JP2008221076A - Porous silica-titania composite material and its production method - Google Patents
Porous silica-titania composite material and its production method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011148 porous material Substances 0.000 claims abstract description 70
- 239000006249 magnetic particle Substances 0.000 claims abstract description 47
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000011246 composite particle Substances 0.000 claims description 25
- 150000004703 alkoxides Chemical class 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 229910000859 α-Fe Inorganic materials 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 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 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 4
- 239000004913 cyclooctene Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- MELPJGOMEMRMPL-UHFFFAOYSA-N 9-oxabicyclo[6.1.0]nonane Chemical compound C1CCCCCC2OC21 MELPJGOMEMRMPL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
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- 230000005389 magnetism Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001047 Hard ferrite Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910001035 Soft ferrite Inorganic materials 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- -1 WO 3 Inorganic materials 0.000 description 1
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000011545 laboratory measurement Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
Description
本発明は、例えば触媒として用いられる多孔質シリカ−チタニア複合材料に関し、詳しくは、多孔質シリカ−チタニア複合材料の回収を容易化するための改善に関する。 The present invention relates to a porous silica-titania composite material used, for example, as a catalyst, and more particularly to an improvement for facilitating the recovery of the porous silica-titania composite material.
触媒は、微粒子化されることにより、特に高機能を発揮する。しかし、触媒は、反応系に分散させて用いられる。微粒子は、反応系からの分離および回収が困難である。例えば、微粒子を短時間で反応系から濾別することは困難である。よって、従来は、凝集法や遠心分離法が採用されているが、利用コストが高くなるという問題がある。 The catalyst exhibits a particularly high function by being finely divided. However, the catalyst is used dispersed in the reaction system. Fine particles are difficult to separate and recover from the reaction system. For example, it is difficult to filter out the fine particles from the reaction system in a short time. Therefore, conventionally, the agglutination method and the centrifugal separation method are employed, but there is a problem that the use cost becomes high.
一方、反応液中から容易に回収することができる複合光触媒として、磁性粒子とその表面に固着された光触媒粒子とを含む材料が提案されている（特許文献１）。光触媒粒子としては、ＴｉＯ2、ＷＯ3、ＺｎＯ等が検討されている。 On the other hand, as a composite photocatalyst that can be easily recovered from a reaction solution, a material including magnetic particles and photocatalyst particles fixed to the surface has been proposed (Patent Document 1). As photocatalyst particles, TiO 2 , WO 3 , ZnO and the like have been studied.
しかし、触媒活性を高めるためには、様々な構造を有する多孔質材料を利用することが望まれる。特に、珪素原子とチタン原子とを含む多孔質シリカ−チタニア複合材料は、機能性材料として有用であり、様々な反応に触媒活性を有し、分子ふるい機能を有するものが多い。
本発明は、珪素原子とチタン原子とを含み、高機能を有する多孔質材料に、磁性粒子を内包させることにより、反応系からの回収が容易な多孔質シリカ−チタニア複合材料を提供するものである。 The present invention provides a porous silica-titania composite material that can be easily recovered from a reaction system by encapsulating magnetic particles in a porous material that contains silicon atoms and titanium atoms and has high functionality. is there.
本発明は、磁性粒子と、磁性粒子の表面の少なくとも一部を被覆する酸化物と、酸化物表面の少なくとも一部を被覆する多孔質材料とを含み、多孔質材料が、珪素原子およびチタン原子を含む、多孔質シリカ−チタニア複合材料に関する。 The present invention includes a magnetic particle, an oxide that covers at least a part of the surface of the magnetic particle, and a porous material that covers at least a part of the surface of the oxide, and the porous material includes silicon atoms and titanium atoms. And a porous silica-titania composite material.
本発明の多孔質シリカ−チタニア複合材料は、直径０．５〜５０ｎｍの細孔を有することが好ましく、かつ２００ｍ2／ｇ以上の比表面積を有することが好ましい。
多孔質材料に含まれるチタン原子は、４個の隣接酸素原子を有する４配位構造を有することが好ましい。
The porous silica-titania composite material of the present invention preferably has pores having a diameter of 0.5 to 50 nm, and preferably has a specific surface area of 200 m 2 / g or more.
The titanium atom contained in the porous material preferably has a tetracoordinate structure having four adjacent oxygen atoms.
多孔質材料は、メソポーラスシリカ骨格またはゼオライト骨格を有し、その骨格中の珪素原子またはアルミニウム原子の一部が、チタン原子で置換されている材料であることが好ましい。 The porous material is preferably a material having a mesoporous silica skeleton or a zeolite skeleton, and a part of silicon atoms or aluminum atoms in the skeleton being substituted with titanium atoms.
磁性粒子の表面の少なくとも一部を被覆する酸化物は、酸化珪素を含むことが好ましい。
磁性粒子は、例えばフェライト材料を含む。
The oxide covering at least a part of the surface of the magnetic particle preferably contains silicon oxide.
The magnetic particles include, for example, a ferrite material.
本発明は、また、（i）磁性粒子の表面の少なくとも一部を酸化物で被覆して、第１複合粒子を形成し、（ii）第１複合粒子を、珪素原子含有アルコキシドと、チタン原子含有アルコキシドと、構造規制剤とを含む液に分散させ、第１複合粒子の表面の少なくとも一部を多孔質材料の前駆体で被覆して、第２複合粒子を形成し、（iii）第２複合粒子を焼成して、多孔質材料の前駆体を多孔質材料に変化させる、ことを含む多孔質シリカ−チタニア複合材料の製造方法に関する。 In the present invention, (i) at least a part of the surface of the magnetic particle is coated with an oxide to form a first composite particle, and (ii) the first composite particle is composed of a silicon atom-containing alkoxide and a titanium atom. (Iii) a second composite particle, which is dispersed in a liquid containing an alkoxide containing and a structure-regulating agent, and at least a part of the surface of the first composite particle is coated with a precursor of a porous material. The present invention relates to a method for producing a porous silica-titania composite material, comprising firing composite particles to change a precursor of the porous material into a porous material.
工程（i）は、珪素原子含有アルコキシドを含む液中に磁性粒子を分散させ、磁性粒子の表面の少なくとも一部を酸化珪素の前駆体で被覆し、得られた粒子を焼成する工程を含むことが好ましい。 Step (i) includes a step of dispersing magnetic particles in a liquid containing a silicon atom-containing alkoxide, coating at least a part of the surface of the magnetic particles with a silicon oxide precursor, and firing the obtained particles. Is preferred.
