JP2987440B1 - Photocatalyst comprising titanium mesoporous silica and method for producing the same - Google Patents
Photocatalyst comprising titanium mesoporous silica and method for producing the sameInfo
- Publication number
- JP2987440B1 JP2987440B1 JP10250800A JP25080098A JP2987440B1 JP 2987440 B1 JP2987440 B1 JP 2987440B1 JP 10250800 A JP10250800 A JP 10250800A JP 25080098 A JP25080098 A JP 25080098A JP 2987440 B1 JP2987440 B1 JP 2987440B1
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- mesoporous silica
- silica material
- alkylamine
- producing
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000010936 titanium Substances 0.000 title claims abstract description 67
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010419 fine particle Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000013335 mesoporous material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- 239000011148 porous material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000002894 organic compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 150000004703 alkoxides Chemical class 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011238 particulate composite Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BRXOKRLIIVYICJ-UHFFFAOYSA-N butoxy(trihydroxy)silane Chemical compound CCCCO[Si](O)(O)O BRXOKRLIIVYICJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
【要約】
【課題】 高活性な光触媒能を有するチタン含有シリカ
メソ多孔体と、その製造方法を提供する。
【解決手段】 シリカメソ多孔体中のケイ素原子の１〜
６モル％がチタン原子で同形置換されていることを特徴
とするチタン含有シリカメソ多孔体が提供される。チタ
ン含有シリカメソ多孔体の製造方法において、Ｓｉ−ア
ルコキシド、Ｔｉ−アルコキシド及び１−アルキルアミ
ンからなる混合液に酸性水溶液を添加して、チタン、ケ
イ素及び１−ｎ−アルキルアミンからなる複合体微粒子
を生成させ、得られた懸濁液から該複合体微粒子を分離
し、乾燥した後、該複合体微粒子を焼成し、それに含ま
れている１−ｎ−アルキルアミンを分解除去することを
特徴とする前記方法。シリカメソ多孔体中のケイ素原子
の１〜６モル％がチタン原子で同形置換されているチタ
ン含有シリカメソ多孔体からなる光触媒。A titanium-containing mesoporous silica having high photocatalytic activity and a method for producing the same are provided. SOLUTION: One to one of silicon atoms in a mesoporous silica material is provided.
A titanium-containing mesoporous silica material is provided, wherein 6 mol% is isomorphously substituted with a titanium atom. In the method for producing a titanium-containing mesoporous silica material, an acidic aqueous solution is added to a mixed solution composed of Si-alkoxide, Ti-alkoxide and 1-alkylamine to form composite fine particles composed of titanium, silicon and 1-n-alkylamine. After the composite fine particles are separated from the resulting suspension and dried, the composite fine particles are baked, and the 1-n-alkylamine contained therein is decomposed and removed. The method. A photocatalyst comprising a titanium-containing mesoporous silica material in which 1 to 6 mol% of silicon atoms in the mesoporous silica material are isomorphously substituted with titanium atoms.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、チタン含有シリカ
メソ多孔体からなる光触媒及びその製造方法に関するも
のである。The present invention relates to a photocatalyst comprising a titanium-containing mesoporous silica material and a method for producing the same.
【０００２】[0002]
【従来の技術】Ｓｉの一部をＴｉで同形置換した多孔性
物質は酸化触媒能、光触媒能を有することから、基礎研
究及び応用開発の両面で極めて注目されている。酸化触
媒能の発現はシリケート骨格中のＳｉを同形置換したＴ
ｉが、Ｈ2Ｏ2あるいはＴＢＨＰ等の酸化剤と容易に反応
し、活性なｐｅｒｏｘｏ型複合体を形成することに起因
することが知られている。また、光触媒能の発現もＳｉ
を置換したＴｉが紫外線から可視光領域の光を吸収する
ことに起因していると考えられる。近年、Ｓｉの一部を
Ｔｉで置換した種々のマイクロ孔及びメソ孔多孔体、例
えばＴＳ−１，ＴＳ−２、Ｔｉ−β、Ｔｉ−ＭＣＭ−４
１（４８）およびＴｉ−ＨＭＳが開発されている。ＴＳ
−１、ＴＳ−２およびＴｉ−βはゼオライト類縁化合物
のマイクロ孔多孔体であり、界面活性剤である１分子を
鋳型分子として合成される。これに対してＴｉ−ＭＣＭ
−４１等は多くの界面活性剤の協調的な集合体である液
晶型分子を鋳型にして無機溶存種を析出させることで合
成されるメソ孔多孔体である。2. Description of the Related Art A porous substance in which a part of Si is replaced by Ti in the same form has an oxidation catalytic activity and a photocatalytic activity, and thus has been attracting much attention in both basic research and application development. Oxidation catalytic activity is expressed by isomorphous substitution of Si in the silicate skeleton.
