JP6044756B2 - Method for synthesizing porous inorganic oxide nanoparticles, and porous inorganic oxide nanoparticles and spherical porous inorganic oxide nanoparticles produced by the synthesis method - Google Patents
Method for synthesizing porous inorganic oxide nanoparticles, and porous inorganic oxide nanoparticles and spherical porous inorganic oxide nanoparticles produced by the synthesis method Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims description 152
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 30
- 230000002194 synthesizing effect Effects 0.000 title claims description 27
- 238000001308 synthesis method Methods 0.000 title description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 162
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 37
- 239000012530 fluid Substances 0.000 claims description 20
- 235000019253 formic acid Nutrition 0.000 claims description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 13
- 150000002484 inorganic compounds Chemical class 0.000 claims description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 claims description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 9
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 9
- UDMNVTJFUISBFD-UHFFFAOYSA-N 2-fluoro-6-methylpyridine Chemical compound CC1=CC=CC(F)=N1 UDMNVTJFUISBFD-UHFFFAOYSA-N 0.000 claims description 8
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 claims description 8
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 claims description 8
- 229940071536 silver acetate Drugs 0.000 claims description 8
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 claims description 7
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 54
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 54
- 239000000843 powder Substances 0.000 description 28
- 239000000126 substance Substances 0.000 description 21
- 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 19
- 238000002441 X-ray diffraction Methods 0.000 description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 238000000926 separation method Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000013507 mapping Methods 0.000 description 12
- 238000004506 ultrasonic cleaning Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 229910000420 cerium oxide Inorganic materials 0.000 description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- 229910052691 Erbium Inorganic materials 0.000 description 7
- 229910052693 Europium Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 229910021426 porous silicon Inorganic materials 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000010944 silver (metal) Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000012377 drug delivery Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 titanium alkoxide Chemical class 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000002771 cell marker Substances 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001476 gene delivery Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QBHQQYMEDGADCQ-UHFFFAOYSA-N oxozirconium(2+);dinitrate;dihydrate Chemical compound O.O.[Zr+2]=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBHQQYMEDGADCQ-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compounds Of Iron (AREA)
Description
本発明は、多孔質無機酸化物ナノ粒子の合成方法、並びに該合成方法により製造される多孔質無機酸化物ナノ粒子及び球状多孔質無機酸化物ナノ粒子に関するものである。 The present invention relates to a method for synthesizing porous inorganic oxide nanoparticles, and to porous inorganic oxide nanoparticles and spherical porous inorganic oxide nanoparticles produced by the synthesis method.
近年、多孔質ナノ粒子が、物質の吸着、分離、除去、触媒といった様々な用途で用いられている。多孔質ナノ粒子とは、径２〜５０ｎｍの孔（メソポア）を有するナノ粒子のことをいう。
特に、酸化チタンの多孔質ナノ粒子は、特有の光学特性、光電子特性、生物学的特性、徐放性、電気特性及び化学特性を有するので、白色顔料、触媒担持、光触媒、反応触媒、光半導体、太陽電池、遺伝子導入試薬、薬物送達、細胞マーカーなどに主に用いられている。
In recent years, porous nanoparticles have been used in various applications such as adsorption, separation, removal, and catalyst of substances. The porous nanoparticle refers to a nanoparticle having pores (mesopores) having a diameter of 2 to 50 nm.
In particular, porous nanoparticles of titanium oxide have unique optical properties, optoelectronic properties, biological properties, sustained release properties, electrical properties, and chemical properties, so white pigments, catalyst support, photocatalysts, reaction catalysts, and optical semiconductors It is mainly used for solar cells, gene transfer reagents, drug delivery, cell markers and the like.
多孔質酸化チタンナノ粒子が球状であることにより、優れた安定性、単分散性、高い集光特性、再利用の容易さなどの優れた特性を示すことが明らかとなってきている。
従来用いられてきた球状多孔質酸化チタンナノ粒子の合成方法としては、水熱法、ゾル‐ゲル法、自己集合（自己組織化）法などがある。
It has been clarified that the porous titanium oxide nanoparticles have excellent characteristics such as excellent stability, monodispersibility, high light collection characteristics, and ease of reuse due to the spherical shape.
Conventionally used methods for synthesizing spherical porous titanium oxide nanoparticles include a hydrothermal method, a sol-gel method, and a self-assembly (self-assembly) method.
非特許文献１には、水熱法による、光触媒に用いられる球状多孔質酸化チタンナノ粒子の合成法が記載されている。詳しくは、Ｔｉ（ＳＯ４）２とＮＨ４ＦとＨ２Ｏとを１６０℃で６時間反応させることにより、球状多孔質酸化チタンナノ粒子を合成する方法が記載されている。
非特許文献２には、ゾル‐ゲル法による、太陽電池に用いられる球状多孔質酸化チタンナノ粒子の合成法が記載されている。詳しくは、Ｔｉ（ＯＣ４Ｈ９）４とジエチレングリコールとをアセトン中で８時間攪拌し、次いで１時間遠心分離することにより、球状多孔質酸化チタンナノ粒子を合成する方法が記載されている。
非特許文献３には、自己集合（自己組織化）法による、生物化学分野（ドラッグデリバリ）に用いられる球状多孔質酸化チタンナノ粒子の合成法が記載されている。詳しくは、酸化チタン粒子を集合させ、ＳｉＯ２でコーティングしてクラスターを形成し、焼成、シリカエッチングにより、球状多孔質酸化チタンナノ粒子を合成する方法が記載されている。
しかしながら、これら従来の合成方法は、非常に複雑であり、合成に長時間を要するという問題があった。
Non-Patent Document 1 describes a method for synthesizing spherical porous titanium oxide nanoparticles used for a photocatalyst by a hydrothermal method. Specifically, a method of synthesizing spherical porous titanium oxide nanoparticles by reacting Ti (SO 4 ) 2 , NH 4 F and H 2 O at 160 ° C. for 6 hours is described.
Non-Patent Document 2 describes a method for synthesizing spherical porous titanium oxide nanoparticles used in solar cells by a sol-gel method. Specifically, a method of synthesizing spherical porous titanium oxide nanoparticles by stirring Ti (OC 4 H 9 ) 4 and diethylene glycol in acetone for 8 hours and then centrifuging for 1 hour is described.
Non-Patent Document 3 describes a method for synthesizing spherical porous titanium oxide nanoparticles used in the field of biochemistry (drug delivery) by a self-assembly (self-assembly) method. Specifically, a method is described in which titanium oxide particles are aggregated, coated with SiO 2 to form clusters, and spherical porous titanium oxide nanoparticles are synthesized by firing and silica etching.
However, these conventional synthesis methods are very complicated and have a problem that a long time is required for synthesis.
超臨界流体中における球状多孔質ナノ粒子の合成法も知られてきている。
非特許文献４には、超臨界流体中で球状多孔質Ｆｅ３Ｏ４ナノ粒子を合成する方法、非特許文献５には、超臨界流体中で球状多孔質ＴｉＯ２ナノ粒子を合成する方法が記載されている。
超臨界流体中でチタンテトライソプロポキシドと有機修飾剤を用い、球状多孔質酸化チタンナノ粒子を合成する方法も知られている。有機修飾剤としては、ヘキサン酸、ヘキサナール、デシルホスホン酸などが知られている。
これらの超臨界流体中における球状多孔質ナノ粒子の合成法は、ワンポット合成であり、反応時間が短く操作が容易であるという利点がある。
しかしながら、これらの合成法では、用途に応じて球状多孔質酸化チタンナノ粒子の粒子径や孔径を調整することは容易ではなかった。
A method for synthesizing spherical porous nanoparticles in a supercritical fluid is also known.
