JP4765801B2 - Method for producing metal oxide particles - Google Patents
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- JP4765801B2 JP4765801B2 JP2006190335A JP2006190335A JP4765801B2 JP 4765801 B2 JP4765801 B2 JP 4765801B2 JP 2006190335 A JP2006190335 A JP 2006190335A JP 2006190335 A JP2006190335 A JP 2006190335A JP 4765801 B2 JP4765801 B2 JP 4765801B2
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- 229910044991 metal oxide Inorganic materials 0.000 title claims description 83
- 150000004706 metal oxides Chemical class 0.000 title claims description 83
- 239000002245 particle Substances 0.000 title claims description 78
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 150000001412 amines Chemical class 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000003223 protective agent Substances 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 239000011164 primary particle Substances 0.000 claims description 15
- 229920003169 water-soluble polymer Polymers 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- -1 lanthanoid metals Chemical class 0.000 claims description 9
- 239000006104 solid solution Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
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- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229920000729 poly(L-lysine) polymer Polymers 0.000 claims description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims description 2
- 239000001253 polyvinylpolypyrrolidone Substances 0.000 claims description 2
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 36
- 229910052684 Cerium Inorganic materials 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
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- 238000010304 firing Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
本発明は、一次粒子径がナノメートルオーダである金属酸化物粒子（金属酸化物ナノ粒子）を製造する金属酸化物粒子の製造方法に関し、このような金属酸化物ナノ粒子は、例えば、自動車排ガス用の助触媒粒子、空気質浄化用の光触媒粒子などに適用できるものである。 The present invention relates to a method for producing metal oxide particles for producing metal oxide particles (metal oxide nanoparticles) having a primary particle size on the order of nanometers. Such metal oxide nanoparticles are, for example, automobile exhaust gas. It can be applied to co-catalyst particles for use in air, photocatalyst particles for air quality purification, and the like.
金属酸化物粒子は、様々な用途に用いられており、例えば、自動車用触媒では、助触媒粒子として酸化セリウムや酸化セリウム・酸化ジルコニウム固溶体などが使われ、空気質浄化用としては、酸化チタンなどが使われている（たとえば、特許文献１参照）。 Metal oxide particles are used in various applications. For example, cerium oxide and cerium oxide / zirconium oxide solid solution are used as promoter particles in automobile catalysts, and titanium oxide and the like are used for air quality purification. (For example, refer to Patent Document 1).
近年、粒子の結晶サイズすなわち一次粒子径をナノメートルオーダに微細化することで、表面積が急激に増加し、バルク体には見られない効果（ナノサイズ効果）を発現することが明らかになってきており、金属酸化物においても、ナノサイズ化することで、従来にはない高付加価値が発現する可能性があると言われている。 In recent years, it has been clarified that by reducing the crystal size of the particle, that is, the primary particle diameter to the nanometer order, the surface area increases rapidly and an effect (nanosize effect) that is not seen in the bulk body is developed. Even in the case of metal oxides, it is said that there is a possibility that a high added value that has not existed in the past may be realized by making it nano-sized.
従来の金属酸化物粒子の製造方法としては、固相法、液相法、気相法の様々な手法があるが、いずれの方法においても、前駆体を高温で焼成する、高圧下で処理する等の必要があるため、酸化物の粒径が、結晶成長してしまう問題があった。 Various conventional methods for producing metal oxide particles include a solid phase method, a liquid phase method, and a gas phase method. In any method, the precursor is calcined at a high temperature and processed under a high pressure. Therefore, there has been a problem that the grain size of the oxide causes crystal growth.
具体例をあげると、固相法では、酸化物前駆体を５００℃以上で焼成することで、金属酸化物を生成するが、高温焼成する必要があるため、結晶成長し、金属酸化物の粒径はマイクロオーダとなり、ナノサイズ効果を発現するは困難である。 As a specific example, in the solid phase method, a metal oxide is produced by firing the oxide precursor at 500 ° C. or higher. The diameter is in the micro order, and it is difficult to develop the nano-size effect.
また、従来の液相法では、溶液内で金属イオンが分散した状態から反応が開始するので、固相法よりも、粒径を小さくすることは可能であるが、例えば、共沈した金属酸化物前駆体を分離、乾燥焼成する必要があるため、結果として、結晶成長してしまい、粒径はマイクロオーダとなってしまう。 In the conventional liquid phase method, since the reaction starts from a state in which metal ions are dispersed in the solution, the particle size can be made smaller than that in the solid phase method. Since the product precursor needs to be separated and dried and fired, as a result, crystals grow and the particle size becomes micro-order.