It is known that i reacts easily with an oxidizing agent such as H 2 O 2 or TBHP to form an active peroxo-type complex. In addition, the expression of photocatalytic ability
Is considered to be caused by the absorption of light in the visible light region from ultraviolet light. In recent years, various microporous and mesoporous materials in which a part of Si is replaced with Ti, for example, TS-1, TS-2, Ti-β, Ti-MCM-4
1 (48) and Ti-HMS have been developed. TS
-1, TS-2 and Ti-β are microporous bodies of zeolite analogs, and are synthesized using one molecule as a surfactant as a template molecule. On the other hand, Ti-MCM
-41 and the like are mesoporous materials synthesized by precipitating inorganic dissolved species using a liquid crystal type molecule, which is a coordinated aggregate of many surfactants, as a template.
【０００３】しかし、上記のマイクロ及びメソ孔多孔体
の合成は、（ｉ）常温で行われる場合には溶媒としてア
ルコール等の添加を行ったり、（ii）溶媒の添加が行わ
れない場合には１００℃以上の高温での水熱反応を必要
とする。また、シリケート骨格中のＳｉ置換率は低く、
Ｔｉ含有率は２〜３モル％程度であって、新規触媒を開
発するためにはその置換率を増加するための合成方法の
確立が期待されている。また、Ｔｉ及びＳｉ−アルコキ
シドを出発原料としてこれらを作製する場合には、両化
合物の加水分解速度の差異を解消することが主要な課題
である。そのため活性なＴｉ−アルコキシドをキレート
化することによって安定化したり、活性の低いＳｉ−ア
ルコキシドをあらかじめ加水分解させることによって、
両アルコキシドの加水分解速度および縮合速度の差異を
解消することが一般的に良く行われている。しかし、得
られる生成物は非晶質なＴｉ−Ｓｉ混合酸化物であり、
高活性な触媒として利用することはできない。[0003] However, the synthesis of the micro and mesoporous materials described above involves (i) addition of an alcohol or the like as a solvent when performed at room temperature, or (ii) addition of a solvent when not performed. It requires a hydrothermal reaction at a high temperature of 100 ° C. or higher. Also, the Si substitution rate in the silicate skeleton is low,
The Ti content is about 2 to 3 mol%, and in order to develop a new catalyst, establishment of a synthesis method for increasing the substitution rate is expected. In the case where Ti and Si-alkoxides are prepared as starting materials, it is a major problem to eliminate the difference between the hydrolysis rates of the two compounds. Therefore, by stabilizing the active Ti-alkoxide by chelation or by previously hydrolyzing the low-activity Si-alkoxide,
It is common practice to eliminate the difference between the hydrolysis and condensation rates of both alkoxides. However, the resulting product is an amorphous Ti-Si mixed oxide,
It cannot be used as a highly active catalyst.
【０００４】[0004]
【発明が解決しようとする課題】そこで本発明は、高活
性なチタン含有シリカメソ多孔体からなる光触媒と、そ
の製造方法を提供することをその課題とする。Accordingly, an object of the present invention is to provide a photocatalyst comprising a highly active titanium-containing mesoporous silica material and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意研究を重ねた結果、本発明を完成す
るに至った。即ち、本発明によれば、シリカメソ多孔体
中のケイ素原子の１〜６モル％がチタン原子で同形置換
されていることを特徴とするチタン含有シリカメソ多孔
体からなる光触媒が提供される。また、本発明によれ
ば、前記チタン含有シリカメソ多孔体からなる光触媒の
製造方法において、Ｓｉ−アルコキシド、Ｔｉ−アルコ
キシド及び１−アルキルアミンからなる混合液に酸性水
溶液を添加して、チタン、ケイ素及び１−ｎ−アルキル
アミンからなる複合体微粒子を生成させ、得られた懸濁
液から該複合体微粒子を分離し、乾燥した後、該複合体
微粒子を焼成し、それに含まれている１−ｎ−アルキル
アミンを分解除去することを特徴とする前記方法が提供
される。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, titanium-containing silica mesoporous material is characterized in that 1 to 6 mol% of silicon atoms in the mesoporous silica material are isomorphously substituted with titanium atoms.
A photocatalyst comprising a body is provided. According to the present invention, in the method for producing a photocatalyst comprising the titanium-containing mesoporous silica, an acidic aqueous solution is added to a mixed solution comprising Si-alkoxide, Ti-alkoxide and 1-alkylamine, and titanium, silicon and After generating composite fine particles composed of 1-n-alkylamine, separating the composite fine particles from the obtained suspension, and drying, the composite fine particles are baked, and the 1-n -The method is provided, wherein the alkylamine is decomposed and removed.
