JP6774014B2 - Method for producing metal oxide nanoparticles - Google Patents
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- JP6774014B2 JP6774014B2 JP2016160933A JP2016160933A JP6774014B2 JP 6774014 B2 JP6774014 B2 JP 6774014B2 JP 2016160933 A JP2016160933 A JP 2016160933A JP 2016160933 A JP2016160933 A JP 2016160933A JP 6774014 B2 JP6774014 B2 JP 6774014B2
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- 229910044991 metal oxide Inorganic materials 0.000 title claims description 34
- 150000004706 metal oxides Chemical class 0.000 title claims description 34
- 239000002105 nanoparticle Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000007858 starting material Substances 0.000 claims description 17
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001507 metal halide Inorganic materials 0.000 claims description 10
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 10
- 150000005309 metal halides Chemical class 0.000 claims description 9
- 239000002245 particle Substances 0.000 description 39
- 239000007789 gas Substances 0.000 description 25
- 239000013078 crystal Substances 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- JQYHQFPJDPCKMM-UHFFFAOYSA-N OOO.[Sn] Chemical compound OOO.[Sn] JQYHQFPJDPCKMM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000001548 androgenic effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical compound O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- IQPZCSUTUZFACW-UHFFFAOYSA-L tin(2+);chloride;fluoride Chemical compound F[Sn]Cl IQPZCSUTUZFACW-UHFFFAOYSA-L 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Description
この発明は、粒子径がナノオーダーの金属酸化物の製造方法に関する。 The present invention relates to a method for producing a metal oxide having a particle size of nano-order.
金属酸化物微粒子は、セラミックス、電子材料、触媒等の種々の分野において広く利用されているが、その粒径がナノオーダーの領域に入ってくると、例えば、蛍光発光、触媒の高活性化、溶融温度・焼成温度の大幅な低下といった、バルクとは大きく異なった物理的、化学的特性を示すことが知られており、金属酸化物粒子をナノサイズ化することが求められている。 Metal oxide fine particles are widely used in various fields such as ceramics, electronic materials, and catalysts. When the particle size enters the nano-order region, for example, fluorescence emission, high activation of the catalyst, etc. It is known that it exhibits physical and chemical properties that are significantly different from those of bulk, such as a significant decrease in melting temperature and firing temperature, and it is required to make metal oxide particles nano-sized.
ところで、金属酸化物微粒子の製造方法としては、気相中で原料をプラズマにより化学反応させて粒子を生成するプラズマＣＶＤ法、金属アルコキシド等の加水分解を利用した加熱加水分解法、密閉容器中に出発物質と水を入れ、容器を密閉したまま加熱することで、生成物を得る水熱合成法、易溶性塩の金属イオンを水酸化物、炭酸塩、シュウ酸塩等の難溶性金属塩に変化させて沈殿させた後、この沈殿物を焼成して金属酸化物に変化させる化学沈殿法等がある。 By the way, as a method for producing metal oxide fine particles, a plasma CVD method in which a raw material is chemically reacted with plasma in a gas phase to generate particles, a heating hydrolysis method using hydrolysis of a metal alkoxide or the like, or a method in a closed container. A hydrothermal synthesis method that obtains a product by adding a starting material and water and heating while the container is sealed. Metal ions of easily soluble salts are converted into poorly soluble metal salts such as hydroxides, carbonates, and oxalates. There is a chemical precipitation method or the like in which the precipitate is changed and precipitated, and then the precipitate is calcined to change it into a metal oxide.