Non-Patent Document 4 discloses a method of synthesizing spherical porous Fe 3 O 4 nanoparticles in a supercritical fluid, and Non-Patent Document 5 discloses a method of synthesizing spherical porous TiO 2 nanoparticles in a supercritical fluid. Have been described.
A method of synthesizing spherical porous titanium oxide nanoparticles using titanium tetraisopropoxide and an organic modifier in a supercritical fluid is also known. As the organic modifier, hexanoic acid, hexanal, decylphosphonic acid and the like are known.
The method for synthesizing spherical porous nanoparticles in these supercritical fluids is one-pot synthesis and has an advantage that the reaction time is short and the operation is easy.
However, in these synthesis methods, it is not easy to adjust the particle size and pore size of the spherical porous titanium oxide nanoparticles according to the application.
本出願人は、上述したような課題を解決するべく、国際出願ＰＣＴ／ＪＰ２０１２／５１８８４において、超臨界メタノール中でチタンテトライソプロポキシドとカルボン酸とを反応させる工程を備える球状多孔質酸化チタンナノ粒子の合成方法を出願している。
しかしながら、酸化チタン以外の他の無機酸化物について上述したような課題を解決した合成方法は未だ達成されていない。
In order to solve the above-described problems, the present applicant, in the international application PCT / JP2012 / 51884, has a step of reacting titanium tetraisopropoxide and a carboxylic acid in supercritical methanol. We have applied for a synthesis method.
However, a synthesis method that has solved the above-described problems with respect to inorganic oxides other than titanium oxide has not yet been achieved.
本発明は、上述したような問題点を解決すべくなされたものであって、操作が容易であり、合成に長い時間を必要とせず、用途に応じて多孔質無機酸化物ナノ粒子の粒径や孔径を容易に調整することができる多孔質無機酸化物ナノ粒子の合成方法、及び該合成方法により製造される多孔質無機酸化物ナノ粒子及び球状多孔質無機酸化物ナノ粒子を提供するものである。 The present invention has been made to solve the above-described problems, is easy to operate, does not require a long time for synthesis, and the size of the porous inorganic oxide nanoparticles depending on the application. And a method for synthesizing porous inorganic oxide nanoparticles whose pore diameter can be easily adjusted, and porous inorganic oxide nanoparticles and spherical porous inorganic oxide nanoparticles produced by the synthesis method is there.
請求項１に係る発明は、超臨界流体中で無機化合物とカルボン酸とを反応させる工程を備える多孔質無機酸化物ナノ粒子の合成方法であって、前記超臨界流体が超臨界メタノール又は超臨界エタノールであり、前記無機化合物が、Ｔｉ（ＯｉＰｒ）４、Ｚｒ（ＯｉＰｒ）４、ＺｒＯ（ＮＯ３）２２Ｈ２Ｏ、Ｃｅ（ＮＯ３）３６Ｈ２Ｏ、Ｆｅ（ＮＯ３）３９Ｈ２Ｏ、Ｎｉ（ＮＯ３）２６Ｈ２Ｏ又はＳｉ（ＯＣ２Ｈ５）４であり、前記カルボン酸が、ギ酸、酢酸又はオルトフタル酸であることを特徴とする多孔質無機酸化物ナノ粒子の合成方法に関する。 The invention according to claim 1 is a method for synthesizing porous inorganic oxide nanoparticles comprising a step of reacting an inorganic compound and a carboxylic acid in a supercritical fluid, wherein the supercritical fluid is supercritical methanol or supercritical fluid. Ethanol, and the inorganic compound is Ti (O i Pr) 4 , Zr (O i Pr) 4 , ZrO (NO 3 ) 2 2H 2 O, Ce (NO 3 ) 3 6H 2 O, Fe (NO 3 ) 3 9H 2 O, Ni (NO 3 ) 2 6H 2 O, or Si (OC 2 H 5 ) 4 , wherein the carboxylic acid is formic acid, acetic acid, or orthophthalic acid. The present invention relates to a method for synthesizing particles.
請求項２に係る発明は、前記工程において、さらに超臨界流体中に、酢酸エルビウム４水和物、酢酸ユーロピウムｎ水和物、酢酸セリウム一水和物、酢酸金、酢酸銀又は酢酸パラジウムを加えることを特徴とする請求項１記載の多孔質無機酸化物ナノ粒子の合成方法に関する。 In the invention according to claim 2, in the step, erbium acetate tetrahydrate, europium acetate n-hydrate, cerium acetate monohydrate, gold acetate, silver acetate or palladium acetate is further added to the supercritical fluid. The method for synthesizing porous inorganic oxide nanoparticles according to claim 1.
請求項３に係る発明は、請求項１記載の多孔質無機酸化物ナノ粒子の合成方法により製造される球状多孔質無機酸化物ナノ粒子に関する。 The invention according to claim 3 relates to spherical porous inorganic oxide nanoparticles produced by the method for synthesizing porous inorganic oxide nanoparticles according to claim 1.
請求項４に係る発明は、請求項２記載の多孔質無機酸化物ナノ粒子の合成方法により製造される多孔質無機酸化物ナノ粒子であって、Ｅｒ、Ｅｕ、Ｃｅ、Ａｕ、Ａｇ又はＰｄがドープされたことを特徴とする請求項３記載の多孔質無機酸化物ナノ粒子に関する。 The invention according to claim 4 is a porous inorganic oxide nanoparticle produced by the method for synthesizing a porous inorganic oxide nanoparticle according to claim 2, wherein Er, Eu, Ce, Au, Ag or Pd is The porous inorganic oxide nanoparticles according to claim 3, which are doped.
請求項５に係る発明は、Ａｕ又はＰｄが核内にドープされたことを特徴とする請求項４記載の多孔質無機酸化物ナノ粒子に関する。 The invention according to claim 5 relates to the porous inorganic oxide nanoparticles according to claim 4, wherein Au or Pd is doped in the nucleus.
請求項１に係る発明によれば、超臨界メタノール又は超臨界エタノール中でＴｉ（ＯｉＰｒ）４、Ｚｒ（ＯｉＰｒ）４、ＺｒＯ（ＮＯ３）２２Ｈ２Ｏ、Ｃｅ（ＮＯ３）３６Ｈ２Ｏ、Ｆｅ（ＮＯ３）３９Ｈ２Ｏ、Ｎｉ（ＮＯ３）２６Ｈ２Ｏ又はＳｉ（ＯＣ２Ｈ５）４とギ酸、酢酸又はオルトフタル酸とを反応させる工程を備えることにより、一次粒子同士が分離することなく球状多孔質の酸化チタンナノ粒子、酸化ジルコニウムナノ粒子、酸化セリウムナノ粒子、酸化鉄ナノ粒子、酸化ニッケルナノ粒子、酸化ケイ素ナノ粒子を合成することができる。また、ワンポット合成とすることができ、反応時間が短く操作が容易である合成法とすることができる。 According to the invention of claim 1, in supercritical methanol or supercritical ethanol, Ti (O i Pr) 4 , Zr (O i Pr) 4 , ZrO (NO 3 ) 2 2H 2 O, Ce (NO 3 ) By comprising the step of reacting 3 6H 2 O, Fe (NO 3 ) 3 9H 2 O, Ni (NO 3 ) 2 6H 2 O or Si (OC 2 H 5 ) 4 with formic acid, acetic acid or orthophthalic acid, Spherical porous titanium oxide nanoparticles, zirconium oxide nanoparticles, cerium oxide nanoparticles, iron oxide nanoparticles, nickel oxide nanoparticles, and silicon oxide nanoparticles can be synthesized without separation of primary particles. Further, it can be a one-pot synthesis, and can be a synthesis method with a short reaction time and easy operation.
