient. It is well oxidized. Therefore, when the reaction rate of the hydrophobic reaction component is faster and there are a plurality of reaction components having different degrees of hydrophobicity as compared with the conventional porous ceramic film-coated titanium oxide whose surface is not modified. Improves the selectivity of the reaction. In addition, reactions such as oxidation reactions proceed smoothly even in organic solvents.
一方、表面修飾のために導入される前記金属化合物を構成する金属元素としては、特に限定されないが、周期表２〜１５族の金属元素を用いる場合が多い。なお、本明細書では、ホウ素Ｂも金属元素に含まれるものとする。例えば、前記金属元素として、周期表２族元素（Ｍｇ、Ｃａ、Ｓｒ、Ｂａなど）、３族元素（Ｓｃ、ランタノイド元素、アクチノイド元素など）、４族元素（Ｔｉ、Ｚｒ、Ｈｆなど）、５族元素（Ｖなど）、６族元素（Ｃｒ、Ｍｏ、Ｗなど）、７族元素（Ｍｎなど）、８族元素（Ｆｅ、Ｒｕなど）、９族元素（Ｃｏ、Ｒｈなど）、１０族元素（Ｎｉ、Ｐｄ、Ｐｔなど）、１１族元素（Ｃｕなど）、１２族元素（Ｚｎなど）、１３族元素（Ｂ、Ａｌ、Ｉｎなど）、１４族元素（Ｓｎ、Ｐｂなど）、１５族元素（Ｓｂ、Ｂｉなど）などが挙げられる。好ましい金属元素には、遷移金属元素（周期表３〜１２族元素）が含まれる。なかでも、周期表５〜１１族元素、特に５族〜９族元素が好ましく、とりわけＶ、Ｍｏ、Ｍｎ、Ｃｏなどが好ましい。金属元素の原子価は特に制限されず、例えば０〜６価程度である。 On the other hand, the metal element constituting the metal compound introduced for surface modification is not particularly limited, but a metal element belonging to Groups 2 to 15 of the periodic table is often used. In this specification, boron B is also included in the metal element. For example, as the metal element, a periodic table group 2 element (Mg, Ca, Sr, Ba, etc.), a group 3 element (Sc, lanthanoid element, actinoid element, etc.), a group 4 element (Ti, Zr, Hf, etc.), 5 Group elements (such as V), Group 6 elements (such as Cr, Mo, W), Group 7 elements (such as Mn), Group 8 elements (such as Fe and Ru), Group 9 elements (such as Co and Rh), and Group 10 elements (Ni, Pd, Pt, etc.), Group 11 elements (Cu, etc.), Group 12 elements (Zn, etc.), Group 13 elements (B, Al, In, etc.), Group 14 elements (Sn, Pb, etc.), Group 15 elements (Sb, Bi, etc.). Preferred metal elements include transition metal elements (periodic group 3-12 elements). Among them, periodic table group 5-11 elements, particularly group 5-9 elements are preferable, and V, Mo, Mn, Co and the like are particularly preferable. The valence of the metal element is not particularly limited, and is about 0 to 6, for example.
金属化合物としては、前記金属元素の単体、水酸化物、酸化物（複合酸化物を含む）、ハロゲン化物（フッ化物、塩化物、臭化物、ヨウ化物）、オキソ酸塩（例えば、硝酸塩、硫酸塩、リン酸塩、ホウ酸塩、炭酸塩など）、イソポリ酸の塩、ヘテロポリ酸の塩、無機錯体などの無機化合物；有機酸塩（例えば、酢酸塩、プロピオン酸塩、青酸塩、ナフテン酸塩、ステアリン酸塩など）、有機錯体などの有機化合物が挙げられる。金属錯体（無機錯体又は有機錯体）を構成する配位子としては、ＯＨ（ヒドロキソ）、アルコキシ（メトキシ、エトキシ、プロポキシ、ブトキシなど）、アシル（アセチル、プロピオニルなど）、アルコキシカルボニル（メトキシカルボニル、エトキシカルボニルなど）、アセチルアセトナト、シクロペンタジエニル基、ハロゲン原子（塩素、臭素など）、ＣＯ、ＣＮ、酸素原子、Ｈ2Ｏ（アコ）、ホスフィン（トリフェニルホスフィンなどのトリアリールホスフィンなど）のリン化合物、ＮＨ3（アンミン）、ＮＯ、ＮＯ2（ニトロ）、ＮＯ3（ニトラト）、エチレンジアミン、ジエチレントリアミン、ピリジン、フェナントロリン、ベンズイミダゾール、ピロールなどの窒素含有化合物などが挙げられる。金属錯体には補酵素等の天然物も含まれる。好ましい錯体には、コバルトコリン錯体（補酵素Ｂ12；疎水性ビタミンＢ12）等のコバルト錯体等が含まれる。金属化合物は単独で又は２種以上を組み合わせて使用できる。前記金属化合物の中でも金属錯体が特に好ましい。 Examples of the metal compound include simple substances, hydroxides, oxides (including composite oxides), halides (fluorides, chlorides, bromides, iodides), oxo acid salts (eg, nitrates, sulfates) of the above metal elements. , Phosphates, borates, carbonates, etc.), salts of isopolyacids, salts of heteropolyacids, inorganic complexes, etc .; organic acid salts (eg acetates, propionates, cyanates, naphthenates) And organic compounds such as organic complexes. As a ligand constituting a metal complex (inorganic complex or organic complex), OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxy) Carbonyl, etc.), acetylacetonato, cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, oxygen atom, H 2 O (aco), phosphine (triarylphosphine such as triphenylphosphine) Examples thereof include phosphorus compounds, nitrogen-containing compounds such as NH 3 (ammine), NO, NO 2 (nitro), NO 3 (nitrato), ethylenediamine, diethylenetriamine, pyridine, phenanthroline, benzimidazole, and pyrrole. Metal complexes also include natural products such as coenzymes. Preferred complexes include cobalt complexes such as cobalt choline complex (coenzyme B 12 ; hydrophobic vitamin B 12 ). A metal compound can be used individually or in combination of 2 or more types. Among the metal compounds, metal complexes are particularly preferable.
