JP4469975B2 - Photocatalyst composite and organic substance conversion method using the same - Google Patents
Photocatalyst composite and organic substance conversion method using the same Download PDFInfo
- Publication number
- JP4469975B2 JP4469975B2 JP2004085082A JP2004085082A JP4469975B2 JP 4469975 B2 JP4469975 B2 JP 4469975B2 JP 2004085082 A JP2004085082 A JP 2004085082A JP 2004085082 A JP2004085082 A JP 2004085082A JP 4469975 B2 JP4469975 B2 JP 4469975B2
- Authority
- JP
- Japan
- Prior art keywords
- organic
- photocatalyst
- substance
- porous body
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000126 substance Substances 0.000 title claims description 106
- 239000011941 photocatalyst Substances 0.000 title claims description 66
- 238000000034 method Methods 0.000 title claims description 36
- 238000006243 chemical reaction Methods 0.000 title claims description 19
- 239000002131 composite material Substances 0.000 title claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 51
- 230000001699 photocatalysis Effects 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 239000012488 sample solution Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 125000001165 hydrophobic group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- -1 n-octyl group Chemical group 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 45
- 239000000243 solution Substances 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 230000007613 environmental effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- BNEWZYZRLNNWNR-UHFFFAOYSA-N 4-heptylaniline Chemical compound CCCCCCCC1=CC=C(N)C=C1 BNEWZYZRLNNWNR-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 7
- 239000005556 hormone Substances 0.000 description 7
- 229940088597 hormone Drugs 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 231100000507 endocrine disrupting Toxicity 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000012002 vanadium phosphate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Images
Landscapes
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Description
本発明は、光触媒複合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機物質変換に有用な光触媒複合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 photocatalyst complex and an organic substance conversion method using the same, and more particularly to a photocatalyst complex and an organic substance conversion method useful for environmental purification and organic substance conversion 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。そこで、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. Therefore, it is required to perform high-performance purification in wastewater treatment and purification processes 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、光触媒法による浄化が挙げられる。 Conventional purification techniques include a method of decomposing toxic substances and a method of adsorbing and removing with a porous material. Examples of the method 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 purification using 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.
しかし、上述のような従来の方法では、接触した有機物を非選択的に分解除去していくため、多種多様な有機物が比較的高濃度で存在する排水中を浄化する場合に非効率的であった。すなわち、従来の方法では、高濃度で存在する有機物の分解除去が先行し、これだけで系の分解除去機能が飽和してしまうため、微量濃度で存在する有害化合物を除去することが難しかった。 However, the conventional methods as described above are inefficient when purifying wastewater in which a wide variety of organic substances exist at a relatively high concentration because the organic substances that have come into contact are decomposed and removed selectively. It was. That is, in the conventional method, decomposition and removal of organic substances existing at a high concentration precedes, and this alone saturates the decomposition and removal function of the system, so that it is difficult to remove harmful compounds existing at a minute concentration.
したがって、環境ホルモン等の微量濃度でも有害性が高い物質は、その濃度の何千倍、何万倍もの高濃度の他の有機物や阻害物質により、浄化が効率的に行われず、目標濃度のppbレベル以下にまで浄化することはほとんど不可能であった。 Therefore, substances that are highly harmful even at trace concentrations, such as environmental hormones, cannot be purified efficiently by other organic substances and inhibitors that are thousands of times or tens of thousands of times higher than their concentrations. It was almost impossible to purify below the level.
そこで、本願発明者らは、有機基が、ある有害物質と選択的に結合することを見出し、これを利用して有害物質を選択的に除去する方法を提案している。その１つの方法は、シリカ多孔体表面に有機基修飾を施し、有害物質を選択的に吸着除去する方法である（非特許文献１、３）。また、光触媒の表面に有機物を修飾することで選択的に有害物質を分解する方法も提案している（特許文献１）。
しかしながら、非特許文献１、３の方法は、有害化合物を単に吸着する作用しかないため、一定時間使用後に吸着飽和した多孔体を高温加熱処理などにより再生する必要があり、多量のエネルギー消費、コスト増、設備の複雑化が避けられない。
However, since the methods of
また、特許文献１の方法は、選択的に有害物質と結合して除去することができるが、ある程度の期間使用すると、光触媒が修飾された有機基を分解するおそれがある。この場合、有機基による選択的吸着の効果が見込めなくなるため、長期間安定した浄化作用を保持することが難しかった。
Moreover, although the method of
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、有害物質を選択的に除去でき、かつ長期間安定した除去作用を示す光触媒複合体を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a photocatalyst complex capable of selectively removing harmful substances and exhibiting a stable removal action for a long period of time.
本発明者らはこのような課題を解決するために、低濃度の有害物質を選び出して吸着する機能と、その吸着した有害物質を分解除去する機能とを、多孔体に付すことで、安定して有害物質を選択的に分解する光触媒複合体が製造できることを見出した。 In order to solve such problems, the present inventors have stably provided a porous body with a function of selecting and adsorbing a low-concentration harmful substance and a function of decomposing and removing the adsorbed harmful substance. The present inventors have found that a photocatalyst complex that selectively decomposes harmful substances can be produced.
すなわち、本発明の光触媒複合体は、多孔体の細孔表面に、光触媒活性をもつ光触媒物質と、有機基とが固定されていることを特徴としている。 That is, the photocatalyst complex of the present invention is characterized in that a photocatalytic substance having photocatalytic activity and an organic group are fixed on the pore surfaces of the porous body.
これによれば、多孔体の細孔表面に有機基を固定することで、細孔表面に疎水部が形成される。そして、この疎水部により目的の有機物質を多孔体細孔に選択的に吸着できるので細孔内に有機物質が濃縮される。さらに、多孔体の表面には光触媒物質が固定されているので、有機基が選択的に吸着した有機物質を光触媒物質が変換するので、吸着飽和することがない。したがって、再生の作業をすることなく、長期間有害な有機物質を取り除く、あるいは有機物質から有用な他の物質へ変換することができる。 According to this, the hydrophobic part is formed on the pore surface by fixing the organic group on the pore surface of the porous body. Since the target organic substance can be selectively adsorbed to the porous pores by the hydrophobic portion, the organic substance is concentrated in the pores. Furthermore, since the photocatalytic substance is fixed on the surface of the porous body, the photocatalytic substance converts the organic substance on which the organic group is selectively adsorbed, so that the adsorption saturation does not occur. Therefore, it is possible to remove a harmful organic substance for a long period of time or to convert the organic substance into another useful substance without performing a regeneration operation.