一方、気相法では、最も理想的な金属酸化物ナノ粒子が作り易いが、生産性などに課題も多く、また、ナノ粒子の二次凝集化が強く、気相状態で作製したナノ粒子を例えば溶媒に分散させようとすると、二次凝集してしまうなどの課題があった。 On the other hand, in the vapor phase method, the most ideal metal oxide nanoparticles can be easily produced, but there are many problems in productivity, and the secondary aggregation of the nanoparticles is strong. For example, when dispersed in a solvent, there are problems such as secondary aggregation.
これら従来の工法で作製した金属酸化物粒子の二次凝集を解砕する手段もあるが、結晶成長してしまった粒子の場合、一次粒径以下には微粒化することが困難なこと、一次粒子径が小さいものでも、製造工程数が増加する等の問題点があるため、安価な製造方法を探索する必要があった。
本発明は、上記事情題に鑑みてなされたものであり、金属酸化物粒子を製造するにあたって、常温かつ常圧下にて、一次粒子径がナノメートルオーダである金属酸化物粒子を製造できるようにすることを目的とする。 The present invention has been made in view of the above-mentioned problems, and in producing metal oxide particles, it is possible to produce metal oxide particles having a primary particle size of nanometer order at room temperature and normal pressure. The purpose is to do.
上記目的を達成するため、本発明は、一次粒子径が１０ｎｍ以下である金属酸化物粒子を製造する金属酸化物粒子の製造方法であって、常温かつ常圧下にて、金属酸化物の金属元素が水溶液中にイオン状態で存在する金属酸化物の原料に対して、水溶性アミン類を添加することにより、金属酸化物粒子を生成し、水溶液のｐＨを、水溶性アミン類の添加により４以上とし、水溶性アミン類の添加量を、金属酸化物の原料のモル数に対して、１モル当量以上５モル当量以下とすることを特徴とする。 In order to achieve the above object, the present invention provides a metal oxide particle production method for producing metal oxide particles having a primary particle diameter of 10 nm or less , wherein the metal element of the metal oxide is at room temperature and normal pressure. Is added to the raw material of the metal oxide in an ionic state in the aqueous solution to produce metal oxide particles, and the pH of the aqueous solution is 4 or more by addition of the water-soluble amine. And the amount of water-soluble amines added is from 1 to 5 molar equivalents relative to the number of moles of the metal oxide raw material .
本発明は、実験的に得られたものであり、金属酸化物の金属元素がイオン状態で存在する水溶液中に、水溶性アミン類を添加することにより、常温かつ常圧下にて、一次粒子径がナノメートルオーダである金属酸化物粒子を製造することができる。 The present invention was obtained experimentally, and by adding a water-soluble amine to an aqueous solution in which the metal element of the metal oxide is present in an ionic state, the primary particle size at room temperature and normal pressure. Can produce metal oxide particles having a nanometer order.
反応開始剤である水溶性アミン類は、金属イオンを金属酸化物にするために必要であるゆえ、少なくとも、金属イオンと同等以上のモル当量を添加する必要がある。また、水溶性アミン類を５モル当量以上、添加すると、水溶液のｐＨが１１以上になってしまい、反応速度が速く、金属酸化物の粒径が大きくなってしまう。 Since the water-soluble amines which are reaction initiators are necessary for converting metal ions into metal oxides, it is necessary to add at least a molar equivalent equivalent to or higher than that of the metal ions. Moreover, when 5 mol equivalent or more of water-soluble amines are added, pH of aqueous solution will become 11 or more, reaction rate will be quick, and the particle size of a metal oxide will become large.
また、上記製造方法において、さらに、金属酸化物粒子が生成された水溶液を、ｐＨが１以上４以下に調製した後、超音波を照射することで、当該水溶液中にて金属酸化物粒子を一次粒子に単分散させるようにすれば、一次粒子径がナノメートルオーダである金属酸化物粒子を適切に製造できる。 Moreover, in the said manufacturing method, after adjusting aqueous solution in which the metal oxide particle was produced | generated further to pH 1 or more and 4 or less, by irradiating an ultrasonic wave, a metal oxide particle is primary in the said aqueous solution. If the particles are monodispersed, metal oxide particles having a primary particle size on the order of nanometers can be appropriately produced.
本実施形態の金属酸化物粒子の作製方法は、常温でかつ常圧での合成法であり、加熱源、温度調整を必要としない点で非常に安価な作製法である。 The method for producing metal oxide particles of the present embodiment is a synthesis method at normal temperature and normal pressure, and is a very inexpensive production method in that a heating source and temperature adjustment are not required.
