JP2003119024A - Method of producing mesoporous titania particle - Google Patents
Method of producing mesoporous titania particleInfo
- Publication number
- JP2003119024A JP2003119024A JP2001317632A JP2001317632A JP2003119024A JP 2003119024 A JP2003119024 A JP 2003119024A JP 2001317632 A JP2001317632 A JP 2001317632A JP 2001317632 A JP2001317632 A JP 2001317632A JP 2003119024 A JP2003119024 A JP 2003119024A
- Authority
- JP
- Japan
- Prior art keywords
- mesoporous titania
- titania particles
- surfactant
- anionic surfactant
- titanium
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000002245 particle Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title abstract description 8
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 28
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkyl quaternary ammonium salt Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000005526 alkyl sulfate group Chemical group 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 29
- 235000010215 titanium dioxide Nutrition 0.000 description 58
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 13
- 239000000693 micelle Substances 0.000 description 13
- 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 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 229940067741 sodium octyl sulfate Drugs 0.000 description 10
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- YVIGPQSYEAOLAD-UHFFFAOYSA-L disodium;dodecyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOP([O-])([O-])=O YVIGPQSYEAOLAD-UHFFFAOYSA-L 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- SNOJPWLNAMAYSX-UHFFFAOYSA-N 2-methylpropan-1-ol;titanium Chemical compound [Ti].CC(C)CO.CC(C)CO.CC(C)CO.CC(C)CO SNOJPWLNAMAYSX-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- KEVJCNRSLHIUNP-UHFFFAOYSA-M cesium;dodecyl hydrogen phosphate Chemical compound [Cs+].CCCCCCCCCCCCOP(O)([O-])=O KEVJCNRSLHIUNP-UHFFFAOYSA-M 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080236 sodium cetyl sulfate Drugs 0.000 description 1
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、メソポーラスチタ
ニア粒子の製造方法に関し、更に詳細には、種々の細孔
径のメスポーラスチタニア粒子を得ることのできるメソ
ポーラスチタニア粒子の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing mesoporous titania particles, and more particularly to a method for producing mesoporous titania particles capable of obtaining mesoporous titania particles having various pore sizes.
【０００２】[0002]
【従来の技術】チタニア（二酸化チタン）は、光励起時
に強い酸化・還元力が誘起されるため、光触媒や湿式太
陽電池などに応用されている。このチタニアの比表面積
を更に増大させ、反応物質をトラップすることの出来る
構造とすることができれば、チタニアの光触媒や湿式太
陽電池などへの応用の効率はさらに増大すると考えられ
る。2. Description of the Related Art Titania (titanium dioxide) is applied to photocatalysts, wet solar cells, etc. because it induces a strong oxidation / reduction power upon photoexcitation. If the specific surface area of this titania can be further increased and a structure capable of trapping the reaction substance can be formed, it is considered that the efficiency of application of titania to a photocatalyst or a wet solar cell will be further increased.
【０００３】近年、界面活性剤が形成する分子集合体を
鋳型として用いる方法により、規則的な細孔を有し、比
表面積の大きなチタニア粒子（メソポーラスチタニア粒
子）を調製できることが報告された。しかし、この方法
では、メソポーラスチタニア粒子は形成されるものの、
細孔径は、一定の範囲のものであり、種々の細孔径のも
のを得ることは困難であった。Recently, it has been reported that titania particles (mesoporous titania particles) having regular pores and a large specific surface area can be prepared by a method of using a molecular assembly formed by a surfactant as a template. However, although mesoporous titania particles are formed by this method,
The pore size was in a certain range, and it was difficult to obtain various pore sizes.
【０００４】しかしながら、チタニアを光触媒や湿式太
陽電池などとして使用するためには、その活性や、反応
選択性の異なるものが必要となり、そのためには、種々
の細孔径のチタニアを調製することが必要であった。However, in order to use titania as a photocatalyst or a wet solar cell, it is necessary to have different activities and different reaction selectivities. For that purpose, it is necessary to prepare titania having various pore sizes. Met.
【０００５】[0005]
【発明が解決しようとする課題】従って本発明は、種々
の細孔径、ひいては異なる表面積を有するメソポーラス
チタニア粒子を製造する方法の提供をその課題とするも
のである。SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a method for producing mesoporous titania particles having various pore diameters and thus different surface areas.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、まず、こ
れまでの界面活性剤が形成する分子集合体を鋳型として
用いるメソポーラスチタニア粒子の製造法について検討
を行った。そして、細孔径を大きく変えることができな
い理由は、鋳型として用いる分子集合体が、単一の界面
活性剤であることに気づいた。[Means for Solving the Problems] First, the present inventors investigated a method for producing mesoporous titania particles using a conventional molecular assembly formed by a surfactant as a template. Then, the reason why the pore diameter cannot be greatly changed was that the molecular assembly used as the template was a single surfactant.