請求項２に係る発明によれば、前記工程において、さらに超臨界流体中に、酢酸エルビウム４水和物、酢酸ユーロピウムｎ水和物、酢酸セリウム一水和物、酢酸金、酢酸銀又は酢酸パラジウムを加えることにより、Ｅｒ、Ｅｕ、Ｃｅ、Ａｕ、Ａｇ又はＰｄがドープされた多孔質無機酸化物ナノ粒子を合成することができる。このＥｒ又はＥｕがドープされた多孔質無機酸化物ナノ粒子は、光を照射することにより発光するので、無機物の細胞マーカーとしての利用が期待できる。また，Ｃｅ、Ａｕ、Ａｇ又はＰｄがドープされた多孔質無機酸化物ナノ粒子は、光触媒、化学触媒としての利用が期待できる。 According to the invention of claim 2, in the step, erbium acetate tetrahydrate, europium acetate n hydrate, cerium acetate monohydrate, gold acetate, silver acetate or palladium acetate is further added in the supercritical fluid. Can be added to synthesize porous inorganic oxide nanoparticles doped with Er, Eu, Ce, Au, Ag or Pd. Since these porous inorganic oxide nanoparticles doped with Er or Eu emit light when irradiated with light, they can be expected to be used as inorganic cell markers. In addition, porous inorganic oxide nanoparticles doped with Ce, Au, Ag, or Pd can be expected to be used as photocatalysts and chemical catalysts.
請求項３に係る発明によれば、一次粒子同士が分離することなく、優れた安定性、単分散性、高い集光特性、再利用の容易さなどの優れた特性を示す球状多孔質無機酸化物ナノ粒子とすることができる。
According to the invention of 請 Motomeko 3 without between primary particles are separated, excellent stability, monodispersity, high condensing characteristics of spherical porous inorganic showing excellent properties such as ease of re-use It can be an oxide nanoparticle.
請求項４に係る発明によれば、Ｅｒ又はＥｕがドープされた多孔質無機酸化物ナノ粒子は、光を照射することにより発光するので、無機物の細胞マーカーとしての利用が期待できる。さらに，Ｃｅ、Ａｕ、Ａｇ又はＰｄがドープされた多孔質無機酸化物ナノ粒子は、光触媒、化学触媒としての利用が期待できる。 According to the invention of claim 4, since the porous inorganic oxide nanoparticles doped with Er or Eu emit light when irradiated with light, it can be expected to be used as an inorganic cell marker. Further, the porous inorganic oxide nanoparticles doped with Ce, Au, Ag or Pd can be expected to be used as a photocatalyst or a chemical catalyst.
請求項５に係る発明によれば、Ａｕ又はＰｄが核内に包含されていることにより、多孔質殻内外に化学ポテンシャルを発生し，新奇化学触媒としての機能を発現するという効果がある。 According to the invention according to claim 5, since Au or Pd is contained in the nucleus, there is an effect that a chemical potential is generated inside and outside the porous shell and a function as a novel chemical catalyst is expressed.
以下、本発明に係る多孔質無機酸化物ナノ粒子の合成方法、並びに該合成方法により製造される多孔質無機酸化物ナノ粒子及び球状多孔質無機酸化物ナノ粒子について説明する。 Hereinafter, the method for synthesizing porous inorganic oxide nanoparticles according to the present invention, and the porous inorganic oxide nanoparticles and spherical porous inorganic oxide nanoparticles produced by the synthesis method will be described.
本発明に係る多孔質無機酸化物ナノ粒子の合成方法は、超臨界流体中で無機化合物とカルボン酸とを反応させる工程を備える多孔質無機酸化物ナノ粒子の合成方法である。
超臨界流体とは、臨界点以上の温度及び圧力下においた物質の状態のことをいい、気体と液体の区別がつかない状態といわれ、気体の拡散性と液体の溶解性をもつ。
本発明において、超臨界流体として超臨界メタノール又は超臨界エタノールが用いられる。
超臨界メタノール又は超臨界エタノールを用いることにより、一次粒子同士が分離することなく球状多孔質の無機酸化物ナノ粒子を合成することができる。
The method for synthesizing porous inorganic oxide nanoparticles according to the present invention is a method for synthesizing porous inorganic oxide nanoparticles comprising a step of reacting an inorganic compound and a carboxylic acid in a supercritical fluid.
A supercritical fluid refers to a state of a substance placed at a temperature and pressure above the critical point, and is said to be indistinguishable between gas and liquid, and has gas diffusibility and liquid solubility.
In the present invention, supercritical methanol or supercritical ethanol is used as the supercritical fluid.
By using supercritical methanol or supercritical ethanol, spherical porous inorganic oxide nanoparticles can be synthesized without separation of primary particles.
本発明の超臨界流体中でカルボン酸と反応させる無機化合物は、Ｔｉ（ＯｉＰｒ）４、Ｚｒ（ＯｉＰｒ）４、ＺｒＯ（ＮＯ３）２２Ｈ２Ｏ、Ｃｅ（ＮＯ３）３６Ｈ２Ｏ、Ｆｅ（ＮＯ３）３９Ｈ２Ｏ、Ｎｉ（ＮＯ３）２６Ｈ２Ｏ又はＳｉ（ＯＣ２Ｈ５）４である。 Inorganic compounds to be reacted with carboxylic acid in the supercritical fluid of the present invention are Ti (O i Pr) 4 , Zr (O i Pr) 4 , ZrO (NO 3 ) 2 2H 2 O, Ce (NO 3 ) 3 6H. 2 O, Fe (NO 3 ) 3 9H 2 O, Ni (NO 3 ) 2 6H 2 O, or Si (OC 2 H 5 ) 4 .
Ｔｉ（ＯｉＰｒ）４（ｉＰｒはイソプロピル基：−ＣＨ（ＣＨ３）２）（チタンテトライソプロポキシド）とは、チタンアルコキシドの一種であり、ＣＡＳ．Ｎｏ．５４６−６８−９であって、下記（式１）に示す構造を有している。 Ti (O i Pr) 4 ( i Pr is an isopropyl group: —CH (CH 3 ) 2 ) (titanium tetraisopropoxide) is a kind of titanium alkoxide, and CAS. No. 546-68-9, which has the structure shown in the following (Formula 1).
Ｚｒ（ＯｉＰｒ）４（ｉＰｒはイソプロピル基：−ＣＨ（ＣＨ３）２）（ジルコニウムテトライソプロポキシド）とは、ジルコニウムアルコキシドの一種であり、ＣＡＳ．Ｎｏ．２１７１−９８−４であって、下記（式２）に示す構造を有している。 Zr (O i Pr) 4 ( i Pr is an isopropyl group: —CH (CH 3 ) 2 ) (zirconium tetraisopropoxide) is a kind of zirconium alkoxide, which is a CAS. No. 2171-98-4, which has the structure shown in the following (Formula 2).
ＺｒＯ（ＮＯ３）２２Ｈ２Ｏ（硝酸ジルコニル二水和物）とは、ＣＡＳ．Ｎｏ．１４９８５−１８−３であって、下記（式３）に示す構造を有している。 ZrO (NO 3 ) 2 2H 2 O (zirconyl nitrate dihydrate) refers to CAS. No. 14985-18-3, which has the structure shown in the following (formula 3).
Ｃｅ（ＮＯ３）３６Ｈ２Ｏ（硝酸セリウム六水和物）とは、ＣＡＳ．Ｎｏ．１０２９４−４１−４であって、下記（式４）に示す構造を有している。 Ce (NO 3 ) 3 6H 2 O (cerium nitrate hexahydrate) refers to CAS. No. 10294-41-4, which has the structure shown in the following (formula 4).