しかしながら、上述したプラズマＣＶＤ法は、純物質を気化させ、その蒸気を凝集させる方法であるため、高純度で粒子径の小さい金属酸化物が得られやすいが、生産効率及びエネルギー効率が悪いために製造コストが高くなるという問題がある。また、加熱加水分解法や水熱合成法は、オートクレーブを用い、比較的長い時間反応または熟成させる必要があるので、生産効率が悪いといった問題がある。また、化学沈殿法は、焼成により粒子の凝集が起こるため、得られる金属酸化物ナノ粒子の粒子径が大きくなるという問題がある。 However, since the plasma CVD method described above is a method of vaporizing a pure substance and aggregating the vapor, it is easy to obtain a metal oxide having high purity and a small particle size, but the production efficiency and energy efficiency are poor. There is a problem that the manufacturing cost becomes high. Further, the heat hydrolysis method and the hydrothermal synthesis method have a problem of poor production efficiency because they need to be reacted or aged for a relatively long time using an autoclave. Further, the chemical precipitation method has a problem that the particle size of the obtained metal oxide nanoparticles becomes large because the particles are agglomerated by firing.
そこで、この発明の課題は、粒子径の小さい金属酸化物ナノ粒子を低コストで簡単に製造することができる金属酸化物ナノ粒子の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a method for producing metal oxide nanoparticles, which can easily produce metal oxide nanoparticles having a small particle size at low cost.
上記の課題を解決するため、請求項１に係る発明は、金属のハロゲン化物である塩化アンチモンまたはフッ化スズを出発物質とする金属酸化物ナノ粒子の製造方法であって、塩化アンチモン水溶液またはフッ化スズ水溶液に、アルカリ水溶液を加えてｐＨ１１以上に調整した後、オゾンガスを通気することを特徴としている。 In order to solve the above problems, the invention according to claim 1 is a method for producing metal oxide nanoparticles using antimony chloride or tin fluoride as a starting material, which is an aqueous antimony chloride solution or a fluoride. It is characterized in that ozone gas is aerated after adjusting the pH to 11 or higher by adding an alkaline aqueous solution to the tin dioxide aqueous solution .
出発物質である塩化アンチモンやフッ化スズを構成しているアンチモンやスズは、その水酸化物がｐＨ１１以上のアルカリ水溶液に難溶性である。なお、ここにいう「難溶性」とは、溶解度が１ｇ／１００ｇ水溶液以下の溶解度であることを意味する。 Antimony and tin, which constitute the starting substances antimony chloride and tin fluoride, are sparingly soluble in an alkaline aqueous solution whose hydroxide is pH 11 or higher. The term "poorly soluble" as used herein means that the solubility is 1 g / 100 g aqueous solution or less.
使用するアルカリとしては、水溶性のアルカリ金属水酸化物が好ましく、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化セシウムが挙げられる。 The alkali used is preferably a water-soluble alkali metal hydroxide, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide.
また、オゾンガスの通気量は、１Ｌ／ｍｉｎ／１００ｍＬ以上１０Ｌ／ｍｉｎ／１００ｍＬ以下であることが好ましく、２Ｌ／ｍｉｎ／１００ｍＬ以上５Ｌ／ｍｉｎ／１００ｍＬ以下であることがより好ましい。 The air volume of ozone gas is preferably 1 L / min / 100 mL or more and 10 L / min / 100 mL or less, and more preferably 2 L / min / 100 mL or more and 5 L / min / 100 mL or less.
また、請求項２に係る発明は、金属のハロゲン化物である塩化アンチモンまたはフッ化スズを出発物質とする金属酸化物ナノ粒子の製造方法であって、塩化アンチモンまたはフッ化スズにｐＨ１１以上に調整したオゾン水を加えることを特徴としている。 The invention according to claim 2 is a method for producing metal oxide nanoparticles using antimony chloride or tin fluoride, which is a metal halide, as a starting material, and adjusts the pH to 11 or more to antimony chloride or tin fluoride. It is characterized by adding the added ozone water.
オゾン水は、出発物質である金属ハロゲン化物の濃度が１Ｍｏｌ／Ｌに対してオゾン濃度が１ｐｐｍ以上であることが好ましく、出発物質である金属ハロゲン化物の濃度が１Ｍｏｌ／Ｌに対してオゾン濃度が５ｐｐｍ以上であることがより好ましい。 Ozone water departure is preferably ozone concentration is 1ppm or more with respect to materials in which metal halide concentrations 1 Mol / L, ozone concentration is the concentration of the metal halide relative to 1 Mol / L starting material Is more preferably 5 ppm or more.