工程（ii）は、第１複合粒子と、珪素原子含有アルコキシドと、チタン原子含有アルコキシドと、構造規制剤とを含む液を、加圧下で加熱する工程を含んでもよい。 Step (ii) may include a step of heating the liquid containing the first composite particles, the silicon atom-containing alkoxide, the titanium atom-containing alkoxide, and the structure regulating agent under pressure.
本発明によれば、様々な構造を有する多孔質シリカ−チタニア複合材料に、磁性粒子を内包させることができる。本発明の多孔質シリカ−チタニア複合材料は、磁性粒子を内包しているため、磁力により引き寄せられる。よって、多孔質シリカ−チタニア複合材料を触媒として用いる場合には、磁石などを利用して、触媒を反応系から容易に回収することができる。更に、磁性粒子は多孔質材料に内包されているため、触媒の活性サイトに影響を与えない。 According to the present invention, magnetic particles can be included in a porous silica-titania composite material having various structures. Since the porous silica-titania composite material of the present invention contains magnetic particles, it is attracted by a magnetic force. Therefore, when the porous silica-titania composite material is used as a catalyst, the catalyst can be easily recovered from the reaction system using a magnet or the like. Furthermore, since the magnetic particles are encapsulated in the porous material, the active sites of the catalyst are not affected.
本発明の多孔質シリカ−チタニア複合材料は、磁性粒子（すなわち磁性材料の粒子）を内包している。磁性材料の種類は特に限定されないが、安価である点で、酸化物磁性体が好ましい。酸化物磁性体の中でも磁力の強いフェライト材料が好ましく、軟磁性を示すソフトフェライト材料でも、硬磁性を示すハードフェライト材料でもよい。フェライト材料の結晶構造も、特に限定されないが、例えばスピネルフェライト材料、六方晶フェライト材料、ガーネットフェライトなどを用いることができる。最も一般的な磁性材料として、三酸化二鉄（Ｆｅ2Ｏ3）、四酸化三鉄（Ｆｅ3Ｏ4）などが挙げられる。磁性粒子の一次粒子径は、特に限定されないが、１．０〜５０ｎｍ程度であることが好ましい。 The porous silica-titania composite material of the present invention includes magnetic particles (that is, magnetic material particles). The type of the magnetic material is not particularly limited, but an oxide magnetic material is preferable because it is inexpensive. Among oxide magnetic materials, a ferrite material having a strong magnetic force is preferable, and a soft ferrite material exhibiting soft magnetism or a hard ferrite material exhibiting hard magnetism may be used. The crystal structure of the ferrite material is not particularly limited. For example, spinel ferrite material, hexagonal ferrite material, garnet ferrite, or the like can be used. The most common magnetic materials include ferric trioxide (Fe 2 O 3 ) and triiron tetroxide (Fe 3 O 4 ). The primary particle size of the magnetic particles is not particularly limited, but is preferably about 1.0 to 50 nm.
本発明の多孔質シリカ−チタニア複合材料は、珪素原子およびチタン原子を含む多孔質材料を含む。多孔質材料は、例えば骨格内にチタン原子を含有する珪酸塩を含む。なお、珪酸塩は、珪素原子およびチタン原子以外の金属原子を含んでもよい。そのような金属原子としては、例えばアルミニウム、マグネシウム、ナトリウムなどが挙げられる。 The porous silica-titania composite material of the present invention includes a porous material containing silicon atoms and titanium atoms. The porous material includes, for example, a silicate containing a titanium atom in the skeleton. The silicate may contain metal atoms other than silicon atoms and titanium atoms. Examples of such metal atoms include aluminum, magnesium, sodium and the like.
優れた触媒活性を得る観点からは、多孔質材料に含まれるチタン原子は、珪酸塩の骨格内に取り込まれていることが好ましく、４個の隣接酸素原子を有する４配位構造を有することが好ましい。なかでも、多孔質材料は、メソポーラスシリカ骨格またはゼオライト骨格を有し、その骨格中の珪素原子またはアルミニウム原子の一部が、チタン原子で置換されている材料であることが特に好ましい。 From the viewpoint of obtaining excellent catalytic activity, the titanium atoms contained in the porous material are preferably incorporated in the silicate skeleton, and have a four-coordinate structure having four adjacent oxygen atoms. preferable. Among these, the porous material is particularly preferably a material having a mesoporous silica skeleton or a zeolite skeleton, and a part of silicon atoms or aluminum atoms in the skeleton being substituted with titanium atoms.
メソポーラスシリカ骨格を有する多孔質材料の中では、例えばＭＣＭ−４１、ＭＣＭ−４８、ＭＣＭ−５０などの珪素原子の一部をチタン原子で置換した材料が好ましい。メソポーラス骨格を有する多孔質材料は、規則的に配列した複数の筒状のメソ細孔を有する。筒状のメソ細孔は、例えばハニカム状に配列しており、メソ細孔は、ほぼ均一な大きさを有する。メソ細孔の内径は、一般に２〜５０ｎｍ程度であるが、これに限定されない。 Among porous materials having a mesoporous silica skeleton, for example, materials in which a part of silicon atoms are substituted with titanium atoms, such as MCM-41, MCM-48, and MCM-50, are preferable. A porous material having a mesoporous skeleton has a plurality of cylindrical mesopores regularly arranged. The cylindrical mesopores are arranged in a honeycomb shape, for example, and the mesopores have a substantially uniform size. The inner diameter of the mesopores is generally about 2 to 50 nm, but is not limited thereto.
ゼオライト骨格を有する多孔質材料の中では、例えばアルミノシリケート、シリカライト、チタノシリカライトなどの珪素原子またはアルミニウム原子の一部をチタン原子で置換した材料が好ましい。 Among the porous materials having a zeolite skeleton, for example, a material in which a silicon atom or a part of an aluminum atom is substituted with a titanium atom, such as aluminosilicate, silicalite, and titanosilicalite, is preferable.
