JP5194249B2 - Composite porous body, method for producing the same, and organic substance conversion method using the same - Google Patents
Composite porous body, method for producing the same, and organic substance conversion method using the same Download PDFInfo
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- JP5194249B2 JP5194249B2 JP2004311071A JP2004311071A JP5194249B2 JP 5194249 B2 JP5194249 B2 JP 5194249B2 JP 2004311071 A JP2004311071 A JP 2004311071A JP 2004311071 A JP2004311071 A JP 2004311071A JP 5194249 B2 JP5194249 B2 JP 5194249B2
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- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 description 1
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- 229910004613 CdTe Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
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- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 description 1
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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Images
Description
本発明は、複合多孔体およびこれを用いた有機物質変換方法に関し、特に環境浄化や水中の有害物質除去に有用な複合多孔体および有機物質変換方法に関するものである。 The present invention relates to a composite porous body and an organic substance conversion method using the same, and more particularly to a composite porous body and an organic substance conversion method useful for environmental purification and removal of harmful substances in water.
環境問題への関心が高まり、地球規模での環境保全が叫ばれる中、産業活動に伴い廃棄される種々の有害化学物質が問題となっている。上記有害化学物質としては、例えば、内分泌攪乱物質（以下、環境ホルモンという。）や有機塩素化合物などの難分解性物質が挙げられ、これらは河川等の水環境から検出されている。特に、環境ホルモンであるノニルフェノールなどのアルキルフェノール群は、微量でも内分泌攪乱性を有するため、生態系に対する影響が懸念されている。このような状況を鑑み、廃水処理、浄化プロセスにおいて高性能な浄化を行い、これらの物質を除去することが求められている。 As interest in environmental issues increases and environmental conservation on a global scale is called out, various hazardous chemical substances that are disposed of along with industrial activities have become a problem. Examples of the harmful chemical substances include persistent degradable substances such as endocrine disrupting substances (hereinafter referred to as environmental hormones) and organochlorine compounds, which are detected from the water environment such as rivers. In particular, alkylphenol groups such as nonylphenol, which is an environmental hormone, have endocrine disrupting properties even in trace amounts, and there is concern about the impact on the ecosystem. In view of such a situation, it is required to perform high-performance purification in a wastewater treatment and purification process to remove these substances.
従来の浄化技術としては、有害物質を分解する方法や、多孔体等で吸着して除去する方法がある。有害物質を分解する方法としては、活性汚泥を用いる方法、触媒を用いた湿式酸化法、オゾンによる酸化除去法、光触媒法が挙げられる。 Conventional purification techniques include a method of decomposing toxic substances and a method of adsorbing and removing with a porous material. Examples of methods for decomposing toxic substances include a method using activated sludge, a wet oxidation method using a catalyst, an oxidation removal method using ozone, and a photocatalyst method.
活性汚泥法は、汚泥中の微生物の作用を利用して有機物を分解し除去する方法である。湿式酸化法は、貴金属触媒などの共存下、酸素又は他の酸化剤を用いて有機物を酸化し分解するものである。オゾン酸化法は、オゾンの酸化力を利用して有機物を水中で酸化し分解して除去する。光触媒法は、半導体系の光触媒に光を照射し触媒表面で水から生成するヒドロキシラジカル等の作用により有機物を分解して除去する。 The activated sludge method is a method for decomposing and removing organic substances using the action of microorganisms in the sludge. In the wet oxidation method, an organic substance is oxidized and decomposed using oxygen or another oxidizing agent in the presence of a noble metal catalyst or the like. In the ozone oxidation method, organic matter is oxidized in water using the oxidizing power of ozone and decomposed to be removed. In the photocatalytic method, a semiconductor photocatalyst is irradiated with light, and organic substances are decomposed and removed by the action of hydroxy radicals or the like generated from water on the catalyst surface.
そして、さらに吸着・分解を組み合わせて除去効果を高める方法として、吸着作用のある多孔体表面に光触媒を担持させる方法が提案されている（特許文献１〜６参照）。担持の方法としては、特許文献１には、ＲＦスパッタリング法や蒸着、イオンプレーティングの方法が記載されており、特許文献２〜５には、多孔体に光触媒を含浸あるいはコーティングさせて加熱焼成する方法が記載されている。また、特許文献６には、ファンデルワールス力によって凝集したシリカ粒子に、焼結により膜状の光触媒成分を担持させることが記載されている。
しかしながら、特許文献１〜６の方法のような、多孔体の表面に光触媒をコーティングする方法で、吸着・分解作用を有する光触媒複合体を製造しようとすると、光触媒物質を多孔体に１０重量％より多く担持させることができず、十分な触媒作用が得られなかった。また、光触媒の担持量を調節することができず、触媒作用の強さを調節することもできなかった。
However, when a photocatalyst complex having an adsorption / decomposition action is produced by a method of coating a photocatalyst on the surface of a porous material, such as the methods of
また、光触媒を多孔体にコーティングした場合は、光触媒物質の結晶が乱れ、本来の分解能を発揮できないという問題もあった。 Further, when the photocatalyst is coated on the porous body, there is a problem that the crystal of the photocatalytic substance is disturbed and the original resolution cannot be exhibited.
本発明は、上記問題点に鑑みなされたものであり、その目的は、多孔体に、高い結晶性を保ちながら多量の固体微粒子を担持した複合多孔体およびその製造方法、並びにそれを用いた有機物質変換方法を提供することにある。 The present invention has been made in view of the above problems, and its object is to provide a composite porous body in which a large amount of solid fine particles are supported while maintaining high crystallinity on the porous body, a method for producing the same, and an organic material using the same. It is to provide a material conversion method.
本発明者らはこのような課題を解決するために、多孔体形成後に固体微粒子を付与するのでなく、多孔体の骨格が形成される前に、多孔体の原料もしくは多孔体が生成する溶液、ゾル、ゲル等の合成媒体に固体微粒子を混ぜ込んで、固体微粒子を含んだ多孔体を形成することで、より良好な有機物質の吸着・分解機能を有する複合多孔体が製造できることを見出した。 In order to solve such problems, the present inventors do not give solid fine particles after the formation of the porous body, but before the porous body skeleton is formed, the porous material or the solution in which the porous body is generated, It has been found that a composite porous body having a better function of adsorbing and decomposing organic substances can be produced by mixing solid fine particles in a synthesis medium such as sol and gel to form a porous body containing solid fine particles.
すなわち、本発明の複合多孔体の製造方法は、液体、ゾル、またはゲル状の合成媒体中で、複合多孔体を形成する複合多孔体の製造方法であって、多孔体の骨格が生成する前に合成媒体に固体微粒子を混合分散させる工程と、固体微粒子が分散した合成媒体中で、多孔体の骨格を生成させることにより多孔体と固体微粒子とが複合化した複合多孔体を形成させる工程と、を含むことを特徴としている。 That is, the method for producing a composite porous body of the present invention is a method for producing a composite porous body that forms a composite porous body in a liquid, sol, or gel-like synthetic medium before the skeleton of the porous body is generated. A step of mixing and dispersing solid fine particles in a synthetic medium, and a step of forming a composite porous body in which the porous body and the solid fine particles are complexed by generating a porous skeleton in the synthetic medium in which the solid fine particles are dispersed. It is characterized by including.
ここで、「合成媒体」とは、液体またはゾル、ゲルの中で多孔体を形成する場合の、液体、ゾル、もしくはゲルを指す。 Here, the “synthetic medium” refers to a liquid, sol, or gel when a porous body is formed in the liquid, sol, or gel.
これによれば、多孔体の原料が固化成形される前の合成媒体に固体微粒子が混合されているので、固体微粒子が合成媒体中に分散して存在し、この合成溶媒中で多孔体の原料が固化されることで、固体微粒子と多孔体とが複合化した、つまり多孔体と固体微粒子とが一体的に結合した複合多孔体が形成される。 According to this, since the solid fine particles are mixed in the synthetic medium before the porous raw material is solidified and formed, the solid fine particles are dispersed in the synthetic medium, and the porous raw material is contained in this synthetic solvent. Is solidified to form a composite porous body in which the solid fine particles and the porous body are combined, that is, the porous body and the solid fine particles are integrally bonded.
なお、多孔体の材料は、固体微粒子が添加される前の合成媒体に含まれていてもよく、固体微粒子を分散させた後に、合成媒体に添加してもよい。 The porous material may be included in the synthesis medium before the solid fine particles are added, or may be added to the synthesis medium after the solid fine particles are dispersed.
これにより、簡単な製造手順で多孔体と固体微粒子との複合体が形成できるとともに、多孔体の表面積に関わらず、所望の量の固体微粒子を多孔体に付与できる。 Thereby, a complex of the porous body and the solid fine particles can be formed by a simple manufacturing procedure, and a desired amount of the solid fine particles can be imparted to the porous body regardless of the surface area of the porous body.
また、このような方法で複合化することで、多量に固体微粒子を付与しても多孔体の細孔構造が保たれ、さらに、多孔体成形後に固体微粒子を付加する場合と比べ、固体微粒子の結晶構造が良好になるので、その機能が損なわれることがない。 In addition, by compositing in this way, the pore structure of the porous body is maintained even when a large amount of solid fine particles are applied. Since the crystal structure becomes good, its function is not impaired.