Ｆｅ（ＮＯ３）３９Ｈ２Ｏ（硝酸鉄九水和物）とは、ＣＡＳ．Ｎｏ．７７８２−６１−８であって、下記（式５）に示す構造を有している。 Fe (NO 3 ) 3 9H 2 O (iron nitrate nonahydrate) refers to CAS. No. 772-61-8, which has the structure shown in the following (formula 5).
Ｎｉ（ＮＯ３）２６Ｈ２Ｏ（硝酸ニッケル六水和物）とは、ＣＡＳ．Ｎｏ．１３４７８−００−７であって、下記（式６）に示す構造を有している。 Ni (NO 3 ) 2 6H 2 O (nickel nitrate hexahydrate) refers to CAS. No. 13478-00-7, which has a structure shown in the following (formula 6).
Ｓｉ（ＯＣ２Ｈ５）４（テトラエトキシシラン）とは、ＣＡＳ．Ｎｏ．７８−１０−４であって、下記（式７）に示す構造を有している。 Si (OC 2 H 5 ) 4 (tetraethoxysilane) refers to CAS. No. 78-10-4, which has a structure shown in the following (formula 7).
これら無機化合物のメタノール又はエタノールに対する濃度としては、０．０１〜１．０ｍｏｌ／Ｌが好ましい。 The concentration of these inorganic compounds with respect to methanol or ethanol is preferably 0.01 to 1.0 mol / L.
本発明において、無機化合物と反応させるカルボン酸は、ギ酸、酢酸又はオルトフタル酸である。 In the present invention, the carboxylic acid to be reacted with the inorganic compound is formic acid, acetic acid or orthophthalic acid.
ギ酸は、ＣＡＳ．Ｎｏ．６４−１８−６の低級カルボン酸の一種である。化学式ＨＣＯＯＨであって、下記（式８）に示す構造を有している。 Formic acid is available from CAS. No. It is a kind of lower carboxylic acid of 64-18-6. It has the chemical formula HCOOH and has the structure shown below (Formula 8).
酢酸は、ＣＡＳ．Ｎｏ．６４−１９−７の低級カルボン酸の一種である。化学式ＣＨ３ＣＯＯＨであって、下記（式９）に示す構造を有している。 Acetic acid is obtained from CAS. No. It is a kind of lower carboxylic acid of 64-19-7. Chemical formula CH 3 COOH, which has the structure shown in the following (formula 9).
オルトフタル酸は、ＣＡＳ．Ｎｏ．８８−９９−３の芳香族カルボン酸の一種である。化学式Ｃ６Ｈ４（ＣＯＯＨ）２であって、下記（式１０）に示す構造を有している。 Orthophthalic acid is available from CAS. No. It is a kind of 88-99-3 aromatic carboxylic acid. A chemical formula C 6 H 4 (COOH) 2 , and has a structure shown below (Equation 10).
上記のカルボン酸を、超臨界メタノール又は超臨界エタノール中で上記無機化合物と反応させることにより、一次粒子同士が分離することなく球状多孔質の酸化チタンナノ粒子、酸化ジルコニウムナノ粒子、酸化セリウムナノ粒子、酸化鉄ナノ粒子、酸化ニッケルナノ粒子、酸化ケイ素ナノ粒子を生成することができる。
上記のカルボン酸のメタノール又はエタノールに対する濃度としては、０．０５〜５．０ｍｏｌ／Ｌが好ましい。
By reacting the above carboxylic acid with the above inorganic compound in supercritical methanol or supercritical ethanol, spherical porous titanium oxide nanoparticles, zirconium oxide nanoparticles, cerium oxide nanoparticles, oxidation without separation of primary particles. Iron nanoparticles, nickel oxide nanoparticles, silicon oxide nanoparticles can be generated.
As a density | concentration with respect to methanol or ethanol of said carboxylic acid, 0.05-5.0 mol / L is preferable.
超臨界メタノール又は超臨界エタノール中で上記無機化合物と上記カルボン酸とを反応させる工程において、上記カルボン酸の他に、超臨界メタノール又は超臨界エタノール中に酢酸エルビウム４水和物、酢酸ユーロピウムｎ水和物、酢酸セリウム一水和物、酢酸金、酢酸銀又は酢酸パラジウムを加えることができる。これにより、Ｅｒ、Ｅｕ、Ｃｅ、Ａｕ、Ａｇ又はＰｄがドープされた多孔質無機酸化物ナノ粒子を生成することができる。 In the step of reacting the inorganic compound and the carboxylic acid in supercritical methanol or supercritical ethanol, in addition to the carboxylic acid, erbium acetate tetrahydrate, europium acetate n water in supercritical methanol or supercritical ethanol. Japanese, cerium acetate monohydrate, gold acetate, silver acetate or palladium acetate can be added. Thereby, porous inorganic oxide nanoparticles doped with Er, Eu, Ce, Au, Ag or Pd can be generated.
酢酸エルビウム４水和物は、ＣＡＳ．Ｎｏ．１５２８０−５７−６の化合物である。化学式Ｅｒ（ＣＨ３ＣＯＯ）３・４Ｈ２Ｏで表され、下記（式１１）に示す構造を有している。 Erbium acetate tetrahydrate is available from CAS. No. 15280-57-6. It is represented by the chemical formula Er (CH 3 COO) 3 .4H 2 O and has the structure shown below (Formula 11).
酢酸エルビウム４水和物のメタノール又はエタノールに対する濃度としては、０．００１〜０．０２ｍｏｌ／Ｌが好ましい。
エルビウムドープ球状多孔質無機酸化物ナノ粒子は、赤外レーザ光を照射することにより緑色発光するので、無機物の細胞マーカーとしての利用が期待できる。
The concentration of erbium acetate tetrahydrate with respect to methanol or ethanol is preferably 0.001 to 0.02 mol / L.
Since erbium-doped spherical porous inorganic oxide nanoparticles emit green light when irradiated with infrared laser light, they can be expected to be used as inorganic cell markers.
酢酸ユーロピウムｎ水和物は、ＣＡＳ．Ｎｏ．６２６６７−６４−５の化合物である。化学式Ｅｕ（ＣＨ３ＣＯＯ）３・ｎＨ２Ｏで表され、下記（式１２）に示す構造を有している。 Europium acetate n hydrate is available from CAS. No. It is a compound of 62667-64-5. It is represented by the chemical formula Eu (CH 3 COO) 3 .nH 2 O and has a structure shown in the following (Formula 12).
酢酸ユーロピウムｎ水和物のメタノール又はエタノールに対する濃度としては、０．００１〜０．１ ｍｏｌ／Ｌが好ましい。
ユーロピウムドープ球状多孔質無機酸化物ナノ粒子は、紫外光で励起すると蛍光発光するので、無機蛍光体や細胞マーカーとしての利用が期待できる。
The concentration of europium acetate n hydrate with respect to methanol or ethanol is preferably 0.001 to 0.1 mol / L.
Europium-doped spherical porous inorganic oxide nanoparticles emit fluorescence when excited with ultraviolet light, and can be expected to be used as inorganic phosphors and cell markers.
酢酸セリウム一水和物は、ＣＡＳ．Ｎｏ．５３７−００−８の化合物である。化学式（ＣＨ３ＣＯＯ）３Ｃｅ・Ｈ２Ｏで表され、下記（式１３）に示す構造を有している。 Cerium acetate monohydrate is available from CAS. No. 537-00-8. It is represented by the chemical formula (CH 3 COO) 3 Ce · H 2 O and has the structure shown in the following (Formula 13).