【０００６】[0006]
【発明の実施の形態】本発明のチタン含有シリカメソ多
孔体からなる光触媒（以下、単にチタン含有シリカメソ
多孔体ともいう。）の製造においては、先ず、Ｓｉ−ア
ルコキシドとＴｉ−アルコキシドと１−ｎ−アルキルア
ミンを含む混合液中に酸性溶液を添加する。これによ
り、酸性混合溶液が得られるが、この酸性混合溶液中で
イオン化して生成した各々の溶存種が、酸由来の陰イオ
ンを媒介として協調的な相互作用を行い、有機・無機溶
存種が規則構造を持って配列した複合体を形成される。
すなわち、本発明のチタン含有シリカメソ多孔体の合成
では、境界相である酸性水溶液相中における、アルコキ
シドから生成したアルコキシド溶存種と１−ｎ−アルキ
ルアミンとの急速な相互作用によって生成する微粒子状
の有機／無機複合体を前駆体として作製する。次に、こ
の複合体を溶液相から分離・乾燥後、１−ｎ−アルキル
アミンを除去する。これによって、メソ孔が規則的に配
列したチタン含有シリカメソ多孔体が生成する。メソ孔
の大きさは酸溶液の種類、濃度、容量及びアミンの種類
によって制御が可能である。BEST MODE FOR CARRYING OUT THE INVENTION The titanium-containing silica mesopoly of the present invention
Porous photocatalyst (hereinafter simply referred to as titanium-containing silica meso
Also called a porous body. In the production of (1 ) , first, an acidic solution is added to a mixed solution containing Si-alkoxide, Ti-alkoxide, and 1-n-alkylamine. As a result, an acidic mixed solution is obtained, and the respective dissolved species generated by ionization in the acidic mixed solution interact in a coordinated manner via an anion derived from an acid, and organic and inorganic dissolved species are formed. A complex is formed that has an ordered structure.
That is, in the synthesis of the titanium-containing mesoporous silica material of the present invention, in the acidic aqueous solution phase as the boundary phase, the fine particles formed by rapid interaction between the alkoxide dissolved species generated from the alkoxide and 1-n-alkylamine. An organic / inorganic composite is prepared as a precursor. Next, after separating and drying this complex from the solution phase, the 1-n-alkylamine is removed. Thereby, a titanium-containing mesoporous silica material in which mesopores are regularly arranged is produced. The size of the mesopores can be controlled by the type, concentration and volume of the acid solution and the type of amine.
【０００７】本発明のチタン含有シリカメソ多孔体は、
前記のように、従来になく単純な反応系において室温で
合成でき、しかも周期的に配列する細孔を有し、その大
きさが容易にコントロール可能で耐熱性にも優れている
ことはもとより、光触媒能を有することから、これまで
にない新規なチタン含有シリカメソ多孔体として分類で
きる。[0007] The titanium-containing mesoporous silica material of the present invention comprises:
As described above, it can be synthesized at room temperature in an unprecedented simple reaction system, and has pores that are periodically arranged, and in addition to being easily controllable in size and excellent in heat resistance, Since it has photocatalytic activity, it can be classified as a novel titanium-containing mesoporous silica.
【０００８】図１は、チタン含有シリカメソ多孔体のＸ
線回折図であり、底面反射の存在は細孔の配列が不規則
的ではないことを示している。しかし高温ではＴｉ含有
量が多いとピークとしては認めがたくなるが、依然とし
て低角に高い反射が認められ、完全には細孔構造が破壊
されていないことが分かる。また、図２はその紫外可視
スペクトルであり、比較のため市販アナターゼのスペク
トルも示す。２２０ｎｍ付近のピークはＴｉが４配位で
ありＳｉと置換したＴｉに対応している。３１０ｎｍ付
近のピークはアナターゼのピークに対応しており、Ｔｉ
含有率が高くなると６配位のＴｉが共存することが明ら
かである。FIG. 1 is a cross-sectional view of a mesoporous silica containing titanium.
FIG. 4 is a line diffraction diagram, showing the presence of bottom surface reflection that the arrangement of pores is not irregular. However, at high temperatures, when the Ti content is large, the peak is hardly recognized, but high reflection is still observed at a low angle, indicating that the pore structure is not completely destroyed. FIG. 2 shows the ultraviolet-visible spectrum, and also shows the spectrum of commercially available anatase for comparison. The peak near 220 nm corresponds to Ti in which Ti has four coordinates and is substituted for Si. The peak near 310 nm corresponds to the peak of anatase,
It is clear that the higher the content, the more the coordination of hexacoordinated Ti.