なお、上記固体微粒子が光触媒機能を有するものであれば、複合多孔体は、多孔体で吸着された有機物質を固体微粒子が他の物質へ変換するので、有害な有機物質の除去あるいは有機物質からの有用物質の合成が可能となる。このとき、多孔体と親和性が高い有機分子が、多孔体に選択的に吸着、変換されるので、分子選択的な変換機能が実現できる。 If the solid fine particles have a photocatalytic function, the composite porous body converts organic substances adsorbed by the porous bodies into other substances, so that harmful organic substances can be removed or removed from organic substances. This makes it possible to synthesize useful substances. At this time, organic molecules having high affinity with the porous body are selectively adsorbed and converted to the porous body, so that a molecular selective conversion function can be realized.
さらに、上記方法で製造することにより、固体微粒子を多孔体細孔表面に付着させる工程が必要なくなるとともに、多孔体の表面積に関わらず、所望の量の固体微粒子を多孔体に付与でき、所望の有機物質変換能力を多孔体に付与することができる。 Furthermore, the production by the above method eliminates the need for the step of adhering the solid fine particles to the surface of the porous material pores, and can impart a desired amount of solid fine particles to the porous material regardless of the surface area of the porous material. Organic substance conversion ability can be imparted to the porous body.
また、このような方法で複合化することで、多孔体の細孔構造が保たれ、さらに、固体微粒子の結晶構造が良好になるので、有機物の吸着・変換性能も向上する。 In addition, by combining in this manner, the pore structure of the porous body is maintained, and further, the crystal structure of the solid fine particles is improved, so that the adsorption / conversion performance of organic matter is improved.
上記混合工程においては、超音波をかけて固体微粒子を分散させることで、混合液中に固体微粒子が良好に分散し、均等に固体微粒子が分散した複合多孔体を製造できる。 In the mixing step, by applying the ultrasonic wave to disperse the solid fine particles, a composite porous body in which the solid fine particles are well dispersed in the mixed liquid and the solid fine particles are uniformly dispersed can be produced.
上記固体微粒子としては二酸化チタンを使用することがより好ましい。これによれば、多孔体に吸着された有機物質を良好に他の物質に変換することができる。 More preferably, titanium dioxide is used as the solid fine particles. According to this, the organic substance adsorbed on the porous body can be favorably converted into another substance.
また、上記固体微粒子の平均粒径が、２ｎｍ以上５００００ｎｍ以下であれば、良好に固体微粒子を多孔体に複合化できる。 Moreover, when the average particle diameter of the solid fine particles is 2 nm or more and 50000 nm or less, the solid fine particles can be favorably combined with the porous body.
光触媒などでは固体微粒子の表面積が大きい方が好ましい。この観点からは微粒子の粒径は小さい方がよい。また、光触媒では微粒子の結晶性が高いほうが好ましく、この観点からは、微粒子の粒径は小さすぎない方がよい。光触媒としての用途ならば、微粒子径はさらに好ましくは、２ｎｍ以上５０００ｎｍ以下、さらに好ましくは、５ｎｍ以上１０００ｎｍ以下である。 In the case of a photocatalyst or the like, it is preferable that the solid fine particles have a large surface area. From this viewpoint, it is preferable that the particle diameter of the fine particles is small. In addition, in the photocatalyst, it is preferable that the crystallinity of the fine particles is high. From this viewpoint, the particle diameter of the fine particles should not be too small. For use as a photocatalyst, the fine particle diameter is more preferably 2 nm to 5000 nm, and still more preferably 5 nm to 1000 nm.
また、上記固体微粒子の添加量は、多孔体の原料と固体微粒子との合計量に対して、１０重量％以上であることが望ましい。これによれば、複合多孔体に含まれる固体微粒子の量が十分に多くなるので、固体微粒子の機能が良好に発揮される。例えば、固体微粒子が光触媒機能を有する物質である場合、有害な有機物質の除去や化合物の変換が効果的に行える。 The amount of the solid fine particles added is desirably 10% by weight or more based on the total amount of the porous material and the solid fine particles. According to this, since the amount of the solid fine particles contained in the composite porous body is sufficiently increased, the function of the solid fine particles is satisfactorily exhibited. For example, when the solid fine particles are a substance having a photocatalytic function, it is possible to effectively remove harmful organic substances and convert compounds.
上記多孔体は、多孔質シリカ、合成ゼオライト、多孔質アルミナ、多孔質シリカアルミナから選ばれる少なくとも１つの多孔体であることが好ましく、メソ多孔質シリカ、あるいはメソ多孔質シリカアルミナであることがより好ましい。これによれば、良好な吸着機能を有する複合多孔体が製造できる。 The porous body is preferably at least one porous body selected from porous silica, synthetic zeolite, porous alumina, and porous silica alumina, more preferably mesoporous silica or mesoporous silica alumina. preferable. According to this, the composite porous body which has a favorable adsorption function can be manufactured.
また、上記多孔体が、平均細孔直径が０．５ｎｍ以上１００ｎｍ以下の多孔体であること、好ましくは、平均細孔直径が１．５ｎｍ以上であることにより良好な吸着機能を有する複合多孔体が製造できる。 In addition, the porous body is a porous body having an average pore diameter of 0.5 nm or more and 100 nm or less, preferably a composite porous body having a good adsorption function when the average pore diameter is 1.5 nm or more. Can be manufactured.
また、本発明の複合多孔体は、上記製造方法により製造されているので、所望の量の固体微粒子を多孔体に付与できる。したがって、固体微粒子の機能が良好に発揮できる複合多孔体となる。
Moreover, since the composite porous body of this invention is manufactured by the said manufacturing method, a desired quantity of solid microparticles | fine-particles can be provided to a porous body. Therefore, it becomes a composite porous body in which the function of the solid fine particles can be satisfactorily exhibited.
また、本発明の複合多孔体は、多孔体の細孔直径よりも大きい直径固体微粒子を含ませることができる。従来の方法では、多孔体生成後に複合化を行うため、細孔径より大きな微粒子は複合化できない。このため、微粒子の結晶性が乱れやすく、高い光触媒活性が得られない。また、本発明の方法では、多孔体の細孔径や表面積に制限されることなく、固体微粒子の粒径や含有量を自由に選択することができる。 Moreover, the composite porous body of the present invention can contain solid particles having a diameter larger than the pore diameter of the porous body. In the conventional method, since the composite is performed after the production of the porous body, fine particles larger than the pore diameter cannot be combined. For this reason, the crystallinity of the fine particles tends to be disturbed, and high photocatalytic activity cannot be obtained. In the method of the present invention, the particle size and content of the solid fine particles can be freely selected without being limited by the pore size and surface area of the porous body.
本発明の有機物質変換方法は、上記複合多孔体を試料液と接触させ、固体微粒子にその固体微粒子を活性化する波長領域の光を照射することにより、試料液中の有機物質を反応させるものである。 In the organic substance conversion method of the present invention, the composite porous body is brought into contact with a sample liquid, and the organic substance in the sample liquid is reacted by irradiating the solid fine particles with light in a wavelength region that activates the solid fine particles. It is.
これによれば、上記複合多孔体が試料液に接触することで、試料液中の有機物質が多孔体に吸着され、固体微粒子に光をあてて活性化することで、固体微粒子により試料中の有機物質が他の物質に変換される。したがって、有害な有機物質の除去あるいは、有機物質からの有用物質の合成を、効果的に行うことができる。このとき、多孔体と親和性が高い有機分子が、多孔体に選択的に吸着、変換されるので、分子選択的な変換機能が実現できる。 According to this, when the composite porous body comes into contact with the sample liquid, the organic substance in the sample liquid is adsorbed by the porous body, and is activated by applying light to the solid fine particles. Organic substances are converted into other substances. Therefore, it is possible to effectively remove harmful organic substances or synthesize useful substances from organic substances. At this time, organic molecules having high affinity with the porous body are selectively adsorbed and converted to the porous body, so that a molecular selective conversion function can be realized.
本発明の複合多孔体の製造方法は、以上のように、液体、ゾル、またはゲル状の合成媒体中で、複合多孔体を形成する複合多孔体の製造方法であって、多孔体の骨格が生成する前に合成媒体に固体微粒子を混合分散させる工程と、固体微粒子が分散した合成媒体中で、多孔体の骨格を生成させることにより多孔体と固体微粒子とが複合化した複合多孔体を形成させる工程と、を含んでいる。それゆえ、複合多孔体に固体微粒子を任意の量だけ含有させられる。また、多孔体成形後に固体微粒子を付加する場合と比べ、固体微粒子の結晶性が良好になる。よって、固体微粒子の機能を良好に発揮できる。
As described above, the method for producing a composite porous body of the present invention is a method for producing a composite porous body that forms a composite porous body in a liquid, sol, or gel-like synthetic medium. A process of mixing and dispersing solid particles in a synthetic medium before production, and forming a composite porous material in which the porous material and solid particles are combined by generating a porous skeleton in the synthetic medium in which the solid particles are dispersed And a step of causing. Therefore, the composite porous body can contain solid fine particles in an arbitrary amount. Further, the crystallinity of the solid fine particles is improved as compared with the case where the solid fine particles are added after forming the porous body. Therefore, the function of the solid fine particles can be exhibited well.
