JP4948257B2 - Porous silica coating-coated titanium oxide photocatalyst and organic compound oxidation method using porous silica coating-coated titanium oxide photocatalyst - Google Patents
Porous silica coating-coated titanium oxide photocatalyst and organic compound oxidation method using porous silica coating-coated titanium oxide photocatalyst Download PDFInfo
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- JP4948257B2 JP4948257B2 JP2007127930A JP2007127930A JP4948257B2 JP 4948257 B2 JP4948257 B2 JP 4948257B2 JP 2007127930 A JP2007127930 A JP 2007127930A JP 2007127930 A JP2007127930 A JP 2007127930A JP 4948257 B2 JP4948257 B2 JP 4948257B2
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- titanium oxide
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- porous silica
- oxide photocatalyst
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
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 titanium oxide photocatalyst that exhibits functions such as oxidation, deodorization, air purification, water purification, decomposition of harmful substances and dirt, antibacterial activity, and antifungal activity, and an organic compound oxidation method using the photocatalyst.
酸化チタン光触媒(二酸化チタン光触媒)は、光を照射することで強力な酸化還元力を発現し、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。 Titanium oxide photocatalyst (titanium dioxide photocatalyst) develops strong redox power when irradiated with light, and functions such as deodorization, air purification, water purification, decomposition of harmful substances and dirt, antibacterial and antifungal functions Therefore, it is used as an environmental 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.
また、酸化チタン光触媒がある特定の有機物(有機化合物、有機分子)のみに選択的に作用することができるように、分子選択性を有する酸化チタン光触媒(分子認識能を有する酸化チタン光触媒)も求められてきている。 There is also a need for a titanium oxide photocatalyst having a molecular selectivity (a titanium oxide photocatalyst having molecular recognition ability) so that the titanium oxide photocatalyst can selectively act only on certain organic substances (organic compounds, organic molecules). It has been.
有機素材が分解するという問題に対して、例えば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膜被覆酸化チタン光触媒(マスクメロン型酸化チタン光触媒)が提案されているが、孔の大きさが大きく、孔の大きさがまちまちであるため、分子ふるいのような役割をすることはなかった(特許文献1参照)。また、光半導体が多孔性被覆部により被覆されてなる光触媒活性を有する機能材料も提案されているが、添加剤とシラン系化合物との混合物を用いて酸化チタン粒子をコーティングしているため、多数の孔を有するものの、所望の位置に孔を開けることができず、また添加剤として分子の大きい有機高分子等を用いるため、シリカ膜に設けた孔に起因する分子選択性を有することはなかった(特許文献2参照)。 For the problem that organic materials decompose, for example, a porous ceramic film-coated titanium oxide photocatalyst (mask melon type titanium oxide photocatalyst) in which the surface of the titanium oxide photocatalyst is coated with a coating made of porous ceramics has been proposed. Since the size of the pores is large and the size of the pores varies, it did not act like a molecular sieve (see Patent Document 1). In addition, a functional material having a photocatalytic activity in which an optical semiconductor is coated with a porous coating portion has been proposed. However, since titanium oxide particles are coated using a mixture of an additive and a silane compound, many However, since the organic polymer having a large molecule is used as an additive, it does not have molecular selectivity due to the pores provided in the silica membrane. (See Patent Document 2).
有機素材の分解を防止しつつ、分子選択性を有する酸化チタン光触媒として、例えば、表面が多孔質セラミックス被膜で被覆された表面修飾酸化チタン光触媒が提案されている(特許文献3参照)。該酸化チタン光触媒は、光触媒表面が多孔質セラミックス膜で覆われているため、有機素材の分解等を抑制することができる一方、酸化チタン表面の修飾により、反応の選択性の向上がみられた。しかし、この触媒では官能基の種類の違いによる反応の選択性は可能であるものの、分子の大きさの違いによる反応の選択性を向上させることは難しい。 As a titanium oxide photocatalyst having molecular selectivity while preventing decomposition of an organic material, for example, a surface-modified titanium oxide photocatalyst whose surface is coated with a porous ceramic coating has been proposed (see Patent Document 3). The titanium oxide photocatalyst has a photocatalyst surface covered with a porous ceramic film, so that decomposition of organic materials can be suppressed, while modification of the titanium oxide surface has improved reaction selectivity. . However, with this catalyst, the selectivity of the reaction depending on the type of functional group is possible, but it is difficult to improve the selectivity of the reaction due to the difference in molecular size.
従って、本発明の目的は、シリカ被膜に設けた孔に起因する分子選択性を有する多孔性シリカ被膜被覆酸化チタン光触媒を得ることにある。
本発明の他の目的は、シリカ被膜に設けた孔に起因する分子選択性を有する多孔性シリカ被膜被覆酸化チタン光触媒を用いた有機化合物の選択的酸化方法を提供することにある。
Accordingly, an object of the present invention is to obtain a porous silica coating-coated titanium oxide photocatalyst having molecular selectivity due to pores provided in the silica coating.
Another object of the present invention is to provide a method for selective oxidation of an organic compound using a porous silica coating-coated titanium oxide photocatalyst having molecular selectivity due to pores provided in the silica coating.
本発明者らは上記の問題を解決するために鋭意検討した結果、酸化チタン粒子表面を、極性基を有する化合物で処理した後、シラン系化合物でコーティング処理し、次いで前記極性基を有する化合物を除去して孔(細孔)を形成すると、該孔が分子ふるいのような役割を果たし、非選択性である酸化チタン光触媒に分子認識能を付与できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have treated the surface of the titanium oxide particles with a compound having a polar group, followed by coating with a silane compound, and then the compound having the polar group. When the pores (pores) were formed by removing the pores, the pores acted as molecular sieves, and it was found that molecular recognition ability could be imparted to the non-selective titanium oxide photocatalyst, thereby completing the present invention.
すなわち、本発明は、酸化チタン粒子表面を、R−X(Rは有機基を示し、官能基Xは、Rに直接単結合により結合している官能基であって、カルボキシル基、水酸基、アミノ基のいずれかである)で表される極性基を有する化合物で処理した後、シラン系化合物でコーティング処理し、次いで前記極性基を有する化合物を除去して有機基Rの形状の孔を形成することにより得られる有機基Rの分子構造を含む有機化合物を酸化するための多孔性シリカ被膜被覆酸化チタン光触媒を提供する。 That is, in the present invention, the surface of the titanium oxide particles is converted to R—X (R represents an organic group, and the functional group X is a functional group directly bonded to R by a single bond, and includes a carboxyl group, a hydroxyl group, an amino group, Is treated with a compound having a polar group represented by any one of the following groups) , followed by coating with a silane-based compound, and then removing the compound having the polar group to form an organic group R-shaped hole. Provided is a porous silica coating-coated titanium oxide photocatalyst for oxidizing an organic compound containing the molecular structure of the organic group R obtained in this way.
官能基Xは、カルボキシル基であることが好ましい。 Officer functional group X is preferably a carboxyl group.
シラン系化合物は、アルコキシシラン化合物、又はハロゲン化シラン化合物であることが好ましい。特に、アルコキシシラン化合物であることが好ましい。また、R−Xにおける有機基Rとしては、ベンゼン環若しくはナフタレン環で構成される芳香族炭化水素基、又はアダマンチル基であることが好ましい。 The silane compound is preferably an alkoxysilane compound or a halogenated silane compound. In particular, an alkoxysilane compound is preferable. Further, the organic group R in R—X is preferably an aromatic hydrocarbon group composed of a benzene ring or a naphthalene ring, or an adamantyl group.
極性基を有する化合物の除去手段は、アルカリ水溶液による洗浄であることが好ましい。 The means for removing the compound having a polar group is preferably washing with an alkaline aqueous solution.
さらに、本発明は、前記多孔性シリカ被膜被覆酸化チタン光触媒を用いて、有機基Rの分子構造を含む有機化合物を酸化することを特徴とする有機化合物の酸化方法を提供する。 Furthermore, the present invention provides an organic compound oxidation method characterized by oxidizing an organic compound containing a molecular structure of an organic group R using the porous silica film-coated titanium oxide photocatalyst.