また、光触媒物質と有機基とのそれぞれが、多孔体の細孔表面に固定されていることで、相互に作用し合うことなく近接して配置できるので、有機基を安定に保持しつつ、吸着・変換を効果的に行える。したがって、有機物質の選択的変換を、長時間安定して行うことができる。なお、有機基は、多孔体細孔表面において、光触媒物質とは別の領域に固定されている。 In addition, since each of the photocatalytic substance and the organic group is fixed on the pore surface of the porous body, it can be placed close to each other without interacting with each other.・ Conversion can be done effectively. Therefore, the selective conversion of the organic substance can be performed stably for a long time. Incidentally, the organic group, the porous material pore surfaces, the photocatalytic material that is fixed to another area.
上記多孔体としてシリカ多孔体を用いれば、より安定に光触媒物質と有機基とを保持でき、吸着・変換の機能も良好に発揮できる。 If a silica porous body is used as the porous body, the photocatalytic substance and the organic group can be more stably retained, and the adsorption / conversion function can be exhibited well.
また、上記光触媒物質としては金属酸化物であることが好ましく、二酸化チタンであることがより好ましい。これによれば、上記有機基とともに多孔体に良好に固定され、吸着された有害物質を良好に変換することができる。 Further, the photocatalytic substance is preferably a metal oxide, and more preferably titanium dioxide. According to this, it is possible to satisfactorily convert the adsorbed harmful substance that is well fixed to the porous body together with the organic group.
また、上記有機基は、アルキル基であることが好ましく、炭素数が１から１８の飽和アルキル基であることがより好ましく、炭素数が４から１４の飽和アルキル基であることがさらに好ましい。ノニルフェノール類を吸着する場合は、ｎ−オクチル基である事が最も好ましい。これによれば、有機物質として、環境ホルモンとして問題となっている有機物質を選択的に吸着することができる。したがって、試料液に本光触媒複合体を作用させることで、環境ホルモンやそれに類する有害化学物質を選択的に除去できる。 The organic group is preferably an alkyl group, more preferably a saturated alkyl group having 1 to 18 carbon atoms, and further preferably a saturated alkyl group having 4 to 14 carbon atoms. When adsorbing nonylphenols, it is most preferably an n-octyl group. According to this, the organic substance which is a problem as an environmental hormone can be selectively adsorbed as the organic substance. Therefore, by causing the photocatalyst complex to act on the sample solution, it is possible to selectively remove environmental hormones and similar harmful chemical substances.
本発明の有機物質変換方法は、上記光触媒複合体を試料液と接触させ、光触媒物質にその光触媒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ことを特徴としている。 The organic substance conversion method of the present invention comprises reacting an organic substance in a sample solution by bringing the photocatalyst complex into contact with a sample solution and irradiating the photocatalyst material with light in a wavelength region that activates the photocatalyst. It is a feature.
これによれば、上記光触媒複合体が試料液に接触することで、試料液中の有機物質が有機基に吸着され、光触媒物質に光をあてて活性化することで、吸着した有機物質が変換される。したがって、有害物質を長期間安定して変換することができる。 According to this, when the photocatalyst complex comes into contact with the sample liquid, the organic substance in the sample liquid is adsorbed by the organic group, and the photocatalyst substance is activated by applying light to the photocatalyst substance to convert the adsorbed organic substance. Is done. Therefore, harmful substances can be stably converted for a long time.
なお、ここで言う「変換」とは、有機物質に何らかの化学反応を起こさせることを言い、試料中の有害な有機物質を除去するために分解することも、有機物質から有用な化合物を合成することをも含んでいる。 The term “conversion” as used herein refers to causing some kind of chemical reaction to the organic substance, which can be decomposed to remove harmful organic substances in the sample, or synthesize useful compounds from the organic substances. It also includes that.
また、上述したように、光触媒物質と有機基とが、多孔体に固定されていることで、相互に作用し合うことが防がれ、有機基が安定に保持される。したがって、有害物質の選択的分解を、長時間安定して行うことができる。 Further, as described above, since the photocatalytic substance and the organic group are fixed to the porous body, they are prevented from interacting with each other, and the organic group is stably held. Therefore, selective decomposition of harmful substances can be performed stably for a long time.
また、上記有機物質変換方法によって、一分子中に親水基と疎水基とを併せ持つ化合物を変換することができる。 In addition, a compound having both a hydrophilic group and a hydrophobic group in one molecule can be converted by the organic substance conversion method.
変換する有機物質が一分子中に親水基と疎水基とを併せ持つ化合物であれば、有機物質の疎水基が有機基の疎水基に吸着し、有機物質の親水基が、親水性を持つ光触媒表面に強く相互作用する。よって、本有機物質変換方法により効率的に変換される。 If the organic substance to be converted is a compound that has both a hydrophilic group and a hydrophobic group in one molecule, the hydrophobic group of the organic substance is adsorbed to the hydrophobic group of the organic group, and the hydrophilic group of the organic substance has a hydrophilic photocatalytic surface. Interact strongly with. Therefore, it is efficiently converted by the present organic substance conversion method.
本発明の光触媒複合体は、以上のように、多孔体の細孔表面に、光触媒活性をもつ光触媒物質と、有機基とが固定されているので、細孔に選択的に吸着され、高濃度で濃縮された有機物質を、光触媒反応により変換できる。それゆえ、有機物質を選択的に変換できる。また、光触媒物質と有機基とが、多孔体に固定されていることで、相互に作用することが防がれ、有機基が安定に保持される。したがって、長時間安定して有機物質の選択的変換を行え、有害な有機物質の除去あるいは有機物質からの有用な物質の合成ができる。 As described above, the photocatalyst composite of the present invention has a photocatalytic activity having a photocatalytic activity and an organic group fixed to the surface of the pores of the porous body. The organic substance concentrated in can be converted by photocatalytic reaction. Therefore, organic substances can be selectively converted. Further, since the photocatalytic substance and the organic group are fixed to the porous body, they are prevented from interacting with each other, and the organic group is stably maintained. Therefore, selective conversion of organic substances can be performed stably for a long time, and harmful organic substances can be removed or useful substances can be synthesized from organic substances.
また、本発明の有機物質変換方法は、上記光触媒複合体を試料液と接触させ、前記光触媒複合体にその光触媒を活性化する波長領域の光を照射することにより、前記試料液中の有機物質を変換している。これによれば、上記光触媒複合体が試料液に接触することで、試料液中の有害物質が有機基に吸着され、光触媒に光をあてて活性化することで、吸着した有機物質が変換される。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長期間安定して行うことができる。 In the organic substance conversion method of the present invention, the photocatalyst complex is brought into contact with a sample liquid, and the photocatalyst complex is irradiated with light in a wavelength region that activates the photocatalyst. Has been converted. According to this, when the photocatalyst complex comes into contact with the sample solution, harmful substances in the sample solution are adsorbed on the organic group, and the photocatalyst is activated by applying light to convert the adsorbed organic material. The Therefore, removal of harmful organic substances or synthesis of useful substances from organic substances can be performed stably for a long period of time.