ゼオライトの構造は、特に限定されないが、Ｘ型、Ｙ型、ＺＳＭ−５、ＺＳＭ−４８などが好ましい。なかでも、熱的安定性が高く、各種の選択反応を可能とする細孔を有する点で、国際ゼオライト学会（ＩＺＡ）により制定された結晶構造であるＭＦＩ構造が特に好ましい。ゼオライトの細孔の内径は、一般に０．５〜２ｎｍ程度であるが、これに限定されない。 The structure of the zeolite is not particularly limited, but X-type, Y-type, ZSM-5, ZSM-48 and the like are preferable. Among these, the MFI structure, which is a crystal structure established by the International Zeolite Society (IZA), is particularly preferable in that it has high thermal stability and has pores that allow various selective reactions. The inner diameter of the pores of zeolite is generally about 0.5 to 2 nm, but is not limited thereto.
多孔質材料に含まれるチタン原子と珪素原子とのモル比：Ｔｉ／Ｓｉは、０．０００５≦Ｔｉ／Ｓｉ≦０．１が好ましく、０．００５≦Ｔｉ／Ｓｉ≦０．０５が更に好ましい。チタンの含有量が上記の下限よりも少ないと、多孔質材料の単位表面積当りのチタン原子数が少なくなり、触媒活性が低下する場合がある。一方、チタンの含有量が上記の上限より多いと、多孔質材料の細孔内に酸化チタンが存在するようになり、チタン原子の分散性が低下する。結果として、触媒活性が低下する場合がある。 The molar ratio of titanium atoms to silicon atoms contained in the porous material: Ti / Si is preferably 0.0005 ≦ Ti / Si ≦ 0.1, and more preferably 0.005 ≦ Ti / Si ≦ 0.05. If the titanium content is less than the above lower limit, the number of titanium atoms per unit surface area of the porous material may decrease, and the catalytic activity may decrease. On the other hand, when the content of titanium is higher than the above upper limit, titanium oxide is present in the pores of the porous material, and the dispersibility of titanium atoms is lowered. As a result, the catalyst activity may decrease.
磁性粒子の表面の少なくとも一部は、酸化物で被覆されている。すなわち、磁性粒子と多孔質材料との間には、酸化物が介在している。酸化物は、多孔質材料と磁性粒子との結合力を高めるとともに、多孔質材料の結晶構造の発達を促進する役割を果たすと考えられる。なお、磁性粒子の表面に、４配位構造を有する高活性なチタン原子を含む珪酸塩を、直接担持させることは困難である。また、磁性粒子の表面に、メソポーラスシリカ骨格またはゼオライト骨格を有する珪酸塩を、直接担持させることは困難である。これは、磁性粒子が、メソポーラスシリカ骨格またはゼオライト骨格の形成を阻害するためと考えられる。 At least a part of the surface of the magnetic particle is coated with an oxide. That is, an oxide is interposed between the magnetic particles and the porous material. The oxide is considered to play a role of enhancing the bonding force between the porous material and the magnetic particles and promoting the development of the crystal structure of the porous material. It is difficult to directly support a silicate containing a highly active titanium atom having a tetracoordinate structure on the surface of the magnetic particle. Further, it is difficult to directly support a silicate having a mesoporous silica skeleton or a zeolite skeleton on the surface of magnetic particles. This is presumably because the magnetic particles inhibit the formation of mesoporous silica skeleton or zeolite skeleton.
磁性粒子の表面の少なくとも一部を被覆する酸化物は、特に限定されないが、磁性粒子との結合性、および、多孔質材料との結合性に優れている点で、酸化珪素を含むことが好ましい。また、磁性粒子との結合性を高める観点から、酸化珪素は、非晶質の領域を含むことが好ましい。 The oxide covering at least a part of the surface of the magnetic particles is not particularly limited, but preferably contains silicon oxide in terms of excellent binding properties with magnetic particles and porous materials. . Moreover, it is preferable that a silicon oxide contains an amorphous area | region from a viewpoint of improving the bondability with a magnetic particle.
本発明の多孔質シリカ−チタニア複合材料は、直径０．５〜５０ｎｍの細孔を有することが好ましい。細孔の直径が上記の下限未満では、大きな分子の酸化反応などに対する触媒性能の低下を招く場合がある。一方、細孔の直径が上記の上限を超えると、多孔質シリカ−チタニア複合材料の表面積の低下や、細孔空間を利用した選択反応の選択性の低下を招く場合がある。 The porous silica-titania composite material of the present invention preferably has pores having a diameter of 0.5 to 50 nm. When the diameter of the pore is less than the lower limit, there may be a case where the catalyst performance is deteriorated with respect to an oxidation reaction of a large molecule. On the other hand, if the diameter of the pores exceeds the above upper limit, the surface area of the porous silica-titania composite material may be reduced, or the selectivity of the selective reaction utilizing the pore space may be reduced.
本発明の多孔質シリカ−チタニア複合材料の比表面積は、２００ｍ2／ｇ以上であることが好ましく、２５０〜１０００ｍ2／ｇであることが更に好ましい。比表面積が上記の下限未満では、触媒活性サイト数の減少を招く場合がある。 Porous silica of the present invention - a specific surface area of the titania composite material is preferably at 200 meters 2 / g or more, more preferably 250~1000m 2 / g. If the specific surface area is less than the above lower limit, the number of catalytically active sites may be reduced.
本発明の多孔質シリカ−チタニア複合材料に含まれる、多孔質材料の量は、磁性粒子１００重量部あたり、１００〜１０００重量部が好適である。多孔質材料の量が多すぎると、多孔質シリカ−チタニア複合材料の回収が困難となる場合がある。一方、多孔質材料の量が少なすぎると、チタン原子数が少なくなり、触媒活性が低下する場合がある。 The amount of the porous material contained in the porous silica-titania composite material of the present invention is preferably 100 to 1000 parts by weight per 100 parts by weight of the magnetic particles. If the amount of the porous material is too large, it may be difficult to recover the porous silica-titania composite material. On the other hand, if the amount of the porous material is too small, the number of titanium atoms decreases, and the catalytic activity may decrease.
磁性材料の表面の少なくとも一部を被覆する酸化物の量は、磁性粒子１００重量部あたり、１０〜５００重量部が好適である。酸化物の量が多すぎると、多孔質シリカ−チタニア複合材料に占める多孔質材料の割合が相対的に小さくなり、触媒活性が低下する場合がある。一方、酸化物の量が少なすぎると、磁性粒子と多孔質材料との結合力が不十分になったり、多孔質材料の細孔構造が充分に発達しなかったりする場合がある。 The amount of oxide covering at least a part of the surface of the magnetic material is preferably 10 to 500 parts by weight per 100 parts by weight of the magnetic particles. If the amount of the oxide is too large, the proportion of the porous material in the porous silica-titania composite material becomes relatively small, and the catalytic activity may decrease. On the other hand, if the amount of oxide is too small, the binding force between the magnetic particles and the porous material may be insufficient, or the pore structure of the porous material may not be sufficiently developed.