【０００７】そこで本発明者らは、界面活性剤に他の成
分を組み合わせること、具体的には、ベシクルや棒状ミ
セルなどの比較的大きな分子集合体を形成することが知
られているアニオン界面活性剤とカチオン界面活性剤の
組合せや、界面活性剤と重合を抑制する重合抑制剤との
組合せの元にメソポーラスチタニア粒子を調製したとこ
ろ、細孔径は一定の範囲に広がることを見出し、本発明
を完成した。Therefore, the present inventors have known that anionic surface active agents, which are known to combine a surfactant with other components, specifically, to form relatively large molecular aggregates such as vesicles and rod-shaped micelles. When mesoporous titania particles were prepared based on a combination of an agent and a cationic surfactant, or a combination of a surfactant and a polymerization inhibitor that suppresses polymerization, it was found that the pore size spreads within a certain range, and the present invention completed.
【０００８】すなわち本発明は、チタニア前駆体を、ア
ニオン性界面活性剤と、カチオン性界面活性剤もしくは
重合抑制剤との存在下重合させることを特徴とするメソ
ポーラスチタニア粒子の製造方法を提供するものであ
る。That is, the present invention provides a method for producing mesoporous titania particles, which comprises polymerizing a titania precursor in the presence of an anionic surfactant and a cationic surfactant or a polymerization inhibitor. Is.
【０００９】[0009]
【発明の実施の形態】本発明のメソポーラスチタニア粒
子の製造方法には、チタニア前駆体を、アニオン性界面
活性剤とカチオン性界面活性剤との存在下重合させる方
法（以下、「第一発明」という）と、チタニア前駆体
を、アニオン性界面活性剤と重合抑制剤との存在下重合
させる方法（以下、「第二発明」という）が含まれる。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing mesoporous titania particles of the present invention comprises a method of polymerizing a titania precursor in the presence of an anionic surfactant and a cationic surfactant (hereinafter referred to as "first invention"). )) And a titania precursor in the presence of an anionic surfactant and a polymerization inhibitor (hereinafter referred to as “second invention”).
【００１０】このうち、第一発明を実施するには、アニ
オン性界面活性剤と、カチオン性界面活性剤の混合溶液
中に、溶解したチタニア前駆体を加え、これを十分に攪
拌した後、ろ過、洗浄、乾燥させれば良い。Of these, in order to carry out the first invention, a dissolved titania precursor is added to a mixed solution of an anionic surfactant and a cationic surfactant, and the mixture is sufficiently stirred and then filtered. It can be washed and dried.
【００１１】この第一発明において使用されるアニオン
性界面活性剤としては、例えば、オクチル硫酸ナトリウ
ム、デシル硫酸ナトリウム、ドデシル硫酸ナトリウム、
ミリスチル硫酸ナトリウム、セチル硫酸ナトリウム、ス
テアリル硫酸ナトリウム等の中鎖ないし長鎖アルキル硫
酸塩が好ましく、またカチオン性界面活性剤としては、
セチルトリメチルアンモニウムブロマイド、ドデシルト
リメチルアンモニウムブロマイド、ミリスチルトリメチ
ルアンモニウムブロマイド、ステアリルトリメチルアン
モニウムブロマイドやこれらのクロライド等のアルキル
第四級アンモニウム塩が好ましい。As the anionic surfactant used in the first invention, for example, sodium octyl sulfate, sodium decyl sulfate, sodium dodecyl sulfate,
Medium-chain or long-chain alkyl sulfates such as sodium myristyl sulfate, sodium cetyl sulfate, and sodium stearyl sulfate are preferable, and as the cationic surfactant,
Preferred are alkyl quaternary ammonium salts such as cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, myristyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide and chlorides thereof.
【００１２】また、第一発明において使用されるチタニ
ア前駆体としては、酸化硫酸チタン、四塩化チタン等の
チタン無機塩が好ましい。As the titania precursor used in the first invention, titanium inorganic salts such as titanium oxide sulfate and titanium tetrachloride are preferable.