本発明の光触媒複合体は、光触媒活性をもつ光触媒物質を担持した多孔体の表面に有機基が固定されているので、有機基が選択的に有害化合物を吸着し、光触媒物質が有機化合物を変換する。また、多孔体にて光触媒物質および有機基を保持することで、互いが作用することなく、安定した有害化合物の除去ができる。 In the photocatalyst complex of the present invention, an organic group is immobilized on the surface of a porous body supporting a photocatalytic substance having photocatalytic activity. Therefore, the organic group selectively adsorbs harmful compounds, and the photocatalytic substance converts the organic compound. To do. In addition, by holding the photocatalytic substance and the organic group in the porous body, it is possible to stably remove harmful compounds without mutual action.
上記多孔体としては特に限定されるものではないが、アルミナ、シリカ、シリカゲル、多孔質ガラス、シリカアルミナ、マグネシア、ジルコニア、活性炭、リン酸アルミニウム、リン酸ジルコニウム、リン酸バナジウム、酸化タングステン、酸化マンガン、粘土鉱物でもあるモンモリロナイトおよびそれから誘導される多孔体等が挙げられ、特にシリカアルミナの多孔体が好ましい。 The porous body is not particularly limited, but alumina, silica, silica gel, porous glass, silica alumina, magnesia, zirconia, activated carbon, aluminum phosphate, zirconium phosphate, vanadium phosphate, tungsten oxide, manganese oxide Examples thereof include montmorillonite which is also a clay mineral and a porous body derived therefrom, and a porous body of silica alumina is particularly preferable.
多孔体の有する細孔直径についても、特に限定されるものではないが、有機物質の濃縮効果の観点からは、好ましくは細孔直径が５０００ｎｍ以下、さらに好ましくは０．５ｎｍ−５００ｎｍである。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 pore diameter of the porous body is not particularly limited, but from the viewpoint of the organic substance concentration effect, the pore diameter is preferably 5000 nm or less, more preferably 0.5 nm to 500 nm. 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.
光触媒物質としては、光触媒活性を有する有機金属化合物や、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、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。
Any photocatalytic substance may be used as long as it is an organometallic compound having photocatalytic activity or a semiconductor having characteristics as a semiconductor. Of these, metal sulfides and metal oxides are preferable, and metal oxides are most preferable. Specific ones, TiO 2, SrTiO 3, WO 3, Fe 2 O 3, Bi 2 O 3,
また、有機基としては、除去対象となる有機物質（目的分子）の分子構造を吸着するような分子構造を設定すればよい。このとき、目的分子の疎水基の大きさ、疎水性の強さによって、上記有機基の種類、長さ、表面密度（単位表面積あたりの有機基の数）を最適化することが好ましい。 Further, as the organic group, a molecular structure that adsorbs the molecular structure of the organic substance (target molecule) to be removed may be set. At this time, it is preferable to optimize the type, length, and surface density (number of organic groups per unit surface area) of the organic group according to the size of the hydrophobic group and the hydrophobicity of the target molecule.
このような有機基により、親水性と疎水性を併せ持ち水中に溶解している分子ならば多様な分子を選択的に吸着できる。特に一分子中に親水基と疎水基を併せ持つ分子には高い分子認識性を発現する。この中には環境ホルモンとして問題になっているノニルフェノールなどのアルキルフェノール群やビスフェノールＡを初め、一般に界面活性剤と呼ばれている物質群が含まれる。 With such an organic group, various molecules can be selectively adsorbed as long as they are both hydrophilic and hydrophobic and dissolved in water. In particular, a molecule having both a hydrophilic group and a hydrophobic group in one molecule exhibits high molecular recognition. This includes a group of substances generally called surfactants, including alkylphenols such as nonylphenol and bisphenol A, which are problematic as environmental hormones.
例えば、光触媒を二酸化チタン、有機基をアルキル基とした場合には、アルキルフェノール系の分子を選択的に認識し、除去することができる。有機基のアルキル基の炭素数は、除去しようとする目的分子のアルキル基の炭素数に応じて設定することができる。一般的な有機物の除去には、有機基のアルキル基の炭素数を１〜１８の範囲とすることが好ましい。現在特に問題となっている有機物質を目的分子とすること考えると、有機基としてアルキル基の炭素数が４〜１４の飽和アルキル基を採用することが特に適当である。例えば、有機基を炭素鎖長が８のオクチル基とした場合、代表的な環境ホルモンである極低濃度のノニルフェノールを、極めて高い選択性で吸着濃縮でき（非特許文献１および３）、また、ノニルフェノールの原因物質であるノニルフェノールポリエトキシレート（以下、ＰＥＧ−ＮＰ）を効率的に吸着濃縮し分解除去できる（後述の実施例参照）。
For example, when the photocatalyst is titanium dioxide and the organic group is an alkyl group, alkylphenol-based molecules can be selectively recognized and removed. The carbon number of the alkyl group of the organic group can be set according to the carbon number of the alkyl group of the target molecule to be removed. For the removal of general organic substances, the number of carbon atoms of the organic alkyl group is preferably in the range of 1-18. Considering that an organic substance that is currently a problem is a target molecule, it is particularly appropriate to employ a saturated alkyl group having 4 to 14 carbon atoms as the organic group. For example, when the organic group is an octyl group having a carbon chain length of 8, a very low concentration of nonylphenol, which is a typical environmental hormone, can be adsorbed and concentrated with extremely high selectivity (
このような有機基を固定した光触媒複合体の分子認識機能を調べる目的で、本発明の光触媒複合体への分子吸着を測定すると、アルキル基をもたないフェノールは吸着がほとんど観測されなかった（後述の実施例２参照）。 For the purpose of examining the molecular recognition function of the photocatalyst complex having such an organic group immobilized, when the molecular adsorption to the photocatalyst complex of the present invention was measured, almost no adsorption of phenol having no alkyl group was observed ( See Example 2 below).
また、本発明の光触媒複合体により、目的分子として、疎水部分であるアルキル基の炭素数が７である４−ｎ−ヘプチルアニリン、アルキル基の炭素数が９であるノニルフェノールの除去効率を観察したところ、炭素数が増えるに従い、吸着量が増大した。このことは、この光触媒複合体が、分子の疎水性を認識して吸着分子を取り込んでいることを示す。 In addition, with the photocatalyst complex of the present invention, the removal efficiency of 4-n-heptylaniline having 7 carbon atoms in the alkyl group as the hydrophobic moiety and nonylphenol having 9 carbon atoms in the alkyl group as the target molecules was observed. However, the amount of adsorption increased as the number of carbons increased. This indicates that this photocatalyst complex has taken in adsorbed molecules by recognizing the hydrophobicity of the molecules.