本明細書には、上記発明の他に、酸化チタン粒子表面を、極性基を有する化合物で処理した後、シラン系化合物でコーティング処理し、次いで前記極性基を有する化合物を除去して孔を形成することにより得られる多孔性シリカ被膜被覆酸化チタン光触媒についても記載する。In the present specification, in addition to the above-described invention, the surface of the titanium oxide particles is treated with a compound having a polar group, then coated with a silane compound, and then the compound having the polar group is removed to form pores. The porous silica coating-coated titanium oxide photocatalyst obtained by doing so is also described.
本発明の多孔性シリカ被膜被覆酸化チタン光触媒は、前記構成を有しているので、シリカ被膜に設けた孔に起因する分子選択性を有する。該シリカ被膜に設けた孔に起因する分子選択性を有する多孔性シリカ被膜被覆酸化チタン光触媒は、特定の有機化合物を選択的に効率よく酸化することができ、また、有機化合物の特定の部位のみを効率よく酸化することができる。 Since the porous silica coating-coated titanium oxide photocatalyst of the present invention has the above-described configuration, it has molecular selectivity due to pores provided in the silica coating. The porous silica coating-coated titanium oxide photocatalyst having molecular selectivity due to pores provided in the silica coating can selectively oxidize a specific organic compound efficiently, and only a specific portion of the organic compound Can be oxidized efficiently.
多孔性シリカ被膜被覆酸化チタン光触媒は、酸化チタン粒子表面が多数の孔(貫通孔)を有するシリカ被膜で覆われる構成を有しており、酸化チタン粒子表面を、極性基を有する化合物で処理した後、シラン系化合物でコーティング処理し、次いで前記極性基を有する化合物を除去して孔を形成させることにより作製することができる。 The porous silica coating-coated titanium oxide photocatalyst has a structure in which the titanium oxide particle surface is covered with a silica coating having a large number of pores (through holes), and the titanium oxide particle surface is treated with a compound having a polar group. Then, it can be produced by coating with a silane compound and then removing the compound having a polar group to form pores.
酸化チタン(二酸化チタン)粒子は、光が照射されることによって粒子表面に吸着した有機化合物を酸化する機能を有する限り特に限定されず、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−ルチル型混合二酸化チタン)等のいずれの二酸化チタン(結晶性二酸化チタン)の粒子であってもよい。 Titanium oxide (titanium dioxide) particles are not particularly limited as long as they have a function of oxidizing an organic compound adsorbed on the particle surface when irradiated with light. Titanium dioxide having a rutile crystal structure (rutile titanium dioxide), Particles of any titanium dioxide (crystalline titanium dioxide) such as titanium dioxide having an anatase type crystal structure (anatase type titanium dioxide) and a mixture thereof (anatase-rutile type mixed titanium dioxide) may be used.
酸化チタン粒子は、その形状や平均粒子径などについて特に制限されることはないが、本発明においては、例えば、球状であり、5〜50μm程度の平均粒子径を有し、さらに100〜250m2/g程度の比表面積を有するものを好ましく用いることができる。 The titanium oxide particles are not particularly limited in terms of their shape and average particle diameter, but in the present invention, for example, they are spherical, have an average particle diameter of about 5 to 50 μm, and further 100 to 250 m 2. Those having a specific surface area of about / g can be preferably used.
酸化チタン粒子表面の極性基を有する化合物による処理は、酸化チタン粒子表面への極性基を有する化合物の担持を目的とする処理であり、該処理によって酸化チタン粒子表面に極性基を有する化合物を担持することができる限り特に制限されない。このような処理としては、例えば、表面に極性基を有する化合物と酸化チタン粒子との混合が挙げられる。なお、混合の際に、溶媒(例えば、水や有機溶媒)を用いてもよい。 The treatment with the compound having a polar group on the surface of the titanium oxide particle is a treatment aimed at supporting the compound having the polar group on the surface of the titanium oxide particle, and the compound having the polar group is supported on the surface of the titanium oxide particle by the treatment. There is no particular limitation as long as it can be done. Examples of such treatment include mixing of a compound having a polar group on the surface and titanium oxide particles. In mixing, a solvent (for example, water or an organic solvent) may be used.
極性基を有する化合物は、分子選択性を有する多孔性シリカ被膜被覆酸化チタン光触媒において、酸化チタン表面に担持された状態でシリカコーティングされることにより、分子ふるい的な役割をするシリカ被膜に設けた孔の形状(空洞)を作り出す分子(「鋳型分子」と称する場合がある)である。 The compound having a polar group was provided on a silica coating that plays a molecular sieve role by being coated with silica in a state of being supported on the surface of titanium oxide in a porous silica coating-coated titanium oxide photocatalyst having molecular selectivity. Molecules that create pore shapes (cavities) (sometimes referred to as “template molecules”).
このような極性基を有する化合物としては、化合物中に少なくとも一つの極性基を有する化合物である限り、特に制限されないが、R−X(官能基Xは、Rに直接単結合により結合している極性基)で表される有機分子が好ましい。 The compound having such a polar group is not particularly limited as long as it is a compound having at least one polar group in the compound, but R—X (the functional group X is directly bonded to R through a single bond). Organic molecules represented by polar groups) are preferred.
前記R−X(官能基Xは、Rに直接単結合により結合している極性基)で表される有機分子において、Rは有機基を意味する。このような有機基としては、特に制限されず、炭化水素基、複素環式基などが挙げられる。 In the organic molecule represented by R—X (the functional group X is a polar group bonded directly to R through a single bond), R means an organic group. Such an organic group is not particularly limited, and examples thereof include a hydrocarbon group and a heterocyclic group.
前記炭化水素基には、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基及びこれらが結合した基が含まれる。 The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded.
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、デシル、ドデシル基などの炭素数1〜20(好ましくは1〜10、さらに好ましくは1〜3)程度のアルキル基;ビニル、アリル、1−ブテニル基などの炭素数2〜20(好ましくは2〜10、さらに好ましくは2〜3)程度のアルケニル基;エチニル、プロピニル基などの炭素数2〜20(好ましくは2〜10、さらに好ましくは2〜3)程度のアルキニル基などが挙げられる。 Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 10, more preferably an alkyl group of about 1 to 3); an alkenyl group of about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as vinyl, allyl, 1-butenyl group; Examples thereof include alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as propynyl 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、シクロオクチル基などの3〜20員(好ましくは3〜15員、さらに好ましくは5〜8員)程度のシクロアルキル基;シクロペンテニル、シクロへキセニル基などの3〜20員(好ましくは3〜15員、さらに好ましくは5〜8員)程度のシクロアルケニル基;パーヒドロナフタレン−1−イル基、ノルボルニル基、アダマンチル基、ビアダマンチル基、テルアダマンチル基、クアテルアダマンチル基、テトラシクロ[4.4.0.12,5.17,10]ドデカン−3−イル基などの橋かけ環式炭化水素基などが挙げられる。 As the alicyclic hydrocarbon group, for example, a cycloalkyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups; Cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl groups, norbornyl groups, adamantyl groups, Biadamantyl group, teradamantyl group, quateradamantyl group, tetracyclo [4.4.0.1 2,5 . 1 7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups.
芳香族炭化水素基を構成する環としては、例えばベンゼン環、縮合炭素環(例えば、ナフタレン、アズレン、インダセン、ビフェニレン、アセナフチレン、フルオレン、アントラセン、フェナントレン、トリフェニレン、ピレンなどの2〜10個の4〜7員炭素環が縮合した縮合炭素環など)などが挙げられる。 Examples of the ring constituting the aromatic hydrocarbon group include a benzene ring and a condensed carbocycle (for example, 2 to 10 4 to 4 such as naphthalene, azulene, indacene, biphenylene, acenaphthylene, fluorene, anthracene, phenanthrene, triphenylene, pyrene). And a condensed carbocycle condensed with a 7-membered carbocycle).