また、本発明の複合多孔体は、以上のように、多孔体と、多孔体の細孔直径よりも大きい直径の固体微粒子と、を含むものである。従来の方法では、多孔体生成後に複合化を行うため、細孔径より大きな微粒子は複合化できない。このため、微粒子の結晶性が乱れやすく、高い光触媒活性が得られない。しかし、本発明の方法では、多孔体の細孔径や表面積に制限されることなく、固体微粒子の粒径や含有量を自由に選択することができる。 In addition, the composite porous body of the present invention includes the porous body and solid fine particles having a diameter larger than the pore diameter of the porous body as described above. In the conventional method, since the composite is performed after the production of the porous body, fine particles larger than the pore diameter cannot be combined. For this reason, the crystallinity of the fine particles tends to be disturbed, and high photocatalytic activity cannot be obtained. However, in the method of the present invention, the particle size and content of the solid fine particles can be freely selected without being limited by the pore size and surface area of the porous body.
また、本発明の有機物質変換方法は、上記複合多孔体を試料液と接触させ、上記複合多孔体にその固体微粒子を活性化する波長領域の光を照射することにより、上記試料液中の有害物質を分解している。これによれば、上記複合多孔体が試料液に接触することで、多孔体に有機物質が吸着され、固体微粒子に光を当てて活性化することで、吸着した有機物質が効果的に他の物質に変換される。このとき、多孔体と親和性が高い有機分子が、多孔体に選択的に吸着、変換されるので、分子選択的な変換機能が実現できる。 Further, the organic substance conversion method of the present invention is a method in which the composite porous body is brought into contact with a sample liquid, and the composite porous body is irradiated with light in a wavelength region that activates the solid fine particles, thereby causing harmful effects in the sample liquid. Decomposing the material. According to this, when the composite porous body comes into contact with the sample liquid, the organic substance is adsorbed on the porous body, and the solid organic fine particles are activated by irradiating the light with the solid fine particles. Converted into substance. At this time, organic molecules having high affinity with the porous body are selectively adsorbed and converted to the porous body, so that a molecular selective conversion function can be realized.
本発明の複合多孔体の製造方法は、多孔体が固化形成される前の、多孔体の原料が液体の状態で固体微粒子と混合・分散させ、多孔体の原料を固化させることで複合多孔体を製造する方法である。このようにして製造された複合多孔体は、複合多孔体に固体微粒子を任意の量を含有させられ、また、多孔体成形後に固体微粒子を付加する場合と比べ、固体微粒子の結晶性が良好になる。 The method for producing a composite porous body according to the present invention comprises mixing and dispersing the porous raw material with solid fine particles in a liquid state before the porous body is solidified to solidify the porous raw material. It is a method of manufacturing. The composite porous body produced in this way can contain an arbitrary amount of solid fine particles in the composite porous body, and the solid fine particles have better crystallinity than the case where solid fine particles are added after forming the porous body. Become.
本発明の複合多孔体の製造方法は、主に、混合工程と、形成工程とに分けられる。 The method for producing a composite porous body of the present invention is mainly divided into a mixing step and a forming step.
上記混合工程では、液体、ゾル、またはゲル状の合成媒体に、固体微粒子を混合する。このとき、多孔体の原料は、固体微粒子を混合する前にあらかじめ合成媒体に添加されていてもよく、固体微粒子混合後に添加していても構わない。 In the mixing step, solid fine particles are mixed in a liquid, sol, or gel-like synthesis medium. At this time, the raw material of the porous body may be added to the synthesis medium in advance before mixing the solid fine particles, or may be added after mixing the solid fine particles.
上記多孔体の原料としては、多孔体を形成するものであれば特に限られるものではないが、テトラエトキシシランのような金属アルコキシドやケイ酸ナトリウムのような金属塩、その他金属酢酸塩やアセチルアセトン錯体などの有機金属化合物や、これらを含むゾルやゲルが挙げられる。 The raw material of the porous body is not particularly limited as long as it forms a porous body, but metal alkoxide such as tetraethoxysilane, metal salt such as sodium silicate, other metal acetates and acetylacetone complexes. And organic metal compounds such as sols and gels containing them.
また、金属酸化物などの固体微粒子を多孔体原料として用いることもできる。この微粒子は、複合化する微粒子とは異なり、合成媒体内でいったん溶解し、多孔体の骨格を形成する原料となる。 Also, solid fine particles such as metal oxides can be used as the porous material. Unlike fine particles to be combined, these fine particles are once dissolved in a synthesis medium and become a raw material for forming a porous skeleton.
また、この多孔体の原料は、金属酸化物からなる多孔体、多孔質シリカ、ゼオライト、多孔質アルミナ、シリカアルミナ等からなる多孔体、あるいは、これらの混合物からなる多孔体を形成できる材料が挙げられ、特にシリカアルミナの多孔体を形成するものが好ましい。中でも、有機物を鋳型として合成される無機多孔体、特にメソ多孔体が、特に好ましい。その理由は、細孔径が均質となり、特定の分子を吸着する分子選択性が発現しやすいからである。 Examples of the raw material for the porous body include materials capable of forming a porous body made of a metal oxide, a porous body made of porous silica, zeolite, porous alumina, silica alumina, or the like, or a porous body made of a mixture thereof. In particular, those that form a porous body of silica alumina are preferred. Among them, an inorganic porous material synthesized using an organic material as a template, particularly a mesoporous material is particularly preferable. The reason is that the pore diameter is uniform, and the molecular selectivity for adsorbing specific molecules is easily developed.
また、上記固体微粒子としては、マグネシア、アルミナ、シリカ、リン酸アルミニウム、ホウ素、炭素、窒化シリコン、窒化アルミニウムなど無機の酸化物、塩化物、窒化物、ホウ化物、炭化物、硫化物などのほか、ポリエチレンなどの樹脂の粒子など、有機物を用いることも可能であるが、特に光触媒機能を有する微粒子であることが好ましい。光触媒機能を有する微粒子（以下、光触媒微粒子）としては、半導体としての特性を有し光触媒特性を持つとされるものであれば、あらゆるものが使用可能である。なかでも、金属硫化物や金属酸化物が好ましく、チタニア、ジルコニア、酸化ニオブ、酸化タングステン等の金属酸化物が最も好ましい。具体的なものとしては、ＴｉＯ2，ＳｒＴｉＯ3，ＷＯ3，Ｆｅ2Ｏ3，Ｂｉ2Ｏ3，ＭｏＳ2，ＣｄＳ，ＣｄＳｅ，ＧａＰ，ＧａＡｓ，ＭｏＳｅ2，ＣｄＴｅ，Ｎｂ2Ｏ5，Ｔａ2Ｏ5，ＮｂとＴａの複合酸化物の他、Ｈ3ＰＷ12Ｏ40やＨ3ＰＭｏ12Ｏ40などのヘテロポリ酸及びそれらの塩などを挙げることができる。なかでも、光触媒活性が高いことが知られているＴｉＯ2（二酸化チタン）が好ましい。なお、光触媒粒子としては、凝集していない細かい粒子状のもの（例えば独デグサ社製のＰ−２５）を用いることが好ましい。
The solid fine particles include magnesia, alumina, silica, aluminum phosphate, boron, carbon, silicon nitride, aluminum nitride and other inorganic oxides, chlorides, nitrides, borides, carbides, sulfides, etc. Although organic substances such as resin particles such as polyethylene can be used, fine particles having a photocatalytic function are particularly preferable. Any fine particles having a photocatalytic function (hereinafter referred to as photocatalyst fine particles) may be used as long as they have characteristics as a semiconductor and have photocatalytic characteristics. Of these, metal sulfides and metal oxides are preferable, and metal oxides such as titania, zirconia, niobium oxide, and tungsten oxide are most preferable. Specific ones, TiO 2, SrTiO 3, WO 3, Fe 2
固体微粒子としては、平均粒径が２ｎｍ以上５００００ｎｍ以下の細孔を形成するものであることが好ましい。下限としては、５ｎｍ以上がより好ましく、１０ｎｍ以上がさらに好ましい。上限としては、５０００ｎｍ以下がより好ましく、１０００ｎｍ以下がさらに好ましい。 The solid fine particles preferably form pores having an average particle diameter of 2 nm or more and 50000 nm or less. As a minimum, 5 nm or more is more preferable, and 10 nm or more is further more preferable. As an upper limit, 5000 nm or less is more preferable, and 1000 nm or less is further more preferable.
固体微粒子の平均直径が上記範囲より小さいと微粒子の結晶性が悪くなり、光触媒活性が低くなる。上記範囲より大きいと微粒子の表面積が小さくなるため、やはり触媒活性が低くなる。 If the average diameter of the solid fine particles is smaller than the above range, the crystallinity of the fine particles is deteriorated and the photocatalytic activity is lowered. If it is larger than the above range, the surface area of the fine particles becomes small, so that the catalytic activity is also lowered.
固体微粒子の添加割合は、多孔体の原料と固体微粒子との合計量に対して、１０重量％以上であることが好ましく、２０重量％以上にするのがより好ましく、５０重量％以上にするのが好ましい。上限としては９８重量％以下にするのがより好ましく、９５重量％以下にするのがさらに好ましい。これにより、固体微粒子が良好かつ効果的に機能を発揮する。 The addition ratio of the solid fine particles is preferably 10% by weight or more, more preferably 20% by weight or more, and more preferably 50% by weight or more based on the total amount of the porous material and the solid fine particles. Is preferred. The upper limit is more preferably 98% by weight or less, and still more preferably 95% by weight or less. Thereby, a solid fine particle exhibits a function effectively and effectively.