多孔体に光触媒や有機基を固定する方法は、通常用いられる方法を適用すればよい。例えば、光触媒と有機基とが細孔表面に散在するように固定してもよい。また、多孔体に光触媒と有機基とを固定する順番も限定されない。 As a method for fixing the photocatalyst or the organic group to the porous body, a commonly used method may be applied. For example, you may fix so that a photocatalyst and an organic group may be scattered on the pore surface. Further, the order of fixing the photocatalyst and the organic group to the porous body is not limited.
具体的には、シリカ系のナノ多孔体に塩化チタンを付与して、加熱、焼成することで、二酸化チタンを担持させ、さらに、二酸化チタンを担持したナノ多孔体に、アルキル基をシランカップリング剤で固定する方法が挙げられる。 Specifically, titanium dioxide is applied to silica-based nanoporous material, heated and fired to support titanium dioxide, and alkyl groups are silane-coupled to the nanoporous material supporting titanium dioxide. The method of fixing with an agent is mentioned.
多孔体に光触媒を固定する方法は、この他に、金属塩水溶液を多孔体に含浸させ、乾燥、焼成して金属酸化物微粒子を分散担持する方法や、有機金属化合物の溶液または蒸気と多孔体を反応させる方法などが考えられる。 Other methods for fixing the photocatalyst to the porous body include impregnating the porous body with an aqueous metal salt solution, drying and firing, and dispersing and supporting the metal oxide fine particles, or a solution or vapor of an organometallic compound and the porous body. The method of making this react can be considered.
また、多孔体に有機基を固定する方法は、この他に、多孔体合成時にシランカップリング剤を添加する方法が考えられる。 As another method for fixing the organic group to the porous body, a method of adding a silane coupling agent during the synthesis of the porous body can be considered.
また、光触媒が、光触媒複合体全体に対する含有量で２重量％以上５０重量％以下が好ましく、５重量％以上２０重量％以下がより好ましい。これより光触媒が少ないと光触媒活性が低くなり、これより多いと必要量の有機基を安定した細孔内に保持できなくなる。なお、光触媒物質を加熱焼成する場合は、１０重量％程度とすることが好ましい。 Further, the content of the photocatalyst is preferably 2% by weight or more and 50% by weight or less, and more preferably 5% by weight or more and 20% by weight or less, based on the total amount of the photocatalyst complex. If the photocatalyst is less than this, the photocatalytic activity is lowered, and if it is more than this, the required amount of organic groups cannot be retained in the stable pores. When the photocatalytic substance is heated and fired, the amount is preferably about 10% by weight.
また、有機基は、多孔体表面に０．１〜６分子／ｎｍ２以上固定することが好ましく、０．５〜２分子／ｎｍ２固定することがより好ましい。これより有機基が少ないと分子の選択的吸着がうまく行われなくなる。また、有機基がこれより多いと、光触媒物質が有機物質に接触しにくくなり、分解が良好に行われなくなる。 The organic group is preferably secured to the porous surface 0.1-6 molecules / nm 2 or more, and more preferably 2 fixed 0.5-2 molecules / nm. If there are fewer organic groups than this, selective adsorption of molecules will not be performed well. On the other hand, when there are more organic groups, the photocatalytic substance is less likely to come into contact with the organic substance and the decomposition is not performed well.
本発明の光触媒複合体は、試料液に接触させながら光触媒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。このとき、有機物質としては、親水基と疎水基とを一分子内に有するもの、特に、親水性および疎水性が強いものが挙げられ、このような分子であれば選択的な吸着・変換がしやすい。また、パラ位に親水基を持つアルキルフェノールであればより良好に選択的な吸着・変換ができる。 The photocatalyst complex of the present invention can convert an organic substance in a sample solution by being irradiated with light in a wavelength region that activates the photocatalyst while being in contact with the sample solution. In this case, examples of the organic substance include those having a hydrophilic group and a hydrophobic group in one molecule, in particular, those having strong hydrophilicity and hydrophobicity. Such molecules can selectively adsorb and convert. It's easy to do. Moreover, if it is alkylphenol which has a hydrophilic group in para position, selective adsorption | suction and conversion can be selected more favorably.
また、光触媒による有機物質の変換は、試料液中に含まれる有機物質を除去するために行われるものであってもよく、試料液中に含まれる有機物質から有用物質を合成するために行われるものであってもよい。 Moreover, the conversion of the organic substance by the photocatalyst may be performed to remove the organic substance contained in the sample solution, and is performed to synthesize a useful substance from the organic substance contained in the sample solution. It may be a thing.
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、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。 EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.
〔製造方法〕
本実施例の光触媒複合体の製造方法を説明する。なお、本実施例の製造方法は非特許文献２に記載のＴｉＯ２を担持する多孔体の製造方法にしたがっている。
〔Production method〕
The manufacturing method of the photocatalyst complex of a present Example is demonstrated. The manufacturing method of this embodiment is in accordance with the manufacturing method of the porous body carrying the TiO 2 described in
まず、シリカ多孔体の製造について図１（ａ）を用いて説明する。２６％ＴＭＡＯＨ（）を２２．６ｇ、Ｎａ４ＳｉＯ４を２８．６ｇ、Ｃ１８ＴＭＡＢｒを２４．４ｇ、Ｈ２Ｏを１８２．７ｇ混合した溶液を準備し、アルミ源としてＡｌＯ（ＯＨ）（ベーマイト）を０．２６８ｇ添加した。そして、ｐＨを１０．５に保ちながら、１００℃で９６時間加熱することで、水熱合成を行った。反応後の溶液をろ過・水洗浄した後、乾燥させることで、鋳型となった界面活性剤が細孔に詰まった状態のａｓ−ｓｙｎｔｈｅｓｉｚｅｄ ＭＣＭ−４１を得た。 First, the production of the porous silica will be described with reference to FIG. A solution prepared by mixing 22.6 g of 26% TMAOH (), 28.6 g of Na 4 SiO 4 , 24.4 g of C18TMABr and 182.7 g of H 2 O was prepared, and AlO (OH) (boehmite) was used as an aluminum source. 0.268 g was added. And hydrothermal synthesis was performed by heating at 100 degreeC for 96 hours, maintaining pH at 10.5. The solution after the reaction was filtered and washed with water, and then dried to obtain as-synthesized MCM-41 in which the surfactant as a template was clogged with pores.