具体的には、金属酸化物の原料を水溶液に溶解して、当該金属酸化物の金属が水溶液中にイオン状態で存在するようにする。そして、この水溶液に対して、常温かつ常圧下にて、水溶性アミン類を添加することにより、一次粒子径がナノメートルオーダである金属酸化物粒子を生成する。 Specifically, a metal oxide raw material is dissolved in an aqueous solution so that the metal of the metal oxide exists in an ionic state in the aqueous solution. And water-soluble amines are added with respect to this aqueous solution at normal temperature and a normal pressure, The metal oxide particle whose primary particle diameter is a nanometer order is produced | generated.
ここで、水溶性アミン類は反応開始剤として用いるものであり、水に溶解できるものであれば、特に問題なく、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン等が溶解性、粘性の面から望ましい。 Here, the water-soluble amines are used as a reaction initiator, and can be dissolved in water without any particular problem, for example, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, Tripropanolamine or the like is desirable from the viewpoint of solubility and viscosity.
これら水溶性アミン類が反応開始剤として、最適である詳細メカニズムは良くわかっていないが、おそらく水溶性アミン添加による水酸化物の生成とそれに続く加水分解のスピードが適度であるためではないかと考えられる。 Although the detailed mechanism by which these water-soluble amines are optimal as initiators is not well understood, it is probably due to the moderate speed of hydroxide formation and subsequent hydrolysis by addition of water-soluble amines. It is done.
例えば、水溶性アミン添加ということであれば、アンモニア水などでも良いと考えられるが、アンモニアでは、局所排気装置などが必要なうえ、アンモニアの反応スピードが速いため、生成したものの結晶粒子が大きいなどの問題がある。 For example, if it is a water-soluble amine addition, it is considered that ammonia water may be used. However, ammonia requires a local exhaust device and the reaction speed of ammonia is high, so that the generated crystal particles are large. There is a problem.
また、ＮａＯＨなどを用いても、同様の効果が期待できるが、Ｎａイオンの分離が困難であること、たとえ焼成しても不純物金属として残存することなどの課題がある。 Further, even when NaOH is used, the same effect can be expected, but there are problems such as difficulty in separating Na ions and remaining as an impurity metal even if baked.
本実施形態の製造方法においては、水酸化物の生成とそれに続く加水分解のために、水溶液のｐＨをコントロールすることが重要である。本発明者は、多くの実験事実より、水溶液のｐＨが４よりも小さいと、ＯＨイオン濃度が少ないために水酸化物の形成が困難で、したがって、金属酸化物粒子の生成がなされないことを見出した。 In the production method of this embodiment, it is important to control the pH of the aqueous solution for the production of hydroxide and subsequent hydrolysis. The present inventor has shown from many experimental facts that when the pH of the aqueous solution is lower than 4, it is difficult to form a hydroxide due to a low concentration of OH ions, and therefore metal oxide particles are not generated. I found it.
水溶液のｐＨをコントロールするためには、反応開始剤である水溶性アミン類の添加量を制御すればよい。また、水溶性アミン類は、金属イオンを金属酸化物にするために必要であるゆえ、少なくとも、金属イオンと同等以上のモル当量を添加する必要がある。 In order to control the pH of the aqueous solution, the amount of water-soluble amine that is a reaction initiator may be controlled. Further, since the water-soluble amines are necessary for converting metal ions into metal oxides, it is necessary to add at least a molar equivalent equivalent to or higher than that of the metal ions.
これらのことから、反応開始剤である水溶性アミン類は、金属イオンの１モル当量以上５モル当量以下であること、すなわち金属酸化物の原料のモル数に対して１モル当量以上５モル当量以下であることが必要である。水溶性アミン類を５モル当量以上、添加すると、水溶液のｐＨが１１以上になってしまい、反応速度が速く、金属酸化物の粒径が大きくなってしまう。 From these, the water-soluble amines that are reaction initiators are 1 to 5 mole equivalents of metal ions, that is, 1 to 5 mole equivalents relative to the number of moles of the metal oxide raw material. It is necessary that: When 5 mole equivalents or more of water-soluble amines are added, the pH of the aqueous solution becomes 11 or more, the reaction rate is high, and the particle size of the metal oxide becomes large.
このような条件下で作製可能な金属酸化物粒子の金属元素種は、アルカリ金属類、アルカリ土類金属類、遷移金属類、ランタノイド金属類、典型金属類などであり、水溶液中にイオン状態で溶解できる金属種であれば、金属酸化物を作製することは可能である。 The metal element species of the metal oxide particles that can be produced under such conditions are alkali metals, alkaline earth metals, transition metals, lanthanoid metals, typical metals, and the like in an ionic state in an aqueous solution. Any metal species that can be dissolved can be used to produce a metal oxide.