固体微粒子が光触媒粒子である場合、含有量が１０重量％以下であると、複合多孔体の有機物質を変換する能力が十分でなく、有害な有機物質の除去や有用物質の合成が十分に行えない。また、光触媒粒子は上記範囲より多く含ませても、効果をそれ以上に向上させることはできないので、コストの面から上記上限より小さくすることが好ましい。 When the solid fine particles are photocatalyst particles, if the content is 10% by weight or less, the ability to convert the organic material of the composite porous body is not sufficient, and the removal of harmful organic materials and the synthesis of useful materials can be sufficiently performed. Absent. Moreover, even if it contains more photocatalyst particles than the said range, since an effect cannot be improved more than it, it is preferable to make it smaller than the said upper limit from the surface of cost.
なお、混合工程では、この他に水等の溶媒や、ｐＨを調節するための酸および塩基、微粒子の分散性や多孔体との親和性を向上させるための界面活性剤等を加えてもよい。 In addition, in the mixing step, a solvent such as water, an acid and a base for adjusting the pH, a surfactant for improving the dispersibility of the fine particles and the affinity with the porous body may be added. .
また、混合工程においては、固体微粒子に超音波をかけることにより、より良好に固体微粒子が混合液に分散させるようにしてもよい。 In the mixing step, the solid fine particles may be more favorably dispersed in the mixed liquid by applying ultrasonic waves to the solid fine particles.
次に、形成工程にて、多孔体の原料を固化して、固体微粒子が複合化した多孔体を成形する。 Next, in the forming step, the raw material of the porous body is solidified to form a porous body in which the solid fine particles are combined.
ここで、多孔体の原料を固化することで、複合多孔体が固化し、多孔体の骨格を形成させることで、複合多孔体が固体として成形される。多孔体の骨格を形成させる反応条件は多孔体や原料の種類により様々であり、それぞれに適した条件が選ばれる。例えば、テトラエトキシシランを原料にシリカ多孔体を合成するときは、水の存在下、室温〜８０℃程度で行われる。ケイ酸塩を含むゲルから多孔体を合成する場合は、耐圧容器（オートクレーブ）を用いて、１００℃〜１５０℃の温度で水熱合成される。また、多孔体の骨格を形成させるときには、鋳型となる有機化合物を共存させてもよい。特に、メソ多孔シリカやシリカアルミナを多孔体として用いる場合は、直鎖アルキル基を持つ界面活性剤が鋳型剤としてよく用いられる。 Here, by solidifying the raw material of the porous body, the composite porous body is solidified, and by forming a skeleton of the porous body, the composite porous body is formed as a solid. The reaction conditions for forming the skeleton of the porous body vary depending on the type of the porous body and the raw material, and conditions suitable for each are selected. For example, when a silica porous body is synthesized using tetraethoxysilane as a raw material, it is performed at room temperature to about 80 ° C. in the presence of water. When a porous body is synthesized from a gel containing silicate, hydrothermal synthesis is performed at a temperature of 100 ° C. to 150 ° C. using a pressure vessel (autoclave). Moreover, when forming the skeleton of the porous body, an organic compound as a template may coexist. In particular, when mesoporous silica or silica alumina is used as a porous body, a surfactant having a linear alkyl group is often used as a template agent.
得られた複合多孔体は、有機物や鋳型剤を取り除くために焼成されることが多い。このとき、加熱焼成の時間や温度は、多孔体が良好に形成できるように適宜設定すればよい。例えば、温度は、多孔体材料が１５０℃以上、より好ましくは２５０℃以上となるようにすればよい。また、上限としては１０００℃以下、より好ましくは８００℃以下とすればよい。焼成の時間としては、１時間から１０時間程度が好ましい。 The obtained composite porous body is often baked to remove organic substances and templating agents. At this time, the time and temperature for heating and firing may be appropriately set so that the porous body can be formed satisfactorily. For example, the temperature of the porous material may be 150 ° C. or higher, more preferably 250 ° C. or higher. The upper limit may be 1000 ° C. or lower, more preferably 800 ° C. or lower. The firing time is preferably about 1 to 10 hours.
以上のような工程で製造された複合多孔体は、固体微粒子の含有割合が多くても、多孔体の細孔が保たれており、固体微粒子の結晶も崩れていないので、効果的に有機物質の変換等の機能を発揮する複合多孔体となる。しかも、多孔体の細孔構造が崩れていないので、有機物質を吸着する機能をも有する。 The composite porous body produced by the above-described process effectively maintains the pores of the porous body even if the content ratio of the solid fine particles is large, and the crystals of the solid fine particles are not broken. It becomes a composite porous body that exhibits functions such as conversion. Moreover, since the pore structure of the porous body is not broken, it also has a function of adsorbing organic substances.
この多孔体としては、平均細孔直径が０．５ｎｍ以上１００ｎｍ以下であることが好ましい。下限としては、１ｎｍ以上がより好ましく、１．５ｎｍ以上がさらに好ましい。上限としては、５０ｎｍ以下がより好ましく、１０ｎｍ以下がさらに好ましい。多孔体の細孔の平均直径が上記範囲より小さくても、大きくても、有機物質の吸着を良好に行うことができない。なお、実施例に用いたような比較的小さい分子が吸着対象であれば、直径０．５ｎｍ-５００ｎｍ、さらに好ましくは１ｎｍ-５０ｎｍの範囲にある細孔を有する多孔体が通常用いられる。また、溶液の拡散を促進したり流路を確保する観点からは、上記より大きな細孔を含んでいた方が有利であり、上記のような細孔に加えて直径１マイクロメートル以上の大きな細孔を含む多孔体を用いることもできる。 The porous body preferably has an average pore diameter of 0.5 nm or more and 100 nm or less. As a minimum, 1 nm or more is more preferable, and 1.5 nm or more is further more preferable. As an upper limit, 50 nm or less is more preferable, and 10 nm or less is further more preferable. Even if the average diameter of the pores of the porous body is smaller or larger than the above range, the organic substance cannot be favorably adsorbed. If relatively small molecules such as those used in the examples are to be adsorbed, a porous body having pores having a diameter in the range of 0.5 nm to 500 nm, more preferably 1 nm to 50 nm is usually used. In addition, from the viewpoint of promoting the diffusion of the solution or securing the flow path, it is advantageous to include a larger pore than the above, and in addition to the above-described pore, a large fine particle having a diameter of 1 micrometer or more. A porous body containing pores can also be used.
また、上記した工程で製造された複合多孔体は、多孔体と、多孔体の細孔径よりも大きい固体微粒子と、を含んでいるので、固体微粒子の多孔体との接触面積が小さくても、より多くの固体微粒子を多孔体に担持できるようになる。また、固体微粒子が多孔体の細孔径よりも大きい場合、従来の、多孔体の細孔より小さい粒径の固体微粒子が、多孔体細孔内にコーティングされている場合と比べ、固体微粒子の結晶構造に与える影響が少ないので、固体微粒子の機能が良好に発揮させる。つまり、複合多孔体に含まれる固体微粒子の量が多く、多孔体、固体微粒子が良好に形成される複合多孔体となる。 In addition, since the composite porous body manufactured in the above-described process includes a porous body and solid fine particles larger than the pore diameter of the porous body, even if the contact area of the solid fine particles with the porous body is small, More solid fine particles can be supported on the porous body. Further, when the solid fine particles are larger than the pore diameter of the porous body, the solid fine particle crystals are smaller than the conventional case where the solid fine particles having a particle size smaller than the pores of the porous body are coated in the pores of the porous body. Since the influence on the structure is small, the function of the solid fine particles is exhibited well. That often amount of solid particles contained in the composite porous body, a porous body, a composite porous solid particles are satisfactorily formed.
この場合、多孔体細孔の直径が平均直径０．５ｎｍ以上１００ｎｍ以下であり、かつ、固体微粒子の平均粒径が２ｎｍ以上５００００ｎｍ以下であることが好ましく、多孔体細孔の直径が平均直径１ｎｍ以上１００ｎｍ以下であり、かつ、固体微粒子の平均粒径が１０ｎｍ以上５００ｎｍ以下であることがより好ましい。これにより、固体微粒子を良好に担持できる。 In this case, the diameter of the porous body pores is preferably 0.5 nm to 100 nm in average diameter, and the average particle diameter of the solid fine particles is preferably 2 nm to 50000 nm, and the diameter of the porous body pores is preferably 1 nm in average diameter. More preferably, the average particle size is 10 nm or more and 500 nm or less. Thereby, solid fine particles can be favorably supported.
そして、以上のような複合多孔体は、試料液に接触させながら固体微粒子を活性化する波長領域の光を照射されることで、試料液中の有機物質を変換できる。これにより、試料液中に含まれる有害な有機物質を除去することや、試料液中に含まれる有機物質から有用物質を合成することができる。 And the above composite porous body can convert the organic substance in a sample liquid by irradiating the light of the wavelength range which activates a solid fine particle, contacting a sample liquid. Thereby, harmful organic substances contained in the sample liquid can be removed, and useful substances can be synthesized from the organic substances contained in the sample liquid.
さらに、多孔体表面に、特定の有機物質と選択的に結合したり、親和性の高い有機基を付与することで、多孔体の選択的吸着能力を高めてもよい。 Furthermore, the selective adsorption ability of the porous body may be enhanced by selectively binding to a specific organic substance or imparting an organic group with high affinity to the surface of the porous body.