次に、図１（ｂ）を用いて、得られたａｓ−ｓｙｎｔｈｅｓｉｚｅｄ ＭＣＭ−４１に、光触媒としてのＴｉＯ２と有機基とを固定する方法を説明する。 Next, a method for fixing TiO 2 as a photocatalyst and an organic group to the obtained as-synthesized MCM-41 will be described with reference to FIG.
ヘキサン溶媒６０ｍｌ中にＴｉＣｌ４０．４２ｇを溶解した溶液を、２５０℃で真空乾燥した上記ａｓ−ｓｙｎｔｈｅｓｉｚｅｄ ＭＣＭ−４１に窒素雰囲気で含浸させ、７．５時間攪拌する。攪拌後、混合溶液をろ過して真空乾燥する。乾燥後の生成物を、窒素中５５０℃で２時間加熱した後、空気中５５０℃で１０時間過熱焼成することにより、シリカ多孔体にＴｉＯ２が固定されたＴｉＯ２−ＭＣＭ−４１を得た。このＴｉＯ２−ＭＣＭ−４１中のＴｉＯ２含有量を原子吸光により求めると、８．７重量％であった。 A solution obtained by dissolving 0.42 g of TiCl 4 in 60 ml of a hexane solvent is impregnated in the above-mentioned as-synthesized MCM-41 vacuum-dried at 250 ° C. in a nitrogen atmosphere and stirred for 7.5 hours. After stirring, the mixed solution is filtered and dried in vacuum. The dried product was heated in nitrogen at 550 ° C. for 2 hours and then heated in air at 550 ° C. for 10 hours to obtain TiO 2 -MCM-41 in which TiO 2 was fixed to the porous silica. . The content of TiO 2 in this TiO 2 -MCM-41 was determined by atomic absorption to be 8.7% by weight.
得られたＴｉＯ２−ＭＣＭ−４１、０．３６ｇを、ｎ−オクチルトリエトキシシラン２．６ｇとともに、アルゴン環境下でトルエン溶媒に混合し、１４０℃４８時間で還流した。得られた生成物を、洗浄・乾燥することで、シリカ多孔体にＴｉＯ２および有機基（８Ｃの炭素鎖）が付加されたＣ８−ＴｉＯ２−ＭＣＭ−４１を得た。このＣ８−ＴｉＯ２−ＭＣＭ−４１の炭素含有量を元素分析測定し、これから単位面積あたりのオクチル基の数を計算すると、０．６０分子／ｎｍ２となった。 The obtained TiO 2 -MCM-41, 0.36 g was mixed with a toluene solvent under an argon environment together with 2.6 g of n-octyltriethoxysilane, and refluxed at 140 ° C. for 48 hours. The obtained product was washed and dried to obtain C8-TiO 2 -MCM-41 in which TiO 2 and an organic group (8C carbon chain) were added to the porous silica. When the carbon content of this C8-TiO 2 -MCM-41 was measured by elemental analysis and the number of octyl groups per unit area was calculated from this, it was 0.60 molecule / nm 2 .
このようにして製造されるＭＣＭ−４１、ＴｉＯ２−ＭＣＭ−４１、Ｃ８−ＴｉＯ２−ＭＣＭ−４１について、窒素吸着測定により比表面積、細孔直径について測定すると、図２のような結果が得られた。図２によると、Ｃ８−ＴｉＯ２−ＭＣＭ−４１では、ＭＣＭ−４１と同様の比表面積を持つことから、ＭＣＭ−４１にその細孔構造を保ったままＴｉＯ２が固定されていることが分かる。 When MCM-41, TiO 2 -MCM-41, and C8-TiO 2 -MCM-41 produced in this way are measured for specific surface area and pore diameter by nitrogen adsorption measurement, the results shown in FIG. 2 are obtained. It was. According to FIG. 2, C8-TiO 2 -MCM-41 has a specific surface area similar to that of MCM-41, and thus it can be seen that TiO 2 is fixed to MCM-41 while maintaining its pore structure. .
〔実験例１〕
上記のように製造したＴｉＯ２−ＭＣＭ−４１（比較例）とＣ８−ＴｉＯ２−ＭＣＭ−４１とについて、吸着特性の違いを測定した。
[Experimental Example 1]
The difference in adsorption characteristics was measured for TiO 2 -MCM-41 (Comparative Example) and C8-TiO 2 -MCM-41 produced as described above.
吸着性は、ＴｉＯ２−ＭＣＭ−４１またはＣ８−ＴｉＯ２−ＭＣＭ−４を１０ｍｇ、３００ｍｌのフェノール溶液または４−ｎ−ヘプチルアニリン溶液に投与した後の、溶液中の有機化合物の濃度の変化を測定することで判定した。結果を図３（フェノール溶液）、図４（４−ｎ−ヘプチルアニリン溶液）に示す。 The adsorptivity is the change in the concentration of organic compounds in the solution after TiO 2 -MCM-41 or C8-TiO 2 -MCM-4 is administered to 10 mg, 300 ml of phenol solution or 4-n-heptylaniline solution. Judgment was made by measuring. The results are shown in FIG. 3 (phenol solution) and FIG. 4 (4-n-heptylaniline solution).
図３によれば、フェノール溶液の場合は２時間後にもフェノール溶液の濃度は変化しておらず、ＴｉＯ２−ＭＣＭ−４１およびＣ８−ＴｉＯ２−ＭＣＭ−４はほとんどフェノールを吸着しておらず、分解も起こしていないことが分かる。 According to FIG. 3, in the case of the phenol solution, the concentration of the phenol solution did not change even after 2 hours, and TiO 2 -MCM-41 and C8-TiO 2 -MCM-4 hardly adsorbed phenol. It can be seen that no decomposition occurred.
一方、図４によれば、ＴｉＯ２−ＭＣＭ−４１による４−ｎ−ヘプチルアニリンの吸着はごくわずかで、しかも遅い。一方、Ｃ８−ＴｉＯ２−ＭＣＭ−４１には４−ｎ−ヘプチルアニリンがよく吸着し、かつ吸着速度も速く、２時間後には半分近くまで減少する。したがって、有機基を細孔内に植え付けることにより、大きな疎水基を持つ４−ｎ−ヘプチルアニリンを細孔内へ効率的に吸着濃縮できることがわかった。 On the other hand, according to FIG. 4, the adsorption of 4-n-heptylaniline by TiO 2 -MCM-41 is negligible and slow. On the other hand, 4-n-heptylaniline adsorbs well on C8-TiO 2 -MCM-41, and the adsorption rate is fast, and it decreases to nearly half after 2 hours. Therefore, it was found that 4-n-heptylaniline having a large hydrophobic group can be efficiently adsorbed and concentrated in the pores by implanting organic groups in the pores.