表面に金属化合物が導入された表面修飾酸化チタン光触媒は、例えば、（ｉ）多孔質セラミックス膜被覆酸化チタンを分散させた分散液中に金属化合物溶液を添加し、必要に応じて溶媒を留去することにより、該金属化合物を多孔質セラミックス膜被覆酸化チタンの表面に吸着させる方法、（ii）金属化合物を構成する配位子（例えば、平面配位子等）などにシランカップリング剤等により反応性シリル基を導入した後、多孔質セラミックス膜被覆酸化チタンとトルエン等の不活性溶媒中で混合撹拌して、前記反応性シリル基と多孔質セラミックス膜被覆酸化チタンの表面水酸基とを反応させる方法などにより製造できる。配位子等への反応性シリル基の導入法としては、有機化合物に反応性シリル基を導入する際に通常用いられる方法を採用できる。 The surface-modified titanium oxide photocatalyst in which a metal compound is introduced on the surface is, for example, (i) a metal compound solution is added to a dispersion in which a porous ceramic film-coated titanium oxide is dispersed, and the solvent is distilled off as necessary. A method of adsorbing the metal compound on the surface of the porous ceramic film-coated titanium oxide, and (ii) a ligand (for example, a planar ligand) constituting the metal compound with a silane coupling agent or the like After introducing the reactive silyl group, the porous ceramic film-coated titanium oxide is mixed and stirred in an inert solvent such as toluene to react the reactive silyl group with the surface hydroxyl group of the porous ceramic film-coated titanium oxide. It can be manufactured by a method or the like. As a method for introducing a reactive silyl group into a ligand or the like, a method usually used when introducing a reactive silyl group into an organic compound can be employed.
こうして得られる金属化合物が導入された表面修飾酸化チタン光触媒は、触媒表面に金属化合物が存在するので、該金属化合物を助触媒又は共触媒として機能させることにより酸化反応等の反応速度を促進できる。また、金属化合物の配位子等を選択することにより、反応の選択性をコントロールできる。さらに、酸化チタン内に生成した励起電子やホールを受け取った二酸化チタン表面に導入された核金属化合物は、酸化や還元反応の助触媒として働くだけでなく、その金属化合物特有の反応（異性化反応、炭素−炭素結合生成反応など）を発現することが可能となるという利点もある。 Since the surface-modified titanium oxide photocatalyst into which the metal compound thus obtained is introduced has a metal compound on the catalyst surface, the reaction rate of an oxidation reaction or the like can be promoted by causing the metal compound to function as a promoter or a cocatalyst. The selectivity of the reaction can be controlled by selecting a ligand of the metal compound. Furthermore, the nuclear metal compound introduced to the surface of titanium dioxide that has received excited electrons and holes generated in the titanium oxide not only acts as a co-catalyst for oxidation and reduction reactions, but also a reaction unique to the metal compound (isomerization reaction). , Carbon-carbon bond formation reaction, etc.).
図２は金属化合物が導入された本発明の表面修飾酸化チタン光触媒を示す模式図（概念図）である。この表面修飾酸化チタン光触媒は、ほぼ球状をなす酸化チタン（ＴｉＯ2）が多数の細孔（貫通孔）を有するセラミック膜［「Porus Silica」（多孔質シリカ）と表記］で被覆されているとともに、前記セラミック膜又は露出している酸化チタンの表面に金属化合物［「Catalyst (Metal Complex)」（触媒（金属錯体））と表記］が結合又は吸着している。この光触媒に光（hν）が照射されると、電子（e-）と正孔（h+）という２つのキャリアが生じる。この光触媒は表面に金属化合物を有しているため、反応成分（有機物質）が、酸化チタンと金属化合物の双方の触媒作用により、前記正孔において効率よく酸化される。従って、従来の表面が修飾されていない多孔質セラミックス膜被覆酸化チタンと比較して反応速度が速くなるとともに、金属化合物の配位子等を適宜選択することにより反応の選択性も向上させることができる。 FIG. 2 is a schematic diagram (conceptual diagram) showing the surface-modified titanium oxide photocatalyst of the present invention in which a metal compound is introduced. This surface-modified titanium oxide photocatalyst is coated with a ceramic film [denoted as “Porus Silica” (porous silica)] in which titanium oxide (TiO 2 ) having a substantially spherical shape has a large number of pores (through holes). The metal compound [“Catalyst (Metal Complex)” (denoted as catalyst (metal complex))] is bound or adsorbed on the surface of the ceramic film or the exposed titanium oxide. When this photocatalyst is irradiated with light (hν), two carriers of electrons (e − ) and holes (h + ) are generated. Since this photocatalyst has a metal compound on its surface, the reaction component (organic substance) is efficiently oxidized in the holes by the catalytic action of both titanium oxide and the metal compound. Accordingly, the reaction rate is faster than conventional porous ceramic film-coated titanium oxide whose surface is not modified, and the selectivity of the reaction can be improved by appropriately selecting a ligand of the metal compound. it can.
また、表面修飾のために導入される前記分子認識基としては、特に限定されないが、例えば、クラウンエーテル、シクロデキストリン、カリックスアレーンに対応する基などが挙げられる。分子認識基は１種又は２種以上を組み合わせて導入できる。 Further, the molecular recognition group introduced for surface modification is not particularly limited, and examples thereof include groups corresponding to crown ether, cyclodextrin, calixarene, and the like. Molecular recognition groups can be introduced alone or in combination of two or more.