なお、本発明の複合多孔体の製造方法は、多孔体と、固体微粒子とを複合化した光触媒複合体の製造方法であって、溶媒に、多孔体の原料と、固体微粒子とを混合した混合液を製造する工程と、当該混合液中の多孔体原料を固化する工程、とを含むものであってもよい。 The method for producing a composite porous body of the present invention is a method for producing a photocatalyst composite in which a porous body and solid fine particles are composited, wherein a mixture of a porous material and solid fine particles in a solvent is mixed. It may include a step of producing a liquid and a step of solidifying the porous material in the mixed solution.
また、本発明の複合多孔体の製造方法は、固体として生成する前の多孔体の原料と、分散された固体微粒子と、を含む溶液を製造する工程と、当該溶液中の多孔体の原料を固化することで、多孔体と固体微粒子とを複合化した複合多孔体を形成する工程、とを含むものであってもよい。 Further, the method for producing a composite porous body of the present invention comprises a step of producing a solution containing a raw material of a porous body before being produced as a solid and dispersed solid fine particles, and a raw material of the porous body in the solution. And a step of forming a composite porous body in which the porous body and solid fine particles are composited by solidification.
なお、本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and can be obtained by appropriately combining technical means disclosed in different embodiments. Embodiments are also included in the technical scope of the present invention.
以下に、固体微粒子として光触媒粒子を使用した本発明を実施例によってさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention using photocatalyst particles as solid fine particles will be described in more detail by way of examples. However, the present invention is not limited to these examples.
〔製造方法〕
本実施例の複合多孔体の製造方法を図１を用いて説明する。
〔Production method〕
The manufacturing method of the composite porous body of a present Example is demonstrated using FIG.
多孔体の鋳型となる界面活性剤として、ヘキサデシルトリメチルアンモニウムブロミド（Ｃ１６ＴＭＡＢｒ）４．４ｇを脱イオン水２５０ｍｌに溶解した後、ＴｉＯ２粉末（Ｐ−２５（商品名）：アナターゼ型二酸化チタンとルチン型二酸化チタンの両方を成分として含む）を加え、超音波をかけて分散させた。このときの、Ｐ−２５の添加量は、０．８６ｇ、あるいは２．１ｇ、７．３ｇ、１９．５ｇの４種類のものを用意した。次に、アンモニア水を加えて溶液のｐＨを１１．８に調整した後、テトラエトキシシラン（Ｓｉ（ＯＣ２Ｈ５）４）を一気に加えた。これにより、テトラエトキシシランの加水分解が起こり上記界面活性剤のミセルの周りにシリカが形成された。 As a surfactant used as a porous material template, 4.4 g of hexadecyltrimethylammonium bromide (C16TMABr) is dissolved in 250 ml of deionized water, and then TiO 2 powder (P-25 (trade name): anatase type titanium dioxide and rutin. (Including both types of titanium dioxide as components) and dispersed by applying ultrasonic waves. The amount of P-25 added at this time was 0.86 g, or four types of 2.1 g, 7.3 g, and 19.5 g were prepared. Next, ammonia water was added to adjust the pH of the solution to 11.8, and then tetraethoxysilane (Si (OC 2 H 5 ) 4 ) was added all at once. As a result, hydrolysis of tetraethoxysilane occurred and silica was formed around the micelles of the surfactant.
この混合溶液を約１時間攪拌後、ろ過して生成物を回収し、一晩加熱乾燥した後、５４０℃で焼成して、メソ多孔体シリカ−ＴｉＯ２複合体（以下、ＭＰＳ−ＴｉＯ２）を得た。得られたＭＰＳ−ＴｉＯ２中のＴｉＯ２の含有量は、それぞれ、１５重量％、３０重量％、６０重量％、８０重量％である（以下、それぞれＭＰＳ−ＴｉＯ２（ｘｗｔ％）ｘ＝１５，３０，６０，８０と称する）。また、比較例として、上記製造方法において、Ｐ−２５を加えないメソ多孔体シリカ（以下ＭＰＳ）を合成した。 After stirring this mixed solution for about 1 hour, the product was collected by filtration, heated and dried overnight, and then calcined at 540 ° C. to obtain a mesoporous silica-TiO 2 composite (hereinafter referred to as MPS-TiO 2 ). Got. The contents of TiO 2 in the obtained MPS-TiO 2 are 15 wt%, 30 wt%, 60 wt%, and 80 wt%, respectively (hereinafter, MPS-TiO 2 (xwt%) x = 15, respectively). , 30, 60, 80). As a comparative example, mesoporous silica (hereinafter referred to as MPS) in which P-25 was not added in the above production method was synthesized.
上記した４種類のＭＰＳ−ＴｉＯ２、あるいは、ＭＰＳの窒素吸着を測定した結果を図２の吸着脱着等温線に示す。図２は、横軸が相対圧を、縦軸が窒素吸着量（１ｇあたりの吸着窒素の体積）を示している。これによると、ＴｉＯ２の含有量に関わらず、すべてのＭＰＳ−ＴｉＯ２で、メソ多孔体に特有の吸着脱着等温線（すなわち、相対圧０．３付近で毛管凝縮による吸着量の増加が見られ、それ以上の相対圧では吸着量の変化がほとんどない吸着脱着等温線）となっており、上記製造方法のＭＰＳ−ＴｉＯ２は、ＴｉＯ２の含有量を高めても、メソ多孔体の構造を保っていることを示していた。また、ＴｉＯ２の含有量が増えるにしたがって、細孔容量の減少が見られるが、これは単位重量あたりでのＭＰＳの割合が減少しているためである。 The adsorption / desorption isotherm of FIG. 2 shows the results of measuring the nitrogen adsorption of the above four types of MPS-TiO 2 or MPS. In FIG. 2, the horizontal axis represents the relative pressure, and the vertical axis represents the nitrogen adsorption amount (volume of adsorbed nitrogen per 1 g). According to this, regardless of the content of TiO 2, in all MPS-TiO 2, specific adsorption desorption isotherm mesoporous material (i.e., an increase in the adsorption amount by the capillary condensation in the vicinity of the relative pressure 0.3 see is has become more than a relative pressure and adsorption desorption isotherm) there is little change in the adsorption amount, MPS-TiO 2 of the manufacturing method described above, even if increasing the content of TiO 2, of the mesoporous structure It was shown that I kept it. In addition, as the content of TiO 2 increases, the pore volume decreases, because the ratio of MPS per unit weight decreases.
また、上記した４種類のＭＰＳ−ＴｉＯ２、あるいは、ＭＰＳの細孔半径の分布を調べた。これによると、ＴｉＯ２の含有量に関わらず、すべてのＭＰＳ−ＴｉＯ２で、２．６〜３．０ｎｍの細孔が形成されており、これからも、上記製造方法のＭＰＳ−ＴｉＯ２は、ＴｉＯ２の含有量を高めても、メソ多孔体の構造が保たれていることが示された。 Further, the distribution of the pore radius of the above four types of MPS-TiO 2 or MPS was examined. According to this, regardless of the content of TiO 2, in all MPS-TiO 2, pores 2.6~3.0nm is formed, from now, MPS-TiO 2 of the manufacturing method described above, It was shown that the structure of the mesoporous material was maintained even when the content of TiO 2 was increased.
さらに、上記した４種類のＭＰＳ−ＴｉＯ２およびＭＰＳのＸＲＤパターンを測定した。低角度側のＸＲＤパターン（図３（ａ））より、ピーク強度はＴｉＯ２含有量が増加するにつれて減少しているものの、ＭＰＳの細孔の配列に特有のピークが見られる。したがって、上記製造方法のＭＰＳ−ＴｉＯ２で細孔が保たれていることが分かる。一方、高角度側のＸＲＤパターン（図３（ｂ））では、Ｐ−２５に由来するＴｉＯ２の結晶のピークが観察できた。 Furthermore, the XRD patterns of the four types of MPS-TiO 2 and MPS described above were measured. From the XRD pattern on the low angle side (FIG. 3A), although the peak intensity decreases as the TiO 2 content increases, a peak peculiar to the MPS pore arrangement is seen. Therefore, it can be seen that pores in MPS-TiO 2 of the manufacturing method is maintained. On the other hand, in the XRD pattern on the high angle side (FIG. 3B), the peak of the TiO 2 crystal derived from P-25 could be observed.
以上の結果から、４種類のＭＰＳ−ＴｉＯ２は、いずれも、ＴｉＯ２粒子がメソ多孔シリカの内部に取り込まれた形で多孔体細孔を保ちながら複合化している事がわかる。 From the above results, it can be seen that all of the four types of MPS-TiO 2 are complexed while maintaining the porous pores in such a form that TiO 2 particles are taken into the mesoporous silica.
〔実験例１〕
上記のように製造した４種のＭＰＳ−ＴｉＯ２について、４−ｎ−プロピルフェノールと４−ｎ−ヘプチルフェノールとをほぼ等濃度で有する混合液３００ｍｌに対する吸着分解能を測定した。比較例として、ＭＰＳとＰ−２５を実施例と同量混合したものを用いた。
[Experimental Example 1]
About four MPS-TiO 2 prepared as described above was measured adsorption resolution for mixture 300ml and a 4-n-propyl-phenol and 4-n-heptyl phenol nearly equal concentrations. As a comparative example, a mixture of MPS and P-25 in the same amount as in the examples was used.