酢酸セリウム一水和物のメタノール又はエタノールに対する濃度としては、０．００１〜０．１ｍｏｌ／Ｌが好ましい。
セリウムドープ球状多孔質無機酸化物ナノ粒子は、紫外光を吸収し蛍光発光するので、紫外光吸収剤，無機蛍光体や細胞マーカーとしての利用が期待できる。また，触媒としての利用も期待できる。
The concentration of cerium acetate monohydrate with respect to methanol or ethanol is preferably 0.001 to 0.1 mol / L.
Since the cerium-doped spherical porous inorganic oxide nanoparticles absorb ultraviolet light and emit fluorescence, they can be expected to be used as ultraviolet light absorbers, inorganic phosphors, and cell markers. It can also be used as a catalyst.
酢酸金は、ＣＡＳ．Ｎｏ．１５８０４−３２−７の化合物である。化学式（ＣＨ３ＣＯＯ）３Ａｕで表され、下記（式１４）に示す構造を有している。 Gold acetate is available from CAS. No. 15804-32-7. It is represented by the chemical formula (CH 3 COO) 3 Au and has the structure shown in the following (Formula 14).
酢酸金のメタノール又はエタノールに対する濃度としては、０．００１〜０．２ｍｏｌ／Ｌが好ましい。
金ドープ球状多孔質無機酸化物ナノ粒子は、金原子が多孔質ナノ粒子に分散しているので、化学触媒としての利用が期待できる。
The concentration of gold acetate with respect to methanol or ethanol is preferably 0.001 to 0.2 mol / L.
The gold-doped spherical porous inorganic oxide nanoparticles can be expected to be used as a chemical catalyst since gold atoms are dispersed in the porous nanoparticles.
酢酸銀は、ＣＡＳ．Ｎｏ．５６３−６３−３の化合物である。化学式ＣＨ３ＣＯＯＡｇで表され、下記（式１５）に示す構造を有している。 Silver acetate is available from CAS. No. It is a compound of 563-63-3. It is represented by the chemical formula CH 3 COOAg and has a structure shown below (Formula 15).
酢酸銀のメタノール又はエタノールに対する濃度としては、０．００１〜０．１ｍｏｌ／Ｌが好ましい。
銀ドープ球状多孔質無機酸化物ナノ粒子は、銀原子が多孔質ナノ粒子に分散しているので、化学触媒としての利用が期待できる。
The concentration of silver acetate with respect to methanol or ethanol is preferably 0.001 to 0.1 mol / L.
The silver-doped spherical porous inorganic oxide nanoparticles can be expected to be used as a chemical catalyst because silver atoms are dispersed in the porous nanoparticles.
酢酸パラジウムは、ＣＡＳ．Ｎｏ．３３７５−３１−３の化合物である。化学式（ＣＨ３ＣＯＯ）２Ｐｄで表され、下記（式１６）に示す構造を有している。 Palladium acetate is available from CAS. No. 3375-31-3. It is represented by the chemical formula (CH 3 COO) 2 Pd and has a structure shown in the following (Formula 16).
酢酸パラジウムのメタノール又はエタノールに対する濃度としては、０．００１〜０．１ｍｏｌ／Ｌが好ましい。
パラジウムドープ多孔質無機酸化物ナノ粒子は、パラジウム原子が多孔質ナノ粒子に分散しているので、化学触媒としての利用が期待できる。
The concentration of palladium acetate with respect to methanol or ethanol is preferably 0.001 to 0.1 mol / L.
The palladium-doped porous inorganic oxide nanoparticles can be expected to be used as a chemical catalyst because palladium atoms are dispersed in the porous nanoparticles.
このうち、ＡｕとＰｄについては、多孔質無機酸化物ナノ粒子の核の中へドープすることができる。これにより、化学ポテンシャルが多孔質ナノ粒子の内外に生じるため，高機能化学触媒となる。 Of these, Au and Pd can be doped into the nuclei of the porous inorganic oxide nanoparticles. As a result, the chemical potential is generated inside and outside the porous nanoparticle, so that it becomes a highly functional chemical catalyst.
本発明において、反応温度は２００℃以上が好ましく、３００〜４００℃がより好ましい。
反応温度が２００℃より低い場合、一次粒子径が小さくなることにより孔径が小さくなりすぎ多孔質粒子を形成できないため好ましくない。
In this invention, 200 degreeC or more is preferable and, as for reaction temperature, 300-400 degreeC is more preferable.
When the reaction temperature is lower than 200 ° C., it is not preferable because the pore size becomes too small due to the primary particle size becoming small and porous particles cannot be formed.
本発明において、反応時間は少なくとも１秒以上が好ましく、１〜１０分がより好ましい。 In the present invention, the reaction time is preferably at least 1 second or more, more preferably 1 to 10 minutes.
以下の実施例に基づいてさらに詳細に説明するが、本発明に係る多孔質無機酸化物ナノ粒子の合成方法、並びに該合成方法により製造される多孔質無機酸化物ナノ粒子及び球状多孔質無機酸化物ナノ粒子は、これらに限定されるものではない。 The method for synthesizing porous inorganic oxide nanoparticles according to the present invention, and the porous inorganic oxide nanoparticles and spherical porous inorganic oxide produced by the synthesis method will be described in more detail based on the following examples. The product nanoparticles are not limited to these.
実施例１
ＺｒＯ（ＮＯ３）２２Ｈ２Ｏ２７８ｍｇとメタノール１０ｍＬを混合し，有機修飾剤としてギ酸２３５ｍｇを０．５ｍｏｌ／Ｌとなるように添加した。この溶液を３００℃まで上昇させ、超臨界メタノールとし、１０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥して球状多孔質酸化ジルコニウムナノ粒子の粉体を得た。
球状多孔質酸化ジルコニウムナノ粒子のＳＥＭ写真を図１に示す。
Example 1
278 mg of ZrO (NO 3 ) 2 2H 2 O and 10 mL of methanol were mixed, and 235 mg of formic acid as an organic modifier was added to 0.5 mol / L. This solution was raised to 300 ° C. to make supercritical methanol and reacted for 10 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain spherical porous zirconium oxide nanoparticle powders.
A SEM photograph of the spherical porous zirconium oxide nanoparticles is shown in FIG.
実施例２
実施例１とは温度を４００℃としたこと以外は同じ条件で、球状多孔質酸化ジルコニウムナノ粒子の粉体を得た。
球状多孔質酸化ジルコニウムナノ粒子のＳＥＭ写真を図２に示す。
Example 2
A powder of spherical porous zirconium oxide nanoparticles was obtained under the same conditions as in Example 1 except that the temperature was 400 ° C.
An SEM photograph of the spherical porous zirconium oxide nanoparticles is shown in FIG.
実施例３
実施例１とはギ酸の代わりにオルトフタル酸を用いたこと以外は同じ条件で、球状多孔質酸化ジルコニウムナノ粒子の粉体を得た。
Example 3
A powder of spherical porous zirconium oxide nanoparticles was obtained under the same conditions as in Example 1 except that orthophthalic acid was used instead of formic acid.
実施例４
実施例３とは温度を４００℃としたこと以外は同じ条件で、球状多孔質酸化ジルコニウムナノ粒子の粉体を得た。
Example 4
A spherical porous zirconium oxide nanoparticle powder was obtained under the same conditions as in Example 3 except that the temperature was 400 ° C.
実施例５
Ｚｒ（ＯｉＰｒ）４３８８ｍｇとメタノール１０ｍＬを混合し，有機修飾剤としてギ酸２３５ｍｇを０．５ｍｏｌ／Ｌとなるように添加した。この溶液を３００℃まで上昇させ、超臨界メタノールとし、１０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥して球状多孔質酸化ジルコニウムナノ粒子の粉体を得た。
得られた球状多孔質酸化ジルコニウムナノ粒子のＸ線回析結果を図３に、球状多孔質酸化ジルコニウムナノ粒子のＳＥＭ写真を図４に示す。
Example 5
388 mg of Zr (O i Pr) 4 and 10 mL of methanol were mixed, and 235 mg of formic acid as an organic modifier was added to 0.5 mol / L. This solution was raised to 300 ° C. to make supercritical methanol and reacted for 10 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain spherical porous zirconium oxide nanoparticle powders.