前記クラウンエーテルとしては、クラウンエーテル化合物、チアクラウンエーテル化合物、アザクラウンエーテル化合物、クリプタンド化合物等が挙げられる。これらの中でもクラウンエーテル化合物が好ましい。クラウンエーテルの代表的な例として、例えば、１２−クラウン−４、１５−クラウン−５、１８−クラウン−６、２１−クラウン−７、２４−クラウン−８、３０−クラウン−１０、ジベンゾ−１４−クラウン−４、ベンゾ−１５−クラウン−５、ベンゾ−１８−クラウン−６、ジベンゾ−１８−クラウン−６、ジベンゾ−２１−クラウン−７、ジベンゾ−２４−クラウン−８、ジベンゾ−３０−クラウン−１０、トリベンゾ−２４−クラウン−８等が挙げられる。クラウンエーテルは置換基を有していてもよい。 Examples of the crown ether include crown ether compounds, thiacrown ether compounds, azacrown ether compounds, and cryptand compounds. Among these, a crown ether compound is preferable. Representative examples of the crown ether include, for example, 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 30-crown-10, dibenzo-14. -Crown-4, benzo-15-crown-5, benzo-18-crown-6, dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, dibenzo-30-crown -10, tribenzo-24-crown-8, and the like. The crown ether may have a substituent.
シクロデキストリンとしては、特に限定されないが、例えば、α−シクロデキストリン、β−シクロデキストリン、γ−シクロデキストリン、β，γ−シクロデキストリン等が挙げられる。シクロデキストリンは置換基を有していてもよい。 Although it does not specifically limit as cyclodextrin, For example, (alpha) -cyclodextrin, (beta) -cyclodextrin, (gamma) -cyclodextrin, (beta), (gamma) -cyclodextrin etc. are mentioned. Cyclodextrin may have a substituent.
カリックスアレーンとしては、特に制限はないが、例えば、カリックス（４）アレン、カリックス（６）アレン、カリックス（８）アレン、カリックス［６］アレーン−ｐ−スルホン酸六ナトリウムｎ水和物（ｎは自然数を示す）、カリックス［８］アレーン−ｐ−スルホン酸八ナトリウムｎ水和物（ｎは自然数を示す）、チアカリックス（４）アレン、チアカリックス（６）アレン、スルホニルカリックス（４）アレン等が挙げられる。カリックスアレーンは置換基を有していてもよい。 The calixarene is not particularly limited. For example, calix (4) allene, calix (6) allene, calix (8) allene, calix [6] arene-p-sulfonic acid hexasodium n hydrate (n is Natural number), calix [8] arene-p-sulfonic acid octasodium n hydrate (n represents a natural number), thiacalix (4) allene, thiacalix (6) allene, sulfonylcalix (4) allene, etc. Is mentioned. The calixarene may have a substituent.
表面に分子認識基が導入された表面修飾酸化チタン光触媒は、例えば、分子認識基を有する化合物（クラウンエーテル、シクロデキストリン、カリックスアレーン等）にシランカップリング剤等により反応性シリル基を導入した後、多孔質セラミックス膜被覆酸化チタンとトルエン等の不活性溶媒中で混合撹拌して、前記反応性シリル基と多孔質セラミックス膜被覆酸化チタンの表面水酸基とを反応させる方法などにより製造できる。クラウンエーテル等への反応性シリル基の導入法としては、有機化合物に反応性シリル基を導入する際に通常用いられる方法を採用できる。 The surface-modified titanium oxide photocatalyst having a molecular recognition group introduced on its surface is, for example, after introducing a reactive silyl group into a compound having a molecular recognition group (crown ether, cyclodextrin, calixarene, etc.) with a silane coupling agent or the like. The porous ceramic film-coated titanium oxide can be produced by a method of mixing and stirring in an inert solvent such as toluene to react the reactive silyl group with the surface hydroxyl group of the porous ceramic film-coated titanium oxide. As a method for introducing a reactive silyl group into a crown ether or the like, a method usually used when introducing a reactive silyl group into an organic compound can be employed.
こうして得られる分子認識基が導入された表面修飾酸化チタン光触媒は、触媒表面に分子認識基を有するので、所望の有機物質（基質）が選択的に触媒表面に接近するため、酸化反応等の反応速度を速くできるだけでなく反応の選択性も大幅に向上できる。また、水溶液又は水分散液中での酸化反応等の反応を円滑に進行させることができる。さらに、様々な官能基（アミノ基、カルボキシル基等）を有した分子認識基を導入することにより、その空孔径に基づく分子の大きさを認識するのみならず、官能基に基づく多元的な相互作用（静電相互作用など）との連携により、捕捉する分子の形を選択することが可能となるという利点もある。 The surface-modified titanium oxide photocatalyst into which the molecular recognition group thus obtained is introduced has a molecular recognition group on the catalyst surface, so that a desired organic substance (substrate) selectively approaches the catalyst surface. Not only can the speed be increased, but the selectivity of the reaction can be greatly improved. In addition, a reaction such as an oxidation reaction in an aqueous solution or an aqueous dispersion can be smoothly advanced. Furthermore, by introducing molecular recognition groups having various functional groups (amino group, carboxyl group, etc.), not only can the size of the molecule be recognized based on the pore diameter, but also the multidimensional interaction based on the functional group. There is also an advantage that the shape of the molecule to be captured can be selected by cooperation with an action (such as electrostatic interaction).