より望ましくは、当該金属元素種が、Ｃｅ、Ｚｒ、Ｔｉ、Ｆｅ、Ａｌ、Ｉｎ、Ｃａ、Ｍｇ、Ｍｎ、Ｃｏ、Ｎｉ、Ｌａ等であれば、容易に金属酸化物粒子を合成することが可能である。 More preferably, if the metal element species is Ce, Zr, Ti, Fe, Al, In, Ca, Mg, Mn, Co, Ni, La, etc., it is possible to easily synthesize metal oxide particles. It is.
つまり、本実施形態では、金属酸化物粒子としては、ＣｅＯ2、ＺｒＯ2、ＴｉＯ2、Ｆｅ2Ｏ3、Ａｌ2Ｏ3、Ｉｎ2Ｏ3、ＣａＯ、ＭｇＯ、ＭｎＯ2、ＣｏＯ、ＮｉＯ、Ｌａ2Ｏ3から選ばれる１種の酸化物粒子、あるいは、２種以上の固溶酸化物粒子を作製することが可能である。 That is, in this embodiment, as the metal oxide particles, CeO 2 , ZrO 2 , TiO 2 , Fe 2 O 3 , Al 2 O 3 , In 2 O 3 , CaO, MgO, MnO 2 , CoO, NiO, La It is possible to produce one kind of oxide particle selected from 2 O 3 or two or more kinds of solid solution oxide particles.
これらについては、水溶液中に金属イオンを１種溶解させておけば、単金属酸化物が作製可能であり、金属イオンを２種以上溶解させておけば、２種以上からなる固溶体または混合体を作製することができる。 For these, a single metal oxide can be produced by dissolving one kind of metal ion in an aqueous solution, and a solid solution or mixture comprising two or more kinds can be prepared by dissolving two or more kinds of metal ions. Can be produced.
なお、遷移金属の場合、多くのイオン価数を取り得るが、多くの場合、最安定な価数を取り易く、また、出発原料である金属イオンの価数に影響されることが多い。 In the case of transition metals, many ionic valences can be obtained. However, in many cases, the most stable valence is easily obtained, and it is often influenced by the valence of metal ions that are starting materials.
また、金属イオンの原料としては、水溶液に溶解するものであれば、特に問題ないが、望ましくは、硝酸塩、水酸化物、塩化物、硫酸塩がよい。 The metal ion raw material is not particularly limited as long as it dissolves in an aqueous solution, but nitrates, hydroxides, chlorides, and sulfates are preferable.
さらに、ｐＨ４から８で金属酸化物ナノ粒子を合成した溶液は、出発原料（たとえば硝酸イオン、塩化物イオンなど）や反応開始剤に由来する有機物が混在しているために、遠心分離などを用いて、金属酸化物ナノ粒子のみを分離し、洗浄する必要がある。
Furthermore, the solution in which metal oxide nanoparticles are synthesized at
洗浄分離した金属酸化物ナノ粒子をペーストとして使用するためには、水に再分散させる必要があるが、この際に、硝酸などを加えてｐＨを１以上４以下にコントロールし、超音波を照射すれば、より効果的に、高分散させることが可能である。 In order to use the washed and separated metal oxide nanoparticles as a paste, it is necessary to re-disperse in water. At this time, nitric acid is added to control the pH to 1 to 4 and irradiate with ultrasonic waves. If so, it is possible to achieve high dispersion more effectively.
本製造方法では金属元素が水溶液中にイオン状態で存在する金属酸化物の原料に対して、水溶性アミン類を作用させることにより、一次粒子径がナノメートルオーダに制御された金属酸化物粒子が得られる。一次粒子が凝集することなくナノメートルオーダに制御できるのは、ＧＣ−ＭＳによる分析結果から明らかなように、作用させる水溶性アミン自体が金属酸化物の表面を被覆できるからである。金属酸化物粒子の表面を被覆する有機成分である水溶性アミンが粒子中に５〜３０％含まれることは、熱分析（ＴＧ−ＤＴＡ）により確認された。 In this production method, metal oxide particles whose primary particle diameter is controlled to the nanometer order are obtained by allowing water-soluble amines to act on the metal oxide raw material in which the metal element exists in an ionic state in an aqueous solution. can get. The reason why the primary particles can be controlled to the nanometer order without agglomeration is that the water-soluble amine to be acted on itself can coat the surface of the metal oxide, as is apparent from the analysis result by GC-MS. It was confirmed by thermal analysis (TG-DTA) that the water-soluble amine, which is an organic component covering the surface of the metal oxide particles, was contained in the particles in an amount of 5 to 30%.