The X-ray diffraction result of the obtained spherical porous zirconium oxide nanoparticles is shown in FIG. 3, and the SEM photograph of the spherical porous zirconium oxide nanoparticles is shown in FIG.
実施例６
Ｃｅ（ＮＯ３）３６Ｈ２Ｏ４４３ｍｇとメタノール１０ｍＬを混合し，有機修飾剤としてギ酸２５ｍｇを０．５ｍｏｌ／Ｌとなるように添加した。この溶液を３００℃まで上昇させ、超臨界メタノールとし、１０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥して球状多孔質酸化セリウムナノ粒子の粉体を得た。
得られた球状多孔質酸化セリウムナノ粒子のＸ線回析結果を図５に、球状多孔質酸化セリウムナノ粒子のＳＥＭ写真を図６に示す。
Example 6
Ce (NO 3 ) 3 6H 2 O (443 mg) and methanol (10 mL) were mixed, and 25 mg of formic acid as an organic modifier was added to a concentration of 0.5 mol / L. This solution was raised to 300 ° C. to make supercritical methanol and reacted for 10 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain spherical porous cerium oxide nanoparticle powders.
FIG. 5 shows an X-ray diffraction result of the obtained spherical porous cerium oxide nanoparticles, and FIG. 6 shows an SEM photograph of the spherical porous cerium oxide nanoparticles.
実施例７
実施例６とは温度を４００℃としたこと以外は同じ条件で、球状多孔質酸化セリウムナノ粒子の粉体を得た。
Example 7
A spherical porous cerium oxide nanoparticle powder was obtained under the same conditions as in Example 6 except that the temperature was 400 ° C.
実施例８
実施例６とはギ酸の代わりにオルトフタル酸を用いたこと以外は同じ条件で、球状多孔質酸化セリウムナノ粒子の粉体を得た。
Example 8
A spherical porous cerium oxide nanoparticle powder was obtained under the same conditions as in Example 6 except that orthophthalic acid was used instead of formic acid.
実施例９
実施例８とは温度を４００℃としたこと以外は同じ条件で、球状多孔質酸化セリウムナノ粒子の粉体を得た。
Example 9
A spherical porous cerium oxide nanoparticle powder was obtained under the same conditions as in Example 8, except that the temperature was 400 ° C.
実施例１０
Ｆｅ（ＮＯ３）３９Ｈ２Ｏ４０８ｍｇとメタノール１０ｍＬを混合し，有機修飾剤としてギ酸２３５ｍｇを０．５ｍｏｌ／Ｌとなるように添加した。この溶液を４００℃まで上昇させ、超臨界メタノールとし、１０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥して球状多孔質酸化鉄ナノ粒子の粉体を得た。
Example 10
408 mg of Fe (NO 3 ) 3 9H 2 O and 10 mL of methanol were mixed, and 235 mg of formic acid was added as an organic modifier so as to be 0.5 mol / L. This solution was raised to 400 ° C. to make supercritical methanol and reacted for 10 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain spherical porous iron oxide nanoparticle powders.
実施例１１
実施例１０とはギ酸の代わりにオルトフタル酸を用いたこと以外は同じ条件で、球状多孔質酸化鉄ナノ粒子の粉体を得た。
Example 11
A powder of spherical porous iron oxide nanoparticles was obtained under the same conditions as in Example 10 except that orthophthalic acid was used instead of formic acid.
実施例１２
Ｎｉ（ＮＯ３）２６Ｈ２Ｏ２９７ｍｇとメタノール１０ｍＬを混合し，有機修飾剤としてギ酸２３５ｍｇを０．５ｍｏｌ／Ｌとなるように添加した。この溶液を４００℃まで上昇させ、超臨界メタノールとし、１０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥して球状多孔質酸化ニッケルナノ粒子の粉体を得た。
Example 12
297 mg of Ni (NO 3 ) 2 6H 2 O and 10 mL of methanol were mixed, and 235 mg of formic acid as an organic modifier was added to 0.5 mol / L. This solution was raised to 400 ° C. to make supercritical methanol and reacted for 10 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain powders of spherical porous nickel oxide nanoparticles.
実施例１３
実施例１２とはギ酸の代わりにオルトフタル酸を用いたこと以外は同じ条件で、球状多孔質酸化ニッケルナノ粒子の粉体を得た。
Example 13
A powder of spherical porous nickel oxide nanoparticles was obtained under the same conditions as in Example 12 except that orthophthalic acid was used instead of formic acid.
実施例１４
Ｓｉ（ＯＣ２Ｈ５）４０．２４ｍＬとエタノール１０ｍＬを混合し，有機修飾剤としてギ酸８４８ｍｇを０．５ｍｏｌ／Ｌとなるように添加した。この溶液を４００℃まで上昇させ、超臨界メタノールとし、１０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥して球状多孔質酸化ケイ素ナノ粒子の粉体を得た。
Example 14
Si (OC 2 H 5 ) 4 0.24 mL and ethanol 10 mL were mixed, and 848 mg of formic acid as an organic modifier was added to 0.5 mol / L. This solution was raised to 400 ° C. to make supercritical methanol and reacted for 10 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain spherical porous silicon oxide nanoparticle powders.
実施例１５
実施例１４とはエタノールの代わりにメタノール，ギ酸の代わりにオルトフタル酸を用いたこと以外は同じ条件で、球状多孔質酸化ケイ素ナノ粒子の粉体を得た。
球状多孔質酸化ケイ素ナノ粒子のＳＥＭ写真を図７に示す。
Example 15
A powder of spherical porous silicon oxide nanoparticles was obtained under the same conditions as in Example 14 except that methanol was used instead of ethanol and orthophthalic acid was used instead of formic acid.
An SEM photograph of the spherical porous silicon oxide nanoparticles is shown in FIG.
実施例１６
実施例１４とはギ酸の代わりにオルトフタル酸を用いたこと以外は同じ条件で、球状多孔質酸化ケイ素ナノ粒子の粉体を得た。
球状多孔質酸化ケイ素ナノ粒子のＳＥＭ写真を図８に示す。
Example 16
A spherical porous silicon oxide nanoparticle powder was obtained under the same conditions as in Example 14 except that orthophthalic acid was used instead of formic acid.
An SEM photograph of the spherical porous silicon oxide nanoparticles is shown in FIG.
実施例１７
酢酸２３５ｍｇの１０ｍＬメタノール溶液０．５ｍｏｌ／Ｌに０．３３ｍＬ（１ｍｍｏｌ）のチタンテトライソプロポキシドを激しく攪拌しながら加えた。そこに、酢酸エルビウム４水和物４３．９ｍｇを加え、一晩攪拌した。この溶液を３．５ｍＬ計り取り、同様のＳＵＳ３１６反応に移し、この溶液を４００℃まで上昇させ、超臨界メタノールとし、６０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥してＥｒドープ球状多孔質酸化チタンナノ粒子の粉体を得た。
得られたＥｒドープ球状多孔質酸化チタンナノ粒子のＸ線回析結果を図９に、Ｅｒドープ球状多孔質酸化チタンナノ粒子の粉体のＴＥＭ写真及びＥＤＸマッピングを図１０に示す。
Example 17
0.33 mL (1 mmol) of titanium tetraisopropoxide was added to 0.5 mol / L of 235 mg of acetic acid in 10 mL of methanol with vigorous stirring. Thereto, 43.9 mg of erbium acetate tetrahydrate was added and stirred overnight. 3.5 mL of this solution was weighed and transferred to the same SUS316 reaction, and this solution was raised to 400 ° C. to make supercritical methanol and reacted for 60 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain powder of Er-doped spherical porous titanium oxide nanoparticles.