請求項１、２に係る発明の金属酸化物ナノ粒子の製造方法では、水酸化物がｐＨ１１以上のアルカリ水溶液に難溶性の金属のハロゲン化物である塩化アンチモンまたはフッ化スズを出発物質としているので、ｐＨ１１以上のアルカリ水溶液中に存在する金属イオンが少なく、オゾンガスやオゾン水による酸化工程において生成されるナノオーダーの金属酸化物微粒子の粒成長が抑制され、粒子径の小さな金属酸化物ナノ粒子が製造できる。 In the claims 1, 2 manufacturing method of the metal oxide nanoparticles of the invention according to, hydroxides are chloride antimony or tin fluoride starting material is a metal Ha androgenic compound sparingly soluble in an aqueous alkaline solution than pH11 Therefore, there are few metal ions present in the alkaline aqueous solution having a pH of 11 or higher, the grain growth of nano-order metal oxide fine particles generated in the oxidation process with ozone gas or ozone water is suppressed, and the metal oxide nanoparticles having a small particle size are suppressed. Can be manufactured.
また、請求項１、２に係る発明の金属酸化物ナノ粒子の製造方法によれば、水酸化物がｐＨ１１以上のアルカリ水溶液に難溶性の金属のハロゲン化物である塩化アンチモンまたはフッ化スズを原料として用い、アルカリの添加及びオゾンガスの通気、ｐＨ１１以上に調整したオゾン水の添加という簡易な工程によって、１００℃以下の温度範囲において、粒子径の小さな金属酸化物ナノ粒子を低コストで製造することができる。 According to the manufacturing method according to claim 1, 2 in accordance metal oxide nanoparticles of the invention, the hydroxide is antimony or tin fluoride chloride is Ha androgenic compound of the metal of poorly soluble in an aqueous alkaline solution than pH11 Used as a raw material, metal oxide nanoparticles with a small particle size can be produced at low cost in a temperature range of 100 ° C or lower by a simple process of adding alkali, aerating ozone gas, and adding ozone water adjusted to pH 11 or higher. be able to.
以下、本発明の実施例について図面を参照して説明するが、本発明の金属酸化物ナノ粒子の製造方法はこれらの実施例に限定されるものではない。 Hereinafter, examples of the present invention will be described with reference to the drawings, but the method for producing metal oxide nanoparticles of the present invention is not limited to these examples.
（実施例１）
レーザー回折式粒度分布測定装置（Ｌｅｅｄ ＆ Ｎｏｒｔｈｒｕｐ社製 Ｍｉｃｒｏｔｏｒａｃ ＦＲＡ）により測定した個数平均粒子径が０．３３８μｍの三酸化二アンチモン２．５ｇに１Ｎの水酸化カリウム水溶液を４７．５ｇ加えた懸濁液（ｐＨ１４）を３００ｍＬの三角フラスコに注ぎ、酸素を一部オゾンに変換することで発生させた含オゾンガスを２Ｌ／ｍｉｎの流量で通気した。なお、含オゾンガス中のオゾン含有量は０．０２５ｇ／Ｌであり、含オゾンガスを２Ｌ／ｍｉｎで通気した場合、０．０５ｇ／ｍｉｎでオゾンガスを通気したことになる。懸濁液は、初期時点で白く白濁していたが、含オゾンガスを約４０分間通気させることにより透明となった。
(Example 1)
Suspension in which 47.5 g of 1N potassium hydroxide aqueous solution was added to 2.5 g of diantimony trioxide having a number average particle diameter of 0.338 μm measured by a laser diffraction type particle size distribution measuring device (Microtorac FRA manufactured by Lead & Northrup). The liquid (pH 14) was poured into a 300 mL Erlenmeyer flask, and the ozone-containing gas generated by partially converting oxygen into ozone was aerated at a flow rate of 2 L / min. The ozone content in the ozone-containing gas is 0.025 g / L, and when the ozone-containing gas is aerated at 2 L / min, the ozone gas is aerated at 0.05 g / min. The suspension was white and cloudy at the initial stage, but became transparent by aerating ozone-containing gas for about 40 minutes.