【００１３】この第一発明においては、アニオン性界面
活性剤と、カチオン性界面活性剤の混合割合が、メソポ
ーラスチタニア粒子の生成や、その細孔径に大きな影響
を与える。すなわち、カチオン性界面活性剤としてセチ
ルトリメチルアンモニウムブロマイド（ＣＴＡＢ）、ア
ニオン性界面活性剤としてドデシル硫酸ナトリウム（Ｓ
ＤＳ）を使用した場合、ＣＴＡＢとＳＤＳが１００：０
から５０：５０までの範囲において、細孔を有するメソ
ポーラスチタニア粒子が得られるが、この範囲外におい
ては、細孔を有するメソポーラスチタニア粒子は得られ
ない。これは、アニオン性界面活性剤としてオクチル硫
酸ナトリウム（ＳＯＳ）を使用した場合もほぼ同じであ
る。In the first invention, the mixing ratio of the anionic surfactant and the cationic surfactant has a great influence on the formation of mesoporous titania particles and the pore size thereof. That is, cetyl trimethyl ammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (S) as an anionic surfactant.
DS) is used, CTAB and SDS are 100: 0.
In the range from 50 to 50:50, mesoporous titania particles having pores can be obtained, but outside this range, mesoporous titania particles having pores cannot be obtained. This is almost the same when sodium octyl sulfate (SOS) is used as the anionic surfactant.
【００１４】またこの細孔径も、上記のアニオン性界面
活性剤と、カチオン性界面活性剤の混合割合により、調
整することができる。すなわち、カチオン性界面活性剤
が１００％の状態からアニオン性界面活性剤を加えて行
くと、細孔径は徐々に大きくなり、カチオン性界面活性
剤がＣＴＡＢ、アニオン性界面活性剤がＳＤＳの場合
は、ＣＴＡＢとＳＤＳの比が１.７５：０.２５におい
て、アニオン性界面活性剤がＳＯＳの場合は、ＣＴＡＢ
とＳＤＳの比が１.５：０.５においてそれぞれ最大とな
る。The pore size can also be adjusted by the mixing ratio of the anionic surfactant and the cationic surfactant. That is, when the anionic surfactant is added from the state where the cationic surfactant is 100%, the pore size gradually increases, and when the cationic surfactant is CTAB and the anionic surfactant is SDS, , CTAB to SDS ratio of 1.75: 0.25 and the anionic surfactant is SOS, CTAB
And the SDS ratio is maximum at 1.5: 0.5, respectively.
【００１５】従って、使用するアニオン性界面活性剤
と、カチオン性界面活性剤の種類およびその混合割合を
調整することにより、目的とする細孔径を有するメソポ
ーラスチタニア粒子が得られる。Therefore, the mesoporous titania particles having a desired pore size can be obtained by adjusting the types of anionic surfactant and cationic surfactant to be used and the mixing ratio thereof.
【００１６】一方、本発明の第二発明を実施するには、
アニオン性界面活性剤の溶液中に、チタニア前駆体と重
合抑制剤を加え、これを攪拌した後、ある程度の温度で
十分に静置し、ろ過、洗浄、乾燥させれば良い。On the other hand, in order to carry out the second invention of the present invention,
A titania precursor and a polymerization inhibitor may be added to a solution of an anionic surfactant, which may be stirred, then allowed to stand still at a certain temperature, filtered, washed and dried.
【００１７】この第二発明において使用されるアニオン
性界面活性剤としては、例えば、ラウリルリン酸ジナト
リウム、ラウリルリン酸ジカリウム、ラウリルリン酸モ
ノセシウム等のアルキルリン酸塩が好ましく、また重合
抑制剤としては、アセチルアセトン等が好ましい。As the anionic surfactant used in the second invention, alkyl phosphates such as disodium lauryl phosphate, dipotassium lauryl phosphate and monocesium lauryl phosphate are preferable, and a polymerization inhibitor is also used. As such, acetylacetone and the like are preferable.
【００１８】また、第二発明において使用されるチタニ
ア前駆体としては、チタンテトライソプロポキシド、チ
タンテトラ２−エチル−１−ヘキサノラート、チタンテ
トライソブトキシド、チタンテトライソプロポキシド等
のチタンテトラアルコキシドが好ましい。As the titania precursor used in the second invention, titanium tetraalkoxides such as titanium tetraisopropoxide, titanium tetra-2-ethyl-1-hexanolate, titanium tetraisobutoxide and titanium tetraisopropoxide are used. preferable.