The X-ray diffraction result of the obtained Er-doped spherical porous titanium oxide nanoparticles is shown in FIG. 9, and a TEM photograph and EDX mapping of the powder of Er-doped spherical porous titanium oxide nanoparticles are shown in FIG.
実施例１８
酢酸２３５ｍｇの１０ｍＬメタノール溶液０．５ｍｏｌ／Ｌに０．３３ｍＬ（１ｍｍｏｌ）のチタンテトライソプロポキシドを激しく攪拌しながら加えた。そこに、酢酸ユーロピウムｎ水和物３５ｍｇを加え、一晩攪拌した。この溶液を３．５ｍＬ計り取り、同様のＳＵＳ３１６反応に移し、この溶液を４００℃まで上昇させ、超臨界メタノールとし、６０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥してＥｕドープ球状多孔質酸化チタンナノ粒子の粉体を得た。
得られたＥｕドープ球状多孔質酸化チタンナノ粒子のＸ線回析結果を図１１に、Ｅｕドープ球状多孔質酸化チタンナノ粒子の粉体のＴＥＭ写真を図１２に、ＥＤＸマッピングを図１３に示す。
Example 18
0.33 mL (1 mmol) of titanium tetraisopropoxide was added to 0.5 mol / L of 235 mg of acetic acid in 10 mL of methanol with vigorous stirring. Thereto, 35 mg of europium acetate n hydrate was added and stirred overnight. 3.5 mL of this solution was weighed and transferred to the same SUS316 reaction, and this solution was raised to 400 ° C. to make supercritical methanol and reacted for 60 minutes. Thereafter, centrifugation, ultrasonic cleaning with methanol, and drying were performed to obtain a powder of Eu-doped spherical porous titanium oxide nanoparticles.
The X-ray diffraction results of the obtained Eu-doped spherical porous titanium oxide nanoparticles are shown in FIG. 11, a TEM photograph of the powder of Eu-doped spherical porous titanium oxide nanoparticles is shown in FIG. 12, and EDX mapping is shown in FIG.
実施例１９
酢酸２３５ｍｇの１０ｍＬメタノール溶液０．５ｍｏｌ／Ｌに０．３３ｍＬ（１ｍｍｏｌ）のチタンテトライソプロポキシドを激しく攪拌しながら加えた。そこに、酢酸セリウム一水和物（ＣＨ３ＣＯＯ）３ＣｅＨ２Ｏ３４ｍｇを加え、一晩攪拌した。この溶液を３．５ｍＬ計り取り、同様のＳＵＳ３１６反応に移し、この溶液を４００℃まで上昇させ、超臨界メタノールとし、６０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥してＣｅドープ球状多孔質酸化チタンナノ粒子の粉体を得た。
得られたＣｅドープ球状多孔質酸化チタンナノ粒子のＸ線回析結果を図１４に、Ｃｅドープ球状多孔質酸化チタンナノ粒子の粉体のＴＥＭ写真を図１５に、ＥＤＸマッピングを図１６に示す。
Example 19
0.33 mL (1 mmol) of titanium tetraisopropoxide was added to 0.5 mol / L of 235 mg of acetic acid in 10 mL of methanol with vigorous stirring. Thereto, 34 mg of cerium acetate monohydrate (CH 3 COO) 3 CeH 2 O was added and stirred overnight. 3.5 mL of this solution was weighed and transferred to the same SUS316 reaction, and this solution was raised to 400 ° C. to make supercritical methanol and reacted for 60 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain Ce-doped spherical porous titanium oxide nanoparticle powders.
FIG. 14 shows an X-ray diffraction result of the obtained Ce-doped spherical porous titanium oxide nanoparticles, FIG. 15 shows a TEM photograph of the powder of Ce-doped spherical porous titanium oxide nanoparticles, and FIG. 16 shows an EDX mapping.
実施例２０
酢酸２３５ｍｇの１０ｍＬメタノール溶液０．５ｍｏｌ／Ｌに０．３３ｍＬ（１ｍｍｏｌ）のチタンテトライソプロポキシドを激しく攪拌しながら加えた。そこに、酢酸金（ＣＨ３ＣＯＯ）３Ａｕ２６ｍｇを加え、一晩攪拌した。この溶液を３．５ｍＬ計り取り、同様のＳＵＳ３１６反応に移し、この溶液を４００℃まで上昇させ、超臨界メタノールとし、６０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥してＡｕドープ球状多孔質酸化チタンナノ粒子の粉体を得た。
得られたＡｕドープ球状多孔質酸化チタンナノ粒子のＸ線回析結果を図１７に、Ａｕドープ球状多孔質酸化チタンナノ粒子の粉体のＴＥＭ写真を図１８に、ＥＤＸマッピングを図１９に示す。
Example 20
0.33 mL (1 mmol) of titanium tetraisopropoxide was added to 0.5 mol / L of 235 mg of acetic acid in 10 mL of methanol with vigorous stirring. Thereto, 26 mg of gold acetate (CH 3 COO) 3 Au was added and stirred overnight. 3.5 mL of this solution was weighed and transferred to the same SUS316 reaction, and this solution was raised to 400 ° C. to make supercritical methanol and reacted for 60 minutes. Thereafter, centrifugation, ultrasonic cleaning with methanol, and drying were performed to obtain Au-doped spherical porous titanium oxide nanoparticle powders.
FIG. 17 shows an X-ray diffraction result of the obtained Au-doped spherical porous titanium oxide nanoparticles, FIG. 18 shows a TEM photograph of the powder of Au-doped spherical porous titanium oxide nanoparticles, and FIG. 19 shows an EDX mapping.
実施例２１
酢酸２３５ｍｇの１０ｍＬメタノール溶液０．５ｍｏｌ／Ｌに０．３３ｍＬ（１ｍｍｏｌ）のチタンテトライソプロポキシドを激しく攪拌しながら加えた。そこに、酢酸銀ＣＨ３ＣＯＯＡｇ１７ｍｇを加え、一晩攪拌した。この溶液を３．５ｍＬ計り取り、同様のＳＵＳ３１６反応に移し、この溶液を４００℃まで上昇させ、超臨界メタノールとし、６０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥してＡｇドープ球状多孔質酸化チタンナノ粒子の粉体を得た。
得られたＡｇドープ球状多孔質酸化チタンナノ粒子のＸ線回析結果を図２０に、Ａｇドープ球状多孔質酸化チタンナノ粒子の粉体のＴＥＭ写真を図２１に、ＥＤＸマッピングを図２２に示す。
Example 21
0.33 mL (1 mmol) of titanium tetraisopropoxide was added to 0.5 mol / L of 235 mg of acetic acid in 10 mL of methanol with vigorous stirring. Thereto, 17 mg of silver acetate CH 3 COOAg was added and stirred overnight. 3.5 mL of this solution was weighed and transferred to the same SUS316 reaction, and this solution was raised to 400 ° C. to make supercritical methanol and reacted for 60 minutes. Thereafter, centrifugal separation, ultrasonic cleaning with methanol, and drying were performed to obtain a powder of Ag-doped spherical porous titanium oxide nanoparticles.
The X-ray diffraction result of the obtained Ag-doped spherical porous titanium oxide nanoparticles is shown in FIG. 20, a TEM photograph of the powder of Ag-doped spherical porous titanium oxide nanoparticles is shown in FIG. 21, and EDX mapping is shown in FIG.