【０００９】本発明のチタン含有シリカメソ多孔体の合
成用出発原料であるＳｉ−アルコキシドとしては、テト
ラメチルオルトシリケート、テトラエチルオルトシリケ
ート、テトライソプロピルオルトシリケート、テトラ−
ｎ−ブチルオルトシリケート等を用いることが可能で、
好ましくはテトラエチルオルトシリケート（以下ＴＥＯ
Ｓと略す）を使用する。Ｔｉ−アルコキシドとしては、
テトラエチルオルトチタネート、テトライソプロピルオ
ルトチタネート、テトラ−ｎ−ブチルオルトチタネート
等の使用が可能であり、好ましくはテトラエチルオルト
チタネート（以下ＴＥＯＴと略す）を用いる。１−ｎ−
アルキルアミンとしては、カーボン数８〜１２のものを
使用する。酸としては、塩酸、硝酸あるいは硫酸等を使
用することができるが、好ましくは塩酸が用いられる。The Si-alkoxide which is a starting material for synthesizing the mesoporous titanium-containing silica of the present invention includes tetramethylorthosilicate, tetraethylorthosilicate, tetraisopropylorthosilicate, and tetra-orthosilicate.
It is possible to use n-butyl orthosilicate or the like,
Preferably, tetraethyl orthosilicate (hereinafter TEO)
S). As the Ti-alkoxide,
Tetraethyl orthotitanate, tetraisopropyl orthotitanate, tetra-n-butyl orthotitanate and the like can be used, and tetraethyl orthotitanate (hereinafter abbreviated as TEOT) is preferably used. 1-n-
As the alkylamine, one having 8 to 12 carbon atoms is used. As the acid, hydrochloric acid, nitric acid, sulfuric acid or the like can be used, but hydrochloric acid is preferably used.
【００１０】本発明においては、Ｔｉ含有シリカメソ多
孔体を好ましく製造するために、まず前記Ｓｉ−アルコ
シキドとＴｉ−アルコキシドとの混合溶液を５〜３０分
間の短時間攪拌する。この混合物に１−ｎ−アルキルア
ミンを添加しさらに１〜２０分間攪拌後、塩酸水溶液を
一気に添加して攪拌を継続する。In the present invention, in order to preferably produce a mesoporous silica material containing Ti, first, the mixed solution of the above-mentioned Si-alkoxide and Ti-alkoxide is stirred for a short time of 5 to 30 minutes. 1-n-Alkylamine is added to this mixture, and the mixture is further stirred for 1 to 20 minutes.
【００１１】Ｓｉ−アルコシキドとＴｉ−アルコキシド
の混合割合は、ＳｉとＴｉとのモル比（Ｓｉ／Ｔｉ）で
３以上、好ましくは１０以上である。その上限値は、特
に制約されないが、通常、２００程度である。１−ｎ−
アルキルアミンは、Ｓｉ：１モルに対して０．４〜２．
７モル、好ましくは０．５〜１．０モルである。ＴＥＯ
ＳとＴＥＯＴの混合アルコキシド溶液を５分間以上２０
０〜１０００ｒｐｍで攪拌混合後、アルキルアミンを添
加してそのまま１分以上攪拌する。さらに本混合溶液に
塩酸水溶液を加え、２００〜１０００ｒｐｍで攪拌しな
がら、室温で１０分以上好ましくは１〜２４時間反応さ
せる。出発原料の混合モル比は、ＴＥＯＳ：ＴＥＯＴ：
１−アルキルアミン：ＨＣｌ：水＝１：〜０．１：０．
４〜２．７：０．０７〜１．０：６〜１２０で、好まし
くは、ＴＥＯＳ：ＴＥＯＴ：１−アルキルアミン：ＨＣ
ｌ：水＝１：〜０．１：０．５〜１．０：０．１〜０．
７：１２〜７５である。塩酸は一挙に添加する。The mixing ratio of Si-alkoxide and Ti-alkoxide is 3 or more, preferably 10 or more in molar ratio of Si to Ti (Si / Ti). The upper limit is not particularly limited, but is usually about 200. 1-n-
Alkylamine is used in an amount of from 0.4 to 2.
7 mol, preferably 0.5 to 1.0 mol. TEO
Mix alkoxide solution of S and TEOT for more than 5 minutes 20
After stirring and mixing at 0 to 1000 rpm, alkylamine is added and the mixture is stirred for 1 minute or more. Further, an aqueous hydrochloric acid solution is added to the mixed solution, and the mixture is reacted at room temperature for 10 minutes or more, preferably 1 to 24 hours while stirring at 200 to 1000 rpm. The mixing molar ratio of the starting materials is TEOS: TEOT:
1-alkylamine: HCl: water = 1: to 0.1: 0.
4-2.7: 0.07-1.0: 6-120, preferably TEOS: TEOT: 1-alkylamine: HC
1: water = 1: to 0.1: 0.5 to 1.0: 0.1 to 0.
7: 12-75. Hydrochloric acid is added all at once.