【００１９】この第二発明においては、重合抑制剤の混
合比や、チタニア前駆体としてチタンテトラアルコキシ
ドを用いる場合は、そのアルコキシ基の鎖長がメソポー
ラスチタニア粒子の生成や、その細孔径等に大きな影響
を与える。すなわち、重合抑制剤の混合比が高くなるほ
ど細孔径が小さくなる傾向がある。また、チタンテトラ
アルコキシドのアルコキシ基の鎖長が長くなるほど、規
則性の高い細孔が生成する傾向がある。In the second invention, the mixing ratio of the polymerization inhibitor and, when titanium tetraalkoxide is used as the titania precursor, the chain length of the alkoxy group is large for the formation of mesoporous titania particles and the pore size thereof. Influence. That is, the higher the mixing ratio of the polymerization inhibitor, the smaller the pore size tends to be. In addition, as the chain length of the alkoxy group of titanium tetraalkoxide becomes longer, pores with higher regularity tend to be generated.
【００２０】従って、本発明第二発明では、上記の現象
を利用することにより細孔径の異なるメソポーラスチタ
ニア粒子や、規則性の程度の異なるメソポーラスチタニ
ア粒子を得ることができる。Therefore, in the second invention of the present invention, by utilizing the above phenomenon, mesoporous titania particles having different pore sizes and mesoporous titania particles having different regularity can be obtained.
【００２１】[0021]
【作用】本発明方法において、メソポーラスチタニア粒
子の細孔径や規則性を調製することができる理由は、次
のように考えられている。The reason why the pore size and regularity of the mesoporous titania particles can be adjusted in the method of the present invention is considered as follows.
【００２２】まず、第一発明においては、界面活性剤が
構成する棒状ミセルの電荷が、アニオン性界面活性剤と
カチオン性界面活性剤を組み合わせることにより変化
し、チタニア前駆体の集合に影響を与え、その結果、得
られるメソポーラスチタニア粒子の細孔径が変化するも
のと解される。First, in the first invention, the charge of rod-shaped micelles composed of a surfactant is changed by combining an anionic surfactant and a cationic surfactant, which affects the aggregation of titania precursors. As a result, it is understood that the pore size of the obtained mesoporous titania particles changes.
【００２３】すなわち、例えばカチオン性界面活性剤単
独で構成されるミセルでは、ミセル自体の外側はプラス
の電荷を有し、その外側にマイナスの電荷を有する対イ
オンが存在することになる。これに対し、チタニア前駆
体（酸化硫酸チタン等）から生じるプラスの電荷を有す
るチタンイオンは、まず、対イオンと結合し、その後、
ミセルと結合してメソポーラスチタニアになる。一方、
アニオン性界面活性剤単独あるいはアニオン性界面活性
剤がリッチなミセルでは、ミセルの周りにプラスの電荷
を有する対イオンが存在するため、ミセルと結合するこ
とが困難であり、メソポーラスチタニアにはならない。That is, for example, in a micelle composed of only a cationic surfactant, the outside of the micelle itself has a positive charge, and a counter ion having a negative charge exists outside thereof. On the other hand, a titanium ion having a positive charge generated from a titania precursor (titanium oxide sulfate, etc.) first binds with a counter ion, and then,
Combines with micelles to become mesoporous titania. on the other hand,
In anionic surfactant alone or in micelle rich in anionic surfactant, counter ions having a positive charge are present around the micelle, so that it is difficult to combine with the micelle and does not become mesoporous titania.
【００２４】ところが、カチオン性界面活性剤とアニオ
ン性界面活性剤が適当な比率で構成するミセルでは、プ
ラスの電荷を有する対イオンの数が少ないため、チタン
イオンはミセルに近づき結合しやすく、また、ミセル表
面に適当な電荷が存在するため、反応が進行し、適当な
細孔径のメソポーラスチタニアが得られることになる。
すなわち、カチオン性界面活性剤とアニオン性界面活性
剤の混合比率を変化させることにより、分子集合体であ
るミセルの相状態や表面電荷を変化させ、適当な細孔径
のメソポーラスチタニアを得ることができるのである。However, in a micelle composed of a cationic surfactant and an anionic surfactant in an appropriate ratio, since the number of counterions having a positive charge is small, the titanium ion easily approaches the micelle and is bound to it. Since there is an appropriate charge on the surface of the micelle, the reaction proceeds and mesoporous titania with an appropriate pore size is obtained.
That is, by changing the mixing ratio of the cationic surfactant and the anionic surfactant, the phase state and surface charge of the micelle, which is a molecular assembly, can be changed to obtain mesoporous titania with an appropriate pore size. Of.