このようにして得られた透明のナノ粒子懸濁液には水酸化カリウムが大量に含まれているので、５０ｍＬ程度のエタノールを添加することで脱塩した。エタノールの添加に伴い、透明のナノ粒子分散液は粒子の凝集のため再び白濁した。これを遠心分離（１００００ｒｐｍ、５分）することで、透明ゲル状の沈殿物と上澄み液とに分離し、沈殿物を再び水に分散させると、再度透明ナノ粒子分散液となった。 Since the transparent nanoparticle suspension thus obtained contains a large amount of potassium hydroxide, it was desalted by adding about 50 mL of ethanol. With the addition of ethanol, the transparent nanoparticle dispersion liquid became cloudy again due to the aggregation of particles. By centrifuging this (10000 rpm, 5 minutes), it was separated into a transparent gel-like precipitate and a supernatant liquid, and when the precipitate was dispersed again in water, it became a transparent nanoparticle dispersion liquid again.
再度、エタノールにより凝集させ、Ｘ線回折装置（ＭｉｎｉＦｌｅｘII型 Ｒｉｇａｋｕ社製）を用いてＸ線結晶構造解析を行ったところ、図１に示すＸ線回折チャートから、五酸化二アンチモンと四酸化二アンチモンの複合体（Ｓｂ５＋：Ｓｂ３＋＝８：２）であることが確認された。また、その粒子径はシェラーの式より約８８ｎｍであった。また、得られた凝集体を透過電子顕微鏡（ＴＥＭ）で観察したところ、図２に示すＴＥＭ画像からも５０ｎｍから１００ｎｍ程度の粒子が多数確認されており、シェラー径として算出した結晶子サイズが粒子径と一致している（単結晶の粒子である）ことが確認された。 It was again aggregated with ethanol and X-ray crystal structure analysis was performed using an X-ray diffractometer (MiniFlex II type manufactured by Rigaku). From the X-ray diffraction chart shown in FIG. 1, diantimony pentoxide and diantimony tetroxide It was confirmed that the complex (Sb 5+ : Sb 3+ = 8: 2). The particle size was about 88 nm according to Scheller's formula. Further, when the obtained aggregates were observed with a transmission electron microscope (TEM), a large number of particles of about 50 nm to 100 nm were confirmed from the TEM image shown in FIG. 2, and the crystallite size calculated as the Scheller diameter was the particles. It was confirmed that the particles match the diameter (single crystal particles).
（実施例２）
０．１Ｍの塩化アンチモン水溶液５０ｍＬに０．１Ｍの水酸化ナトリウム水溶液１００ｍＬを加えると、水酸化アンチモンの析出が起こり液は白濁した。この懸濁液にｐＨが１２．０になるまで１Ｍの水酸化ナトリウム水溶液を加え、この懸濁液に含オゾンガスを２Ｌ／ｍｉｎの流量で通気した。なお、含オゾンガス中のオゾン含有量は０．０２５ｇ／Ｌであり、含オゾンガスを２Ｌ／ｍｉｎで通気した場合、０．０５ｇ／ｍｉｎでオゾンガスを通気したことになる。白濁していた懸濁液は、含オゾンガスの通気開始後約４０分で透明になり始め、１時間経過時点で略透明になった。
(Example 2)
When 100 mL of 0.1 M sodium hydroxide aqueous solution was added to 50 mL of 0.1 M antimony chloride aqueous solution, precipitation of antimony hydroxide occurred and the liquid became cloudy. A 1 M aqueous sodium hydroxide solution was added to this suspension until the pH reached 12.0, and the suspension was aerated with ozone gas at a flow rate of 2 L / min. The ozone content in the ozone-containing gas is 0.025 g / L, and when the ozone-containing gas is aerated at 2 L / min, the ozone gas is aerated at 0.05 g / min. The cloudy suspension began to become transparent about 40 minutes after the start of ventilation of the ozone-containing gas, and became substantially transparent after 1 hour.