また、この有機保護基の存在が、洗浄分離した金属酸化物ナノ粒子の水への再分散を可能としている。より効果的な水への高分散性のためには、高分子保護剤を共存させて金属酸化物粒子を製造することもできる。その場合、金属酸化物粒子の表面を被覆する有機成分は粒子中に最大で４０％まで増加させることができる。 In addition, the presence of the organic protecting group enables re-dispersion of the washed and separated metal oxide nanoparticles in water. For more effective high dispersibility in water, metal oxide particles can be produced in the presence of a polymer protective agent. In that case, the organic components covering the surface of the metal oxide particles can be increased up to 40% in the particles.
高分子保護剤としては水溶性の官能基を有する高分子保護剤であればよく、好ましくはポリビニルピロリドン、ポリビニルポリピロリドン、ポリエチレングリコール、ポリエチレンイミン、ポリビニルアルコール、ポリアクリルアミド、ポリアクリル酸、ポリメタクリル酸、ポリイタコン酸、ポリエチレンオキシド、ポリビニルメチルエーテル、ポリプロピレングリコール、ポリ−Ｌ−乳酸、ポリ−Ｌ−リシンなどから選ばれる１種以上の水溶性高分子保護剤を、金属元素の重量（金属元素が２種以上の場合はその合計重量）に対して、好ましくは１〜２０重量％、より好ましくは５〜１０重量％添加してうえで、水溶性アミンを反応させることで水への高分散性を有する金属酸化物粒子の製造が可能となる。 The polymer protective agent may be a polymer protective agent having a water-soluble functional group, and preferably polyvinyl pyrrolidone, polyvinyl polypyrrolidone, polyethylene glycol, polyethylene imine, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polymethacrylic acid. One or more water-soluble polymer protective agents selected from polyitaconic acid, polyethylene oxide, polyvinyl methyl ether, polypropylene glycol, poly-L-lactic acid, poly-L-lysine, etc. In the case of more than species, the total weight) is preferably 1 to 20% by weight, more preferably 5 to 10% by weight, and a high water dispersibility is obtained by reacting with a water-soluble amine. It becomes possible to produce metal oxide particles.
以下に、実施例を記載するが、これらは一例であり、より多くの金属酸化物に適用可能であることは言うまでもない。 Examples are described below, but these are only examples, and it goes without saying that the present invention can be applied to more metal oxides.
ビーカを用いて、金属酸化物粒子の原料である硝酸セリウム５ｇを水１００ｍｌに溶解させた。続いて、攪拌子でこの水溶液を攪拌しながら、ジエタノールアミンをセリウムイオンに対し、１モル当量添加した。２４時間経過後、遠心分離にて、生成物を分離し、水による洗浄を３回繰り返した後に、合成物を得た。 Using a beaker, 5 g of cerium nitrate, which is a raw material for metal oxide particles, was dissolved in 100 ml of water. Subsequently, 1 mol equivalent of diethanolamine was added to cerium ion while stirring the aqueous solution with a stir bar. After 24 hours, the product was separated by centrifugation, and after washing with water three times, a composite was obtained.
水を１０００ｍｌとした以外は、実施例１と同様の方法で合成した。 The synthesis was performed in the same manner as in Example 1 except that the amount of water was changed to 1000 ml.
ジエタノールアミンをセリウムイオンに対し、２モル当量とした以外は、実施例１と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 1 except that diethanolamine was changed to 2 molar equivalents relative to cerium ion.
ジエタノールアミンをセリウムイオンに対して、３モル当量とした以外は、実施例１と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 1 except that diethanolamine was changed to 3 molar equivalents with respect to cerium ion.
ジエタノールアミンをセリウムイオンに対して、５モル当量とした以外は、実施例１と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 1 except that diethanolamine was changed to 5 molar equivalents with respect to cerium ion.
ジエタノールアミンのかわりに、モノエタノールアミンを用いた以外は、実施例１と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 1 except that monoethanolamine was used instead of diethanolamine.
ジエタノールアミンのかわりに、トリエタノールアミアンを用いた以外は、実施例１と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 1 except that triethanolamiane was used in place of diethanolamine.
硝酸セリウムのかわりに、オキシ硝酸ジルコニウムを用いた以外は、実施例１と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 1 except that zirconium oxynitrate was used instead of cerium nitrate.
硝酸セリウムのかわりに、硝酸セリウムとオキシ硝酸ジルコニウムをモル比で５：５としたものを使用した以外は、実施例１と同様の方法で合成物を得た。 A composite was obtained in the same manner as in Example 1 except that cerium nitrate and zirconium oxynitrate having a molar ratio of 5: 5 were used instead of cerium nitrate.