〔実験例２〕
上記した製造方法で製造したＴｉＯ２−ＭＣＭ−４１（比較例）とＣ８−ＴｉＯ２−ＭＣＭ−４１とについて、吸着性と光触媒活性を測定した。
[Experimental example 2]
The adsorptivity and the photocatalytic activity were measured for TiO 2 -MCM-41 (Comparative Example) and C8-TiO 2 -MCM-41 produced by the production method described above.
まず、ＴｉＯ２−ＭＣＭ−４１またはＣ８−ＴｉＯ２−ＭＣＭ−４１を、５〜５０ｍｇの範囲で、ノニルフェノールポリエトキシレートＣ９Ｈ１９Ｃ６Ｈ４Ｏ（Ｃ２Ｈ４Ｏ）ｎＨ（以下、ＰＥＧ−ＮＰ、ｎ＝８．５）水溶液に投与し、その吸着性を測定した。ここでは、ＰＥＧ−ＮＰは６〜３００ｐｐｍの濃度範囲として、各平衡濃度に対する吸着量を測定した。なお、吸着性は、多孔体複合体１ｇあたりのＰＥＧ−ＮＰ吸着量で示している。結果を図５に示す。 First, TiO 2 -MCM-41 or C8-TiO 2 -MCM-41 is added in the range of 5 to 50 mg in a nonylphenol polyethoxylate C 9 H 19 C 6 H 4 O (C 2 H 4 O) n H (hereinafter referred to as “nylphenol polyethoxylate”). , PEG-NP, n = 8.5) was administered to an aqueous solution, and its adsorptivity was measured. Here, the amount of adsorption for each equilibrium concentration was measured with PEG-NP in the concentration range of 6 to 300 ppm. In addition, adsorptivity is shown by the PEG-NP adsorption amount per 1g of porous body composites. The results are shown in FIG.
これによれば、ＴｉＯ２−ＭＣＭ−４１は、ＰＥＧ−ＮＰの濃度が高い場合は効果的に吸着するものの、低濃度では吸着が起こりにくかった。一方、Ｃ８−ＴｉＯ２−ＭＣＭ−４１では、１ｐｐｍの極微量のＰＥＧ−ＮＰ濃度であっても高い吸着性を示していた。これは、ＴｉＯ２−ＭＣＭ−４１に有機基を修飾することで、多孔体細孔内のナノ空間に疎水場が形成され、ＰＥＧ−ＮＰの疎水部分を選択的に捕捉したためと考えられる。 According to this, TiO 2 -MCM-41 was effectively adsorbed when the concentration of PEG-NP was high, but was hardly adsorbed at a low concentration. On the other hand, C8-TiO 2 -MCM-41 showed high adsorptivity even at a very small concentration of PEG-NP of 1 ppm. This is considered to be because by modifying the organic group in TiO 2 -MCM-41, a hydrophobic field was formed in the nanospace in the porous pores, and the hydrophobic portion of PEG-NP was selectively captured.
次に、ＰＥＧ−ＮＰ水溶液にＴｉＯ２−ＭＣＭ−４１を１０ｍｇ、またはＣ８−ＴｉＯ２−ＭＣＭ−４１を３０ｍｇ添加して、多孔体が吸着平衡した後、多孔体に３００Ｗキセノンランプにより紫外線を照射し、溶液中のＰＥＧ−ＮＰの濃度変化を調べた。結果を図６に示す。また、図６には同様の系のＰＥＧ−ＮＰ水溶液に、二酸化チタン粉末（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３０ｍｇ添加したもののＰＥＧ−ＮＰの濃度変化を参照のために示している。 Next, 10 mg of TiO 2 -MCM-41 or 30 mg of C8-TiO 2 -MCM-41 was added to the PEG-NP aqueous solution, and after the porous body was adsorbed and balanced, the porous body was irradiated with ultraviolet rays using a 300 W xenon lamp. Then, the change in the concentration of PEG-NP in the solution was examined. The results are shown in FIG. FIG. 6 also shows a PEG-type aqueous solution of PEG-NP added with 30 mg of titanium dioxide powder (P-25 (trade name): containing both anatase-type titanium dioxide and rutin-type titanium dioxide as components). -NP concentration change is shown for reference.
これによると、ＴｉＯ２−ＭＣＭ−４１を添加しても、ＰＥＧ−ＮＰ水溶液の濃度は４ｐｐｍからほとんど変わらないのに対し、Ｃ８−ＴｉＯ２−ＭＣＭ−４１を添加するとＰＥＧ−ＮＰ濃度の減少が認められ、添加量が多いことを考慮しいても光触媒活性によりＰＥＧ−ＮＰをより効率的に分解していることが分かる。これは、有機修飾することによって、低濃度であっても溶液中のＰＥＧ−ＮＰを効果的に吸着し、細孔内に濃縮されたＰＥＧ−ＮＰをＴｉＯ２が分解することで、効率的にＰＥＧ−ＮＰを分解できたためと考えられる。 According to this, even when TiO 2 -MCM-41 is added, the concentration of the PEG-NP aqueous solution hardly changes from 4 ppm, whereas when C8-TiO 2 -MCM-41 is added, the decrease in the PEG-NP concentration decreases. It can be seen that PEG-NP is decomposed more efficiently due to the photocatalytic activity even when the addition amount is large. This is because organic modification effectively adsorbs PEG-NP in the solution even at low concentrations, and TiO 2 decomposes PEG-NP concentrated in the pores efficiently. This is probably because PEG-NP could be decomposed.
なお、Ｃ８−ＴｉＯ２−ＭＣＭ−４１の分解速度は、Ｐ−２５の分解速度には及ばないが、これはＣ８−ＴｉＯ２−ＭＣＭ−４１が多孔体にＴｉＯ２を担持した状態であるのに対し、Ｐ−２５はＴｉＯ２そのものであり、ＴｉＯ２量が非常に多くなるためである。そこで、ＴｉＯ２重量あたりの分解速度（１時間で分解するＰＥＧ−ＮＰの量）を計算したところ、Ｐ−２５では９．５×１０−５ｍｏｌ／ｈ・ｇであるのに対し、Ｃ８−ＴｉＯ２−ＭＣＭ−４１では１４．１×１０−５ｍｏｌ／ｈ・ｇとなり、Ｐ−２５よりも速い分解速度であった。 The decomposition rate of C8-TiO 2 -MCM-41 does not reach the decomposition rate of P-25, but this is a state in which C8-TiO 2 -MCM-41 carries TiO 2 on a porous body. On the other hand, P-25 is TiO 2 itself, and the amount of TiO 2 is very large. Therefore, when the decomposition rate per 2 weight of TiO (amount of PEG-NP decomposed in 1 hour) was calculated, it was 9.5 × 10 −5 mol / h · g for P-25, whereas C8− TiO 2 -MCM-41 was 14.1 × 10 −5 mol / h · g, which was a decomposition rate faster than P-25.