【００１２】前記の反応により、Ｔｉ、Ｓｉ及び１−ｎ
−アルキルアミンからなる微粒子状複合体が形成され
る。前記の混合操作により、このような微粒子状複合を
含む懸濁液が生成されるが、この懸濁液は、これを固液
分離、例えば、遠心分離し、複合体を得る。この複合体
は、これを室温〜１００℃、好ましくは５０℃で２４時
間以上乾燥させる。最後に１−ｎ−アルキルアミンを除
去して多孔体を作製するために、４００℃以上で１時間
以上、好ましくは５００℃〜９００℃で１〜２時間加熱
処理する。このようにして得られる本発明のチタン含有
シリカメソ多孔体において、その平均細孔径は、１．８
〜４ｎｍ、好ましくは２〜３．４ｎｍであり、そのＴｉ
含有率は、０．５〜１０モル％、好ましくは１〜６モル
％である。本発明のチタン含有シリカメソ多孔体は、シ
リカメソ多孔体中の１〜６モル％ケイ素原子がチタン原
子で同形置換されている。この場合のケイ素原子がチタ
ン原子で同形置換されているということは、チタン原子
が４配位で存在することを意味する。By the above reaction, Ti, Si and 1-n
A particulate composite of the alkylamine is formed. By the mixing operation, a suspension containing such a particulate composite is produced. The suspension is subjected to solid-liquid separation, for example, centrifugation to obtain a composite. The complex is dried at room temperature to 100 ° C, preferably at 50 ° C for 24 hours or more. Finally, in order to remove the 1-n-alkylamine to form a porous body, heat treatment is performed at 400 ° C. or more for 1 hour or more, preferably at 500 ° C. to 900 ° C. for 1 to 2 hours. The thus obtained titanium-containing mesoporous silica material of the present invention has an average pore diameter of 1.8.
-4 nm, preferably 2-3.4 nm, and the Ti
The content is 0.5 to 10 mol%, preferably 1 to 6 mol%. In the mesoporous silica material containing titanium of the present invention, 1 to 6 mol% of silicon atoms in the mesoporous silica material are isomorphously substituted with titanium atoms. In this case, the fact that the silicon atom is isomorphously substituted by the titanium atom means that the titanium atom exists in a tetracoordinate.
【００１３】[0013]
【実施例】次に、本発明を実施例によって更に具体的に
説明するが、本発明はこの実施例によって限定されな
い。 実施例１ ＴＥＯＳとＴＥＯＴをモル比１：０．０２６で混合して
１５分間攪拌後、オクチルアミン（ＴＥＯＳに対するモ
ル比０．６７５）を添加する。この混合溶液を１０分攪
拌後、０．５Ｎ塩酸水溶液（水のＴＥＯＳに対するモル
比２４．７８）を一挙に添加して、生成した懸濁液をさ
らに２４時間攪拌する。生成物を遠心分離し、５０℃で
２日間乾燥させ、最後に５００℃で２時間加熱し有機化
合物を除去してチタン含有シリカメソ多孔体を作製す
る。生成チタン含有シリカメソ多孔体のＴｉ含有率およ
び比表面積等の細孔特性を表１に示す。Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 After mixing TEOS and TEOT at a molar ratio of 1: 0.026 for 15 minutes, octylamine (a molar ratio to TEOS of 0.675) is added. After stirring this mixed solution for 10 minutes, a 0.5N aqueous hydrochloric acid solution (water molar ratio to TEOS is 24.78) is added at once, and the resulting suspension is further stirred for 24 hours. The product is centrifuged, dried at 50 ° C. for 2 days, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. Table 1 shows the pore characteristics such as the Ti content and the specific surface area of the produced mesoporous silica material containing titanium.
【表１】 [Table 1]
【００１４】実施例２ ＴＥＯＳとＴＥＯＴをモル比１：０．０５４で混合して
１５分間攪拌後、オクチルアミン（ＴＥＯＳに対するモ
ル比０．６７５）を添加する。この混合溶液を１０分攪
拌後、０．５Ｎ塩酸水溶液（水のＴＥＯＳに対するモル
比２４．７８）を一挙に添加して、生成した懸濁液をさ
らに２４時間攪拌する。生成物を遠心分離し、５０℃で
２日間乾燥させ、最後に５００℃で２時間加熱し有機化
合物を除去してチタン含有シリカメソ多孔体を作製す
る。生成チタン含有シリカメソ多孔体のＴｉ含有率およ
び比表面積等の細孔特性を表２に示す。Example 2 After mixing TEOS and TEOT at a molar ratio of 1: 0.054 and stirring for 15 minutes, octylamine (a molar ratio to TEOS of 0.675) is added. After stirring this mixed solution for 10 minutes, a 0.5N aqueous hydrochloric acid solution (water molar ratio to TEOS is 24.78) is added at once, and the resulting suspension is further stirred for 24 hours. The product is centrifuged, dried at 50 ° C. for 2 days, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. Table 2 shows the pore characteristics such as the Ti content and the specific surface area of the produced mesoporous silica material containing titanium.