脂肪族炭化水素基と脂環式炭化水素基とが結合した炭化水素基としては、例えばシクロペンチルメチル、シクロヘキシルメチル、2−シクロヘキシルエチル基などのシクロアルキル−アルキル基(例えば、C3-20シクロアルキル−C1-4アルキル基など)などが含まれる。また、脂肪族炭化水素基と芳香族炭化水素基とが結合した炭化水素基には、アラルキル基(例えば、C7-18アラルキル基など)、アルキル置換アリール基(例えば、1〜4個程度のC1-4アルキル基が置換したフェニル基又はナフチル基など)などが挙げられる。 Examples of the hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include cycloalkyl-alkyl groups such as cyclopentylmethyl, cyclohexylmethyl, and 2-cyclohexylethyl groups (for example, C 3-20 cycloalkyl). -C 1-4 alkyl group, etc.). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C 7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). And a phenyl group or a naphthyl group substituted with a C 1-4 alkyl group).
好ましい炭化水素基としては、例えばC1-10アルキル基、C2-10アルケニル基、C2-10アルキニル基、C3-15シクロアルキル基、芳香族炭化水素基、C3-5シクロアルキル−C1-4アルキル基、C7-14アラルキル基、アダマンチル基、ビアダマンチル基等が挙げられる。 Preferred hydrocarbon groups include, for example, C 1-10 alkyl group, C 2-10 alkenyl group, C 2-10 alkynyl group, C 3-15 cycloalkyl group, aromatic hydrocarbon group, C 3-5 cycloalkyl- C 1-4 alkyl group, C 7-14 aralkyl group, adamantyl group, biadamantyl group and the like can be mentioned.
前記炭化水素基は、種々の置換基を有していてもよい。このような置換基としては、例えば、ハロゲン原子、オキソ基(=O)、ヒドロキシル基、置換オキシ基(例えば、アルコキシ基、アリールオキシ基、アラルキルオキシ基、アシルオキシ基など)、カルボキシル基、置換オキシカルボニル基(アルコキシカルボニル基、アリールオキシカルボニル基、アラルキルオキシカルボニル基など)、置換又は無置換カルバモイル基、シアノ基、ニトロ基、置換又は無置換アミノ基、スルホ基、複素環式基などが挙げられる。前記ヒドロキシル基やカルボキシル基は有機合成の分野で慣用の保護基で保護されていてもよい。また、脂環式炭化水素基や芳香族炭化水素基の環には芳香族性又は非芳香属性の複素環が縮合していてもよい。 The hydrocarbon group may have various substituents. Examples of such substituents include halogen atoms, oxo groups (═O), hydroxyl groups, substituted oxy groups (eg, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxy groups. Examples include carbonyl groups (alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, etc.), substituted or unsubstituted carbamoyl groups, cyano groups, nitro groups, substituted or unsubstituted amino groups, sulfo groups, and heterocyclic groups. . The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.
複素環式基(有機基Rとしての複素環式基及び前記炭化水素基の置換基としての複素環式基)を構成する複素環には、芳香族性複素環及び非芳香族性複素環が含まれる。このような複素環としては、例えば、ヘテロ原子として酸素原子を含む複素環(例えば、フラン、テトラヒドロフラン、オキサゾール、イソオキサゾール、γ−ブチロラクトン環などの5員環、4−オキソ−4H−ピラン、テトラヒドロピラン、モルホリン環などの6員環、ベンゾフラン、イソベンゾフラン、4−オキソ−4H−クロメン、クロマン、イソクロマン環などの縮合環、3−オキサトリシクロ[4.3.1.14,8]ウンデカン−2−オン環、3−オキサトリシクロ[4.2.1.04,8]ノナン−2−オン環などの橋かけ環)、ヘテロ原子としてイオウ原子を含む複素環(例えば、チオフェン、チアゾール、イソチアゾール、チアジアゾール環などの5員環、4−オキソ−4H−チオピラン環などの6員環、ベンゾチオフェン環などの縮合環など)、ヘテロ原子として窒素原子を含む複素環(例えば、ピロール、ピロリジン、ピラゾール、イミダゾール、トリアゾール環などの5員環、ピリジン、ピリダジン、ピリミジン、ピラジン、ピペリジン、ピペラジン環などの6員環、インドール、インドリン、キノリン、アクリジン、ナフチリジン、キナゾリン、プリン環などの縮合環など)などが挙げられる。 The heterocyclic ring constituting the heterocyclic group (the heterocyclic group as the organic group R and the heterocyclic group as a substituent of the hydrocarbon group) includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. included. Examples of such a heterocyclic ring include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, 5-membered ring such as furan, tetrahydrofuran, oxazole, isoxazole, and γ-butyrolactone ring, 4-oxo-4H-pyran, tetrahydro 6-membered ring such as pyran, morpholine ring, condensed ring such as benzofuran, isobenzofuran, 4-oxo-4H-chromene, chroman, isochroman ring, 3-oxatricyclo [4.3.1.1 4,8 ] undecane 2-one ring, a bridged ring such as 3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one ring), a heterocycle containing a sulfur atom as a hetero atom (for example, thiophene, 5-membered ring such as thiazole, isothiazole, thiadiazole ring, 6-membered ring such as 4-oxo-4H-thiopyran ring, benzothiophene ring Any condensed ring), heterocycles containing nitrogen atoms as heteroatoms (eg, 5-membered rings such as pyrrole, pyrrolidine, pyrazole, imidazole, and triazole rings, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine, and piperazine rings) Ring, indole, indoline, quinoline, acridine, naphthyridine, quinazoline, a condensed ring such as a purine ring, etc.).
また、複素環式基は、前記炭化水素基が有していてもよい置換基のほか、アルキル基(例えばメチル基、エチル基などのC1-4アルキル基など)、シクロアルキル基、アリール基(例えばフェニル基、ナフチル基など)の置換基を有していてもよい。 In addition to the substituents that the hydrocarbon group may have, the heterocyclic group includes an alkyl group (eg, a C 1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group. It may have a substituent (for example, phenyl group, naphthyl group, etc.).
極性基を有する化合物中の極性基(前記官能基X)としては、例えば、水酸基、カルボキシル基、アミノ基、オキシアルキレン基、エステル基、アミド基、スルホ基、ニトロ基、シアノ基、スルホン酸基、リン酸基などが挙げられる。中でも、極性基を有する化合物の酸化チタン粒子表面への固定化をより安定させる観点から、カルボキシル基、水酸基、アミノ基が好ましく、特にカルボキシル基が好ましい。 Examples of the polar group (the functional group X) in the compound having a polar group include a hydroxyl group, a carboxyl group, an amino group, an oxyalkylene group, an ester group, an amide group, a sulfo group, a nitro group, a cyano group, and a sulfonic acid group. And phosphoric acid groups. Among these, a carboxyl group, a hydroxyl group, and an amino group are preferable, and a carboxyl group is particularly preferable from the viewpoint of further stabilizing the compound having a polar group on the surface of the titanium oxide particles.
また、極性基を有する化合物の分子量は、特に制限されないが、1000以下が好ましく、好ましくは600以下、さらに好ましくは500以下である。 The molecular weight of the compound having a polar group is not particularly limited, but is preferably 1000 or less, preferably 600 or less, more preferably 500 or less.
極性基を有する化合物の代表的な例としては、例えば、ベンゼン環を有する化合物(例えば、フェノール、アニリン、安息香酸など);ナフタレン環を有する化合物(例えば、1−ナフタレンカルボン酸、1−ナフトール、1−ナフタレンアミンなど);アダマンタン骨格を有する化合物(アダマンタン化合物)(例えば、1−アダマンタンカルボン酸、1−アダマンタノール、2−アダマンタノール、1−アダマンタンメタノール、1−アダマンタンエタノール、1−アダマンタンアミン、3−カルボキシ−1,1−ビアダマンタン、3−ヒドロキシ−1,1−ビアダマンタン、3−アミノ−1,1−ビアダマンタンなど)等が挙げられる。 Representative examples of the compound having a polar group include, for example, a compound having a benzene ring (for example, phenol, aniline, benzoic acid, etc.); a compound having a naphthalene ring (for example, 1-naphthalenecarboxylic acid, 1-naphthol, Compounds having an adamantane skeleton (adamantane compounds) (for example, 1-adamantanecarboxylic acid, 1-adamantanol, 2-adamantanol, 1-adamantane methanol, 1-adamantaneethanol, 1-adamantaneamine, 3-carboxy-1,1-biadamantane, 3-hydroxy-1,1-biadamantane, 3-amino-1,1-biadamantane, etc.).