硝酸セリウムのかわりに、硝酸セリウムとオキシ硝酸ジルコニウムをモル比で３：７としたものを使用した以外は、実施例１と同様の方法で合成物を得た。 A composite was obtained in the same manner as in Example 1 except that cerium nitrate and zirconium oxynitrate having a molar ratio of 3: 7 were used instead of cerium nitrate.
硝酸セリウムのかわりに、硝酸セリウムとオキシ硝酸ジルコニウムをモル比で７：３としたものを使用した以外は、実施例１と同様の方法で合成物を得た。 A composite was obtained in the same manner as in Example 1 except that cerium nitrate and zirconium oxynitrate having a molar ratio of 7: 3 were used instead of cerium nitrate.
硝酸セリウムのかわりに、硝酸第二鉄を用いた以外は、実施例１と同様の方法で合成物を得た。 A composite was obtained in the same manner as in Example 1 except that ferric nitrate was used instead of cerium nitrate.
硝酸セリウムのかわりに、硝酸インジウムを用いた以外は、実施例１と同様の方法で合成物を得た。 A composite was obtained in the same manner as in Example 1 except that indium nitrate was used instead of cerium nitrate.
硝酸セリウムのかわりに、硝酸チタニウムを用いた以外は、実施例１と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 1 except that titanium nitrate was used instead of cerium nitrate.
実施例１で得られた合成物に水を加え、スラリー状とした溶液に、超音波を３０分照射することで、金属酸化物粒子が分散したスラリー液を得た。 Water was added to the compound obtained in Example 1 to irradiate the slurry solution with ultrasonic waves for 30 minutes to obtain a slurry liquid in which metal oxide particles were dispersed.
実施例１で得られた合成物に水を加え、スラリー状とした溶液に、硝酸を滴下し、ｐＨを３に調製した。その後、超音波を３０分照射することで、金属酸化物粒子が高分散したスラリー液を得た。 Water was added to the composition obtained in Example 1, and nitric acid was added dropwise to the slurry solution to adjust the pH to 3. Then, the slurry liquid in which the metal oxide particles were highly dispersed was obtained by irradiating with ultrasonic waves for 30 minutes.
硝酸セリウムのかわりに、硝酸セリウムとオキシ硝酸ジルコニウムをモル比で７：３とし、さらに水溶性高分子保護剤としてポリビニルピロリドンＫ−３０（分子量４００００）をセリウムとジルコニウムの合計重量に対して１重量％添加した以外は、実施例１と同様の方法で合成物を得た。 Instead of cerium nitrate, the molar ratio of cerium nitrate and zirconium oxynitrate is 7: 3, and polyvinylpyrrolidone K-30 (molecular weight 40000) as a water-soluble polymer protective agent is 1 weight with respect to the total weight of cerium and zirconium. A synthesized product was obtained in the same manner as in Example 1 except that% was added.
水溶性高分子保護剤としてポリビニルピロリドンＫ−３０（分子量４００００）をセリウムとジルコニウムの合計重量に対して５重量％添加した以外は、実施例１７と同様の方法で合成物を得た。 A synthetic product was obtained in the same manner as in Example 17 except that polyvinylpyrrolidone K-30 (molecular weight 40000) was added as a water-soluble polymer protective agent in an amount of 5% by weight based on the total weight of cerium and zirconium.
水溶性高分子保護剤としてポリビニルピロリドンＫ−３０（分子量４００００）をセリウムとジルコニウムの合計重量に対して１０重量％添加した以外は、実施例１７と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 17 except that polyvinylpyrrolidone K-30 (molecular weight 40000) was added as a water-soluble polymer protective agent in an amount of 10% by weight based on the total weight of cerium and zirconium.
硝酸セリウムのかわりに、硝酸セリウムとオキシ硝酸ジルコニウムをモル比で７：３とし、さらに水溶性高分子保護剤としてポリエチレングリコール＃２００００（平均分子量１５０００〜２５０００）をセリウムとジルコニウムの合計重量に対して１重量％添加した以外は、実施例１と同様の方法で合成物を得た。 Instead of cerium nitrate, the molar ratio of cerium nitrate and zirconium oxynitrate is 7: 3, and polyethylene glycol # 20000 (average molecular weight 15000 to 25000) as a water-soluble polymer protective agent is based on the total weight of cerium and zirconium. A synthesized product was obtained in the same manner as in Example 1 except that 1% by weight was added.
水溶性高分子保護剤としてポリエチレングリコール＃２００００（平均分子量１５０００〜２５０００）をセリウムとジルコニウムの合計重量に対して５重量％添加した以外は、実施例２０と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 20, except that polyethylene glycol # 20000 (average molecular weight 15000 to 25000) was added as a water-soluble polymer protective agent in an amount of 5% by weight based on the total weight of cerium and zirconium.