【表２】 [Table 2]
【００１５】実施例３ ＴＥＯＳとＴＥＯＴをモル比１：０．０８０で混合して
１５分間攪拌後、オクチルアミン（ＴＥＯＳに対するモ
ル比０．６７５）を添加する。この混合溶液を１０分攪
拌後、０．５Ｎ塩酸水溶液（水のＴＥＯＳに対するモル
比２４．７８）を一挙に添加して、生成した懸濁液をさ
らに２４時間攪拌する。生成物を遠心分離し、５０℃で
２日間乾燥させ、最後に５００℃で２時間加熱し有機化
合物を除去してチタン含有シリカメソ多孔体を作製す
る。生成物の粉末Ｘ線回折パターンには低強度のアナタ
ーゼの反射が認められる。生成チタン含有シリカメソ多
孔体のＴｉ含有率および比表面積等の細孔特性を表３に
示す。Example 3 After mixing TEOS and TEOT at a molar ratio of 1: 0.080 for 15 minutes, octylamine (a molar ratio to TEOS is 0.675) is added. After stirring this mixed solution for 10 minutes, a 0.5N aqueous hydrochloric acid solution (water molar ratio to TEOS is 24.78) is added at once, and the resulting suspension is further stirred for 24 hours. The product is centrifuged, dried at 50 ° C. for 2 days, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. The powder X-ray diffraction pattern of the product shows low intensity of anatase reflection. Table 3 shows the pore characteristics such as the Ti content and the specific surface area of the produced mesoporous silica material containing titanium.
【表３】 [Table 3]
【００１６】実施例４ ＴＥＯＳとＴＥＯＴをモル比１：０．１０６で混合して
１５分間攪拌後、オクチルアミン（ＴＥＯＳに対するモ
ル比０．６７５）を添加する。この混合溶液を１０分攪
拌後、０．５Ｎ塩酸水溶液（水のＴＥＯＳに対するモル
比２４．７８）を一挙に添加して、生成した懸濁液をさ
らに２４時間攪拌する。生成物を遠心分離し、５０℃で
２日間乾燥させ、最後に５００℃で２時間加熱し有機化
合物を除去してチタン含有シリカメソ多孔体を作製す
る。生成物の粉末Ｘ線回折パターンには低強度のアナタ
ーゼの反射が認められる。生成チタン含有シリカメソ多
孔体のＴｉ含有率および比表面積等の細孔特性を表４に
示す。Example 4 After mixing TEOS and TEOT at a molar ratio of 1: 0.106 and stirring for 15 minutes, octylamine (a molar ratio to TEOS of 0.675) is added. After stirring this mixed solution for 10 minutes, a 0.5N aqueous hydrochloric acid solution (water molar ratio to TEOS is 24.78) is added at once, and the resulting suspension is further stirred for 24 hours. The product is centrifuged, dried at 50 ° C. for 2 days, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. The powder X-ray diffraction pattern of the product shows low intensity of anatase reflection. Table 4 shows the pore characteristics such as the Ti content and the specific surface area of the produced mesoporous silica containing titanium.
【表４】 [Table 4]
【００１７】実施例５ ＴＥＯＳとＴＥＯＴをモル比１：０．０２６で混合して
１５分間攪拌後、ドデシルアミン（ＴＥＯＳに対するモ
ル比０．４８５）を添加する。この混合溶液を１０分攪
拌後、０．５Ｎ塩酸水溶液（水のＴＥＯＳに対するモル
比２４．７８）を一挙に添加して、生成した懸濁液をさ
らに２４時間攪拌する。生成物を遠心分離し、５０℃で
２日間乾燥させ、最後に５００℃で２時間加熱し有機化
合物を除去してチタン含有シリカメソ多孔体を作製す
る。生成チタン含有シリカメソ多孔体のＴｉ含有率およ
び比表面積等の細孔特性を表５に示す。Example 5 After mixing TEOS and TEOT at a molar ratio of 1: 0.026 and stirring for 15 minutes, dodecylamine (molar ratio to TEOS 0.485) is added. After stirring this mixed solution for 10 minutes, a 0.5N aqueous hydrochloric acid solution (water molar ratio to TEOS is 24.78) is added at once, and the resulting suspension is further stirred for 24 hours. The product is centrifuged, dried at 50 ° C. for 2 days, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. Table 5 shows the pore characteristics such as the Ti content and the specific surface area of the produced mesoporous silica material containing titanium.