本発明の多孔質シリカ−チタニア複合材料の平均粒径（体積基準の粒度分布における５０％値：Ｄ50）は、１０〜５００μｍであることが好ましい。平均粒径が小さすぎると、多孔質シリカ−チタニア複合材料の回収を容易にする効果が低減する。一方、平均粒径が大きすぎると、多孔質シリカ−チタニア複合材料を触媒として用いる場合に、反応系に分散しにくくなる場合がある。 The average particle size (50% value in the volume-based particle size distribution: D 50 ) of the porous silica-titania composite material of the present invention is preferably 10 to 500 μm. If the average particle size is too small, the effect of facilitating the recovery of the porous silica-titania composite material is reduced. On the other hand, if the average particle size is too large, it may be difficult to disperse in the reaction system when the porous silica-titania composite material is used as a catalyst.
次に、多孔質シリカ−チタニア複合材料の製造方法の一例について図１を参照しながら説明する。
（i）磁性粒子１０の表面の少なくとも一部を酸化物１２で被覆し、第１複合粒子１４を形成する。磁性粒子１０の表面に直接結合した多孔質材料を合成することは困難であるが、磁性粒子１０の表面の少なくとも一部を酸化物１２で被覆することにより、磁性粒子１０と細孔構造の発達した多孔質材料１６との複合化が可能となる。
Next, an example of a method for producing a porous silica-titania composite material will be described with reference to FIG.
(I) At least a part of the surface of the magnetic particle 10 is covered with the oxide 12 to form the first composite particle 14. Although it is difficult to synthesize a porous material directly bonded to the surface of the magnetic particle 10, the development of the magnetic particle 10 and the pore structure is achieved by covering at least a part of the surface of the magnetic particle 10 with the oxide 12. The composite with the porous material 16 thus made becomes possible.
例えば、珪素原子含有アルコキシドを含む液中に磁性粒子を分散させる。磁性粒子は、例えば水とアルコールとの混合液中に分散させることが好ましい。アルコールには、エタノール、プロパノールなどを用いることができる。磁性粒子１０を分散させた液中に、攪拌下、珪素原子含有アルコキシド（例えばテトラエトキシシラン：ＴＥＯＳ）を滴下すると、酸化珪素の前駆体と磁性粒子との複合物が得られる。得られた複合物を乾燥させた後、例えば４００Ｋ〜６００Ｋの温度で焼成すると、磁性粒子１０と酸化物１２とを含む第１複合粒子１４が得られる。このときの焼成雰囲気は、酸素を含む雰囲気（例えば空気）であればよい。 For example, magnetic particles are dispersed in a liquid containing a silicon atom-containing alkoxide. The magnetic particles are preferably dispersed, for example, in a mixed liquid of water and alcohol. As the alcohol, ethanol, propanol or the like can be used. When a silicon atom-containing alkoxide (for example, tetraethoxysilane: TEOS) is dropped into the liquid in which the magnetic particles 10 are dispersed with stirring, a composite of a silicon oxide precursor and magnetic particles is obtained. After drying the obtained composite, for example, when fired at a temperature of 400K to 600K, the first composite particles 14 including the magnetic particles 10 and the oxides 12 are obtained. The firing atmosphere at this time may be an atmosphere containing oxygen (for example, air).
（ii）得られた第１複合粒子１４を、珪素原子含有アルコキシド（例えばＴＥＯＳ）と、チタン原子含有アルコキシド（例えばテトライソプロポキシチタン：ＴＰＯＴ）と、構造規制剤（例えばドデシルアミン：ＤＤＡ）とを含む液に分散させる。 (Ii) The obtained first composite particles 14 are obtained by adding a silicon atom-containing alkoxide (for example, TEOS), a titanium atom-containing alkoxide (for example, tetraisopropoxytitanium: TPOT), and a structure regulating agent (for example, dodecylamine: DDA). Disperse in the containing liquid.
構造規制剤は、特に限定されず、様々な界面活性剤を用いることができる。例えばメソポーラスシリカ骨格を有する多孔質材料を形成する場合、ドデシルアミン、ポリエチレングリコールドデシルエーテル、ラウリルポリオキシエチレンエーテルなどの非イオン界面活性剤などを用いることができる。これらは単独で用いてもよく、複数種を組み合わせて用いてもよい。構造規制剤となる界面活性剤の分子量は、２５０〜３０００もしくは３００〜１０００が好適である。 The structure regulating agent is not particularly limited, and various surfactants can be used. For example, when forming a porous material having a mesoporous silica skeleton, nonionic surfactants such as dodecylamine, polyethylene glycol dodecyl ether, and lauryl polyoxyethylene ether can be used. These may be used alone or in combination of two or more. As for the molecular weight of the surfactant used as a structure control agent, 250-3000 or 300-1000 is suitable.
珪素原子含有アルコキシドとしては、オルトケイ酸テトラエチル（テトラエトキシシラン）、テトラメトキシシランなどを用いることができる。また、珪素含有アルコキシドの代わりに、塩化ケイ素、液状の珪酸塩などを用いることもできる。これらは単独で用いてもよく、複数種を組み合わせて用いてもよい。 As the silicon atom-containing alkoxide, tetraethyl orthosilicate (tetraethoxysilane), tetramethoxysilane, or the like can be used. Further, silicon chloride, liquid silicate, or the like can be used instead of the silicon-containing alkoxide. These may be used alone or in combination of two or more.
チタン原子含有アルコキシドとしては、特に限定されないが、例えばテトラエトキシチタン、テトライソプロポキシチタンなどを用いることができる。チタン原子含有アルコキシドは１種を単独で用いてもよく、複数種を組み合わせて用いてもよい。 Although it does not specifically limit as a titanium atom containing alkoxide, For example, tetraethoxy titanium, tetraisopropoxy titanium, etc. can be used. A titanium atom containing alkoxide may be used individually by 1 type, and may be used in combination of multiple types.