このようにして得られた透明ナノ粒子分散液から塩化ナトリウム等の塩を除去するため５０ｍＬ程度のエタノールを添加すると、液は白濁した。これを遠心分離（１００００ｒｐｍ、５分）することで、沈殿物と上澄み液とに分離し、沈殿物を再び水に分散させると、若干白濁のみられるナノ粒子分散液となった。 When about 50 mL of ethanol was added to remove salts such as sodium chloride from the transparent nanoparticle dispersion liquid thus obtained, the liquid became cloudy. By centrifuging this (10000 rpm, 5 minutes), the precipitate and the supernatant were separated, and when the precipitate was dispersed in water again, it became a nanoparticle dispersion liquid that was slightly cloudy.
この分散液を再度エタノールにより凝集させ、上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図３に示すＸ線回折チャートから、三酸化二アンチモンであることが確認された。また、その粒子径はシェラーの式より約５０ｎｍであった。 When this dispersion was again aggregated with ethanol and an X-ray crystal structure analysis was performed using the above-mentioned X-ray diffractometer, it was confirmed from the X-ray diffraction chart shown in FIG. 3 that it was diantimony trioxide. The particle size was about 50 nm according to Scheller's formula.
（実施例３）
０．１Ｍのフッ化スズ水溶液５０ｍＬに０．１Ｍの水酸化ナトリウム水溶液１００ｍＬを加えると、水酸化スズの析出が起こり液は白濁した。この懸濁液にｐＨが１２．０になるまで１Ｍの水酸化ナトリウム水溶液を加え、この懸濁液に含オゾンガスを２Ｌ／ｍｉｎの流量で通気した。なお、含オゾンガス中のオゾン含有量は０．０２５ｇ／Ｌであり、含オゾンガスを２Ｌ／ｍｉｎで通気した場合、０．０５ｇ／ｍｉｎでオゾンガスを通気したことになる。白濁していた懸濁液は、含オゾンガスの通気開始後約４０分で透明になり始め、１時間経過時点で略透明になった。
(Example 3)
When 100 mL of 0.1 M sodium hydroxide aqueous solution was added to 50 mL of 0.1 M tin fluoride aqueous solution, precipitation of tin hydroxide occurred and the liquid became cloudy. A 1 M aqueous sodium hydroxide solution was added to this suspension until the pH reached 12.0, and the suspension was aerated with ozone gas at a flow rate of 2 L / min. The ozone content in the ozone-containing gas is 0.025 g / L, and when the ozone-containing gas is aerated at 2 L / min, the ozone gas is aerated at 0.05 g / min. The cloudy suspension began to become transparent about 40 minutes after the start of ventilation of the ozone-containing gas, and became substantially transparent after 1 hour.
このようにして得られた透明ナノ粒子分散液からフッ化ナトリウム、塩化ナトリウム等の塩を除去するため５０ｍＬ程度のエタノールを添加すると、液は白濁した。これを遠心分離（１００００ｒｐｍ、５分）することで、沈殿物と上澄み液とに分離し、沈殿物を再び水に分散させると、再度透明ナノ粒子分散液となった。 When about 50 mL of ethanol was added to remove salts such as sodium fluoride and sodium chloride from the transparent nanoparticle dispersion liquid thus obtained, the liquid became cloudy. By centrifuging this (10000 rpm, 5 minutes), the precipitate and the supernatant were separated, and when the precipitate was dispersed in water again, the transparent nanoparticle dispersion was obtained again.