多孔性シリカ被膜は、前記酸化チタン粒子を被覆する多孔性の膜であり、シリカ(二酸化ケイ素)により構成されている。シリカは、シラン系化合物を加水分解・縮合重合反応させることにより形成することができる。なお、より緻密な構造を有するシリカ膜を得るために、シラン系化合物を加水分解・縮合重合反応させる際に、必要に応じて、触媒、有機溶媒、酸(例えば酢酸など)を併用してもよい。 The porous silica film is a porous film that coats the titanium oxide particles, and is made of silica (silicon dioxide). Silica can be formed by subjecting a silane compound to a hydrolysis / condensation polymerization reaction. In order to obtain a silica film having a denser structure, a catalyst, an organic solvent, and an acid (for example, acetic acid, etc.) may be used in combination when the silane compound is subjected to a hydrolysis / condensation polymerization reaction. Good.
シラン系化合物としては、加水分解・縮合重合反応してシリカを形成するものである限り特に制限されず、例えば、下記式(1)で表されるハロゲン化シラン化合物やアルコキシシラン化合物が挙げられる。特に、常温下で反応を行うことができる点から、アルコキシ系シラン化合物が好ましい。なお、シラン系化合物は、単独で又は2種以上組み合わせて用いることができる。 The silane compound is not particularly limited as long as it forms a silica by hydrolysis and condensation polymerization reaction, and examples thereof include a halogenated silane compound and an alkoxysilane compound represented by the following formula (1). In particular, an alkoxy-based silane compound is preferable because the reaction can be performed at room temperature. In addition, a silane type compound can be used individually or in combination of 2 or more types.
ハロゲン化シラン化合物の具体的な例としては、テトラブロモシラン、テトラクロロシラン、トリブロモシラン、トリクロロシラン、ジブロモシラン、ジクロロシラン、モノブロモシラン、モノクロロシランなどのハロ系シラン化合物;ジクロロジメチルシラン、ジクロロジエチルシラン、ジクロロメチルシラン、ジクロロエチルシラン、クロロトリメチルシラン、クロロトリエチルシラン、クロロジメチルシラン、クロロジエチルシラン、クロロメチルシラン、クロロエチル、t−ブチルクロロジメチルシラン、t−ブチルクロロジエチルシランハロアルキル系シラン化合物などが挙げられる。 Specific examples of halogenated silane compounds include tetrabromosilane, tetrachlorosilane, tribromosilane, trichlorosilane, dibromosilane, dichlorosilane, monobromosilane, monochlorosilane, and other halo-based silane compounds; dichlorodimethylsilane, dichloro Diethylsilane, dichloromethylsilane, dichloroethylsilane, chlorotrimethylsilane, chlorotriethylsilane, chlorodimethylsilane, chlorodiethylsilane, chloromethylsilane, chloroethyl, t-butylchlorodimethylsilane, t-butylchlorodiethylsilane haloalkyl silane compounds Etc.
アルコキシシラン化合物の具体的な例としては、例えば、テトラメトキシシラン、テトラエトキシシラン、トリメトキシシラン、トリエトキシシラン、ジメトキシシラン、ジエトキシシラン、メトキシシラン、エトキシシランなどのアルコキシ系シラン化合物;ジメトキシメチルシラン、ジエトキシメチルシラン、ジメトキシエチルシラン、ジエトキシエチルシラン、メトキシジメチルシラン、エトキシジメチルシラン、メトキシジエチルシラン、エトキシジエチルシラなどのアルコキシアルキル系シラン化合物が挙げられる。中でも、反応速度の点から、ケイ素原子に4個のアルコキシ基が結合したテトラアルコキシシランが好ましく、特にテトラメトキシシラン(TMOS)、テトラエトキシシラン(TEOS)が好ましい。 Specific examples of the alkoxysilane compound include, for example, alkoxy silane compounds such as tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane, dimethoxysilane, diethoxysilane, methoxysilane, and ethoxysilane; Examples thereof include alkoxyalkyl silane compounds such as silane, diethoxymethylsilane, dimethoxyethylsilane, diethoxyethylsilane, methoxydimethylsilane, ethoxydimethylsilane, methoxydiethylsilane, and ethoxydiethylsila. Among these, from the viewpoint of reaction rate, tetraalkoxysilane in which four alkoxy groups are bonded to a silicon atom is preferable, and tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) are particularly preferable.
シリカ被膜の厚さは、特に制限されないが、シリカ被膜に設けられる孔が分子ふるい的な機能をより発揮しやすくするために、0.3〜8nm程度(好ましくは0.5〜5nm程度)が好ましい。 The thickness of the silica coating is not particularly limited, but is preferably about 0.3 to 8 nm (preferably about 0.5 to 5 nm) so that the pores provided in the silica coating can more easily exert a molecular sieve function. preferable.
シリカ被膜の厚さは、被膜の形成に用いる組成物中のシラン系化合物の量を調整することにより制御することができる。例えば、酸化チタン粒子として商品名「AMT−600」(比表面積:59m2/g、平均粒子径:0.030μm、テイカ社製):6gを、シラン系化合物であるテトラメトキシシラン:6.12gとテトラメトキシシランの2倍モル量の水とを用いて、テトラメトキシシランの加水分解・縮合重合反応を完了させて酸化チタン粒子表面をシリカコーティングすると、そのシリカ被膜の厚さは、2nm程度である。 The thickness of the silica coating can be controlled by adjusting the amount of the silane compound in the composition used for forming the coating. For example, the trade name “AMT-600” (specific surface area: 59 m 2 / g, average particle size: 0.030 μm, manufactured by Teica): 6 g as titanium oxide particles: tetramethoxysilane, which is a silane compound, 6.12 g When the titanium oxide particle surface is silica-coated by completing the hydrolysis / condensation polymerization reaction of tetramethoxysilane using 2 times the molar amount of water of tetramethoxysilane, the thickness of the silica film is about 2 nm. is there.
多孔性シリカ被膜被覆酸化チタン光触媒の孔は、酸化チタン粒子表面を極性基を有する化合物で処理した後にシラン系化合物でコーティング処理することにより得られるシリカ被膜から、極性基を有する化合物を除去することにより形成される。なお、シリカ被膜は酸化チタン粒子表面に担持する形態で極性基を有する化合物を包含するため、形成される孔は、シリカ被膜を貫通する孔である。 The pores of the porous silica coating-coated titanium oxide photocatalyst are to remove compounds having polar groups from the silica coating obtained by coating the surface of titanium oxide particles with a compound having polar groups and then coating with a silane compound. It is formed by. In addition, since the silica film contains the compound which has a polar group in the form carry | supported on the titanium oxide particle surface, the hole formed is a hole which penetrates a silica film.
このような孔は、酸化チタン粒子表面に担持する状態でシリカに覆われている極性基を有する化合物(鋳型分子)をシリカ被膜から除去すること[有機分子で鋳型を取ること(分子インプリティング)]により形成されるため、極性基を有する化合物の大きさ及び形状に合った大きさ及び形状の空洞を有することとなる。 Such pores can be removed by removing a compound (template molecule) having a polar group covered with silica in a state of being supported on the surface of the titanium oxide particles from the silica film [Taking a template with an organic molecule (molecular implementation). Therefore, a cavity having a size and a shape that matches the size and shape of the compound having a polar group is provided.