〔実験例３〕
次に、上記した製造方法で製造したＣ８−ＴｉＯ２−ＭＣＭ−４１について、光触媒を作用させるために紫外線を照射した後も有機基が保持されるかを調べた。
[Experimental Example 3]
Next, it was investigated whether C8-TiO 2 -MCM-41 produced by the above-described production method retained the organic group even after being irradiated with ultraviolet rays to act a photocatalyst.
Ｃ８−ＴｉＯ２−ＭＣＭ−４１、３０ｍｇを水に分散し、実験例２と同じ条件で紫外線照射し、紫外線照射前のものと、紫外線照射３時間後、１０時間後のものについて元素分析を行った。測定された炭素量から修飾されているアルキル基の量を計算した。 C8-TiO 2 -MCM-41, 30 mg, was dispersed in water and irradiated with ultraviolet rays under the same conditions as in Experimental Example 2, and elemental analysis was performed on those before ultraviolet irradiation and those after 3 hours and 10 hours after ultraviolet irradiation. It was. The amount of the modified alkyl group was calculated from the measured amount of carbon.
これによると、紫外線照射前では、アルキル基が９．４×１０−４ｍｏｌであったのに対し、紫外線を３時間照射した後では照射前のアルキル基量の１８ｍｏｌ％が分解されていた。さらに、１０時間照射後は照射前のアルキル基量の２７ｍｏｌ％が分解されていた。ここで、紫外線照射３時間後から１０時間後までの７時間の間では照射前のアルキル基量の９ｍｏｌ％しか分解されておらず、平均すれば１時間あたり１．３ｍｏｌ％しか分解していない。したがって、３時間以降の紫外線照射では分解が非常に遅い速度でしか起こらないことが示唆されている。 According to this, the alkyl group was 9.4 × 10 −4 mol before the ultraviolet irradiation, whereas 18 mol% of the alkyl group before the irradiation was decomposed after the ultraviolet irradiation for 3 hours. Furthermore, after the irradiation for 10 hours, 27 mol% of the alkyl group amount before the irradiation was decomposed. Here, during 7 hours from 3 hours to 10 hours after UV irradiation, only 9 mol% of the alkyl group amount before irradiation was decomposed, and on average, only 1.3 mol% was decomposed per hour. . Therefore, it has been suggested that decomposition occurs only at a very slow rate when irradiated with ultraviolet rays after 3 hours.
また、Ｃ８−ＴｉＯ２−ＭＣＭ−４１のＩＲ測定を行ったところ、紫外光照射後のサンプルでもＣ−Ｈ伸縮やＣ−Ｈ変角によるピークが見られ、その強度も紫外線照射を行っていないサンプルと比較して約３０％減少した程度であり、上記炭素量の分析結果と一致した。 Moreover, when IR measurement of C8-TiO 2 -MCM-41 was performed, a peak due to C—H stretching and C—H deflection was also observed in the sample after irradiation with ultraviolet light, and the intensity was not irradiated with ultraviolet light. It was about a 30% reduction compared to the sample, which was consistent with the carbon content analysis results.
一方、比較実験として、二酸化チタン粉末（Ｐ−２５）の表面に、上記した製造方法と同様の方法でｎ−オクチルトリエトキシシランを植え付けた試料（Ｃ８−Ｐ−２５）について、３０ｍｇを水に分散し、実験例２と同じ条件で紫外線照射した。そして、紫外線照射前の試料と、紫外線照射１０時間後の試料について赤外吸収スペクトルを測定した。結果によると、紫外線照射前に修飾されていたアルキル基は、１０時間の紫外線照射後には、その約８０ｍｏｌ％が反応して、他の物質に変換されていた。
On the other hand, as a comparative experiment, 30 mg of the sample (C8-P-25) in which n-octyltriethoxysilane was planted on the surface of the titanium dioxide powder (P-25) by the same method as the above-described production method in water. The mixture was dispersed and irradiated with ultraviolet rays under the same conditions as in Experimental Example 2. And the infrared absorption spectrum was measured about the sample before ultraviolet irradiation, and the
以上の結果より、有機基（アルキル基）は、二酸化チタンに直接担持される場合では比較的反応して変換されやすく、多孔体に二酸化チタンとともに固定される場合は比較的長期間保持される事がわかった。 From the above results, organic groups (alkyl groups) are relatively easily reacted and converted when directly supported on titanium dioxide, and are retained for a relatively long time when fixed together with titanium dioxide on a porous body. I understood.