液中は酸性もしくは塩基性条件下であることが好ましい。この状態で液を攪拌すると、構造規制剤の主鎖がミセル状に規則的に配列し、その周りを覆うように、チタン原子が組み込まれたシリカマトリックスが形成される。こうして得られた多孔質材料の前駆体が、第１複合粒子の表面の少なくとも一部を被覆することにより、第２複合粒子が形成される。 The liquid is preferably under acidic or basic conditions. When the liquid is stirred in this state, the main chain of the structure-regulating agent is regularly arranged in a micelle shape, and a silica matrix incorporating titanium atoms is formed so as to cover the periphery. The precursor of the porous material thus obtained covers at least part of the surface of the first composite particles, whereby the second composite particles are formed.
なお、ゼオライト骨格を有する多孔質材料を形成する場合には、第１複合粒子と、珪素原子含有アルコキシドと、チタン原子含有アルコキシドと、構造規制剤とを、オートクレーブなどに導入し、加圧下で加熱する。ゼオライト骨格を有する多孔質材料を形成する場合、構造規制剤には、テトラプロピルアンモニウムハイドロキサイド（ＴＰＡＯＨ）、テトラプロピルアンモニウムブロマイド（ＴＰＡＢｒ）などを用いることができる。これらは単独で用いてもよく、複数種を組み合わせて用いてもよい。 When forming a porous material having a zeolite skeleton, first composite particles, a silicon atom-containing alkoxide, a titanium atom-containing alkoxide, and a structure regulating agent are introduced into an autoclave and heated under pressure. To do. When forming a porous material having a zeolite skeleton, tetrapropylammonium hydroxide (TPAOH), tetrapropylammonium bromide (TPABr), or the like can be used as the structure regulating agent. These may be used alone or in combination of two or more.
（iii）得られた第２複合粒子を焼成すると、有機物である構造規制剤は燃焼する。その結果、多孔質材料の前駆体は、規則的な細孔を有する多孔質材料１６に変化し、多孔質シリカ−チタニア複合材料１８が得られる。このときの焼成温度は、例えば７００Ｋ〜９００Ｋであればよく、焼成雰囲気は、酸素を含む雰囲気（例えば空気）であればよい。 (Iii) When the obtained 2nd composite particle is baked, the structure control agent which is organic substance will combust. As a result, the precursor of the porous material is changed to the porous material 16 having regular pores, and the porous silica-titania composite material 18 is obtained. The firing temperature at this time may be, for example, 700K to 900K, and the firing atmosphere may be an atmosphere containing oxygen (for example, air).
磁性粒子であるＦｅ2Ｏ3の粒子と、その表面の少なくとも一部を被覆する酸化珪素（シリカ）と、酸化珪素の少なくとも一部を被覆する多孔質材料とを含み、多孔質材料が、メソポーラスシリカ骨格を有し、骨格中の珪素原子の一部がチタン原子で置換されている、多孔質シリカ−チタニア複合材料（以下、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3）を、以下の要領で作製した。 Fe 2 O 3 particles that are magnetic particles, silicon oxide (silica) covering at least part of the surface, and a porous material covering at least part of the silicon oxide, the porous material being mesoporous A porous silica-titania composite material (hereinafter referred to as Ti-HMS / Fe 2 O 3 ) having a silica skeleton and in which some of the silicon atoms in the skeleton are substituted with titanium atoms was produced in the following manner. .
工程（i）
３つ口フラスコに、塩化鉄(II)四水和物（和光純薬工業株式会社製）を０．３９８ｇと、塩化鉄(III)六水和物（和光純薬工業株式会社製）を１．０８１２ｇとを入れた。フラスコ内を真空排気し、アルゴン置換を数回行った。その後、フラスコ内に脱イオン水２００ｍｌを加え、常温下、メカニカルスターラーで攪拌し、固形分を溶解させ、橙色の溶液を得た。１０分後に２５％アンモニア水（和光純薬工業株式会社製）４ｍｌを滴下すると、黒色粒子のマグネタイト（Ｆｅ3Ｏ4：一次粒子径約９〜１０ｎｍ）が生成した。そのまま常温で３時間攪拌を続けた。
Process (i)
In a three-necked flask, 0.398 g of iron (II) chloride tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 of iron chloride (III) hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.0812 g was added. The flask was evacuated and replaced with argon several times. Thereafter, 200 ml of deionized water was added to the flask, and the mixture was stirred with a mechanical stirrer at room temperature to dissolve the solid content, thereby obtaining an orange solution. Ten minutes later, when 4 ml of 25% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, black particles of magnetite (Fe 3 O 4 : primary particle diameter of about 9 to 10 nm) were produced. Stirring was continued for 3 hours at room temperature.
フラスコ内に、２−プロパノール（特級、和光純薬工業株式会社製）１００ｍｌを加え、３１３Ｋで３０分間攪拌後、テトラエトキシシラン（ＴＥＯＳ）（特級、和光純薬工業株式会社製）を１．２５g滴下し、３１３Ｋで２０時間攪拌した。その後、吸引濾過を行い、得られた黒色粉末を、大気中、３８３Ｋで一晩乾燥した。乾燥後の粉末を、５２３Ｋで５時間焼成し、酸化珪素を担持した酸化鉄からなる第１複合粒子を得た。 Into the flask, 100 ml of 2-propanol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 313K for 30 minutes, and then 1.25 g of tetraethoxysilane (TEOS) (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was added. The solution was added dropwise and stirred at 313 K for 20 hours. Thereafter, suction filtration was performed, and the obtained black powder was dried overnight at 383 K in the air. The dried powder was fired at 523 K for 5 hours to obtain first composite particles made of iron oxide carrying silicon oxide.
工程（ii）
イオン交換水３０ｍｌに構造規制剤としてドデシルアミン（ＤＤＡ）（一級、和光純薬工業株式会社製）３ｇを溶かした溶液と、３６％塩酸（特級、和光純薬工業株式会社製）４３．８ｍｇをイオン交換水１０ｍｌに溶かした溶液とを混合し、溶液Ａを調製した。溶液Ａは１時間攪拌した。
Step (ii)
A solution obtained by dissolving 3 g of dodecylamine (DDA) (primary grade, manufactured by Wako Pure Chemical Industries, Ltd.) as a structure regulating agent in 30 ml of ion-exchanged water, and 43.8 mg of 36% hydrochloric acid (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) A solution dissolved in 10 ml of ion-exchanged water was mixed to prepare a solution A. Solution A was stirred for 1 hour.