【表５】 [Table 5]
【００１８】実施例６ ＴＥＯＳとＴＥＯＴをモル比１：０．１０６で混合して
１５分間攪拌後、ドデシルアミン（ＴＥＯＳに対するモ
ル比０．４８５）を添加する。この混合溶液を１０分攪
拌後、０．５Ｎ塩酸水溶液（水のＴＥＯＳに対するモル
比２４．７８）を一挙に添加して、生成した懸濁液をさ
らに２４時間攪拌する。生成物を遠心分離し、５０℃で
２日間乾燥させ、最後に５００℃で２時間加熱し有機化
合物を除去してチタン含有シリカメソ多孔体を作製す
る。生成チタン含有シリカメソ多孔体のＴｉ含有率およ
び比表面積等の細孔特性を表６に示す。EXAMPLE 6 After mixing TEOS and TEOT at a molar ratio of 1: 0.106 and stirring for 15 minutes, dodecylamine (molar ratio to TEOS 0.485) is added. After stirring this mixed solution for 10 minutes, a 0.5N aqueous hydrochloric acid solution (water molar ratio to TEOS is 24.78) is added at once, and the resulting suspension is further stirred for 24 hours. The product is centrifuged, dried at 50 ° C. for 2 days, and finally heated at 500 ° C. for 2 hours to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. Table 6 shows the pore characteristics such as the Ti content and the specific surface area of the produced mesoporous silica material containing titanium.
【表６】 [Table 6]
【００１９】実施例７ 実施例１の生成物を９００℃で１時間加熱し有機化合物
を除去してチタン含有シリカメソ多孔体を作製する。生
成チタン含有シリカメソ多孔体の細孔特性を表７に示
す。Example 7 The product of Example 1 is heated at 900 ° C. for 1 hour to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. Table 7 shows the pore characteristics of the resulting mesoporous silica material containing titanium.
【表７】 [Table 7]
【００２０】実施例８ 実施例２の生成物を９００℃で１時間加熱し有機化合物
を除去してチタン含有シリカメソ多孔体を作製する。生
成チタン含有シリカメソ多孔体の細孔特性を表８に示
す。Example 8 The product of Example 2 is heated at 900 ° C. for 1 hour to remove organic compounds, thereby producing a titanium-containing mesoporous silica material. Table 8 shows the pore characteristics of the produced mesoporous silica material containing titanium.
【表８】 [Table 8]
【００２１】実施例９ 実施例１、実施例４、実施例７、及び実施例８のチタン
含有シリカメソ多孔体の光触媒能を酢酸水溶液の分解反
応によって検討した。生成多孔体０．５ｇを５００ｍｌ
ビーカーに秤取り、２．６６ｍＭの酢酸水溶液４００ｍ
ｌを添加した。懸濁液に波長２５４ｎｍに最大強度を有
する紫外線ランプ（栄光社製）を直接浸し攪拌しなが
ら、出力１２０Ｗの光源を１時間照射し、反応前後の全
有機炭素を島津（株）製ＴＯＣ計で測定し、酢酸の分解
率を求めた。なお、同一反応条件で光触媒として高活性
で知られる市販アナターゼ（石原産業製ＳＴ−０１）に
ついても光触媒反応を行った。表９に示す結果より、Ｔ
ｉ１モルに対する光触媒能はアナターゼと比較するとい
ずれの場合も高く、実施例７では３８倍にも及ぶことが
わかる。Example 9 The photocatalytic activity of the mesoporous titanium-containing silica materials of Examples 1, 4, 7, and 8 was examined by a decomposition reaction of an aqueous acetic acid solution. 0.5 g of the resulting porous body is 500 ml
Weigh into beaker, 400m 2.66mM acetic acid aqueous solution
1 was added. The suspension was directly immersed in an ultraviolet lamp (manufactured by Eiko Co., Ltd.) having a maximum intensity at a wavelength of 254 nm and irradiated with a light source having an output of 120 W for 1 hour while stirring, and all organic carbon before and after the reaction was measured with a TOC meter manufactured by Shimadzu Corporation. The acetic acid decomposition rate was measured. In addition, the photocatalytic reaction was also performed on commercially available anatase (ST-01, manufactured by Ishihara Sangyo) which is known as a photocatalyst with high activity under the same reaction conditions. From the results shown in Table 9, T
It can be seen that the photocatalytic activity per mole of i was higher than that of anatase in all cases, and was 38 times higher in Example 7.