図３は分子認識基が導入された本発明の表面修飾酸化チタン光触媒を示す模式図（概念図）である。この表面修飾酸化チタン光触媒は、ほぼ球状をなす酸化チタン（ＴｉＯ2）が多数の細孔（貫通孔）を有するセラミック膜［「Porus Silica」（多孔質シリカ）と表記］で被覆されているとともに、前記セラミック膜又は露出している酸化チタンの表面に分子認識基［「Molecular Recognition Sites」と表記］が結合又は吸着している。この光触媒に光（hν）が照射されると、電子（e-）と正孔（h+）という２つのキャリアが生じる。この光触媒は表面に分子認識基を有しているため、反応成分（有機物質）が、分子認識されて捕捉され、前記正孔において効率よく酸化される。従って、従来の表面が修飾されていない多孔質セラミックス膜被覆酸化チタンと比較して反応速度が速くなるとともに、分子認識基を適宜選択することにより反応の選択性を向上させることもできる。また、水溶液又は水分散液中において、酸化反応等が円滑に進行する。 FIG. 3 is a schematic diagram (conceptual diagram) showing the surface-modified titanium oxide photocatalyst of the present invention having a molecular recognition group introduced therein. The surface-modified titanium oxide photocatalyst is coated with a ceramic film [denoted as “Porus Silica” (porous silica)] in which titanium oxide (TiO 2 ) having a substantially spherical shape has a large number of pores (through holes). A molecular recognition group [denoted as “Molecular Recognition Sites”] is bonded or adsorbed on the surface of the ceramic film or the exposed titanium oxide. When this photocatalyst is irradiated with light (hν), two carriers of electrons (e − ) and holes (h + ) are generated. Since this photocatalyst has a molecular recognition group on its surface, the reaction component (organic substance) is recognized and captured by the molecule, and is efficiently oxidized in the holes. Therefore, the reaction rate is faster than that of a conventional porous ceramic film-coated titanium oxide whose surface is not modified, and the selectivity of the reaction can be improved by appropriately selecting a molecular recognition group. Further, the oxidation reaction and the like proceed smoothly in the aqueous solution or aqueous dispersion.
本発明の表面修飾酸化チタン光触媒は、種々の化学反応（例えば、酸化反応、有害物質の分解反応等）や殺菌などの従来の酸化チタン光触媒と同様の分野で利用することができる。 The surface-modified titanium oxide photocatalyst of the present invention can be used in the same fields as conventional titanium oxide photocatalysts such as various chemical reactions (for example, oxidation reaction, decomposition reaction of harmful substances) and sterilization.
本発明の有機化合物の酸化方法は、上記表面修飾酸化チタン光触媒の存在下、被酸化部位を有する有機化合物を光照射下に酸素又は過酸化物により酸化することを特徴としている。 The organic compound oxidation method of the present invention is characterized in that an organic compound having a site to be oxidized is oxidized with oxygen or peroxide under light irradiation in the presence of the surface-modified titanium oxide photocatalyst.
前記有機化合物としては、少なくとも１つの被酸化部位を有する有機化合物であれば特に限定されない。被酸化部位を有する有機化合物としては、（A1）ヘテロ原子の隣接位に炭素−水素結合を有するヘテロ原子含有化合物、（A2）炭素−ヘテロ原子二重結合を有する化合物、（A3）メチン炭素原子を有する化合物、（A4）不飽和結合の隣接位に炭素−水素結合を有する化合物、（A5）非芳香族性環状炭化水素、（A6）共役化合物、（A7）アミン類、（A8）芳香族化合物、（A9）直鎖状アルカン、及び（A10）オレフィン類等が挙げられる。 The organic compound is not particularly limited as long as it is an organic compound having at least one site to be oxidized. Examples of the organic compound having an oxidizable site include (A1) a heteroatom-containing compound having a carbon-hydrogen bond adjacent to the heteroatom, (A2) a compound having a carbon-heteroatom double bond, and (A3) a methine carbon atom. (A4) Compound having a carbon-hydrogen bond adjacent to the unsaturated bond, (A5) Non-aromatic cyclic hydrocarbon, (A6) Conjugated compound, (A7) Amines, (A8) Aromatic Compounds, (A9) linear alkanes, and (A10) olefins.
ヘテロ原子の隣接位に炭素−水素結合を有するヘテロ原子含有化合物（A1）としては、（A1-1）第１級若しくは第２級アルコール又は第１級若しくは第２級チオール、（A1-2）酸素原子の隣接位に炭素−水素結合を有するエーテル又は硫黄原子の隣接位に炭素−水素結合を有するスルフィド、（A1-3）酸素原子の隣接位に炭素−水素結合を有するアセタール（ヘミアセタールも含む）又は硫黄原子の隣接位に炭素−水素結合を有するチオアセタール（チオヘミアセタールも含む）などが例示できる。 As the heteroatom-containing compound (A1) having a carbon-hydrogen bond at the adjacent position of the heteroatom, (A1-1) primary or secondary alcohol or primary or secondary thiol, (A1-2) An ether having a carbon-hydrogen bond adjacent to an oxygen atom or a sulfide having a carbon-hydrogen bond adjacent to a sulfur atom, (A1-3) an acetal having a carbon-hydrogen bond adjacent to an oxygen atom (also a hemiacetal) Thioacetal (including thiohemiacetal) having a carbon-hydrogen bond at a position adjacent to a sulfur atom.
前記炭素−ヘテロ原子二重結合を有する化合物（A2）としては、（A2-1）カルボニル基含有化合物、（A2-2）チオカルボニル基含有化合物、（A2-3）イミン類などが挙げられる。 Examples of the compound (A2) having a carbon-heteroatom double bond include (A2-1) carbonyl group-containing compounds, (A2-2) thiocarbonyl group-containing compounds, (A2-3) imines, and the like.
前記メチン炭素原子を有する化合物（A3）には、（A3-1）環の構成単位としてメチン基（すなわち、メチン炭素−水素結合）を含む環状化合物、（A3-2）メチン炭素原子を有する鎖状化合物が含まれる。 The compound (A3) having a methine carbon atom includes (A3-1) a cyclic compound containing a methine group (that is, a methine carbon-hydrogen bond) as a structural unit of the ring, and (A3-2) a chain having a methine carbon atom. Like compounds.