ＴＥＯＳを１２．５ｇと、テトライソプロポキシチタン（ＴＰＯＴ）（一級、和光純薬工業株式会社製）０．１７１ｇとを、エタノール（特級、和光純薬工業株式会社製）２０ｍｌと２−プロパノール２０ｍｌとの混合液に溶かし、溶液Ｂを調製した。溶液Ｂも１時間攪拌した。 12.5 g of TEOS, 0.171 g of tetraisopropoxy titanium (TPOT) (first grade, manufactured by Wako Pure Chemical Industries, Ltd.), 20 ml of ethanol (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 20 ml of 2-propanol To prepare a solution B. Solution B was also stirred for 1 hour.
次に、上記の第１複合粒子を、エタノール１００ｍｌとともに３つ口フラスコに導入し、更に、上記の攪拌後の溶液Ａと溶液Ｂを導入し、常温下、２０時間の攪拌を行った。その後、吸引濾過を行い、得られた茶色粉末（第２複合粒子）を得た。 Next, the first composite particles were introduced into a three-necked flask together with 100 ml of ethanol, and further, the solution A and the solution B after stirring were introduced, followed by stirring at room temperature for 20 hours. Thereafter, suction filtration was performed to obtain the obtained brown powder (second composite particles).
工程（iii）
得られた第２複合粒子を、大気中、３８３Ｋで一晩乾燥した。乾燥後の粉末を、８２３Ｋで５時間焼成し、多孔質材料であるチタン原子含有メソポーラスシリカを生成させた。最後に粉末をイオン交換水で数回洗浄し、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3を得た。
Step (iii)
The obtained second composite particles were dried overnight at 383 K in the air. The dried powder was fired at 823 K for 5 hours to produce titanium atom-containing mesoporous silica as a porous material. Finally, the powder was washed several times with ion exchanged water to obtain Ti-HMS / Fe 2 O 3 .
なお、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3において、金属元素のモル比は、Ｆｅ：Ｓｉ（酸化珪素部分）：Ｓｉ（チタン原子含有メソポーラスシリカ部分）：Ｔｉ（チタン原子含有メソポーラスシリカ部分）＝１０：１０：１００：１のモル比とした。すなわち、多孔質材料に含まれるＴｉ原子とＳｉ原子とのモル比はＴｉ／Ｓｉ＝０．０１であり、Ｆｅ2Ｏ3１００重量部あたりの多孔質材料の重量は約７５０重量部であり、Ｆｅ2Ｏ3１００重量部あたりの酸化珪素の重量は約７５重量部であった。
Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3の平均粒径（体積基準の粒度分布における５０％値：Ｄ50）は、５０μｍであった。
In Ti-HMS / Fe 2 O 3 , the molar ratio of the metal elements is Fe: Si (silicon oxide portion): Si (titanium atom-containing mesoporous silica portion): Ti (titanium atom-containing mesoporous silica portion) = 10: The molar ratio was 10: 100: 1. That is, the molar ratio of Ti atoms to Si atoms contained in the porous material is Ti / Si = 0.01, and the weight of the porous material per 100 parts by weight of Fe 2 O 3 is about 750 parts by weight, The weight of silicon oxide per 100 parts by weight of Fe 2 O 3 was about 75 parts by weight.
The average particle size of Ti—HMS / Fe 2 O 3 (50% value in the volume-based particle size distribution: D 50 ) was 50 μm.
《比較例１》
工程（ii）において、第１複合粒子を３つ口フラスコに導入しなかったこと以外、実施例１と同様の操作を行った。その結果、多孔質材料であるチタン原子含有メソポーラスシリカ（以下、Ｔｉ−ＨＭＳ）だけが得られた。
<< Comparative Example 1 >>
In the step (ii), the same operation as in Example 1 was performed except that the first composite particles were not introduced into the three-necked flask. As a result, only titanium atom-containing mesoporous silica (hereinafter referred to as Ti-HMS), which is a porous material, was obtained.
［評価］
Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3およびＴｉ−ＨＭＳのキャラクタリゼーションを行った。
（i）Ｘ線回折（ＸＲＤ）
測定は以下の装置、条件で行った。試料はメノウ乳鉢で均一に粉砕して測定用ガラスホルダーに詰めて測定を行った。
測定装置：理学電機株式会社製のＲＩＮＴ２０００縦型ゴニオメーター
Ｘ線：ＣｕＫα線（波長＝１．５４０５６Å）
管電圧：４０ｋＶ
管電流：２０ｍＡ
スリット幅：発散スリット０．５ｄｅｇ
散乱スリット：０．５ｄｅｇ
受光スリット：０．１５ｍｍ
モノクロ受光スリット：０．８ｍｍ
サンプリング幅：０．０２°
計数時間：１秒
スキャンモード：２θ/θ
スキャンタイプ：連続
[Evaluation]
Characterization of Ti-HMS / Fe 2 O 3 and Ti-HMS was performed.
(I) X-ray diffraction (XRD)
The measurement was performed with the following apparatus and conditions. The sample was uniformly pulverized in an agate mortar and packed in a measuring glass holder for measurement.
Measuring apparatus: RINT2000 vertical goniometer manufactured by Rigaku Corporation X-ray: CuKα ray (wavelength = 1.54056 mm)
Tube voltage: 40 kV
Tube current: 20 mA
Slit width: Divergence slit 0.5deg
Scattering slit: 0.5 deg
Receiving slit: 0.15mm
Monochrome light receiving slit: 0.8mm
Sampling width: 0.02 °
Counting time: 1 second Scan mode: 2θ / θ
Scan type: Continuous
図２（Ａ）にＴｉ−ＨＭＳ／Ｆｅ2Ｏ3、図２（Ｂ）にＴｉ−ＨＭＳの低角度ＸＲＤパターンを示す。いずれのパターンにおいても、メソポーラスシリカの（１００）面由来のピークが見られ、メソポーラスシリカ骨格が形成されていることがわかる。Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3のピーク位置は、Ｔｉ−ＨＭＳと比較して、高角度側にシフトしている。（１００）面間隔をＢｒａｇｇ式より求めると３１．５Åであった。 2A shows a Ti-HMS / Fe 2 O 3 , and FIG. 2B shows a Ti-HMS low-angle XRD pattern. In any pattern, a peak derived from the (100) plane of mesoporous silica is seen, indicating that a mesoporous silica skeleton is formed. The peak position of Ti—HMS / Fe 2 O 3 is shifted to the high angle side as compared with Ti—HMS. When the (100) plane spacing was determined from the Bragg equation, it was 31.5 mm.