多孔性シリカ被膜被覆酸化チタン光触媒は、極性基を有する化合物の大きさ及び形状に合った大きさ及び形状を有する孔を有することにより、分子選択性を発揮する。また、多孔性シリカ被膜被覆酸化チタン光触媒は、極性基を有する化合物の大きさ及び形状を調整することによって孔の大きさ及び形状を制御することができるため、極性基を有する化合物(鋳型分子)を選択することにより、さまざまな有機化合物に対する分子識別能を備えることができる。 The porous silica coating-coated titanium oxide photocatalyst exhibits molecular selectivity by having pores having a size and shape that match the size and shape of the compound having a polar group. In addition, since the porous silica coating-coated titanium oxide photocatalyst can control the size and shape of the pores by adjusting the size and shape of the compound having a polar group, the compound having a polar group (template molecule) By selecting, it is possible to provide molecular discrimination ability for various organic compounds.
特に、極性基を有する化合物として前記R−Xで表される化合物を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、Rの分子構造を含む有機化合物を含む混合基質において、Rの分子構造を含む有機化合物に対して分子選択性を有する。 In particular, the porous silica coating-coated titanium oxide photocatalyst using the compound represented by R—X as a compound having a polar group includes a molecular structure of R in a mixed substrate including an organic compound including the molecular structure of R. Has molecular selectivity for organic compounds.
例えば、極性基を有する化合物として1−ナフタレンカルボン酸を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、1−ナフタレンメタノールと9−フルオレニルメタノールの混合基質において、1−ナフタレンメタノールに対して分子選択性を発揮する。また、極性基を有する化合物としてフェノールやアニリン、安息香酸等を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、o−キシレン、m−キシレン、p−キシレンの混合基質下において、p−キシレンに対して分子選択性を発揮する。 For example, a porous silica coating-coated titanium oxide photocatalyst using 1-naphthalenecarboxylic acid as a compound having a polar group is a molecule with respect to 1-naphthalenemethanol in a mixed substrate of 1-naphthalenemethanol and 9-fluorenylmethanol. Exhibits selectivity. In addition, a porous silica coating-coated titanium oxide photocatalyst using phenol, aniline, benzoic acid or the like as a compound having a polar group is based on p-xylene under a mixed substrate of o-xylene, m-xylene, and p-xylene. Show molecular selectivity.
酸化チタン粒子表面に担持する形態で極性基を有する化合物(鋳型分子)を包含するシリカ被膜から、極性基を有する化合物を除去する処理は、極性基を有する化合物(鋳型分子)の大きさ及び形状に合った大きさ及び形状の空洞を有することにより分子選択性を発揮する孔を、シリカ被膜に形成することを目的とする処理である。このような極性基を有する化合物を除去する処理は、特に制限されないが、例えば洗浄処理[例えば、極性基を有する化合物(鋳型分子)が酸性基を有する場合におけるアルカリ水溶液(例えば1%アンモニア水など)による洗浄、極性基を有する化合物(鋳型分子)が塩基性基を有する場合における酸水溶液(例えば0.1N塩酸水溶液、1%酢酸水溶液など)による洗浄など]、焼成処理等が挙げられる。 The treatment for removing a compound having a polar group from a silica coating containing a compound having a polar group (template molecule) in a form supported on the surface of the titanium oxide particles is the size and shape of the compound having a polar group (template molecule). This is a treatment aimed at forming pores that exhibit molecular selectivity by having a cavity with a size and shape suitable for the silica coating. The treatment for removing such a compound having a polar group is not particularly limited. For example, a washing treatment [for example, an alkaline aqueous solution (for example, 1% ammonia water or the like when the compound having a polar group (template molecule) has an acidic group) ), Washing with an acid aqueous solution (for example, 0.1N hydrochloric acid aqueous solution, 1% acetic acid aqueous solution, etc.) in the case where the compound having a polar group (template molecule) has a basic group], a baking treatment, and the like.
なお、高い分子選択性を発揮する孔を得るためには、細孔形成の際に孔がつぶれてしまうことを防止したり、規則正しく制御された貫通孔を形成することが必要である。従って、前記極性基を有する化合物を除去する処理としては、焼結により孔がふさがるおそれのある焼成処理よりは、洗浄処理の方が好ましい。 In order to obtain pores exhibiting high molecular selectivity, it is necessary to prevent the pores from being crushed during pore formation or to form regularly controlled through-holes. Accordingly, the treatment for removing the compound having a polar group is preferably a washing treatment rather than a firing treatment in which pores may be blocked by sintering.
多孔性シリカ被膜被覆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。また、多孔性シリカ被膜で被覆されているため、そのまま有機素材中に混合したとしても、有機素材が分解するという問題が生じることはない。 The porous silica-coated titanium oxide photocatalyst 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, etc.) and sterilization. Moreover, since it is covered with a porous silica film, even if it is mixed in the organic material as it is, there is no problem that the organic material is decomposed.
本発明の多孔性シリカ被膜被覆酸化チタン光触媒を用いた有機化合物の酸化方法は、前記多孔性シリカ被膜被覆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により酸化することを特徴としている。 The method for oxidizing an organic compound using the porous silica-coated titanium oxide photocatalyst of the present invention is characterized in that an organic compound having an oxidizable site is oxidized by light irradiation in the presence of the porous silica-coated titanium oxide photocatalyst. It is said.
被酸化部位を有する有機化合物としては、例えば、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、炭素−ヘテロ原子二重結合を有する化合物、メチン炭素原子を有する化合物、不飽和結合の隣接位に炭素−水素結合を有する化合物、非芳香族性環状炭化水素、共役化合物、アミン類、芳香族化合物、直鎖状アルカン、オレフィン類等が挙げられる。 Examples of the organic compound having an oxidizable site include a heteroatom-containing compound having a carbon-hydrogen bond adjacent to a heteroatom, a compound having a carbon-heteroatom double bond, a compound having a methine carbon atom, and an unsaturated bond. And compounds having a carbon-hydrogen bond at the adjacent position, non-aromatic cyclic hydrocarbons, conjugated compounds, amines, aromatic compounds, linear alkanes, olefins and the like.
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としては、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、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、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。 Examples of the heteroatom-containing compound having a carbon-hydrogen bond adjacent to the heteroatom include a primary or secondary alcohol or primary or secondary thiol, and an ether having a carbon-hydrogen bond adjacent to the oxygen atom. Or a sulfide having a carbon-hydrogen bond adjacent to a sulfur atom, an acetal (including hemiacetal) having a carbon-hydrogen bond adjacent to an oxygen atom, or a thioacetal having a carbon-hydrogen bond adjacent to a sulfur atom ( Examples include thiohemiacetal).
前記炭素−ヘテロ原子二重結合を有する化合物としては、カルボニル基含有化合物、チオカルボニル基含有化合物、イミン類などが挙げられる。 Examples of the compound having a carbon-heteroatom double bond include a carbonyl group-containing compound, a thiocarbonyl group-containing compound, and imines.
前記メチン炭素原子を有する化合物には、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、メチン炭素原子を有する鎖状化合物が含まれる。 The compound having a methine carbon atom includes a cyclic compound having a methine group (that is, a methine carbon-hydrogen bond) as a ring structural unit, and a chain compound having a methine carbon atom.
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としては、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、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。 Examples of the compound having a carbon-hydrogen bond adjacent to the unsaturated bond include an aromatic compound having a methyl group or a methylene group adjacent to the aromatic ring (so-called benzyl position), an unsaturated bond (for example, carbon- A non-aromatic compound having a methyl group or a methylene group at a position adjacent to a carbon unsaturated bond, a carbon-oxygen double bond, or the like.
前記非芳香族性環状炭化水素には、シクロアルカン類及びシクロアルケン類が含まれる。また、アダマンタン骨格を有する化合物などの橋かけ環式不飽和炭化水素類も含まれる。 The non-aromatic cyclic hydrocarbon includes cycloalkanes and cycloalkenes. Also included are bridged cyclic unsaturated hydrocarbons such as compounds having an adamantane skeleton.
前記共役化合物には、共役ジエン類、α,β−不飽和ニトリル、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)などが挙げられる。 Examples of the conjugated compound include conjugated dienes, α, β-unsaturated nitriles, α, β-unsaturated carboxylic acids or derivatives thereof (for example, esters, amides, acid anhydrides, and the like).
前記アミン類としては、第1級または第2級アミンなどが挙げられる。 Examples of the amines include primary or secondary amines.