前記不飽和結合の隣接位に炭素−水素結合を有する化合物（A4）としては、（A4-1）芳香族性環の隣接位（いわゆるベンジル位）にメチル基又はメチレン基を有する芳香族化合物、（A4-2）不飽和結合（例えば、炭素−炭素不飽和結合、炭素−酸素二重結合など）の隣接位にメチル基又はメチレン基を有する非芳香族性化合物などが挙げられる。 As the compound (A4) having a carbon-hydrogen bond at the adjacent position of the unsaturated bond, (A4-1) an aromatic compound having a methyl group or a methylene group at the adjacent position (so-called benzyl position) of the aromatic ring, (A4-2) Non-aromatic compounds having a methyl group or a methylene group at an adjacent position of an unsaturated bond (for example, a carbon-carbon unsaturated bond, a carbon-oxygen double bond, etc.), and the like.
前記非芳香族性環状炭化水素（A5）には、（A5-1）シクロアルカン類及び（A5-2）シクロアルケン類が含まれる。 The non-aromatic cyclic hydrocarbon (A5) includes (A5-1) cycloalkanes and (A5-2) cycloalkenes.
前記共役化合物（A6）には、共役ジエン類（A6-1）、α，β−不飽和ニトリル（A6-2）、α，β−不飽和カルボン酸又はその誘導体（例えば、エステル、アミド、酸無水物等）（A6-3）などが挙げられる。 The conjugated compound (A6) includes conjugated dienes (A6-1), α, β-unsaturated nitriles (A6-2), α, β-unsaturated carboxylic acids or derivatives thereof (for example, esters, amides, acids Anhydride, etc.) (A6-3).
前記アミン類（A7）としては、第１級または第２級アミンなどが挙げられる。 Examples of the amines (A7) include primary or secondary amines.
前記芳香族炭化水素（A8）としては、少なくともベンゼン環を１つ有する芳香族化合物、好ましくは少なくともベンゼン環が複数個（例えば、２〜１０個）縮合している縮合多環式芳香族化合物などが挙げられる。 Examples of the aromatic hydrocarbon (A8) include an aromatic compound having at least one benzene ring, preferably a condensed polycyclic aromatic compound in which a plurality of (for example, 2 to 10) benzene rings are condensed. Is mentioned.
前記直鎖状アルカン（A9）としては、炭素数１〜３０程度（好ましくは炭素数１〜２０程度）の直鎖状アルカンが挙げられる。 Examples of the linear alkane (A9) include linear alkanes having about 1 to 30 carbon atoms (preferably about 1 to 20 carbon atoms).
前記オレフィン類（A10）としては、置換基（例えば、ヒドロキシル基、アシルオキシ基等の前記例示の置換基など）を有していてもよいα−オレフィン及び内部オレフィンの何れであってもよく、ジエンなどの炭素−炭素二重結合を複数個有するオレフィン類も含まれる。 The olefins (A10) may be any of α-olefins and internal olefins which may have a substituent (for example, the above-mentioned exemplified substituents such as a hydroxyl group and an acyloxy group), and diene. Olefins having a plurality of carbon-carbon double bonds such as are also included.
上記の被酸化部位を有する有機化合物は単独で用いてもよく、同種又は異種のものを２種以上組み合わせて用いてもよい。 The organic compound having the site to be oxidized may be used alone, or two or more of the same or different types may be used in combination.
本発明の酸化方法において、前記表面修飾酸化チタン光触媒の使用量は、基質として用いる有機化合物１００重量部に対して、例えば１〜１００００重量部、好ましくは１０〜５０００重量部、さらに好ましくは５０〜２０００重量部程度である。 In the oxidation method of the present invention, the amount of the surface-modified titanium oxide photocatalyst used is, for example, 1 to 10000 parts by weight, preferably 10 to 5000 parts by weight, and more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the organic compound used as the substrate. About 2000 parts by weight.
本発明の方法では、基質としての有機化合物を光照射下に分子状酸素及び／又は過酸化物で酸化する。照射する光としては、通常、３８０ｎｍ未満の紫外線が使用されるが、酸化チタンの種類によっては、例えば３８０ｎｍ以上、６５０ｎｍ程度までの長波長の可視光線を使用することもできる。 In the method of the present invention, an organic compound as a substrate is oxidized with molecular oxygen and / or peroxide under light irradiation. As the light to be irradiated, ultraviolet rays having a wavelength of less than 380 nm are usually used, but depending on the type of titanium oxide, visible light having a long wavelength of, for example, 380 nm to 650 nm can also be used.
分子状酸素としては、純粋な酸素を用いてもよく、窒素、ヘリウム、アルゴン、二酸化炭素などの不活性ガスで希釈した酸素や空気を用いてもよい。分子状酸素の使用量は、基質として用いる有機化合物１モルに対して、例えば０．５モル以上、好ましくは１モル以上である。有機化合物に対して過剰モルの分子状酸素を用いることが多い。 As molecular oxygen, pure oxygen may be used, or oxygen or air diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used. The amount of molecular oxygen used is, for example, 0.5 mol or more, preferably 1 mol or more, with respect to 1 mol of the organic compound used as the substrate. Often an excess of molecular oxygen is used relative to the organic compound.
過酸化物としては、特に限定されず、ペルオキシド、ヒドロペルオキシド等の何れも使用できる。代表的な過酸化物として、過酸化水素、クメンヒドロペルオキシド、ｔ−ブチルヒドロペルオキシド、トリフェニルメチルヒドロペルオキシド、ｔ−ブチルペルオキシド、ベンゾイルペルオキシドなどが挙げられる。上記過酸化水素としては、純粋な過酸化水素を用いてもよいが、取扱性の点から、通常、適当な溶媒、例えば水に希釈した形態（例えば、３０重量％過酸化水素水）で用いられる。過酸化物の使用量は、基質として用いる有機化合物１モルに対して、例えば０．１〜５モル程度、好ましくは０．３〜１．５モル程度である。 The peroxide is not particularly limited, and any of peroxide, hydroperoxide and the like can be used. Representative peroxides include hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, triphenylmethyl hydroperoxide, t-butyl peroxide, benzoyl peroxide, and the like. As the hydrogen peroxide, pure hydrogen peroxide may be used, but from the viewpoint of handleability, it is usually used in a form diluted with an appropriate solvent such as water (for example, 30% by weight hydrogen peroxide). It is done. The usage-amount of a peroxide is about 0.1-5 mol with respect to 1 mol of organic compounds used as a substrate, Preferably it is about 0.3-1.5 mol.