上記混合液に、ＭＰＳ−ＴｉＯ２（１５ｗｔ％）を３０ｍｇ投入し、３００Ｗのキセノンランプで光照射した場合の有機化合物の濃度変化を図４に示す。なお、横軸は光照射開始時を０時間とする時間経過である。これによると、両有機化合物の濃度が光照射直後から減少し始めた。また、減少速度は、４−ｎ−プロピルフェノールが３時間で７．５ｐｐｍから４ｐｐｍへ減少するのに対し、４−ｎ−ヘプチルフェノールが３時間で７ｐｐｍから０．５ｐｐｍへ減少し、４−ｎ−ヘプチルフェノールを選択に分解している事がわかる。 FIG. 4 shows changes in the concentration of the organic compound when 30 mg of MPS-TiO 2 (15 wt%) is added to the above mixed solution and irradiated with light from a 300 W xenon lamp. In addition, the horizontal axis represents a time lapse when the light irradiation start time is 0 hour. According to this, the concentrations of both organic compounds began to decrease immediately after light irradiation. The rate of decrease was such that 4-n-propylphenol decreased from 7.5 ppm to 4 ppm in 3 hours, while 4-n-heptylphenol decreased from 7 ppm to 0.5 ppm in 3 hours. -It can be seen that heptylphenol is selectively decomposed.
次に、上記混合液に、ＭＰＳ−ＴｉＯ２（３０ｗｔ％）を投入した場合の同様の濃度変化を図５（ａ）に示す。これも、４−ｎ−プロピルフェノールに比べ、４−ｎ−ヘプチルフェノールの減少速度が有意に早く、４−ｎ−ヘプチルフェノールを選択に分解していた。また、ＭＰＳ−ＴｉＯ２（１５ｗｔ％）よりも分解速度が速かった。 Next, FIG. 5A shows the same concentration change when MPS-TiO 2 (30 wt%) is added to the mixed solution. Again, the decrease rate of 4-n-heptylphenol was significantly faster than that of 4-n-propylphenol, and 4-n-heptylphenol was selectively decomposed. Moreover, the decomposition rate was faster than MPS-TiO 2 (15 wt%).
ここで、ＭＰＳ−ＴｉＯ２（３０ｗｔ％）の比較例として、ＭＰＳを２１ｍｇとＰ−２５を９ｍｇ（Ｐ−２５の量は全体の３０ｗｔ％となる）の混合物を投入した場合の、有機化合物の濃度変化を測定した（図５（ｂ））。この場合は、４−ｎ−プロピルフェノールと４−ｎ−ヘプチルフェノールとの減少速度にほとんど違いはなく、選択的分解は行われていなかった。つまり、Ｐ−２５を別々にではなく、本発明のように多孔体に複合させることで、４−ｎ−ヘプチルフェノールの分解を促進させる一方、４−ｎ−プロピルフェノールの分解を抑制する、という選択的分解が行われる。 Here, as a comparative example of MPS-TiO 2 (30 wt%), an organic compound in a case where a mixture of 21 mg of MPS and 9 mg of P-25 (the amount of P-25 is 30 wt% of the whole) is added. The concentration change was measured (FIG. 5 (b)). In this case, there was almost no difference in the decrease rate between 4-n-propylphenol and 4-n-heptylphenol, and selective decomposition was not performed. In other words, P-25 is not separated but combined with a porous body as in the present invention to promote the decomposition of 4-n-heptylphenol while suppressing the decomposition of 4-n-propylphenol. Selective decomposition is performed.
また、上記混合液に、ＭＰＳ−ＴｉＯ２（６０ｗｔ％）を投入した場合の有機化合物の濃度変化（図６）も、４−ｎ−プロピルフェノールに比べ、４−ｎ−ヘプチルフェノールの減少速度が有意に早く、４−ｎ−ヘプチルフェノールを選択に分解していた。また、ＭＰＳ−ＴｉＯ２（３０ｗｔ％）よりも分解速度が速かった。 Moreover, the concentration change of the organic compound when MPS-TiO 2 (60 wt%) was added to the above mixed solution (FIG. 6) also showed a decrease rate of 4-n-heptylphenol compared to 4-n-propylphenol. Significantly earlier, 4-n-heptylphenol was selectively degraded. Moreover, the decomposition rate was faster than MPS-TiO 2 (30 wt%).
上記混合液に、ＭＰＳ−ＴｉＯ２（８０ｗｔ％）を投入した場合の同様の濃度変化（図７（ａ））も、４−ｎ−プロピルフェノールに比べ、４−ｎ−ヘプチルフェノールの減少速度が有意に早く、４−ｎ−ヘプチルフェノールを選択に分解していた。また、ＭＰＳ−ＴｉＯ２（３０ｗｔ％）よりも分解速度が速く、ＭＰＳ−ＴｉＯ２（６０ｗｔ％）と同程度の分解速度であった。 The same concentration change (FIG. 7 (a)) when MPS-TiO 2 (80 wt%) was added to the above mixed solution also showed a decrease rate of 4-n-heptylphenol compared to 4-n-propylphenol. Significantly earlier, 4-n-heptylphenol was selectively degraded. Moreover, the decomposition rate was faster than MPS-TiO 2 (30 wt%), and the decomposition rate was similar to that of MPS-TiO 2 (60 wt%).
ここで、ＭＰＳ−ＴｉＯ２（８０ｗｔ％）の比較例として、ＭＰＳを６ｍｇとＰ−２５を２４ｍｇ（Ｐ−２５の量は全体の８０ｗｔ％となる）の混合物を投入した場合の、有機化合物の濃度変化を測定した（図７（ｂ））。これによると、４−ｎ−プロピルフェノールと４−ｎ−ヘプチルフェノールとの減少速度にほとんど違いはなく、選択的分解は行われていないことが分かる。 Here, as a comparative example of MPS-TiO 2 (80 wt%), an organic compound in a case where a mixture of 6 mg of MPS and 24 mg of P-25 (the amount of P-25 is 80 wt% of the whole) is added. The concentration change was measured (FIG. 7 (b)). According to this, it can be seen that there is almost no difference in the decrease rate between 4-n-propylphenol and 4-n-heptylphenol, and selective decomposition has not been performed.
以上の実験から、ＴｉＯ２は、多孔体と複合化することによって初めて分子選択的分解をし、その分解速度は含有するＴｉＯ２に比例して高まる傾向にあることが示された。 From the above experiments, TiO 2 is the first molecule selective degradation by composite porous body, the rate of degradation has been shown to tend to increase in proportion to the TiO 2 containing.
このような分子選択的分解の機構を探るため、４−ｎ−プロピルフェノールと４−ｎ−ヘプチルフェノールとに対する、ＭＰＳの吸着量を測定した。ここでは、混合水溶液７０ｍｌにＭＰＳ１００ｍｇを加え、吸着開始時と吸着平衡時との溶液濃度の差から吸着量を測定した。 In order to investigate the mechanism of such molecular selective decomposition, the amount of MPS adsorbed on 4-n-propylphenol and 4-n-heptylphenol was measured. Here, 100 mg of MPS was added to 70 ml of the mixed aqueous solution, and the amount of adsorption was measured from the difference in solution concentration at the start of adsorption and at the time of adsorption equilibrium.
これによると、４−ｎ−プロピルフェノールの、平衡濃度４．２０×１０−５ｍｏｌ／ｇの溶液での吸着量が約０．５×１０−５ｍｏｌ／ｇであったのに対し、４−ｎ−ヘプチルフェノールの、平衡濃度１．４０×１０−５ｍｏｌ／ｇの溶液での吸着量が約１．２×１０−５ｍｏｌ／ｇであった。つまり、４−ｎ−ヘプチルフェノールは、４−ｎ−プロピルフェノールに比べて平衡濃度が低いにも拘わらず、ＭＰＳに対して非常によく吸着している。よって、ＭＰＳ−ＴｉＯ２における分子選択的分解は、ＭＰＳの分子選択的吸着がＭＰＳ−ＴｉＯ２でも機能しており、ＭＰＳに選択的に吸着した有機物質を光触媒が分解したためであると考えられる。 According to this, the adsorption amount of 4-n-propylphenol in a solution with an equilibrium concentration of 4.20 × 10 −5 mol / g was about 0.5 × 10 −5 mol / g, whereas The amount of adsorption of n-heptylphenol in a solution having an equilibrium concentration of 1.40 × 10 −5 mol / g was about 1.2 × 10 −5 mol / g. That is, 4-n-heptylphenol adsorbs very well to MPS despite its lower equilibrium concentration than 4-n-propylphenol. Thus, the molecular selective degradation in MPS-TiO 2, the molecular selective adsorption of MPS is functioning even MPS-TiO 2, it is contemplated that organic material selectively adsorbs the MPS is because the photocatalyst is decomposed.
〔実験例２〕
次に、ＭＰＳ−ＴｉＯ２（６０ｗｔ％）を３０ｍｇと、比較例としてのＭＰＳを１２ｍｇとＰ−２５を１６ｍｇ（Ｐ−２５の量は全体の６０ｗｔ％となる）の混合物について、フェノール系有機物混合液、またはアニリン系有機物混合液に投入して、その選択的分解特定を調べた。
[Experimental example 2]
Next, a mixture of MPS-TiO 2 (60wt%) and 30mg, the 12mg and P-25 to MPS 16 mg as a comparative example (the amount of P-25 is a 60 wt% of the total), phenolic organic mixture The solution was put into a liquid or an aniline-based organic liquid mixture, and its selective decomposition was examined.