この分散液を再度エタノールにより凝集させ、上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図４に示すＸ線回折チャートから、酸化スズであることが確認された。また、得られた凝集体を透過電子顕微鏡（ＴＥＭ）で観察したところ、図５に示すＴＥＭ画像からも２ｎｍ〜４ｎｍの結晶性粒子であることが確認された。さらに、蛍光分光測定により青〜青緑の蛍光を示すことが確認できた。蛍光波長の理論式より約２．５ｎｍの粒子径であることが示唆される。 When this dispersion was again aggregated with ethanol and an X-ray crystal structure analysis was performed using the above X-ray diffractometer, it was confirmed from the X-ray diffraction chart shown in FIG. 4 that it was tin oxide. Moreover, when the obtained aggregate was observed with a transmission electron microscope (TEM), it was confirmed from the TEM image shown in FIG. 5 that the particles were crystalline particles having a diameter of 2 nm to 4 nm. Furthermore, it was confirmed by fluorescence spectroscopy that the fluorescence was blue to blue-green. The theoretical formula of fluorescence wavelength suggests that the particle size is about 2.5 nm.
（比較例１）
水酸化物がｐＨ１１以上のアルカリ水溶液に易溶性の金属の酸化物である、シェラー式による粒子径が１７．６ｎｍの酸化亜鉛を出発物質として用いた点を除いて、実施例１と同様の方法を採用した。得られた懸濁液は、凝集により白濁しており、その凝集体について上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図６に示すＸ線回折チャートから、出発物質と同じ酸化亜鉛であることが確認され、凝集体の個数平均粒子径を上記レーザー回折式粒度分布測定装置により測定したところ、約０．７８μｍであった。
(Comparative Example 1)
The same method as in Example 1 except that zinc oxide having a particle size of 17.6 nm according to the Scheller formula, which is an oxide of a metal easily soluble in an alkaline aqueous solution having a pH of 11 or higher, was used as a starting material. It was adopted. The obtained suspension became cloudy due to agglomeration, and when the agglomerates were subjected to X-ray crystal structure analysis using the above-mentioned X-ray diffractometer, the X-ray diffraction chart shown in FIG. It was confirmed that the zinc oxide was the same, and when the number average particle size of the aggregates was measured by the above-mentioned laser diffraction type particle size distribution measuring device, it was about 0.78 μm.
（比較例２）
ｐＨ１０に調整した点を除いて、実施例１と同様の方法を採用した。得られた懸濁液は、凝集により白濁しており、その凝集体について上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図７に示すＸ線回折チャートから、出発物質と同じ三酸化二アンチモンであることが確認され、その個数平均粒子径を上記レーザー回折式粒度分布測定装置により測定したところ、約０．５７μｍであった。
(Comparative Example 2)
The same method as in Example 1 was adopted except that the pH was adjusted to 10. The obtained suspension became cloudy due to aggregation, and when the aggregate was subjected to X-ray crystal structure analysis using the above-mentioned X-ray diffractometer, the X-ray diffraction chart shown in FIG. It was confirmed that they were the same diantimon trioxide, and the number average particle size thereof was measured by the above-mentioned laser diffraction type particle size distribution measuring device and found to be about 0.57 μm.
（比較例３）
ｐＨ１４に調整した点及び含オゾンガスを通気しない点を除いて、実施例１と同様の方法を採用した。得られた懸濁液は、凝集により白濁しており、その凝集体について上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図８に示すＸ線回折チャートから、出発物質と同じ三酸化二アンチモンであることが確認され、その凝集体の個数平均粒子径を上記レーザー回折式粒度分布測定装置により測定したところ、約０．２６μｍであった。
(Comparative Example 3)
The same method as in Example 1 was adopted except that the pH was adjusted to 14 and the ozone-containing gas was not aerated. The obtained suspension became cloudy due to aggregation, and when the aggregate was subjected to X-ray crystal structure analysis using the above-mentioned X-ray diffractometer, the X-ray diffraction chart shown in FIG. It was confirmed that they were the same diantimon trioxide, and the number average particle size of the aggregates was measured by the above-mentioned laser diffraction type particle size distribution measuring device and found to be about 0.26 μm.