本発明では、分子状酸素と過酸化物のうち一方のみを用いてもよいが、分子状酸素と過酸化物とを組み合わせることにより、反応速度が大幅に向上する場合がある。 In the present invention, only one of molecular oxygen and peroxide may be used, but the reaction rate may be significantly improved by combining molecular oxygen and peroxide.
反応は、通常、溶媒存在下で行われる。該溶媒としては、例えば、ヘキサン、ヘプタン、オクタン、リグロイン、石油エーテル等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、シクロヘプタン等の脂環式炭化水素；エチルエーテル、イソプロピルエーテル、テトラヒドロフラン等のエーテル類；酢酸エチル等のエステル類；、アセトニトリル、プロピオニトリル、ブチロニトリル、ベンゾニトリル等のニトリル類；Ｎ，Ｎ−ジメチルホルムアミド等の非プロトン性極性溶媒；酢酸等の有機酸；水；これらの混合溶媒などが挙げられる。 The reaction is usually performed in the presence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, ligroin and petroleum ether; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cycloheptane; ethers such as ethyl ether, isopropyl ether and tetrahydrofuran. Esters such as ethyl acetate; nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile; aprotic polar solvents such as N, N-dimethylformamide; organic acids such as acetic acid; water; mixed solvents thereof Etc.
反応温度は、反応速度及び反応選択性を考慮して適宜選択できるが、一般には−２０℃〜１００℃程度である。反応は室温付近で行われることが多い。反応はバッチ式、セミバッチ式、連続式などの何れの方法で行ってもよい。 Although reaction temperature can be suitably selected in view of reaction rate and reaction selectivity, it is generally about -20 ° C to 100 ° C. The reaction is often performed near room temperature. The reaction may be carried out by any method such as batch, semi-batch and continuous methods.
上記反応により、有機化合物から対応する酸化開裂生成物（例えば、アルデヒド化合物）、キノン類、ヒドロペルオキシド、ヒドロキシル基含有化合物、カルボニル化合物、カルボン酸などの酸素原子含有化合物などが生成する。例えば、アルコールやアルデヒドからは対応するカルボン酸等が生成する。また、アダマンタンからは１−アダマンタノール、２−アダマンタノール、２−アダマンタノンなどが生成する。これらの生成物の生成割合（選択率）は、反応条件等を適宜選択することにより調整できる。 By the above reaction, a corresponding oxidative cleavage product (for example, an aldehyde compound), a quinone, a hydroperoxide, a hydroxyl group-containing compound, a carbonyl compound, a carboxylic acid-containing compound or the like is generated from the organic compound. For example, a corresponding carboxylic acid is generated from alcohol or aldehyde. Further, 1-adamantanol, 2-adamantanol, 2-adamantanone and the like are produced from adamantane. The production ratio (selectivity) of these products can be adjusted by appropriately selecting reaction conditions and the like.
反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段や、これらを組み合わせた分離手段により分離精製できる。また、表面修飾酸化チタン光触媒は濾過により容易に分離でき、分離した触媒は、必要に応じて洗浄等の処理を施した後、リサイクル使用できる。 The reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. Further, the surface-modified titanium oxide photocatalyst can be easily separated by filtration, and the separated catalyst can be recycled after being subjected to treatment such as washing as necessary.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
実施例１
フェニルトリクロロシラン０．８ｇをトルエン７５ｍｌで希釈し、市販の多孔質セラミックス膜被覆酸化チタン［商品名「マスクメロン型光触媒」、太平化学産業（株）製］１．５ｇを加えた。２０時間室温で反応した後、撹拌を止め、５時間静置した。この混合液の上澄み液をデカンテーションにより除いた後、残った沈殿物をトルエン、エタノールの順で数回洗浄した。過剰の修飾された表面の疎水基を除去するため、試料（沈殿物）０．１５ｇを２００ｍｌの水に分散させ、５時間撹拌しながら光照射した。光照射後、水面に浮いている表面修飾酸化チタン光触媒を吸引濾過により濾別し、減圧乾燥した。得られた表面修飾酸化チタン光触媒の元素分析結果を以下に示す。なお、光照射時間を３０時間とした場合も同様の元素分析結果が得られ、表面修飾した疎水性基はそれ以上切断されず、安定性の高いことが確認された。
秤取量2645μｇ；Ｈ（％）2.38，Ｃ（％）13.43，残渣（TiO2）2236μｇ
Example 1
0.8 g of phenyltrichlorosilane was diluted with 75 ml of toluene, and 1.5 g of a commercially available porous ceramic film-coated titanium oxide [trade name “Maskmelon type photocatalyst” manufactured by Taihei Chemical Industry Co., Ltd.] was added. After reacting at room temperature for 20 hours, stirring was stopped and the mixture was allowed to stand for 5 hours. After removing the supernatant of this mixed solution by decantation, the remaining precipitate was washed several times in the order of toluene and ethanol. In order to remove excess modified surface hydrophobic groups, 0.15 g of the sample (precipitate) was dispersed in 200 ml of water and irradiated with light with stirring for 5 hours. After the light irradiation, the surface-modified titanium oxide photocatalyst floating on the water surface was separated by suction filtration and dried under reduced pressure. The elemental analysis results of the obtained surface-modified titanium oxide photocatalyst are shown below. In addition, when the light irradiation time was set to 30 hours, the same elemental analysis result was obtained, and it was confirmed that the surface-modified hydrophobic group was not further cleaved and the stability was high.