【００２５】また、第二発明では、本来反応性の高いチ
タンアルコキシドをチタニア前駆体として用い、これの
反応性を反応抑制剤の添加により調整して、リン酸系な
どのアニオン性界面活性剤が構成する棒状ミセル上で、
重合反応させることにより、適当な細孔径のメソポーラ
スチタニアを得ることができると解されている。Further, in the second invention, titanium alkoxide, which is originally highly reactive, is used as a titania precursor, and the reactivity thereof is adjusted by adding a reaction inhibitor so that an anionic surfactant such as a phosphoric acid-based agent can be prepared. On the rod-shaped micelles that make up,
It is understood that a mesoporous titania having an appropriate pore size can be obtained by carrying out a polymerization reaction.
【００２６】[0026]
【実施例】次に実施例を挙げて本発明を更に詳しく説明
するが、本発明はこれら実施例等に何ら制約されるもの
ではない。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２７】実 施 例 １
注射用蒸留水２５ｍｌに、ドデシル硫酸ナトリウム（Ｓ
ＤＳ；アニオン界面活性剤）とセチルトリメチルアンモ
ニウムブロマイド（ＣＴＡＢ；カチオン界面活性剤）を
合計で２ｍｌとなるよう、下記表１の左欄の比率で加
え、溶解させた。Example 1 25 ml of distilled water for injection was added to sodium dodecyl sulfate (S
DS; anionic surfactant) and cetyltrimethylammonium bromide (CTAB; cationic surfactant) were added and dissolved so that the total amount was 2 ml in the ratio in the left column of Table 1 below.
【００２８】また別に、注射用蒸留水２５ｍｌに粉末状
の酸化硫酸チタン０.５ｇを溶解させ、これに塩酸０.５
ｇを添加した。この溶液を、攪拌状態の前記界面活性剤
溶液に添加した。添加後直ぐに白色粒子が生成する。こ
の溶液を、常温で２４時間攪拌し続けた後、ろ過して粒
子を分取し、注射用蒸留水で洗浄した。Separately, 0.5 g of powdery titanium oxide sulfate was dissolved in 25 ml of distilled water for injection, and 0.5 ml of hydrochloric acid was added thereto.
g was added. This solution was added to the stirred surfactant solution. White particles are formed immediately after the addition. The solution was continuously stirred at room temperature for 24 hours, filtered to separate particles, and washed with distilled water for injection.
【００２９】更に１２０℃で１０時間乾燥処理を行な
い、メソポーラスチタニア粒子を得た。得られたメソポ
ーラスチタニア粒子の粉末Ｘ線回析による回折ピーク
（２θ）および透過型顕微鏡による面間隔（ｎｍ）も表
１に示す。Further, it was dried at 120 ° C. for 10 hours to obtain mesoporous titania particles. Table 1 also shows the diffraction peak (2θ) of the obtained mesoporous titania particles by powder X-ray diffraction and the interplanar spacing (nm) by a transmission microscope.
【００３０】[0030]
【表１】 [Table 1]
【００３１】実 施 例 ２
ドデシル硫酸ナトリウム（ＳＤＳ）をオクチル硫酸ナト
リウム（ＳＯＳ）に代え、それらの比を表２のように変
更する以外は実施例１と同様にしてメソポーラスチタニ
ア粒子を得た。使用したＣＴＡＢとＳＯＳの比率並びに
得られた得られたメソポーラスチタニア粒子の粉末Ｘ線
回析による回折ピーク（２θ）および透過型顕微鏡によ
る面間隔（ｎｍ）を表２に示す。なお、ＣＴＡＢ／ＳＯ
Ｓが１.５０／０.５０の場合の透過型顕微鏡による写真
を図１として示す。Example 2 Mesoporous titania particles were obtained in the same manner as in Example 1 except that sodium octyl sulfate (SOS) was used instead of sodium dodecyl sulfate (SDS), and the ratio thereof was changed as shown in Table 2. Table 2 shows the ratio of CTAB and SOS used, the diffraction peak (2θ) by powder X-ray diffraction of the obtained mesoporous titania particles, and the interplanar spacing (nm) by a transmission microscope. In addition, CTAB / SO
A photograph taken by a transmission microscope when S is 1.50 / 0.50 is shown in FIG.