前記芳香族炭化水素としては、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 include aromatic compounds having at least one benzene ring, preferably condensed polycyclic aromatic compounds in which a plurality of (for example, 2 to 10) benzene rings are condensed. .
前記直鎖状アルカンとしては、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 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 may be any of α-olefins and internal olefins which may have a substituent (for example, the above-described substituents such as hydroxyl group and acyloxy group), and carbon such as diene. -Olefins having multiple carbon double bonds 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.
このような酸化方法において、多孔性シリカ被膜被覆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0.5〜10重量部、好ましくは0.7〜8重量部程度、より好ましくは1〜5重量部程度である。 In such an oxidation method, the amount of the porous silica coating-coated titanium oxide photocatalyst used is, for example, 0.5 to 10 parts by weight, preferably 0.7 to 8 parts by weight with respect to 100 parts by weight of the organic compound used as the substrate. About 1 to 5 parts by weight.
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。 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.
また、多孔性シリカ被膜被覆酸化チタン光触媒を用いて基質としての有機化合物を光照射下で酸化する際、分子状酸素、過酸化物等を併用してもよい。 Further, when an organic compound as a substrate is oxidized under light irradiation using a porous silica coating-coated titanium oxide photocatalyst, molecular oxygen, peroxide, or the like may be used in combination.
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.
なお、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。 Although only one of molecular oxygen and peroxide may be used, the reaction rate may be significantly improved by combining molecular oxygen and peroxide.
酸化反応は、溶媒存在下で行ってもよい。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 oxidation reaction may be 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、アルコールからは対応するカルボニル化合物(ケトン、アルデヒド)やカルボン酸等、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 carbonyl compound (ketone, aldehyde) or carboxylic acid is generated from alcohol, and a corresponding carboxylic acid is generated from 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.
また、極性基を有する化合物として前記R−Xで表される化合物を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、有機基Rの分子構造を含む有機化合物を含む混合基質において、有機基Rの分子構造を含む有機化合物の被酸化部位に対して選択的に酸化する。高い分子選択性を発揮する細孔を有するためである。 In addition, the porous silica coating-coated titanium oxide photocatalyst using the compound represented by R—X as the compound having a polar group is a mixed substrate containing an organic compound having a molecular structure of the organic group R. It selectively oxidizes with respect to the site to be oxidized of an organic compound containing a molecular structure. This is because it has pores that exhibit high molecular selectivity.
例えば、極性基を有する化合物として1−ナフタレンカルボン酸を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、1−ナフタレンメタノールと9−フルオレニルメタノールの混合基質において、1−ナフタレンメタノールを選択的に酸化することができる。また、極性基を有する化合物としてフェノールやアニリン、安息香酸等を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、o−キシレン、m−キシレン、p−キシレンの混合基質下において、p−キシレンを選択的に酸化することができる。 For example, a porous silica coating-coated titanium oxide photocatalyst using 1-naphthalene carboxylic acid as a compound having a polar group is selected from 1-naphthalene methanol selectively in a mixed substrate of 1-naphthalene methanol and 9-fluorenyl methanol. Can be oxidized. The porous silica coating-coated titanium oxide photocatalyst using phenol, aniline, benzoic acid or the like as the compound having a polar group is selected from p-xylene under a mixed substrate of o-xylene, m-xylene, and p-xylene. Can be oxidized.
また、極性基を有する化合物としてフェノールやアニリン、安息香酸等を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、基質としてデュレンを用いた場合、4つ全てのメチル基を全て酸化してピロメリト酸(ベンゼン−1,2,4,5−テトラカルボン酸)を形成することはなく、 特定部位のメチル基のみを酸化することができる。 In addition, when a porous silica coating-coated titanium oxide photocatalyst using phenol, aniline, benzoic acid or the like as a compound having a polar group is used, when durene is used as a substrate, all four methyl groups are oxidized and pyromellitic acid ( Benzene-1,2,4,5-tetracarboxylic acid), and only the methyl group at a specific site can be oxidized.
さらに、極性基を有する化合物としてアダマンタン骨格を有する化合物を用いた多孔性シリカ被膜被覆酸化チタン光触媒は、例えば基質として各種置換基を有するアダマンタン化合物の混合物を用いた場合、特定のアダマンタン化合物のみを酸化することができ、また、基質として一種の多置換アダマンタン化合物を用いた場合、多置換アダマンタン化合物の特定の部位のみを酸化することができる。 Furthermore, a porous silica film-coated titanium oxide photocatalyst using a compound having an adamantane skeleton as a compound having a polar group, for example, oxidizes only a specific adamantane compound when a mixture of adamantane compounds having various substituents is used as a substrate. In addition, when a kind of polysubstituted adamantane compound is used as a substrate, only a specific portion of the polysubstituted adamantane compound can be oxidized.
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、多孔性シリカ被膜被覆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. In addition, the porous silica coating-coated 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)
100mlのエタノールに、鋳型分子としての1−ナフタレンカルボン酸(1−NC):0.637gを溶解させてから、酸化チタン粒子(比表面積:59m2/g、平均粒子径:0.030μm、商品名「AMT−600」テイカ社製):6gを投入し、1時間撹拌してから、テトラメトキシシラン(TMOS):0.765gを添加して、さらに2時間撹拌した。その後、テトラメトキシシランの2倍モル量の水を加えて、テトラメトキシシランの加水分解・縮合重合反応を完了させて、酸化チタン粒子表面をシリカコーティングした。次に、遠心分離して、上澄みを取り除き、得られた粒末を、エタノール中で攪拌することにより洗浄して、真空乾燥した。その後、鋳型分子を取り除くために、1%アンモニア水中で2時間撹拌を行い、さらにイオン水中で1時間撹拌して洗浄を行った。その後、遠心分離して、真空乾燥することにより、シリカコーティング酸化チタン粒子を得た。
Example 1
After dissolving 0.637 g of 1-naphthalenecarboxylic acid (1-NC) as a template molecule in 100 ml of ethanol, titanium oxide particles (specific surface area: 59 m 2 / g, average particle size: 0.030 μm, product) Name “AMT-600” manufactured by Teica): 6 g was added and stirred for 1 hour, then tetramethoxysilane (TMOS): 0.765 g was added, and the mixture was further stirred for 2 hours. After that, water twice the amount of tetramethoxysilane was added to complete the hydrolysis / condensation polymerization reaction of tetramethoxysilane, and the surface of the titanium oxide particles was coated with silica. Next, the mixture was centrifuged to remove the supernatant, and the obtained powder was washed by stirring in ethanol and vacuum dried. Thereafter, in order to remove the template molecules, the mixture was stirred in 1% ammonia water for 2 hours, and further washed in ion water for 1 hour. Then, the silica coating titanium oxide particle was obtained by centrifuging and vacuum-drying.
(実施例2)
テトラメトキシシラン(TMOS):3.06gを添加したこと以外は、実施例1と同様にして、シリカコーティング酸化チタン粒子を得た。
(Example 2)
Tetramethoxysilane (TMOS): Silica-coated titanium oxide particles were obtained in the same manner as in Example 1 except that 3.06 g was added.
(実施例3)
テトラメトキシシラン(TMOS):6.12gを添加したこと以外は、実施例1と同様にして、シリカコーティング酸化チタン粒子を得た。
(Example 3)
Tetramethoxysilane (TMOS): Silica-coated titanium oxide particles were obtained in the same manner as in Example 1 except that 6.12 g was added.
(実施例4)
テトラメトキシシラン(TMOS):12.24gを添加したこと以外は、実施例1と同様にして、シリカコーティング酸化チタン粒子を得た。
Example 4
Silica-coated titanium oxide particles were obtained in the same manner as in Example 1 except that tetramethoxysilane (TMOS): 12.24 g was added.