Weighing amount 2645 μg; H (%) 2.38, C (%) 13.43, Residue (TiO 2 ) 2236 μg
実施例２
オクタデシルトリクロロシラン１．４５ｇをトルエン７５ｍｌで希釈し、市販の多孔質セラミックス膜被覆酸化チタン［商品名「マスクメロン型光触媒」、太平化学産業（株）製］１．５ｇを加えた。２０時間室温で反応した後、撹拌を止め、５時間静置した。この混合液の上澄み液をデカンテーションにより除いた後、残った沈殿物をトルエン、エタノールの順で数回洗浄した。過剰の修飾された表面の疎水基を除去するため、試料（沈殿物）０．１５ｇを２００ｍｌの水に分散させ、５時間撹拌しながら光照射した。光照射後、水面に浮いている表面修飾酸化チタン光触媒を吸引濾過により濾別し、減圧乾燥した。
Example 2
1.45 g of octadecyltrichlorosilane was diluted with 75 ml of toluene, and 1.5 g of a commercially available porous ceramic film-coated titanium oxide [trade name “Maskmelon type photocatalyst”, manufactured by Taihei Chemical Industry Co., Ltd.] was added. After reacting at room temperature for 20 hours, stirring was stopped and the mixture was allowed to stand for 5 hours. After removing the supernatant of this mixed solution by decantation, the remaining precipitate was washed several times in the order of toluene and ethanol. In order to remove excess modified surface hydrophobic groups, 0.15 g of the sample (precipitate) was dispersed in 200 ml of water and irradiated with light with stirring for 5 hours. After the light irradiation, the surface-modified titanium oxide photocatalyst floating on the water surface was separated by suction filtration and dried under reduced pressure.
実施例３
光源から鏡に反射させた反射光が上部から当たるように作製された試験管中に濃度２６ｍｍｏｌ／Ｌのヘキサナールエマルジョン水分散液をとり、実施例２で得られた表面修飾酸化チタン光触媒０．０５ｇを入れ、蓋をしてパラフィルムで密閉した。これを光源から鏡までの距離９．５ｃｍ、鏡から試験管までの距離１３ｃｍとなるような位置に固定し、スライダックで微調整したマグネチックスターラーで撹拌しながら、３５０Ｗ水銀ランプで１時間光照射した。反応中は光による昇温を避けるためドライヤーで冷却した。反応後、アセトニトリル５ｍｌを添加し、遠心分離した。ガスクロマトグラフィーにより上澄み液中の基質の減少濃度、生成物の増加濃度の定量を行った。その結果、ヘキサナールの減少濃度（減少量）は１３．３ｍｍｏｌ／Ｌであり、ヘキサン酸が７．８ｍｍｏｌ／Ｌ生成していた。
Example 3
An aqueous dispersion of hexanal emulsion having a concentration of 26 mmol / L was taken in a test tube prepared so that the reflected light reflected from the light source to the mirror hits from above, and 0.05 g of the surface-modified titanium oxide photocatalyst obtained in Example 2 was obtained. , Covered and sealed with parafilm. This is fixed at a position where the distance from the light source to the mirror is 9.5 cm and the distance from the mirror to the test tube is 13 cm, and the light is irradiated with a 350 W mercury lamp for 1 hour while stirring with a magnetic stirrer finely adjusted with a slider. did. During the reaction, it was cooled with a dryer in order to avoid temperature rise by light. After the reaction, 5 ml of acetonitrile was added and centrifuged. The reduced concentration of the substrate and the increased concentration of the product in the supernatant were quantified by gas chromatography. As a result, the decrease concentration (decrease amount) of hexanal was 13.3 mmol / L, and 7.8 mmol / L of hexanoic acid was produced.
比較例１
表面修飾酸化チタン光触媒０．０５ｇの代わりに、表面修飾していない多孔質セラミックス膜被覆酸化チタン［商品名「マスクメロン型光触媒」、太平化学産業（株）製］を０．０５ｇ用いた以外は実施例３と同様の操作を行った。その結果、ヘキサナールの減少濃度（減少量）は５．７ｍｍｏｌ／Ｌであり、ヘキサン酸が１．９ｍｍｏｌ／Ｌ生成していた。
Comparative Example 1
Instead of using 0.05 g of the surface-modified titanium oxide photocatalyst, 0.05 g of porous ceramic film-coated titanium oxide [trade name “Maskmelon type photocatalyst”, manufactured by Taihei Chemical Sangyo Co., Ltd.] without surface modification was used. The same operation as in Example 3 was performed. As a result, the decreasing concentration (decreasing amount) of hexanal was 5.7 mmol / L, and 1.9 mmol / L of hexanoic acid was generated.