【００３２】[0032]
【表２】 [Table 2]
【００３３】実 施 例 ３
界面活性剤全濃度を６０ｍＭに固定し、アニオン界面活
性剤（ＳＤＳまたはＳＯＳ）とカチオン界面活性剤（Ｃ
ＴＡＢ）の混合割合（モル比）を表３のように代える以
外は実施例１と同様にしてメソポーラスチタニア粒子を
得た。使用したＣＴＡＢとＳＤＳまたはＳＯＳのモル比
並びに（１００）面の回折ピークが存在するか（細孔が
生成するか）を調べた結果を表３に示す。Example 3 The total concentration of the surfactant was fixed at 60 mM, and the anionic surfactant (SDS or SOS) and the cationic surfactant (C
Mesoporous titania particles were obtained in the same manner as in Example 1 except that the mixing ratio (molar ratio) of TAB) was changed as shown in Table 3. Table 3 shows the results of examining the molar ratio of CTAB and SDS or SOS used and whether there is a diffraction peak on the (100) plane (whether pores are generated).
【００３４】[0034]
【表３】 ○ ： （１００）面の回折ピークが存在する。 × ： 〃 存在しない。[Table 3] ◯: There is a diffraction peak on the (100) plane. ×: 〃 does not exist
【００３５】実 施 例 ４
注射用蒸留水２５ｍｌに、ラウリルリン酸ジナトリウム
（界面活性剤）を、８.８ｍｍｏｌ加え、更に塩酸を加
えてｐＨを５.５となるよう調整した。この溶液に、上
記ラウリルリン酸ジナトリウムに対し、モル比で表４の
割合となる量のチタンテトライソプロポキシド（ＴＴＩ
Ｐ）とアセチルアセトン（ａｃａｃ）を混合した。常温
で２時間静置した後、８０℃に温度を上げて２日間静置
し、粒子をろ別して注射用蒸留水で洗浄した。Example 4 To 25 ml of distilled water for injection, 8.8 mmol of disodium lauryl phosphate (surfactant) was added, and hydrochloric acid was further added to adjust the pH to 5.5. Into this solution, an amount of titanium tetraisopropoxide (TTI) in a molar ratio with respect to the disodium lauryl phosphate was obtained.
P) and acetylacetone (acac) were mixed. After standing at room temperature for 2 hours, the temperature was raised to 80 ° C. and standing for 2 days. The particles were filtered off and washed with distilled water for injection.
【００３６】更に１２０℃で１０時間乾燥処理を行な
い、メソポーラスチタニア粒子を得た。得られたメソポ
ーラスチタニア粒子の粉末Ｘ線回析による回折ピーク
（２θ）および透過型顕微鏡による面間隔（ｎｍ）も表
４に示す。なお、界面活性剤、ＴＴＩＰおよびａｃａｃ
の比が１：２：１で調製したメソポーラスチタニア粒子
の、透過型顕微鏡による写真を図２として示す。Further, it was dried at 120 ° C. for 10 hours to obtain mesoporous titania particles. Table 4 also shows the diffraction peak (2θ) of the obtained mesoporous titania particles by powder X-ray diffraction and the interplanar spacing (nm) by a transmission microscope. In addition, surfactant, TTIP and acac
A photograph of the mesoporous titania particles prepared with a ratio of 1: 2: 1 by a transmission microscope is shown as FIG.
【００３７】[0037]
【表４】 [Table 4]
【００３８】実 施 例 ５
チタンテトライソプロポキシド（ＴＴＩＰ）を、チタン
テトラ２−エチル−１−ヘキサノラート、チタンテトラ
イソブトキシドおよびチタンテトライソプロポキシドの
何れかのチタンテトラアルコキシドに代え、ラウリルリ
ン酸ジナトリウムに対し、モル比でチタンテトラアルコ
キシドとアセチルアセトンが２:１となるようにする以
外は、実施例４に準じてメソポーラスチタニア粒子を得
た。Example 5 Titanium tetraisopropoxide (TTIP) was replaced with titanium tetraalkoxide of any one of titanium tetra-2-ethyl-1-hexanolate, titanium tetraisobutoxide and titanium tetraisopropoxide, and lauryl phosphoric acid was used. Mesoporous titania particles were obtained according to Example 4 except that titanium tetraalkoxide and acetylacetone were in a molar ratio of 2: 1 with respect to disodium.
【００３９】得られたメソポーラスチタニア粒子につい
て、粉末Ｘ線回析による回折ピーク（２θ）を調べたと
ころ、チタンテトラアルコキシドのアルコキシ基の鎖長
が長いほど規則性の高い細孔が生成していることが認め
られた。With respect to the obtained mesoporous titania particles, the diffraction peak (2θ) by powder X-ray diffraction was examined, and as the chain length of the alkoxy group of titanium tetraalkoxide became longer, finer pores were formed. Was confirmed.