（ii）ＢＥＴ比表面積
測定は以下の装置、条件で行った。試料を約０．１ｇ秤量してセルに入れ、ＢＥＴ比表面積とＢＪＨ細孔径分布を求めた。
測定装置：マイクロメリティクス社製のＡＳＡＰ２０１０
吸着気体分子：窒素
ＢＥＴ比表面積は９１０ｍ2／ｇであり、メソポアが存在していると考えられる。細孔分布から求めた平均細孔径（細孔の直径）は３.０１ｎｍであった。
(Ii) BET specific surface area The measurement was performed with the following apparatus and conditions. About 0.1 g of the sample was weighed and placed in a cell, and the BET specific surface area and BJH pore size distribution were determined.
Measuring apparatus: ASAP2010 manufactured by Micromeritics
Adsorbed gas molecules: nitrogen The BET specific surface area is 910 m 2 / g, and it is considered that mesopores are present. The average pore diameter (pore diameter) determined from the pore distribution was 3.01 nm.
（iii）ＸＡＦＳスペクトル
測定は以下の装置、条件で行った。スペクトル解析には、理学電機工業株式会社のＥＸＡＦＳデータ解析プログラムＲＥＸ２０００を用いた。
装置：筑波高エネルギー物理学研究所のＰｈｏｔｏｎ Ｆａｃｔｏｒｙ ＢＬ−７Ｃライン
測定元素：ＴｉＫエッジ、室温、蛍光モード
検出ガス：Ｈｅ
いずれの試料においても、一本の鋭いプレエッジピークが見られた。このピークは４配位構造を有するチタン原子の存在を示している。このことは、チタン原子がメソポーラスシリカの骨格に組み込まれていることを示唆している。また、ＦＴ−ＥＸＡＦＳでは、いずれの試料においても、チタニア粉末に現れる２．９Å付近のＴｉ−Ｏ−Ｔｉ結合由来のピークはみられなかった。これらの結果より、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3およびＴｉ−ＨＭＳに含まれるチタン原子は、高分散状態で存在していることがわかる。
(Iii) XAFS spectrum The measurement was performed with the following apparatus and conditions. For the spectrum analysis, EXAFS data analysis program REX2000 of Rigaku Denki Kogyo Co., Ltd. was used.
Apparatus: Photon Factory BL-7C line of Tsukuba High Energy Physics Laboratory Measurement element: TiK edge, room temperature, fluorescence mode Detection gas: He
In each sample, one sharp pre-edge peak was observed. This peak indicates the presence of a titanium atom having a tetracoordinate structure. This suggests that the titanium atom is incorporated in the skeleton of mesoporous silica. In FT-EXAFS, no peak derived from a Ti—O—Ti bond in the vicinity of 2.9% appearing in the titania powder was observed in any sample. From these results, it can be seen that titanium atoms contained in Ti—HMS / Fe 2 O 3 and Ti—HMS exist in a highly dispersed state.
（iv）電子顕微鏡測定
測定は以下の装置、条件で行った。
測定装置：株式会社日立ハイテクノロジーズ製のＳ−５２００ＦＥ−ＳＥＭおよびＨ−８００ＴＥＭ
Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3のＳＥＭ像を確認したところ、粒子は表面に細かな凹凸を有していた。また、酸化鉄粒子は凝集していないことがわかった。Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3のＴＥＭ像と元素マッピングを行ったところ、珪素原子のマトリックス内に鉄原子やチタン原子が高分散な状態で存在していることがわかった。
(Iv) Electron microscope measurement The measurement was performed with the following apparatus and conditions.
Measuring device: S-5200FE-SEM and H-800TEM manufactured by Hitachi High-Technologies Corporation
When an SEM image of Ti—HMS / Fe 2 O 3 was confirmed, the particles had fine irregularities on the surface. It was also found that the iron oxide particles were not aggregated. When a TEM image of Ti—HMS / Fe 2 O 3 and element mapping were performed, it was found that iron atoms and titanium atoms were present in a highly dispersed state in a matrix of silicon atoms.
（v）光触媒反応
石英ガラスの反応管に触媒として、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3およびＴｉ−ＨＭＳを、それぞれ１０ｍｇ量りとり、溶媒のアセトニトリル（特級、和光純薬株式会社製）１５ｍｌ中に分散させた。短い注射針で排気口を確保したゴム栓をして１時間の酸素バブリングした後、反応基質（シクロオクテン（東京化成工業株式会社製））を１０ｍｍｏｌ加え、高圧水銀ランプ（ＳＨＬ−１００ＵＶ）で２４時間光照射した。光照射による温度の上昇を防ぐため、反応セルはファンによって空冷し、水銀灯は石英の冷却管に入れ、室温に保った。
(V) Photocatalytic reaction As a catalyst in a quartz glass reaction tube, 10 mg of Ti-HMS / Fe 2 O 3 and Ti-HMS were weighed and dispersed in 15 ml of a solvent acetonitrile (special grade, manufactured by Wako Pure Chemical Industries, Ltd.). I let you. After a rubber stopper that secured an exhaust port with a short injection needle and bubbling oxygen for 1 hour, 10 mmol of a reaction substrate (cyclooctene (manufactured by Tokyo Chemical Industry Co., Ltd.)) was added, and 24 hours with a high pressure mercury lamp (SHL-100UV). Irradiated for hours. In order to prevent the temperature from rising due to light irradiation, the reaction cell was air-cooled with a fan, and the mercury lamp was placed in a quartz cooling tube and kept at room temperature.
シクロオクテンの光酸化反応の結果（生成物（シクロオクテンオキサイド）の収率とターンオーバー数（ＴＯＮ））を表１に示す。表１の結果より、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3を光触媒として使用した場合、収率やＴＯＮがやや低下したが、Ｔｉ−ＨＭＳを用いた場合と同様に、反応が進行したことがわかる。 Table 1 shows the results of the photo-oxidation reaction of cyclooctene (product (cyclooctene oxide) yield and turnover number (TON)). From the results in Table 1, it can be seen that when Ti—HMS / Fe 2 O 3 was used as a photocatalyst, the yield and TON were slightly reduced, but the reaction proceeded in the same manner as when Ti—HMS was used.