実施例４
光源から鏡に反射させた反射光が上部から当たるように作製された試験管中に水５ｍｌをとり、実施例２で得られた表面修飾酸化チタン光触媒０．０５ｇを入れ、ヘキサナール（反応基質）０．０１００ｇ（２０ｍｍｏｌ／Ｌ）を加え、蓋をしてパラフィルムで密閉した。これを光源から鏡までの距離９．５ｃｍ、鏡から試験管までの距離１３ｃｍとなるような位置に固定し、スライダックで微調整したマグネチックスターラーで撹拌しながら、３５０Ｗ水銀ランプで１時間光照射した。反応中は光による昇温を避けるためドライヤーで冷却した。反応後、アセトニトリル５ｍｌを添加し、遠心分離した。ガスクロマトグラフィーにより上澄み液中の基質の減少濃度、生成物の増加濃度の定量を行った。その結果、ヘキサナールの減少濃度（減少量）は１２．４ｍｍｏｌ／Ｌであり、ヘキサン酸が８．７ｍｍｏｌ／Ｌ生成していた。
Example 4
Take 5 ml of water in a test tube made so that the reflected light reflected from the light source to the mirror hits from the top, put 0.05 g of the surface-modified titanium oxide photocatalyst obtained in Example 2, and hexanal (reaction substrate). 0.0100 g (20 mmol / L) was added, capped and sealed with parafilm. This is fixed at a position where the distance from the light source to the mirror is 9.5 cm and the distance from the mirror to the test tube is 13 cm, and the light is irradiated with a 350 W mercury lamp for 1 hour while stirring with a magnetic stirrer finely adjusted with a slider. did. During the reaction, it was cooled with a dryer in order to avoid temperature rise by light. After the reaction, 5 ml of acetonitrile was added and centrifuged. The reduced concentration of the substrate and the increased concentration of the product in the supernatant were quantified by gas chromatography. As a result, the decreasing concentration (decreasing amount) of hexanal was 12.4 mmol / L, and hexanoic acid was generated at 8.7 mmol / L.
比較例２
表面修飾酸化チタン光触媒０．０５ｇの代わりに、表面修飾していない多孔質セラミックス膜被覆酸化チタン［商品名「マスクメロン型光触媒」、太平化学産業（株）製］を０．０５ｇ用いた以外は実施例４と同様の操作を行った。その結果、ヘキサナールの減少濃度（減少量）は５．０ｍｍｏｌ／Ｌであり、ヘキサン酸が３．６ｍｍｏｌ／Ｌ生成していた。
Comparative Example 2
Instead of using 0.05 g of the surface-modified titanium oxide photocatalyst, 0.05 g of porous ceramic film-coated titanium oxide [trade name “Maskmelon type photocatalyst”, manufactured by Taihei Chemical Sangyo Co., Ltd.] without surface modification was used. The same operation as in Example 4 was performed. As a result, the decreasing concentration (decreasing amount) of hexanal was 5.0 mmol / L and hexanoic acid was generated at 3.6 mmol / L.
実施例５
反応基質として、ヘキサナール０．０１００ｇ（２０ｍｍｏｌ／Ｌ）の代わりに、ノナナール０．０１４２ｇ（２０ｍｍｏｌ／Ｌ）を用いた以外は実施例３と同様の操作を行った。その結果、ノナナールの減少濃度（減少量）は１３．８ｍｍｏｌ／Ｌであり、ノナン酸が１０．４ｍｍｏｌ／Ｌ生成していた。
Example 5
The same operation as in Example 3 was performed except that 0.0142 g (20 mmol / L) nonanal was used instead of 0.0100 g (20 mmol / L) hexanal as a reaction substrate. As a result, the decrease concentration (reduction amount) of nonanal was 13.8 mmol / L, and nonanoic acid was produced at 10.4 mmol / L.
比較例３
表面修飾酸化チタン光触媒０．０５ｇの代わりに、表面修飾していない多孔質セラミックス膜被覆酸化チタン［商品名「マスクメロン型光触媒」、太平化学産業（株）製］を０．０５ｇ用いた以外は実施例５と同様の操作を行った。その結果、ノナナールの減少濃度（減少量）は２．９ｍｍｏｌ／Ｌであり、ノナン酸が２．７ｍｍｏｌ／Ｌ生成していた。
Comparative Example 3
Instead of using 0.05 g of the surface-modified titanium oxide photocatalyst, 0.05 g of porous ceramic film-coated titanium oxide [trade name “Maskmelon type photocatalyst”, manufactured by Taihei Chemical Sangyo Co., Ltd.] without surface modification was used. The same operation as in Example 5 was performed. As a result, the decrease concentration (reduction amount) of nonanal was 2.9 mmol / L, and nonanoic acid was generated at 2.7 mmol / L.
実施例６
反応基質として、ヘキサナール０．０１００ｇ（２０ｍｍｏｌ／Ｌ）の代わりに、ノナナール０．０１４２ｇ（２０ｍｍｏｌ／Ｌ）を用いた以外は実施例４と同様の操作を行った。その結果、ノナナールの減少濃度（減少量）は１９．０ｍｍｏｌ／Ｌであり、ノナン酸が１７．６ｍｍｏｌ／Ｌ生成していた。
Example 6
The same operation as in Example 4 was performed except that 0.0142 g (20 mmol / L) nonanal was used instead of 0.0100 g (20 mmol / L) hexanal as a reaction substrate. As a result, the decrease concentration (reduction amount) of nonanal was 19.0 mmol / L, and 17.6 mmol / L of nonanoic acid was produced.
比較例４
表面修飾酸化チタン光触媒０．０５ｇの代わりに、表面修飾していない多孔質セラミックス膜被覆酸化チタン［商品名「マスクメロン型光触媒」、太平化学産業（株）製］を０．０５ｇ用いた以外は実施例６と同様の操作を行った。その結果、ノナナールの減少濃度（減少量）は８．１ｍｍｏｌ／Ｌであり、ノナン酸が６．９ｍｍｏｌ／Ｌ生成していた。
Comparative Example 4
Instead of using 0.05 g of the surface-modified titanium oxide photocatalyst, 0.05 g of porous ceramic film-coated titanium oxide [trade name “Maskmelon type photocatalyst”, manufactured by Taihei Chemical Sangyo Co., Ltd.] without surface modification was used. The same operation as in Example 6 was performed. As a result, the decrease concentration (reduction amount) of nonanal was 8.1 mmol / L and nonanoic acid was generated at 6.9 mmol / L.
Claims (6)
An organic compound having an oxidizable site oxidized with oxygen or peroxide under light irradiation in the presence of the surface-modified titanium oxide photocatalyst according to any one of claims 1 to 5. Oxidation method.
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