上記フェノール系有機物混合液としては、フェノール１．６０×１０−５ｍｏｌ／ｌ、４−ｎ−プロピルフェノール１．５１×１０−５ｍｏｌ／ｌ、４−ｎ−ヘプチルフェノール１．３９×１０−５ｍｏｌ／ｌ、ノニルフェノール１．３９×１０−５ｍｏｌ／ｌの混合水溶液３００ｍｌを用いた。これに、ＭＰＳ−ＴｉＯ２（６０ｗｔ％）を３０ｍｇ投入した場合の各有機物の濃度変化を表したのが図８（ａ）である。一方、ＭＰＳとＰ−２５との混合物を投入したのが図８（ｂ）である。 Examples of the phenol-based organic mixture include phenol 1.60 × 10 −5 mol / l, 4-n-propylphenol 1.51 × 10 −5 mol / l, 4-n-heptylphenol 1.39 × 10 − 300 ml of a mixed aqueous solution of 5 mol / l and nonylphenol 1.39 × 10 −5 mol / l was used. FIG. 8A shows the change in the concentration of each organic substance when 30 mg of MPS-TiO 2 (60 wt%) is added thereto. On the other hand, FIG. 8B shows a mixture of MPS and P-25.
これによると、ＭＰＳとＰ−２５との混合物を投入した場合はどれもほぼ同じ速度で濃度が減少しているのに対し、ＭＰＳ−ＴｉＯ２（６０ｗｔ％）を投入した場合には、炭素鎖の長い４−ｎ−ヘプチルフェノールおよびノニルフェノールの濃度減少速度が高く、炭素鎖の短いフェノール、４−ｎ−プロピルフェノールの減少速度は比較的遅かった。 According to this, when the mixture of MPS and P-25 was charged, the concentration decreased at almost the same rate, whereas when MPS-TiO 2 (60 wt%) was charged, the carbon chain 4-n-heptylphenol and nonylphenol having a high concentration decrease rate, and a short carbon chain phenol, 4-n-propylphenol, was relatively slow.
したがって、本発明の製造方法でＭＰＳに光触媒を複合化することで、フェノール系有機物の中では炭素鎖の長い有機物を選択的にＭＰＳの細孔内に濃縮し、これを光触媒粒子が分解していると考えられる。 Therefore, by combining the photocatalyst with MPS by the production method of the present invention, among the phenolic organic substances, the organic substance having a long carbon chain is selectively concentrated in the pores of the MPS, and the photocatalyst particles decompose this. It is thought that there is.
また、上記アニリン系有機物混合液としては、ｐ−トルイジン１．８７×１０−５ｍｏｌ／ｌ、４−ｎ−ブチルアニリン２．２４×１０−５ｍｏｌ／ｌ、４−ｎ−ヘプチルアニリン２．２１×１０−５ｍｏｌ／ｌの混合水溶液３００ｍｌを用いた。これに、ＭＰＳ−ＴｉＯ２（６０ｗｔ％）を３０ｍｇ投入した場合の各有機物の濃度変化を表したのが図９（ａ）である。一方、ＭＰＳとＰ−２５との混合物を投入したのが図９（ｂ）である。 Examples of the aniline-based organic liquid mixture include p-toluidine 1.87 × 10 −5 mol / l, 4-n-butylaniline 2.24 × 10 −5 mol / l, 4-n-heptylaniline. 300 ml of a mixed aqueous solution of 21 × 10 −5 mol / l was used. FIG. 9A shows the change in the concentration of each organic substance when 30 mg of MPS-TiO 2 (60 wt%) is added thereto. On the other hand, FIG. 9B shows a mixture of MPS and P-25.
これによると、アニリン系有機物においては、ＭＰＳとＰ−２５との混合物を投入した場合はそれほど速い速度で濃度が減少しなかった４−ｎ−ブチルアニリンが、ＭＰＳ−ＴｉＯ２（６０ｗｔ％）を投入した場合には、減少速度が上がっていた。 According to this, in the case of aniline-based organic matter, 4-n-butylaniline, whose concentration did not decrease at a very high rate when a mixture of MPS and P-25 was added, was replaced with MPS-TiO 2 (60 wt%). When it was introduced, the rate of decrease increased.
したがって、本発明の製造方法でＭＰＳに光触媒を複合化することで、アニリン系有機物に対しても炭素鎖の長い有機物を選択的に吸着除去できる効果があるものと思われる。 Therefore, it seems that by combining the photocatalyst with MPS by the production method of the present invention, an organic substance having a long carbon chain can be selectively adsorbed and removed even with respect to the aniline organic substance.
ここで、実験例１と同様に、上記アニリン類に対する、ＭＰＳの吸着量を測定した。これによると、ｐ−トルイジンの、平衡濃度１．６６×１０−５ｍｏｌ／ｇの溶液での吸着量が約０．８×１０−５ｍｏｌ／ｇであったのに対し、４−ｎ−ブチルアニリンの、平衡濃度１．０２×１０−５ｍｏｌ／ｇの溶液での吸着量が約１．２×１０−５ｍｏｌ／ｇ、４−ｎ−ヘプチルアニリンの、平衡濃度０．５４１×１０−５ｍｏｌ／ｇの溶液での吸着量が約１．３×１０−５ｍｏｌ／ｇであった。つまり、長鎖のアニリン類は、ｐ−トルイジンに比べて平衡濃度が低いにも拘わらず、ＭＰＳに対して非常によく吸着している。よって、ＭＰＳ−ＴｉＯ２における分子選択的分解は、ＭＰＳの分子選択的吸着がＭＰＳ−ＴｉＯ２でも機能しており、ＭＰＳに選択的に吸着した有機物質を光触媒が分解したために起こると考えられる。 Here, as in Experimental Example 1, the amount of MPS adsorbed on the anilines was measured. According to this, the adsorption amount of p-toluidine in a solution having an equilibrium concentration of 1.66 × 10 −5 mol / g was about 0.8 × 10 −5 mol / g, whereas 4-n− The amount of adsorption of butylaniline in a solution having an equilibrium concentration of 1.02 × 10 −5 mol / g is about 1.2 × 10 −5 mol / g, and the equilibrium concentration of 4-n-heptylaniline is 0.541 × 10 6. The adsorption amount in a solution of −5 mol / g was about 1.3 × 10 −5 mol / g. That is, long-chain anilines are adsorbed very well to MPS even though the equilibrium concentration is lower than that of p-toluidine. Therefore, it is considered that the molecular selective decomposition in MPS-TiO 2 occurs because the molecular selective adsorption of MPS also functions in MPS-TiO 2 and the photocatalyst decomposes the organic substance selectively adsorbed on MPS.
〔実験例３〕
ＭＰＳ−ＴｉＯ２の細孔径を制御することが、分子選択性に与える効果を調べるために、以下の実験を行った。
[Experimental Example 3]
In order to investigate the effect of controlling the pore size of MPS-TiO 2 on the molecular selectivity, the following experiment was conducted.
本実験例においては、多孔体の鋳型となる界面活性剤として、アルキル鎖の炭素数の異なる界面活性剤を用いた。複合多孔体の製造方法は、上記製造方法の項において説明した方法と同様にして行った。 In the present experimental example, surfactants having different numbers of carbon atoms in the alkyl chain were used as the surfactant as a template for the porous body. The manufacturing method of the composite porous body was performed in the same manner as the method described in the section of the manufacturing method.
界面活性剤の直鎖アルキルトリメチルアンモニウムブロミド（アルキル鎖の炭素数ｘが８、１０、及び１６のもの）を、イオン交換水に溶かし、アンモニア水でｐＨを１１．８に調整した後、ＴｉＯ２粉末Ｐ−２５を加え超音波をかけて分散させた。次に、このようにして分散させたものに、テトラエトキシシランを加え、約１時間攪拌した後、生成物をろ過して回収した。当該回収した生成物を一晩乾燥させた後、５４０℃で６時間焼成してＴｉＯ２を６０ｗｔ％含んだＭＰＳ（ｘ）ＴｉＯ２を得た（ｘは鋳型として用いた界面活性剤の炭素数を示しており、本実験例ではｘ＝８、１０及び１６である）。 Surfactant linear alkyltrimethylammonium bromide (alkyl chain having carbon number x 8, 10, and 16) was dissolved in ion-exchanged water, pH was adjusted to 11.8 with aqueous ammonia, and TiO 2 was added. Powder P-25 was added and dispersed by applying ultrasonic waves. Next, tetraethoxysilane was added to the dispersion thus obtained, and the mixture was stirred for about 1 hour, and then the product was collected by filtration. After drying the recovered product overnight, the TiO 2 was calcined for 6 hours at 540 ° C. to obtain a 60 wt% inclusive MPS (x) TiO 2 (x is the number of carbon atoms of the surfactant used as a template And x = 8, 10 and 16 in this experimental example).