【００４０】参 考 例
アセチルアセトンを使用しない以外は実施例５と同様に
してメソポーラスチタニア粒子を得た。Reference Example Mesoporous titania particles were obtained in the same manner as in Example 5 except that acetylacetone was not used.
【００４１】得られたメソポーラスチタニア粒子につい
て、粉末Ｘ線回析による回折ピーク（２θ）を調べたと
ころ、チタンテトラ２−エチル−１−ヘキサノラートに
ついては細孔が生成していることが認められたが、チタ
ンテトライソブトキシドおよびチタンテトライソプロポ
キシドに関しては細孔の生成が認められなかった。When the diffraction peak (2θ) of the obtained mesoporous titania particles was examined by powder X-ray diffraction, it was confirmed that pores were formed in titanium tetra-2-ethyl-1-hexanolate. However, no pore formation was observed for titanium tetraisobutoxide and titanium tetraisopropoxide.
【００４２】[0042]
【発明の効果】本発明方法によれば、簡単な手段によ
り、細孔径や規則性の異なるメソポーラスチタニアを任
意に製造することができる。According to the method of the present invention, mesoporous titania having different pore sizes and regularities can be arbitrarily produced by a simple means.
【００４３】従って、本発明により種々の比表面積の異
なるチタニアを得ることができるので、チタニアの光触
媒や湿式太陽電池などへの応用範囲を広げることが可能
となる。Therefore, according to the present invention, various titanias having different specific surface areas can be obtained, so that the range of application of titania to a photocatalyst or a wet solar cell can be expanded.
【図１】 セチルトリメチルアンモニウムブロマイド
と、オクチル硫酸ナトリウムの比が１.５０：０.５０で
調製したメソポーラスチタニア粒子の、透過型顕微鏡に
よる写真。FIG. 1 is a transmission microscope photograph of mesoporous titania particles prepared with a ratio of cetyltrimethylammonium bromide to sodium octylsulfate of 1.50: 0.50.
【図２】 ラウリルリン酸ジナトリウム、ＴＴＩＰおよ
びａｃａｃの比が１：２：１で調製したメソポーラスチ
タニア粒子の、透過型顕微鏡による写真。
以 上FIG. 2 is a transmission electron micrograph of mesoporous titania particles prepared with a disodium lauryl phosphate, TTIP and acac ratio of 1: 2: 1. that's all
───────────────────────────────────────────────────── フロントページの続き (72)発明者 阿部 正彦 千葉県野田市大殿井58−71 (72)発明者 酒井 秀樹 神奈川県鎌倉市玉縄２−17−30 (72)発明者 萩原 英輝 東京都多摩市聖ヶ丘２−13−９ (72)発明者 柿原 敏明 神奈川県横浜市港北区綱島西４−19−10 (72)発明者 山口 有朋 神奈川県横浜市青葉区桂台２−12−32 Ｆターム(参考） 4G047 CA02 CB05 CC03 4G069 AA02 AA08 BA04A BA04B BA48A BC50C BE06C BE11C BE17C DA05 EA02X EA02Y EC09X EC09Y FA01 FC02 FC04 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masahiko Abe 58-71 Odenoi, Noda City, Chiba Prefecture (72) Inventor Hideki Sakai 2-17-30 Tamawa, Kamakura City, Kanagawa Prefecture (72) Inventor Hideki Hagiwara 2-13-9 Kiyogaoka, Tama-shi, Tokyo (72) Inventor Toshiaki Kakihara 4-19-10 Tsunashima Nishi, Kohoku Ward, Yokohama City, Kanagawa Prefecture (72) Inventor Ariomo Yamaguchi 2-12-32 Katsuradai, Aoba-ku, Yokohama-shi, Kanagawa F-term (reference) 4G047 CA02 CB05 CC03 4G069 AA02 AA08 BA04A BA04B BA48A BC50C BE06C BE11C BE17C DA05 EA02X EA02Y EC09X EC09Y FA01 FC02 FC04
Claims (5)
剤と、カチオン性界面活性剤もしくは重合阻害剤との存
在下重合させることを特徴とするメソポーラスチタニア
粒子の製造方法。1. A method for producing mesoporous titania particles, which comprises polymerizing a titania precursor in the presence of an anionic surfactant and a cationic surfactant or a polymerization inhibitor.