(比較例1)
100mlのエタノールに、酸化チタン粒子(比表面積:59m2/g、平均粒子径:0.030μm、商品名「AMT−600」テイカ社製):6gを投入し、1時間撹拌してから、テトラメトキシシラン(TMOS):0.765gを添加して、さらに2時間撹拌した。その後、テトラメトキシシランの2倍モル量の水を加えて、テトラメトキシシランの加水分解・縮合重合反応を完了させて、酸化チタン粒子表面をシリカコーティングした。次に、遠心分離して、上澄みを取り除き、得られた粒末を、エタノール中で攪拌することにより洗浄し、真空乾燥することにより、シリカコーティング酸化チタン粒子を得た。
(Comparative Example 1)
In 100 ml of ethanol, 6 g of titanium oxide particles (specific surface area: 59 m 2 / g, average particle size: 0.030 μm, trade name “AMT-600” manufactured by Teica) was added and stirred for 1 hour. Methoxysilane (TMOS): 0.765 g was added, and the mixture was further stirred for 2 hours. After that, water twice the amount of tetramethoxysilane was added to complete the hydrolysis / condensation polymerization reaction of tetramethoxysilane, and the surface of the titanium oxide particles was coated with silica. Next, the mixture was centrifuged to remove the supernatant, and the resulting powder was washed by stirring in ethanol and vacuum-dried to obtain silica-coated titanium oxide particles.
(比較例2)
テトラメトキシシラン(TMOS):3.06gを添加したこと以外は、比較例1と同様にして、シリカコーティング酸化チタン粒子を得た。
(Comparative Example 2)
Tetramethoxysilane (TMOS): Silica-coated titanium oxide particles were obtained in the same manner as Comparative Example 1 except that 3.06 g was added.
(比較例3)
テトラメトキシシラン(TMOS):6.12gを添加したこと以外は、比較例1と同様にして、シリカコーティング酸化チタン粒子を得た。
(Comparative Example 3)
Tetramethoxysilane (TMOS): Silica-coated titanium oxide particles were obtained in the same manner as in Comparative Example 1 except that 6.12 g was added.
(比較例4)
テトラメトキシシラン(TMOS):12.24gを添加したこと以外は、比較例1と同様にして、シリカコーティング酸化チタン粒子を得た。
(Comparative Example 4)
Silica-coated titanium oxide particles were obtained in the same manner as Comparative Example 1, except that tetramethoxysilane (TMOS): 12.24 g was added.
(参考例1)
酸化チタン粒子として、商品名「AMT−600」(比表面積:59m2/g、平均粒子径:0.030μm、テイカ社製)をそのまま使用した。
(Reference Example 1)
As titanium oxide particles, the trade name “AMT-600” (specific surface area: 59 m 2 / g, average particle size: 0.030 μm, manufactured by Teica) was used as it was.
(評価)
実施例、比較例、及び参考例の酸化チタン粒子に対して、下記の(評価1)〜(評価3)を行うことにより、触媒としての評価を行った。
(Evaluation)
Evaluation as a catalyst was performed by performing the following (Evaluation 1) to (Evaluation 3) on the titanium oxide particles of Examples, Comparative Examples, and Reference Examples.
(評価1)
単独基質の条件下で、酸化チタン粒子の基質選択性について評価した。具体的には、1−ナフタレンメタノールに対する活性評価及び9−フルオレニルメタノールに対する活性評価を、それぞれ行った。なお、各基質の濃度の減少量より、触媒の有する活性を評価することができる。
(Evaluation 1)
The substrate selectivity of titanium oxide particles was evaluated under the condition of a single substrate. Specifically, activity evaluation for 1-naphthalenemethanol and activity evaluation for 9-fluorenylmethanol were performed, respectively. The activity of the catalyst can be evaluated from the amount of decrease in the concentration of each substrate.
(1−ナフタレンメタノールに対する活性評価)
酸化チタン粒子:100mgと1−ナフタレンメタノール:20mMとを、パイレックス(登録商標)試験管に入れ、常圧、空気雰囲気下、25℃にて、攪拌を行いながら、水銀ランプを用いて光照射(250mW/cm2、1時間)を行った。その後、遠心分離で酸化チタン粒子を除去し、ガスクロマトグラフィーを用いて、1−ナフタレンメタノールの減少量を求め、さらに、下記式(1)から、参考例1の減少量に対する実施例及び比較例の減少量の相対値も求めた。これらの結果を表1の1−ナフタレンメタノールの欄に示した。なお、触媒を添加せずに、水銀ランプを用いて光照射(250mW/cm2、1時間)を行っても、1−ナフタレンメタノールの減少や新たな生成物の生成はみられなかった。
(Evaluation of activity against 1-naphthalenemethanol)
Titanium oxide particles: 100 mg and 1-naphthalenemethanol: 20 mM are placed in a Pyrex (registered trademark) test tube and irradiated with light using a mercury lamp while stirring at 25 ° C. under normal pressure and air atmosphere ( 250 mW / cm 2 , 1 hour). Thereafter, the titanium oxide particles were removed by centrifugation, and the amount of 1-naphthalenemethanol was determined using gas chromatography. Further, from the following formula (1), Examples and Comparative Examples for the amount of decrease in Reference Example 1 The relative value of the amount of decrease was also determined. These results are shown in the column of 1-naphthalenemethanol in Table 1. In addition, even if light irradiation (250 mW / cm < 2 >, 1 hour) was performed using the mercury lamp without adding a catalyst, the reduction | decrease of 1-naphthalene methanol and the production | generation of a new product were not seen.
(9−フルオレニルメタノールに対する活性評価)
酸化チタン粒子:100mgと9−フルオレニルメタノール:10mMとを、パイレックス試験管(登録商標)に入れ、常圧、空気雰囲気下、25℃にて、攪拌を行いながら、水銀ランプを用いて光照射(250mW/cm2、1時間)を行った。その後、遠心分離で酸化チタン粒子を除去し、ガスクロマトグラフィーを用いて、9−フルオレニルメタノールの減少量を求め、さらに、下記式(1)から参考例1の減少量に対する実施例及び比較例の減少量の相対値も求めた。これらの結果を表1の9−フルオレニルメタノールの欄に示した。なお、触媒を添加せずに、水銀ランプを用いて光照射(250mW/cm2、1時間)を行っても、9−フルオレニルメタノールの減少や新たな生成物の生成はみられなかった。
(Evaluation of activity against 9-fluorenylmethanol)
Titanium oxide particles: 100 mg and 9-fluorenylmethanol: 10 mM are placed in a Pyrex test tube (registered trademark), and light is emitted using a mercury lamp while stirring at 25 ° C. under normal pressure and air atmosphere. Irradiation (250 mW / cm 2 , 1 hour) was performed. Thereafter, the titanium oxide particles were removed by centrifugation, and the amount of 9-fluorenylmethanol was determined using gas chromatography. Further, Examples and comparisons for the amount of decrease in Reference Example 1 from the following formula (1) The relative value of the reduction amount of the example was also obtained. These results are shown in the column of 9-fluorenylmethanol in Table 1. In addition, even if light irradiation (250 mW / cm < 2 >, 1 hour) was performed using the mercury lamp without adding a catalyst, the reduction | decrease of 9-fluorenyl methanol and the production | generation of a new product were not seen. .
参考例1の基質減少量に対する実施例及び比較例の基質減少量の相対値は、実施例及び比較例の相対値=(実施例及び比較例の基質減少量)/(参考例1の基質減少量)[式(1)]から求めた。 The relative value of the substrate reduction amount of the example and the comparative example with respect to the substrate reduction amount of the reference example 1 is the relative value of the example and the comparative example = (the substrate reduction amount of the example and the comparative example) / (the substrate reduction of the reference example 1). Amount) Obtained from [Equation (1)].
表1より、両基質ともに、参考例1の酸化チタン粒子(シリカコーティングを行っていない酸化チタン粒子)の活性が最もよく、実施例、比較例の順に活性が低下するという共通の傾向が見られた。このため、実施例のシリカコーティング酸化チタン粒子には、鋳型分子としての1−ナフタレンカルボン酸を除去することにより、シリカ被膜に孔が形成されていることが確認できた。
また、実施例のシリカコーティング酸化チタン粒子は、9−フルオレニルメタノールに比べて、1−ナフタレンメタノールに対してより作用していることも確認できた。このことから、鋳型分子としての1−ナフタレンカルボン酸に対してより構造の近い1−ナフタレンメタノールに対する選択性を有することが確認できた。
From Table 1, the activity of the titanium oxide particles of Reference Example 1 (titanium oxide particles not subjected to silica coating) is the best for both substrates, and there is a common tendency that the activity decreases in the order of Examples and Comparative Examples. It was. For this reason, in the silica-coated titanium oxide particles of the examples, it was confirmed that pores were formed in the silica coating by removing 1-naphthalenecarboxylic acid as a template molecule.