アニリン系有機物混合液３００ｍｌに、上記のようにして合成した複合多孔体の試料（ＭＰＳ（ｘ）ＴｉＯ２）３０ｍｇを加え、攪拌しながら３００ＷのＸｅランプ（波長２００ｎｍ〜９００ｎｍ）により光を照射し、各アニリン系有機物の濃度の経時変化を調べた。アニリン系有機物混合液としては、ｐ−トルイジン、４−ｎ−ブチルアニリン、及び４−ｎ−ヘプチルアニリンの各濃度を２．５×１０−５ｍｏｌ／ｌに調整したものを用いた。また、各アニリン系有機物の濃度測定は、液体クロマトグラフを用いて行った。
30 mg of the composite porous material sample (MPS (x) TiO 2 ) synthesized as described above is added to 300 ml of the aniline-based organic mixture, and light is irradiated with a 300 W Xe lamp (
上記の方法によりＭＰＳ（１０）−ＴｉＯ２について測定した結果を、図１０（ａ）に示す。また、比較例として、ＭＰＳ（１０）−ＴｉＯ２と同じ組成にして、ＭＰＳ（１０）とＰ−２５とを機械的に混合した機械混合物についても、同様の測定を行なった。その結果を図１０（ｂ）に示す。図１０（ａ）及び（ｂ）のグラフから、本発明の実施例であるＭＰＳ（１０）−ＴｉＯ２は、比較例である機械混合物よりも、４−ｎ−ヘプチルアニリンの分解が加速されている一方、ｐ−トルイジンの分解が減速されていることが分かる。 FIG. 10A shows the result of measurement for MPS (10) -TiO 2 by the above method. As a comparative example, in the same composition as the MPS (10) -TiO 2, for also mechanically mixture was mechanically mixed with P-25 and MPS (10), was carried out the same measurement. The result is shown in FIG. From the graphs of FIGS. 10A and 10B, MPS (10) -TiO 2 which is an example of the present invention accelerates decomposition of 4-n-heptylaniline more than the mechanical mixture which is a comparative example. On the other hand, it can be seen that the decomposition of p-toluidine is slowed down.
また、上記のＭＰＳ（１０）−ＴｉＯ２と同様にして、ＭＰＳ（８）−ＴｉＯ２、ＭＰＳ（１６）−ＴｉＯ２についても測定を行なった。その結果、Ｐ−２５と複合化した多孔体の細孔径の大きさが異なるＭＰＳ（ｘ）−ＴｉＯ２（ｘ＝８，１０，１６）の試料のいずれについても、３つのアニリン系有機物の分解速度は、４−ｎ−ヘプチルアニリン＞４−ｎ−ブチルアニリン＞ｐ−トルイジンの順に速いことが示された。
In the same manner as the above MPS (10) -TiO 2, were also subjected to measurement for MPS (8) -
各複合多孔体の各アニリン系有機物の分解速度を、同組成の機械混合物の分解速度に対する比（以下、「分解速度比」という。）で表した結果を表１に示す。ここで、複合多孔体の分解速度と、組成が同じ機械混合物の分解速度とが同じ場合、分解速度比（複合多孔体／機械混合物）が１になるから、分解速度比が１より大きければ、複合化により分解が加速されることを示し、分解速度比が１より小さければ、複合化により分解が減速されることを示している。なお、表１に記載した細孔直径及び細孔容積の値は何れも、Ｎ２吸着測定によって算出したものである。 Table 1 shows the result of the decomposition rate of each aniline-based organic substance in each composite porous body expressed as a ratio to the decomposition rate of the mechanical mixture having the same composition (hereinafter referred to as “decomposition rate ratio”). Here, when the decomposition speed of the composite porous body is the same as the decomposition speed of the mechanical mixture having the same composition, the decomposition speed ratio (composite porous body / mechanical mixture) becomes 1, so if the decomposition speed ratio is larger than 1, It shows that the decomposition is accelerated by the combination, and if the decomposition rate ratio is smaller than 1, it indicates that the decomposition is decelerated by the combination. The values of the pore diameter and the pore volume described in Table 1 are all calculated by N 2 adsorption measurement.
表１に示すように、ＭＰＳ（１０）−ＴｉＯ２では、４−ｎ−ヘプチルアニリンの分解速度比が１．３５であり分解が加速されている一方、ｐ−トルイジンの分解速度比が０．２７であり分解が減速されている。このように、本実験例において測定したＭＰＳ（ｘ）−ＴｉＯ２のうち、最も明確なアニリン系有機物に対する分子選択性が認められたものは、ＭＰＳ（１０）−ＴｉＯ２であった。
As shown in Table 1, MPS (10) in -TiO 2, while the degradation rate ratio of 4-n-heptyl aniline is 1.35 decomposition is accelerated, degradation rate ratio of p-
また、ＭＰＳ（１６）−ＴｉＯ２では、複合化により、４−ｎ−ヘプチルアニリン及び４−ｎ−ブチルアニリンの分解が加速される一方、ｐ−トルイジンの分解が減速された。これは、細孔径が変化することにより、細孔内への競争分子吸着・濃縮の選択性が、変化したためと考えられる。 In MPS (16) -TiO 2 , the decomposition of 4-n-heptylaniline and 4-n-butylaniline was accelerated by the complexation, while the decomposition of p-toluidine was decelerated. This is presumably because the selectivity of competitive molecule adsorption / concentration into the pores changed as the pore diameter changed.
また、ＭＰＳ（８）−ＴｉＯ２では、４−ｎ−ヘプチルアニリン、４−ｎ−ブチルアニリン、及びｐ−トルイジンのいずれの分解速度比も１未満であり、複合化によって分解が減速されていることが分かる。これは、ＭＰＳ（８）−ＴｉＯ２の細孔直径は１．３ｎｍとＭＰＳ（１０）−ＴｉＯ２に比べて小さいから、アニリン系有機物と接触できるＴｉＯ２の露出面積も小さくなり、この結果、複合多孔体の活性自体が低くなったためと考えられる。 In MPS (8) -TiO 2 , the decomposition rate ratio of 4-n-heptylaniline, 4-n-butylaniline, and p-toluidine is less than 1, and the decomposition is slowed down by complexing. I understand that. This is because the pore diameter of MPS (8) -TiO 2 is 1.3 nm, which is smaller than that of MPS (10) -TiO 2 , so that the exposed area of TiO 2 that can come into contact with aniline-based organic matter is also reduced. This is probably because the activity of the composite porous body itself has decreased.
以上のように、本実験例の結果によれば、アニリン系有機物を選択的に分解するためには、光触媒機能を有する固体微粒子と複合化する多孔体としては、平均細孔直径が１．５ｎｍ以上のものが好適であることが分かる。 As described above, according to the results of this experimental example, in order to selectively decompose the aniline-based organic matter, the average pore diameter is 1.5 nm as the porous body that is combined with the solid fine particles having the photocatalytic function. It turns out that the above is suitable.
本発明の複合多孔体は、固体微粒子を多量に含有でき、固体微粒子の結晶性も良好にできる。したがって、固体微粒子として光触媒機能を用いた場合は、有機物質を選択的かつ迅速に他の化合物へと変換することができる。よって、有害な有機物質の選択的分解ができ、水や空気から極低濃度の有害物質を除去することができる。この技術は、あらゆる分野での浄化、有害物質除去に利用することができる。特に上水浄化や下水処理等に好適である。 The composite porous body of the present invention can contain a large amount of solid fine particles and the crystallinity of the solid fine particles can be improved. Therefore, when the photocatalytic function is used as the solid fine particles, the organic substance can be selectively and rapidly converted into another compound. Therefore, harmful organic substances can be selectively decomposed, and extremely low concentrations of harmful substances can be removed from water and air. This technology can be used for purification and removal of harmful substances in all fields. It is particularly suitable for water purification and sewage treatment.
Claims (12)
多孔体の骨格が生成する前に合成媒体に固体微粒子を混合分散させる工程と、
固体微粒子が分散した合成媒体中で、多孔体の骨格を生成させることにより多孔体と固体微粒子とが複合化した複合多孔体を形成させる工程と、を含み、
上記多孔体が、メソ多孔質シリカ、あるいはメソ多孔質シリカアルミナであり、かつ、上記固体微粒子が光触媒機能を有するものであり、
上記多孔体が、アルキル鎖の炭素数が１０である直鎖アルキルトリメチルアンモニウムブロミドを鋳型として合成される無機多孔体であり、
上記固体微粒子の添加量が、上記多孔体の原料と上記固体微粒子との合計量に対して、６０重量％以上であることを特徴とする複合多孔体の製造方法。 In a method for producing a composite porous body that forms a composite porous body in a liquid, sol, or gel-like synthesis medium,
Mixing and dispersing solid fine particles in the synthesis medium before the porous skeleton is formed;
Forming a composite porous body in which the porous body and the solid fine particles are combined by generating a skeleton of the porous body in a synthetic medium in which the solid fine particles are dispersed, and
The porous body is mesoporous silica or mesoporous silica alumina, and the solid fine particles have a photocatalytic function,
The porous body, Ri inorganic porous material der carbon number of the alkyl chain is synthesized linear alkyl trimethylammonium bromide is 10 as a template,
The addition amount of the solid particles, the total amount of the raw material and the solid particles of the porous body, method for producing a composite porous body, wherein Der Rukoto 60 wt% or more.
メソ多孔質シリカあるいはメソ多孔質シリカアルミナである多孔体と、固体微粒子とが複合化されており、上記固体微粒子が光触媒機能を有するものであり、
上記固体微粒子の含有量が、上記多孔体の原料と上記固体微粒子との合計量に対して、６０重量％以上であることを特徴とする複合多孔体。 It is manufactured by the method for manufacturing a composite porous body according to any one of claims 1 to 6 ,
And the porous body is a mesoporous silica or mesoporous silica-alumina, and the solid particles are complexed state, and are not the solid particles having a photocatalytic function,
The content of the solid particles, the the total amount of the porous body of the raw material and the solid particles, the composite porous body, wherein Der Rukoto 60 wt% or more.
多孔体の細孔直径よりも大きい直径の固体微粒子と、を含むことを特徴とする請求項７に記載の複合多孔体。 A porous body that is mesoporous silica or mesoporous silica alumina;
The composite porous body according to claim 7 , comprising solid fine particles having a diameter larger than a pore diameter of the porous body.
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