【表９】 [Table 9]
【００２２】[0022]
【発明の効果】本発明のチタン含有シリカメソ多孔体
は、ＴｉのＳｉ置換率が約５．５原子％まで自由にコン
トロール可能であり、しかもこのものは、Ｔｉが高比表
面積担体に高分散で担持した光触媒と捉えることができ
る。さらに適当な径の細孔を多数有していることから形
状選択能を発揮して効率的に種々の有用あるいは有害な
分子、イオンをトラップすることができる。したがっ
て、本発明のチタン含有シリカメソ多孔体は、工業およ
び環境保全の両面で有用な反応に対して優れた光触媒能
を有する。また、本発明の上記チタン含有シリカメソ多
孔体製造方法は、メソ孔ばかりでなくマイクロ孔を有す
るチタン含有シリカ多孔体の製造にも応用可能である。
さらにＴｉ以外、例えばＡｌ、ＶあるいはＺｒ等を含む
種々の新規多孔性物質を製造することが可能と考えられ
る。According to the mesoporous titanium-containing silica of the present invention, the substitution ratio of Ti to Si can be freely controlled up to about 5.5 atomic%. It can be regarded as a supported photocatalyst. Further, since it has a large number of pores having an appropriate diameter, it can exhibit various shapes and selectivity to efficiently trap various useful or harmful molecules and ions. Therefore, the mesoporous titanium-containing silica of the present invention has an excellent photocatalytic ability for a reaction useful in both industrial and environmental conservation. Further, the method for producing a mesoporous titanium-containing silica material of the present invention can be applied to the production of a porous titanium-containing silica material having not only mesopores but also micropores.
Further, it is considered that various novel porous substances including, for example, Al, V, Zr, etc. other than Ti can be produced.
【図１】粉末Ｘ線回析図を示し、図中の（ａ）〜（ｄ）
は、それぞれ（ａ）実施例１、（ｂ）実施例４、（ｃ）
実施例７、（ｄ）実施例８のチタン含有シリカメソ多孔
体の粉末Ｘ線回折図であり、（ｅ）は実施例９の表９中
の市販アナターゼの粉末Ｘ線回析図である。FIG. 1 shows a powder X-ray diffraction diagram, in which (a) to (d) are shown.
Are (a) Example 1, (b) Example 4, and (c), respectively.
9 (d) is a powder X-ray diffraction diagram of the titanium-containing mesoporous silica material of Example 8, and (e) is a powder X-ray diffraction diagram of commercially available anatase in Table 9 of Example 9.
【図２】紫外可視スペクトルを示し、図中の（ａ）〜
（ｅ）はそれぞれ図１の多孔体粉末に対応するものであ
る。FIG. 2 shows an ultraviolet-visible spectrum, and (a) to (a) in the figure.
(E) respectively correspond to the porous material powder of FIG.
Claims (2)
６モル％がチタン原子で同形置換されているチタン含有Titanium containing 6 mol% is isomorphously substituted with titanium atoms
シリカメソ多孔体からなる光触媒。Photocatalyst consisting of mesoporous silica.
からなる光触媒の製造方法において、 Ｓｉ−アルコキシ
ド、Ｔｉ−アルコキシド及び１−ｎ−アルキルアミンか
らなる混合液に酸性水溶液を添加して、チタン、ケイ素
及び１−ｎ−アルキルアミンからなる複合体微粒子を生
成させ、得られた懸濁液から該複合体微粒子を分離し、
乾燥した後、該複合体微粒子を焼成し、それに含まれて
いる１−アルキルアミンを分解除去することを特徴とす
る前記方法。 2. The mesoporous silica material containing titanium according to claim 1.
A method for producing a photocatalyst comprising: adding an acidic aqueous solution to a mixed solution comprising Si-alkoxide, Ti-alkoxide and 1-n-alkylamine to form composite fine particles comprising titanium, silicon and 1-n-alkylamine; Generating, separating the composite fine particles from the obtained suspension,
After drying, the composite fine particles are fired, and the 1-alkylamine contained therein is decomposed and removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10250800A JP2987440B1 (en) | 1998-09-04 | 1998-09-04 | Photocatalyst comprising titanium mesoporous silica and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10250800A JP2987440B1 (en) | 1998-09-04 | 1998-09-04 | Photocatalyst comprising titanium mesoporous silica and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2987440B1 true JP2987440B1 (en) | 1999-12-06 |
| JP2000070710A JP2000070710A (en) | 2000-03-07 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4626099B2 (en) | 2000-07-17 | 2011-02-02 | 株式会社豊田中央研究所 | Photocatalyst |
| FR2838734B1 (en) * | 2002-04-17 | 2005-04-15 | Saint Gobain | SELF-CLEANING COATING SUBSTRATE |
| JP2003335515A (en) * | 2002-05-17 | 2003-11-25 | National Institute Of Advanced Industrial & Technology | Highly three-dimensionally regular nanoporous inorganic body having micropore, method for producing the same, and method for evaluating the same |
| JP4831663B2 (en) * | 2004-10-27 | 2011-12-07 | 独立行政法人産業技術総合研究所 | Thin plate-like porous silica metal composite particles and production method thereof |
| JP4955992B2 (en) * | 2005-12-17 | 2012-06-20 | 本荘ケミカル株式会社 | Method for photo-oxidative decomposition of volatile organic compounds in the gas phase |
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1998
- 1998-09-04 JP JP10250800A patent/JP2987440B1/en not_active Expired - Lifetime
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| JP2000070710A (en) | 2000-03-07 |
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