水溶性高分子保護剤としてポリエチレングリコール＃２００００（平均分子量１５０００〜２５０００）をセリウムとジルコニウムの合計重量に対して１０重量％添加した以外は、実施例２０と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 20 except that polyethylene glycol # 20000 (average molecular weight 15000 to 25000) was added as a water-soluble polymer protective agent in an amount of 10% by weight based on the total weight of cerium and zirconium.
硝酸セリウムのかわりに、硝酸セリウムとオキシ硝酸ジルコニウムをモル比で７：３とし、さらに水溶性高分子保護剤としてポリビニルアルコール（重合度約２０００）をセリウムとジルコニウムの合計重量に対して１重量％添加した以外は、実施例１と同様の方法で合成物を得た。 Instead of cerium nitrate, the molar ratio of cerium nitrate and zirconium oxynitrate is 7: 3, and polyvinyl alcohol (degree of polymerization of about 2000) as a water-soluble polymer protective agent is 1% by weight based on the total weight of cerium and zirconium. A synthesized product was obtained in the same manner as in Example 1 except for the addition.
水溶性高分子保護剤としてポリビニルアルコール（重合度約２０００）をセリウムとジルコニウムの合計重量に対して５重量％添加した以外は、実施例２３と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 23, except that 5% by weight of polyvinyl alcohol (degree of polymerization: about 2000) was added as a water-soluble polymer protective agent with respect to the total weight of cerium and zirconium.
水溶性高分子保護剤としてポリビニルアルコール（重合度約２０００）をセリウムとジルコニウムの合計重量に対して１０重量％添加した以外は、実施例２３と同様の方法で合成物を得た。 A synthesized product was obtained in the same manner as in Example 23 except that polyvinyl alcohol (degree of polymerization: about 2000) was added as a water-soluble polymer protective agent in an amount of 10% by weight based on the total weight of cerium and zirconium.
（比較例１）
硝酸セリウム５ｇを入れたルツボを８００℃で５時間焼成することにより、酸化セリウムを合成した。
(Comparative Example 1)
Cerium oxide was synthesized by firing a crucible containing 5 g of cerium nitrate at 800 ° C. for 5 hours.
（比較例２）
ジエタノールアミンをセリウムイオンに対して、０．５モル当量とした以外は、実施例１と同様の方法で合成物を得た。
(Comparative Example 2)
A synthesized product was obtained in the same manner as in Example 1 except that diethanolamine was changed to 0.5 molar equivalent with respect to cerium ion.
（比較例３）
ジエタノールアミンをセリウムイオンに対して、１０モル当量とした以外は、実施例１と同様の方法で合成物を得た。
(Comparative Example 3)
A synthesized product was obtained in the same manner as in Example 1 except that diethanolamine was changed to 10 molar equivalents with respect to cerium ion.
なお、上記した各実施例においては、金属酸化物の金属元素がイオン状態で存在する水溶液のｐＨを、４以上となるように水溶性アミン類の量を制御して添加している。 In each of the above-described embodiments, the amount of the water-soluble amine is controlled so that the pH of the aqueous solution in which the metal element of the metal oxide exists in an ionic state is 4 or more.
上記各例にて得られた合成物の同定には、ＴＥＭ、粒度分布測定、ＸＲＤ、ＸＲＦ、などを行った。なお、得られた合成物は、水分を含んでいるため、乾式での分析には、乾燥により水分を除去したサンプルを用いた。 TEM, particle size distribution measurement, XRD, XRF, etc. were performed for identification of the synthesized product obtained in each of the above examples. In addition, since the obtained synthetic | combination contains the water | moisture content, the sample which removed the water | moisture content by drying was used for the analysis by a dry type.
図１は上記実施例１〜１０の合成物について、また、図２は上記実施例１１〜１６および比較例１〜３の合成物について、さらに、図３は上記実施例１７〜２５について、それぞれ、収率（％）、ＴＥＭによる一次粒径（ｎｍ）、粒度分布測定装置によりスラリー化した際の平均粒径（ｎｍ）、ＸＲＦにより検出された金属元素、ＸＲＤパターンを示す図表である。なお、この表中の「−」は未測定のものである。 1 shows the composites of Examples 1 to 10, FIG. 2 shows the composites of Examples 11 to 16 and Comparative Examples 1 to 3, and FIG. 3 shows the composites of Examples 17 to 25. , Yield (%), primary particle diameter (nm) by TEM, average particle diameter (nm) when slurried by a particle size distribution measuring device, metal elements detected by XRF, and XRD pattern. In addition, "-" in this table | surface is an unmeasured thing.