本発明の光触媒複合体は、有害物質を選択的に、かつ長期間安定的に分解できる。したがって、有害物質の選択的分解を、長時間安定して行うことができ、水や空気から有害物質を除去することができる。したがって、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 photocatalyst complex of the present invention can decompose harmful substances selectively and stably for a long period of time. Therefore, selective decomposition of harmful substances can be performed stably for a long time, and harmful substances can be removed from water and air. Therefore, it can be used for purification in various fields and removal of harmful substances. It is particularly suitable for water purification and sewage treatment.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004085082A JP4469975B2 (en) | 2004-03-23 | 2004-03-23 | Photocatalyst composite and organic substance conversion method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004085082A JP4469975B2 (en) | 2004-03-23 | 2004-03-23 | Photocatalyst composite and organic substance conversion method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005270734A JP2005270734A (en) | 2005-10-06 |
| JP4469975B2 true JP4469975B2 (en) | 2010-06-02 |
Family
ID=35170956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004085082A Expired - Lifetime JP4469975B2 (en) | 2004-03-23 | 2004-03-23 | Photocatalyst composite and organic substance conversion method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4469975B2 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4849862B2 (en) * | 2005-10-14 | 2012-01-11 | 株式会社きもと | Novel heteropolyacid salt, photocatalyst using the same, and photocatalytic functional member |
| JPWO2008032459A1 (en) * | 2006-09-13 | 2010-01-21 | 独立行政法人科学技術振興機構 | Organic group acid catalyst |
| JP5530074B2 (en) * | 2008-03-31 | 2014-06-25 | 国立大学法人広島大学 | Composite and production method thereof |
| CN102698400B (en) * | 2012-05-18 | 2014-08-20 | 上海交通大学 | Method for degrading amantadine organism by photoelectrocatalysis |
| CN103599804B (en) * | 2013-11-05 | 2015-06-03 | 陕西科技大学 | N-FeVO4/Fe2O3 composite photocatalyst as well as preparation method and application thereof |
| CN103920529A (en) * | 2014-05-13 | 2014-07-16 | 黑龙江大学 | Manufacturing method of magnetic CoFe2O4/MCM-41/TiO2 composite materials |
| CN105727901B (en) * | 2016-04-29 | 2018-11-09 | 河海大学 | A kind of preparation method of optically catalytic TiO 2 sorbing material |
| EP3632558A4 (en) * | 2017-05-31 | 2021-03-17 | Furukawa Electric Co., Ltd. | Photocatalyst structure, photocatalyst structure composition, photocatalyst coating material, production method of photocatalyst structure, and decomposition method of aldehydes |
| EP3632545A4 (en) | 2017-05-31 | 2021-01-27 | Furukawa Electric Co., Ltd. | Steam reforming catalyst structure, reforming device provided with said steam reforming catalyst structure, and production method of steam reforming catalyst structure |
| CN110678259A (en) | 2017-05-31 | 2020-01-10 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| CN110691645A (en) | 2017-05-31 | 2020-01-14 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| AU2018276617B2 (en) | 2017-05-31 | 2021-03-25 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
| JP7306990B2 (en) | 2017-05-31 | 2023-07-11 | 古河電気工業株式会社 | CO-shift or reverse-shift catalyst structures and methods for making same, CO-shift or reverse-shift reactors, methods for producing carbon dioxide and hydrogen, and methods for producing carbon monoxide and water |
| JP7316935B2 (en) | 2017-05-31 | 2023-07-28 | 古河電気工業株式会社 | Catalytic cracking or hydrodesulfurization catalyst structure, catalytic cracking apparatus and hydrodesulfurization apparatus having the catalyst structure, and method for producing catalytic cracking or hydrodesulfurization catalyst structure |
| EP3632554A4 (en) | 2017-05-31 | 2021-04-21 | Furukawa Electric Co., Ltd. | Oxidation catalyst structure for exhaust gas purification and production method thereof, exhaust gas treatment device for vehicle, catalyst molded body, and gas purification method |
| AU2018277967B2 (en) | 2017-05-31 | 2021-05-27 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
| JP7269169B2 (en) | 2017-05-31 | 2023-05-08 | 古河電気工業株式会社 | Methanol reforming catalyst structure, apparatus for methanol reforming, method for producing methanol reforming catalyst structure, and method for producing at least one of olefins and aromatic hydrocarbons |
| CN110678263A (en) | 2017-05-31 | 2020-01-10 | 古河电气工业株式会社 | Catalyst structure for hydrodesulfurization, hydrodesulfurization apparatus provided with same, and method for producing catalyst structure for hydrodesulfurization |
| CN111620513B (en) * | 2020-04-28 | 2022-04-12 | 生态环境部华南环境科学研究所 | Method for grading, treating and recycling rural domestic sewage |
| CN114956177B (en) * | 2022-03-09 | 2024-01-26 | 哈尔滨理工大学 | Polyacid-derived cadmium-molybdenum bimetallic hexagonal prism nano material |
| CN114797979B (en) * | 2022-05-16 | 2023-06-16 | 中山大学 | Porous photocatalyst and preparation method and application thereof |
-
2004
- 2004-03-23 JP JP2004085082A patent/JP4469975B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005270734A (en) | 2005-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4469975B2 (en) | Photocatalyst composite and organic substance conversion method using the same | |
| Bui et al. | Photocatalytic materials for indoor air purification systems: An updated mini-review | |
| Xia et al. | Enhanced performance and conversion pathway for catalytic ozonation of methyl mercaptan on single-atom Ag deposited three-dimensional ordered mesoporous MnO2 | |
| Yuan et al. | Recent advances of SBA-15-based composites as the heterogeneous catalysts in water decontamination: a mini-review | |
| Shu et al. | Catalytic oxidation of VOCs over Mn/TiO2/activated carbon under 185 nm VUV irradiation | |
| Lyu et al. | Considerations to improve adsorption and photocatalysis of low concentration air pollutants on TiO2 | |
| Shukla et al. | Nanosized Co3O4/SiO2 for heterogeneous oxidation of phenolic contaminants in waste water | |
| Liu et al. | Hierarchical mesoporous MnO2 superstructures synthesized by soft-interface method and their catalytic performances | |
| Mamaghani et al. | Effect of titanium dioxide properties and support material on photocatalytic oxidation of indoor air pollutants | |
| US20110150734A1 (en) | Photo-Catalytic Membrane Reactor | |
| KR20020041604A (en) | Novel titania photocatalyst and its manufacturing method | |
| Liu et al. | Preparation and application of efficient TiO2/ACFs photocatalyst | |
| JP5194249B2 (en) | Composite porous body, method for producing the same, and organic substance conversion method using the same | |
| Ding et al. | Designing Co3O4/silica catalysts and intensified ultrafiltration membrane-catalysis process for wastewater treatment | |
| Gokulakrishnan et al. | Catalytic wet peroxide oxidation technique for the removal of decontaminating agents ethylenediaminetetraacetic acid and oxalic acid from aqueous solution using efficient Fenton type Fe-MCM-41 mesoporous materials | |
| RU2478413C1 (en) | Composite photocatalyst for water or air treatment | |
| Paz | Composite titanium dioxide photocatalysts and the" adsorb & shuttle" approach: a review | |
| Zhu et al. | Combination of microwave discharge electrodeless lamp and a TiO2/HZSM-5 composite for the photocatalytic degradation of dimethyl sulphide | |
| JP4505688B2 (en) | Novel photocatalyst and method for producing the same | |
| JP2007054694A (en) | Method for decomposing hardly decomposable chlorinated organic compound, and carbon nanotube composite material | |
| JP2014073956A (en) | Method of oxidizing carbon monoxide to carbon dioxide by light | |
| KR100489219B1 (en) | Manufacturing process of Titanium Dioxide Photocatalysts supporting Silicagel | |
| Nguyen Thi Thuy et al. | Kinetics of photocatalytic degradation of gaseous p‐xylene on UiO‐66‐NH2 and LaFeO3 thin films under combined illumination of ultraviolet and visible lights | |
| Li et al. | Efficient photodecomposition of NO x on carbon modified Ag/TiO 2 nanocomposites | |
| RU2465046C1 (en) | Composite adsorption-catalytic material for photocatalytic oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070227 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090805 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090908 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091022 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20091022 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100202 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4469975 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| EXPY | Cancellation because of completion of term |