（比較例４）
水酸化物がｐＨ１１以上のアルカリ水溶液に難溶性の金属のハロゲン化物である塩化亜鉛を出発物質として用いた点を除いて、実施例３と同様の方法を採用した。生成物について上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図９に示すＸ線回折チャートから、酸化亜鉛であることが確認され、生成された酸化亜鉛の粒子径はシェラーの式より約２９．２ｎｍであった。
(Comparative Example 4)
The same method as in Example 3 was adopted except that zinc chloride, which is a halide of a metal having a poor solubility in an alkaline aqueous solution having a hydroxide of pH 11 or higher, was used as a starting material. When the product was subjected to X-ray crystal structure analysis using the above X-ray diffractometer, it was confirmed from the X-ray diffraction chart shown in FIG. 9 that it was zinc oxide, and the particle size of the produced zinc oxide was Scheller. It was about 29.2 nm according to the formula of.
（比較例５）
ｐＨ１０に調整した点を除いて、実施例３と同様の方法を採用した。得られた懸濁液は、凝集により白濁しており、その凝集体について上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図１０に示すＸ線回折チャートから、酸化スズではなく、オキシ水酸化スズ（Ｓｎ６Ｏ４（ＯＨ）４）であることが確認され、その凝集体の個数平均粒子径を上記レーザー回折式粒度分布測定装置により測定したところ、約２．４μｍであった。
(Comparative Example 5)
The same method as in Example 3 was adopted except that the pH was adjusted to 10. The obtained suspension became cloudy due to aggregation, and when the aggregate was subjected to X-ray crystal structure analysis using the above-mentioned X-ray diffractometer, the X-ray diffraction chart shown in FIG. It was confirmed that it was tin oxyhydroxide (Sn 6 O 4 (OH) 4 ), and the number average particle size of the aggregates was measured by the above-mentioned laser diffraction type particle size distribution measuring device and found to be about 2.4 μm. there were.
（比較例６）
含オゾンガスを通気しない点を除いて、実施例３と同様の方法を採用した。得られた懸濁液は、凝集により白濁しており、その凝集体について上記Ｘ線回折装置を用いてＸ線結晶構造解析を行ったところ、図１１に示すＸ線回折チャートから、酸化スズではなく、オキシ水酸化スズ（Ｓｎ６Ｏ４（ＯＨ）４）であることが確認され、その凝集体の個数平均粒子径を上記レーザー回折式粒度分布測定装置により測定したところ、約０．８３μｍであった。
(Comparative Example 6)
The same method as in Example 3 was adopted except that the ozone-containing gas was not aerated. The obtained suspension became cloudy due to agglomeration, and when the agglomerates were subjected to X-ray crystal structure analysis using the above-mentioned X-ray diffractometer, the X-ray diffraction chart shown in FIG. It was confirmed that it was tin oxyhydroxide (Sn 6 O 4 (OH) 4 ), and the number average particle size of the aggregates was measured by the above-mentioned laser diffraction type particle size distribution measuring device and found to be about 0.83 μm. there were.
上述した実施例１〜３及び比較例１〜６について、出発物質、製造条件（ｐＨ、オゾン処理の有無）、生成物質及びその粒子径を表１にまとめた。 Table 1 summarizes the starting materials, production conditions (pH, presence / absence of ozone treatment), products, and particle diameters thereof for Examples 1 to 3 and Comparative Examples 1 to 6 described above.