（vi）過酸化水素水を用いた触媒反応
反応管に触媒として、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3およびＴｉ−ＨＭＳを、それぞれ１００ｍｇ量りとり、溶媒のアセトニトリル１０ｍｌに分散させた。反応管に反応基質（スチレン（東京化成工業株式会社製）またはシクロオクテン）１ｍｍｏｌを分散させ、更に、３０％過酸化水素水（特級、和光純薬株式会社製）１ｍｌを加え、７０℃で２４時間反応させた。
(Vi) Catalytic reaction using hydrogen peroxide solution As a catalyst, 100 mg of Ti-HMS / Fe 2 O 3 and Ti-HMS were weighed and dispersed in 10 ml of acetonitrile as a solvent. 1 mmol of a reaction substrate (styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) or cyclooctene) is dispersed in a reaction tube, and further 1 ml of 30% hydrogen peroxide (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) is added. Reacted for hours.
スチレン酸化反応の結果（生成物（ベンズアルデヒドおよびスチレンオキサイド）の収率とＴＯＮ）を表２に示す。また、シクロオクテン酸化反応の結果（生成物（シクロオクテンオキサイド）の収率とＴＯＮ）を表３に示す。表２、３の結果より、Ｔｉ−ＨＭＳ／Ｆｅ2Ｏ3を触媒として使用した場合、Ｔｉ−ＨＭＳを用いた場合と同様に、反応が進行したことがわかる。また、磁性粒子による収率やＴＯＮへの影響が小さいことがわかる。 Table 2 shows the results of the styrene oxidation reaction (the yield of products (benzaldehyde and styrene oxide) and TON). Table 3 shows the results of the cyclooctene oxidation reaction (the yield of the product (cyclooctene oxide) and TON). From the results of Tables 2 and 3, it can be seen that when Ti—HMS / Fe 2 O 3 was used as a catalyst, the reaction proceeded in the same manner as when Ti—HMS was used. Moreover, it turns out that the influence on the yield and TON by a magnetic particle is small.
なお、スチレン酸化反応後の反応液をガラス瓶に回収し、ガラス瓶に磁石を近づけたところ、図３のように、触媒だけが磁石に引き寄せられ、液中からの触媒の分離が容易であることが示唆された。 When the reaction liquid after the styrene oxidation reaction is collected in a glass bottle and a magnet is brought close to the glass bottle, only the catalyst is attracted to the magnet as shown in FIG. 3, and it is easy to separate the catalyst from the liquid. It was suggested.
本発明の多孔質シリカ−チタニア複合材料は、触媒、分子ふるい材料などとして有用であり、回収が容易であることから、様々な分野で工業的利用が可能である。本発明の多孔質シリカ−チタニア複合材料は、例えば、過酸化水素による内部オレフィンのエポキシ化反応、末端オレフィンの酸化的開反応などの触媒として利用できる。また、本発明の多孔質シリカ−チタニア複合材料は、光触媒としても有用である。 The porous silica-titania composite material of the present invention is useful as a catalyst, a molecular sieving material, and the like, and can be easily recovered, so that it can be industrially used in various fields. The porous silica-titania composite material of the present invention can be used as a catalyst for, for example, an epoxidation reaction of an internal olefin with hydrogen peroxide and an oxidative opening reaction of a terminal olefin. Moreover, the porous silica-titania composite material of the present invention is also useful as a photocatalyst.
１０ 磁性粒子
１２ 酸化物
１４ 第１複合粒子
１６ 多孔質材料
１８ 多孔質シリカ−チタニア複合材料
DESCRIPTION OF SYMBOLS 10 Magnetic particle 12 Oxide 14 1st composite particle 16 Porous material 18 Porous silica-titania composite material
Claims (9)
前記多孔質材料が、珪素原子およびチタン原子を含む、多孔質シリカ−チタニア複合材料。 Magnetic particles, an oxide covering at least a part of the surface of the magnetic particles, and a porous material covering at least a part of the surface of the oxide,
A porous silica-titania composite material, wherein the porous material contains silicon atoms and titanium atoms.
（ii）前記第１複合粒子を、珪素原子含有アルコキシドと、チタン原子含有アルコキシドと、構造規制剤とを含む液に分散させ、前記第１複合粒子の表面の少なくとも一部を多孔質材料の前駆体で被覆して、第２複合粒子を形成し、
（iii）前記第２複合粒子を焼成して、前記前駆体を多孔質材料に変化させる、多孔質シリカ−チタニア複合材料の製造方法。 (I) coating at least part of the surface of the magnetic particles with an oxide to form first composite particles;
(Ii) The first composite particles are dispersed in a liquid containing a silicon atom-containing alkoxide, a titanium atom-containing alkoxide, and a structure regulating agent, and at least a part of the surface of the first composite particles is a precursor of a porous material. Covering the body to form second composite particles,
(Iii) A method for producing a porous silica-titania composite material, wherein the second composite particles are fired to change the precursor into a porous material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013210395A (en) * | 2011-06-15 | 2013-10-10 | Sanyo Chem Ind Ltd | Method for manufacturing magnetic particle |
| CN104549194A (en) * | 2015-02-03 | 2015-04-29 | 泉州三欣新材料科技有限公司 | Preparation method of TiO2-SiO2 compound nano porous microspheres |
| CN106582809A (en) * | 2016-12-22 | 2017-04-26 | 红宝丽集团股份有限公司 | Catalyst for epoxidation of olefin and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013210395A (en) * | 2011-06-15 | 2013-10-10 | Sanyo Chem Ind Ltd | Method for manufacturing magnetic particle |
| CN104549194A (en) * | 2015-02-03 | 2015-04-29 | 泉州三欣新材料科技有限公司 | Preparation method of TiO2-SiO2 compound nano porous microspheres |
| CN104549194B (en) * | 2015-02-03 | 2016-06-22 | 泉州三欣新材料科技有限公司 | A kind of TiO2-SiO2The preparation method of composite Nano porous microsphere |
| CN106582809A (en) * | 2016-12-22 | 2017-04-26 | 红宝丽集团股份有限公司 | Catalyst for epoxidation of olefin and preparation method thereof |
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