実施例２２
酢酸２３５ｍｇの１０ｍＬメタノール溶液０．５ｍｏｌ／Ｌに０．３３ｍＬ（１ｍｍｏｌ）のチタンテトライソプロポキシドを激しく攪拌しながら加えた。そこに、酢酸パラジウム（ＣＨ３ＣＯＯ）２Ｐｄ２３ｍｇを加え、一晩攪拌した。この溶液を３．５ｍＬ計り取り、同様のＳＵＳ３１６反応に移し、この溶液を４００℃まで上昇させ、超臨界メタノールとし、６０分間反応させた。その後、遠心分離，メタノールでの超音波洗浄、乾燥してＰｄドープ多孔質酸化チタンナノ粒子の粉体を得た。
得られたＰｄドープ多孔質酸化チタンナノ粒子のＸ線回析結果を図２３に、Ｐｄドープ多孔質酸化チタンナノ粒子の粉体のＴＥＭ写真を図２４に、ＥＤＸマッピングを図２５に示す。
Example 22
0.33 mL (1 mmol) of titanium tetraisopropoxide was added to 0.5 mol / L of 235 mg of acetic acid in 10 mL of methanol with vigorous stirring. Thereto was added 23 mg of palladium acetate (CH 3 COO) 2 Pd, and the mixture was stirred overnight. 3.5 mL of this solution was weighed and transferred to the same SUS316 reaction, and this solution was raised to 400 ° C. to make supercritical methanol and reacted for 60 minutes. Thereafter, centrifugation, ultrasonic cleaning with methanol, and drying were performed to obtain a powder of Pd-doped porous titanium oxide nanoparticles.
FIG. 23 shows an X-ray diffraction result of the obtained Pd-doped porous titanium oxide nanoparticles, FIG. 24 shows a TEM photograph of the powder of Pd-doped porous titanium oxide nanoparticles, and FIG. 25 shows an EDX mapping.
図１，２，４，６〜８のＳＥＭ写真に示すように、実施例１〜１６において球状多孔質の酸化ジルコニウムナノ粒子、酸化セリウムナノ粒子、酸化鉄ナノ粒子、酸化ニッケルナノ粒子及び酸化ケイ素ナノ粒子を形成することができた。 As shown in SEM photographs of FIGS. 1, 2, 4 and 6 to 8, spherical porous zirconium oxide nanoparticles, cerium oxide nanoparticles, iron oxide nanoparticles, nickel oxide nanoparticles and silicon oxide nanoparticles in Examples 1 to 16 Particles could be formed.
図１０，１３，１６，１９，２２，２５に示すように、実施例１７〜２２においてそれぞれ、Ｅｒ、Ｅｕ、Ｃｅ、Ａｕ、Ａｇ及びＰｄをドープした多孔質酸化チタンナノ粒子を形成することができた。このうち、Ｅｒ、Ｅｕ、Ｃｅ、Ａｕ、Ａｇをドープした多孔質酸化チタンは球状であり、Ｐｄをドープした多孔質酸化チタンナノ粒子は非球状であった。
また、図１９，２５に示すように、Ａｕ及びＰｄは酸化チタンナノ粒子の核内にドープされていることがわかる。
As shown in FIGS. 10, 13, 16, 19, 22, and 25, porous titanium oxide nanoparticles doped with Er, Eu, Ce, Au, Ag, and Pd can be formed in Examples 17 to 22, respectively. It was. Among these, the porous titanium oxide doped with Er, Eu, Ce, Au, and Ag was spherical, and the porous titanium oxide nanoparticles doped with Pd were non-spherical.
Further, as shown in FIGS. 19 and 25, it can be seen that Au and Pd are doped in the nucleus of the titanium oxide nanoparticles.
本発明は、白色顔料、触媒担持、反応触媒、光触媒、太陽電池、光半導体、遺伝子送達試薬、細胞マーカー、薬物送達試薬、液晶スペーサなどに好適に利用されるものである。 The present invention is suitably used for white pigments, catalyst supports, reaction catalysts, photocatalysts, solar cells, optical semiconductors, gene delivery reagents, cell markers, drug delivery reagents, liquid crystal spacers, and the like.
Claims (2)
前記超臨界流体が超臨界メタノール又は超臨界エタノールであり、
前記超臨界流体中にはさらに、酢酸エルビウム４水和物、酢酸ユーロピウムｎ水和物、酢酸セリウム一水和物、酢酸金、酢酸銀又は酢酸パラジウムが加えられており、
前記無機化合物が、Ｔｉ（ＯｉＰｒ）４、Ｚｒ（ＯｉＰｒ）４、ＺｒＯ（ＮＯ３）２２Ｈ２Ｏ、Ｃｅ（ＮＯ３）３６Ｈ２Ｏ、Ｆｅ（ＮＯ３）３９Ｈ２Ｏ、Ｎｉ（ＮＯ３）２６Ｈ２Ｏ又はＳｉ（ＯＣ２Ｈ５）４であり、
前記カルボン酸が、ギ酸、酢酸又はオルトフタル酸であることを特徴とする多孔質無機酸化物ナノ粒子の合成方法。 A method for synthesizing porous inorganic oxide nanoparticles comprising a step of reacting an inorganic compound and a carboxylic acid in a supercritical fluid,
The supercritical fluid is supercritical methanol or supercritical ethanol;
In the supercritical fluid, erbium acetate tetrahydrate, europium acetate n hydrate, cerium acetate monohydrate, gold acetate, silver acetate or palladium acetate is further added,
The inorganic compound is Ti (O i Pr) 4 , Zr (O i Pr) 4 , ZrO (NO 3 ) 2 2H 2 O, Ce (NO 3 ) 3 6H 2 O, Fe (NO 3 ) 3 9H 2 O Ni (NO 3 ) 2 6H 2 O or Si (OC 2 H 5 ) 4
The method for synthesizing porous inorganic oxide nanoparticles, wherein the carboxylic acid is formic acid, acetic acid or orthophthalic acid.
前記超臨界流体が超臨界メタノール又は超臨界エタノールであり、
前記超臨界流体中にはさらに、酢酸エルビウム４水和物、酢酸ユーロピウムｎ水和物、酢酸セリウム一水和物、酢酸金、酢酸銀又は酢酸パラジウムが加えられており、
前記無機化合物が、Ｔｉ（ＯｉＰｒ）４、Ｚｒ（ＯｉＰｒ）４、ＺｒＯ（ＮＯ３）２２Ｈ２Ｏ、Ｃｅ（ＮＯ３）３６Ｈ２Ｏ、Ｆｅ（ＮＯ３）３９Ｈ２Ｏ、Ｎｉ（ＮＯ３）２６Ｈ２Ｏ又はＳｉ（ＯＣ２Ｈ５）４であり、
前記カルボン酸が、ギ酸、酢酸又はオルトフタル酸であることを特徴とする球状多孔質無機酸化物ナノ粒子の合成方法。 A method for synthesizing spherical porous inorganic oxide nanoparticles comprising a step of reacting an inorganic compound and a carboxylic acid in a supercritical fluid,
The supercritical fluid is supercritical methanol or supercritical ethanol;
In the supercritical fluid, erbium acetate tetrahydrate, europium acetate n hydrate, cerium acetate monohydrate, gold acetate, silver acetate or palladium acetate is further added,
The inorganic compound is Ti (O i Pr) 4 , Zr (O i Pr) 4 , ZrO (NO 3 ) 2 2H 2 O, Ce (NO 3 ) 3 6H 2 O, Fe (NO 3 ) 3 9H 2 O Ni (NO 3 ) 2 6H 2 O or Si (OC 2 H 5 ) 4
The method for synthesizing spherical porous inorganic oxide nanoparticles, wherein the carboxylic acid is formic acid, acetic acid or orthophthalic acid.
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