たとえば、上記実施例１を例に、同定結果を説明すると、ＸＲＤ測定により、結晶パターンが観察され、結晶データベースより、結晶パターンが、ＣｅＯ2に由来するものであることが確認できた。なお、ＸＲＤパターンは、ピークがブロード化しており、これは、ナノ粒子による影響、あるいは、結晶化が完全でないためと考えている。 For example, when the identification result is explained by taking Example 1 as an example, the crystal pattern was observed by XRD measurement, and it was confirmed from the crystal database that the crystal pattern was derived from CeO 2 . Note that the XRD pattern has broad peaks, which is considered to be due to the influence of nanoparticles or incomplete crystallization.
さらに、ＴＥＭ観察により、一次粒径が３〜４ｎｍ程度のナノ粒子が合成できていることも確認できた。以上の結果から、実施例１において、従来の高温焼成や加圧などの工程を行わなくても、金属酸化物ナノ粒子が作製できることがわかった。 Furthermore, it was confirmed by TEM observation that nanoparticles having a primary particle size of about 3 to 4 nm were synthesized. From the above results, it was found that metal oxide nanoparticles can be produced in Example 1 without performing conventional processes such as high-temperature baking and pressurization.
また、同様の同定を行った結果から、いずれの実施例においても、収率も比較的良好であり、一次粒径１０ｎｍ以下の金属酸化物粒子が、常温常圧で作製可能であることが確認された。 In addition, from the results of the same identification, it was confirmed that in any of the examples, the yield was relatively good, and metal oxide particles having a primary particle size of 10 nm or less could be produced at room temperature and normal pressure. It was done.
また、比較例１と比較すれば、明らかなように、各実施例の金属酸化物粒子は、一次結晶粒径分布のばらつきも少なく、粒子径のそろった金属酸化物粒子を作製することが可能である。 Further, as compared with Comparative Example 1, it is clear that the metal oxide particles of each Example have little variation in the primary crystal particle size distribution, and it is possible to produce metal oxide particles having a uniform particle size. It is.
また、上記実施例では、ＣｅＯ2を例にして、そのモル当量を様々な条件にて振っているが、水溶性アミン類の量としては、金属イオンに対して、１モル当量以上５モル当量以下が適当であることが確認された。 In the above embodiment, and the CeO 2 as an example, but the molar equivalents waving at various conditions, the amount of the water-soluble amines, the metal ions, 1 mole equivalent or more 5 molar equivalents The following was confirmed to be appropriate.
比較例２では、添加量が少ないために、収率がかなり低く、逆に比較例３では、収率は高いものの一次結晶粒径が大きくなってしまうなどの問題があることが示された。なお、実施例では割愛したが、他の金属酸化物についても、同様の添加量の範囲にて金属酸化物粒子の製造が良好であることを確認した。 In Comparative Example 2, since the addition amount was small, the yield was considerably low. On the other hand, Comparative Example 3 showed a problem that the primary crystal grain size was increased although the yield was high. Although omitted in the examples, it was confirmed that the production of metal oxide particles was good in the range of the same addition amount for other metal oxides.
また、上記実施例９〜１１では、ＣｅＯ2・ＺｒＯ2固溶体について、配合比を変化させた場合について示したが、いずれの場合においても、仕込値に近い配合比で粒子が作製できており、ＸＲＤよりも、単独酸化物ピークは検出されず、固溶体に由来するピークのみが検出され、目的とする粒子が作製されていることを確認した。 In Examples 9 to 11, the CeO 2 .ZrO 2 solid solution was shown with respect to the case where the blending ratio was changed. In any case, particles were prepared at a blending ratio close to the charged value. A single oxide peak was not detected by XRD, but only a peak derived from a solid solution was detected, confirming that the intended particles were produced.
Claims (10)
常温かつ常圧下にて、前記金属酸化物の金属元素が水溶液中にイオン状態で存在する前記金属酸化物の原料に対して、水溶性アミン類を添加することにより、前記金属酸化物粒子を生成し、
前記水溶液のｐＨを、前記水溶性アミン類の添加により４以上とし、
前記水溶性アミン類の添加量を、前記金属酸化物の原料のモル数に対して、１モル当量以上５モル当量以下とすることを特徴とする金属酸化物粒子の製造方法。 A method for producing metal oxide particles for producing metal oxide particles having a primary particle diameter of 10 nm or less ,
The metal oxide particles are formed by adding water-soluble amines to the raw material of the metal oxide in which the metal element of the metal oxide exists in an aqueous solution at room temperature and normal pressure. And
The pH of the aqueous solution is set to 4 or more by adding the water-soluble amines,
The method for producing metal oxide particles , wherein the addition amount of the water-soluble amines is 1 to 5 molar equivalents relative to the number of moles of the raw material for the metal oxide.
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