Moreover, it has also confirmed that the silica coating titanium oxide particle of an Example was acting more with respect to 1-naphthalene methanol than 9-fluorenyl methanol. From this, it was confirmed that it had selectivity for 1-naphthalenemethanol having a closer structure to 1-naphthalenecarboxylic acid as a template molecule.
(評価2)
混合基質下で、酸化チタン粒子の基質選択性について評価した。
(Evaluation 2)
The substrate selectivity of titanium oxide particles was evaluated under a mixed substrate.
酸化チタン粒子:100mgと混合基質(1−ナフタレンメタノール:10mM、9−フルオレルメタノール:10mM)とを、パイレックス(登録商標)試験管に入れ、常圧、空気雰囲気下、25℃にて、攪拌を行いながら、水銀ランプを用いて光照射(250mW/cm2、1時間)を行い、それぞれの基質濃度の変化を測定した。1−ナフタレンメタノール及び9−フルオレルメタノールの60分後の濃度から、1−ナフタレンメタノール、9−フルオレルメタノールの減少量をそれぞれ求め、さらに、上記式(1)から、1−ナフタレンメタノール及び9−フルオレルメタノールについて、参考例1の減少量に対する実施例及び比較例の減少量の相対値も求めた。これらの結果を表2に示した。なお、触媒を添加せずに、水銀ランプを用いて光照射(250mW/cm2、1時間)を行っても、基質の減少や新たな生成物の生成はみられなかった。 Titanium oxide particles: 100 mg and mixed substrate (1-naphthalenemethanol: 10 mM, 9-fluormethanolmethanol: 10 mM) are placed in a Pyrex (registered trademark) test tube and stirred at 25 ° C. under normal pressure and air atmosphere. Then, light irradiation (250 mW / cm 2 , 1 hour) was performed using a mercury lamp, and changes in the respective substrate concentrations were measured. Decrease amounts of 1-naphthalenemethanol and 9-fluormethanol were determined from the concentrations of 1-naphthalenemethanol and 9-fluormethanol after 60 minutes, respectively, and from the above formula (1), 1-naphthalenemethanol and 9 -The relative value of the amount of reduction of the Example and the comparative example with respect to the amount of reduction of Reference Example 1 was also determined for fluorethanol methanol. These results are shown in Table 2. In addition, even when light irradiation (250 mW / cm 2 , 1 hour) was performed using a mercury lamp without adding a catalyst, no reduction of the substrate or generation of a new product was observed.
両基質(1−ナフタレンメタノール、9−フルオレルメタノール)に対して、参考例1(シリカコーティングなし)、実施例1(TMOS添加量:0.765g)、実施例2(TMOS添加量:3.06g)、実施例4(TMOS添加量:12.24g)の順、すなわち添加するシラン系化合物の量を増加させるにつれて、基質の濃度が低下しない傾向がみられた。このため、添加するシラン系化合物の量を増加させるにつれて、触媒活性が低下することが確認できた。
また、実施例1は、参考例1に対して、1−ナフタレンメタノールで相対値0.89、9−フルオレニルメタノールで相対値0.75の活性を示した。このため、TMOSの添加量が0.765gでは、鋳型分子としての1−ナフタレンカルボン酸により、空洞はできているものの、一部の空洞は、鋳型分子としての1−ナフタレンカルボン酸の形状及び大きさに合った形状及び大きさを有しない(鋳型分子によるインプリントがみられない)と考えられる。
さらに、実施例3、実施例4とTMOSの添加量を増加させた場合、9−フルオレニルメタノールに対しては対応する比較例とほぼ同様の活性を示す一方で、1−ナフタレンメタノールに対しては、参考例1と比較すると活性は低いものの、ある程度の活性は維持していた。特に、実施例4では、1−ナフタレンメタノールと9−フルオレニルメタノールの相対値が約4.3倍となり大きな反応性の差を示した。よって、混合基質下でも、鋳型分子としての1−ナフタレンカルボン酸に対してより構造の近い1−ナフタレンメタノールに対する選択性を有することが確認できた。
For both substrates (1-naphthalenemethanol, 9-fluormethanol), Reference Example 1 (no silica coating), Example 1 (TMOS addition amount: 0.765 g), Example 2 (TMOS addition amount: 3. 06 g) and Example 4 (TMOS addition amount: 12.24 g), that is, as the amount of the silane compound to be added was increased, the substrate concentration tended not to decrease. For this reason, it was confirmed that the catalytic activity decreased as the amount of the silane compound to be added was increased.
In addition, Example 1 showed an activity with respect to Reference Example 1 having a relative value of 0.89 for 1-naphthalenemethanol and a relative value of 0.75 for 9-fluorenylmethanol. For this reason, when the amount of TMOS added is 0.765 g, a cavity is formed by 1-naphthalenecarboxylic acid as a template molecule, but a part of the cavity has a shape and a size of 1-naphthalenecarboxylic acid as a template molecule. It is considered that the shape and size are not suitable (imprint by template molecule is not seen).
Furthermore, when the addition amount of Example 3 and Example 4 and TMOS was increased, 9-fluorenylmethanol showed almost the same activity as the corresponding comparative example, whereas 1-naphthalenemethanol As compared with Reference Example 1, the activity was low, but a certain level of activity was maintained. In particular, in Example 4, the relative value of 1-naphthalenemethanol and 9-fluorenylmethanol was about 4.3 times, indicating a large difference in reactivity. Therefore, even under a mixed substrate, it was confirmed that it had selectivity for 1-naphthalenemethanol having a closer structure to 1-naphthalenecarboxylic acid as a template molecule.
(評価3)
混合基質下で、酸化チタン粒子による基質の酸化反応について評価した。
(Evaluation 3)
Under the mixed substrate, the oxidation reaction of the substrate by the titanium oxide particles was evaluated.
酸化チタン粒子:100mgと混合基質(1−ナフタレンメタノール:10mM、9−フルオレルメタノール:10mM)とを、パイレックス(登録商標)試験管に入れ、常圧、空気雰囲気下、25℃にて、攪拌を行いながら、水銀ランプを用いて光照射(250mW/cm2、1時間)を行った。その後、遠心分離で酸化チタン粒子を除去し、ガスクロマトグラフィーを用いて、1−ナフタレンメタノールの減少量、及び1−ナフタレンカルバルデヒド(1−ナフタレンメタナール)の生成量を求めた。これらの結果は、表3に示した。なお、触媒を添加せずに、水銀ランプを用いて光照射(250mW/cm2、1時間)を行っても、1−ナフタレンメタノールの減少や新たな生成物の生成はみられなかった。 Titanium oxide particles: 100 mg and mixed substrate (1-naphthalenemethanol: 10 mM, 9-fluormethanolmethanol: 10 mM) are placed in a Pyrex (registered trademark) test tube and stirred at 25 ° C. under normal pressure and air atmosphere. Then, light irradiation (250 mW / cm 2 , 1 hour) was performed using a mercury lamp. Thereafter, the titanium oxide particles were removed by centrifugation, and the amount of 1-naphthalenemethanol and the amount of 1-naphthalenecarbaldehyde (1-naphthalenemethanal) produced were determined using gas chromatography. These results are shown in Table 3. In addition, even if light irradiation (250 mW / cm < 2 >, 1 hour) was performed using the mercury lamp without adding a catalyst, the reduction | decrease of 1-naphthalene methanol and the production | generation of a new product were not seen.
TMOSの添加量が増えるにつれて活性が低下する傾向がみられた。 The activity tended to decrease as the amount of TMOS added increased.
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