重合反応をアニオン性界面活性剤と、カチオン性界面活
性剤の存在下で行う請求項第１項記載のメソポーラスチ
タニア粒子の製造方法。2. The titania precursor is a titanium inorganic salt,
The method for producing mesoporous titania particles according to claim 1, wherein the polymerization reaction is carried out in the presence of an anionic surfactant and a cationic surfactant.
塩であり、カチオン性界面活性剤が、アルキル第四級ア
ンモニウム塩である請求項第１項または第２項記載のメ
ソポーラスチタニア粒子の製造方法。3. The method for producing mesoporous titania particles according to claim 1 or 2, wherein the anionic surfactant is an alkyl sulfate and the cationic surfactant is an alkyl quaternary ammonium salt. .
シドであり、重合反応をアニオン性界面活性剤と、重合
阻害剤の存在下で行う請求項第１項記載のメソポーラス
チタニア粒子の製造方法。4. The method for producing mesoporous titania particles according to claim 1, wherein the titania precursor is titanium tetraalkoxide, and the polymerization reaction is carried out in the presence of an anionic surfactant and a polymerization inhibitor.
求項第４項記載のメソポーラスチタニア粒子の製造方
法。5. The method for producing mesoporous titania particles according to claim 4, wherein the polymerization inhibitor is acetylacetone.
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| JP2001317632A JP2003119024A (en) | 2001-10-16 | 2001-10-16 | Method of producing mesoporous titania particle |
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006061367A1 (en) * | 2004-12-06 | 2006-06-15 | Colorobbia Italia S.P.A. | Process for preparing dispersions of tio2 in the form of nanoparticles, and dispersions obtainable with this process and fuctionalization of surfaces by application of tio2 dispersions |
| JP2006327849A (en) * | 2005-05-24 | 2006-12-07 | Masahiko Abe | Manufacturing method of metal oxide nanocapsule |
| KR100822439B1 (en) | 2005-02-16 | 2008-04-24 | (주)선한엠엔티 | A panel having a mesoporous TiO2 thin film and a preparation method thereof |
| JP2008222491A (en) * | 2007-03-13 | 2008-09-25 | Tokyo Univ Of Science | Porous titanium oxide and method for producing the same |
| JP2008280226A (en) * | 2007-05-14 | 2008-11-20 | Kao Corp | Method of preparing mesoporous titania |
| JP2009256137A (en) * | 2008-04-17 | 2009-11-05 | Kao Corp | Crystalline mesoporous titania |
| JP2010269303A (en) * | 2009-05-25 | 2010-12-02 | Sungkyunkwan Univ Foundation For Corporate Collaboration | Photocatalyst, preparation method thereof, photoreactor and photolysis method |
| CN108376742A (en) * | 2018-03-09 | 2018-08-07 | 湖南文理学院 | A kind of preparation method of cerium oxide base solar cell nanometer powder body material and application |
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2001
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006061367A1 (en) * | 2004-12-06 | 2006-06-15 | Colorobbia Italia S.P.A. | Process for preparing dispersions of tio2 in the form of nanoparticles, and dispersions obtainable with this process and fuctionalization of surfaces by application of tio2 dispersions |
| KR100822439B1 (en) | 2005-02-16 | 2008-04-24 | (주)선한엠엔티 | A panel having a mesoporous TiO2 thin film and a preparation method thereof |
| JP2006327849A (en) * | 2005-05-24 | 2006-12-07 | Masahiko Abe | Manufacturing method of metal oxide nanocapsule |
| JP2008222491A (en) * | 2007-03-13 | 2008-09-25 | Tokyo Univ Of Science | Porous titanium oxide and method for producing the same |
| JP2008280226A (en) * | 2007-05-14 | 2008-11-20 | Kao Corp | Method of preparing mesoporous titania |
| JP2009256137A (en) * | 2008-04-17 | 2009-11-05 | Kao Corp | Crystalline mesoporous titania |
| JP2010269303A (en) * | 2009-05-25 | 2010-12-02 | Sungkyunkwan Univ Foundation For Corporate Collaboration | Photocatalyst, preparation method thereof, photoreactor and photolysis method |
| CN108376742A (en) * | 2018-03-09 | 2018-08-07 | 湖南文理学院 | A kind of preparation method of cerium oxide base solar cell nanometer powder body material and application |
| CN108376742B (en) * | 2018-03-09 | 2021-12-07 | 湖南文理学院 | Preparation method and application of cerium oxide-based solar cell nano powder material |
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