以上のように、水酸化物がｐＨ１１以上のアルカリ水溶液に難溶性のアンチモン、スズの酸化物やハロゲン化物を出発物質としている実施例１〜３の金属酸化物ナノ粒子の製造方法では、ｐＨ１１以上のアルカリ水溶液中に存在する金属イオンが少なく、オゾンガスを通気することに伴う酸化工程において生成されるナノオーダーの金属酸化物微粒子の粒成長が抑制され、粒子径の小さな金属酸化物ナノ粒子を製造することができる。 As described above, in the method for producing metal oxide nanoparticles of Examples 1 to 3 using an oxide or halide of antimony or tin, which is sparingly soluble in an alkaline aqueous solution having a hydroxide of pH 11 or higher, as a starting material, the pH is 11 or higher. There are few metal ions present in the alkaline aqueous solution of the above, and the grain growth of nano-order metal oxide fine particles generated in the oxidation process associated with aeration of ozone gas is suppressed, and metal oxide nanoparticles with a small particle size are produced. can do.
また、実施例１〜３の金属酸化物ナノ粒子の製造方法によれば、水酸化物がｐＨ１１以上のアルカリ水溶液に難溶性の金属の酸化物やハロゲン化物を原料として用い、アルカリの添加及びオゾンガスの通気という簡易な工程によって、１００℃以下の温度範囲において、粒子径の小さな金属酸化物ナノ粒子を低コストで製造することができる。 Further, according to the method for producing metal oxide nanoparticles of Examples 1 to 3, using a metal oxide or halide having a poor solubility in an alkaline aqueous solution having a hydroxide of pH 11 or higher as a raw material, addition of alkali and ozone gas. By a simple process of aeration, metal oxide nanoparticles having a small particle size can be produced at low cost in a temperature range of 100 ° C. or lower.
なお、上述した各実施例では、金属酸化物や金属ハロゲン化物水溶液に、アルカリ水溶液を加えてｐＨ１１以上に調整した後、オゾンガスを通気しているが、これに限定されるものではなく、出発物質である金属酸化物や金属ハロゲン化物にｐＨ１１以上に調整されたオゾン水を加えることによっても粒子径の小さな金属酸化物ナノ粒子を製造することができる。この場合、オゾン水は、出発物質である金属酸化物や金属ハロゲン化物の濃度が１Ｍｏｌ／Ｌに対してオゾン濃度が１ｐｐｍ以上であることが好ましく、出発物質である金属酸化物や金属ハロゲン化物の濃度が１Ｍｏｌ／Ｌに対してオゾン濃度が５ｐｐｍ以上であることがより好ましい。 In each of the above-described examples, an alkaline aqueous solution is added to the metal oxide or metal halide aqueous solution to adjust the pH to 11 or higher, and then ozone gas is aerated, but the starting material is not limited to this. It is also possible to produce metal oxide nanoparticles having a small particle size by adding ozone water adjusted to pH 11 or higher to the metal oxide or metal halide. In this case, the ozone water preferably has an ozone concentration of 1 ppm or more with respect to a concentration of 1 Mol / L of the starting material metal oxide or metal halide, and is a starting material of the metal oxide or metal halide. It is more preferable that the ozone concentration is 5 ppm or more with respect to the concentration of 1 Mol / L.
本発明は、粒子径の小さい金属酸化物ナノ粒子を製造する際に利用することができる。 The present invention can be used when producing metal oxide nanoparticles having a small particle size.
Claims (2)
塩化アンチモン水溶液またはフッ化スズ水溶液に、アルカリ水溶液を加えてｐＨ１１以上に調整した後、オゾンガスを通気することを特徴とする金属酸化物ナノ粒子の製造方法。 A method for producing metal oxide nanoparticles using antimony chloride or tin fluoride, which is a metal halide, as a starting material.
A method for producing metal oxide nanoparticles, which comprises adding an alkaline aqueous solution to an antimony chloride aqueous solution or a tin fluoride aqueous solution to adjust the pH to 11 or higher, and then aerating ozone gas.
塩化アンチモンまたはフッ化スズにｐＨ１１以上に調整したオゾン水を加えることを特徴とする金属酸化物ナノ粒子の製造方法。 A method for producing metal oxide nanoparticles using antimony chloride or tin fluoride, which is a metal halide, as a starting material.
A method for producing metal oxide nanoparticles, which comprises adding ozone water adjusted to pH 11 or higher to antimony chloride or tin fluoride.
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