JP6399656B2 - Method for producing metal oxide nanoparticles - Google Patents
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本発明は、金属酸化物ナノ粒子の製造方法に関する。 The present invention relates to a method for producing metal oxide nanoparticles.
物質の大きさがナノメートルオーダーになると、電気特性、光学特性、磁性特性などがバルク状態とは大きく異なってくる（量子サイズ効果）。この量子サイズ効果が現れるナノ粒子は、近年さまざまな分野での応用が期待されている。 When the size of a material is on the order of nanometers, the electrical properties, optical properties, magnetic properties, etc. are greatly different from the bulk state (quantum size effect). Nanoparticles that exhibit this quantum size effect are expected to be applied in various fields in recent years.
ナノ粒子の合成法の多くは、ＣＶＤを中心とする気相法と、還元や熱分解を中心とする液相法に分類される。液相法は比較的均質な粒子が簡単な操作で得られることから広く用いられているが、生成した粒子の成長を制御することが困難という問題がある。気相法は純度の高い粒子が得られるが、生成した粒子の凝集、装置壁への付着などが問題になっている。 Many of the nanoparticle synthesis methods are classified into a vapor phase method centered on CVD and a liquid phase method centered on reduction and thermal decomposition. The liquid phase method is widely used because relatively homogeneous particles can be obtained by a simple operation, but there is a problem that it is difficult to control the growth of the generated particles. In the gas phase method, high-purity particles can be obtained, but aggregation of the generated particles and adhesion to the apparatus wall are problematic.
これらの方法に加え、近年では、高分子ゲルを金属酸化物ナノ粒子生成の場として用い、そのなかでナノ粒子を合成する方法が提案されている（非特許文献１）。この方法はｉｎ ｓｉｔｕ法と呼ばれ、まず、乾燥した高分子ゲルを金属イオン溶液に浸漬させて、金属イオンを高分子ゲル中に取り込む。そして、金属イオンが取り込まれた高分子ゲルを塩基性溶液に浸漬させることで、高分子ゲル中に金属酸化物のナノ粒子を生成させている。 In addition to these methods, in recent years, a method has been proposed in which a polymer gel is used as a field for producing metal oxide nanoparticles, and among these methods, nanoparticles are synthesized (Non-Patent Document 1). This method is called an in situ method. First, a dried polymer gel is immersed in a metal ion solution, and the metal ions are taken into the polymer gel. And the metal oxide nanoparticle was produced | generated by immersing the polymer gel in which the metal ion was taken in in a basic solution.
高分子ゲル中での金属酸化物ナノ粒子の合成は、有効細孔径が数ｎｍ程度のゲルネットワーク内部で行われるので、ネットワークが粒子の凝集・成長を妨げ、ネットワークの有効細孔径より大きな粒子は生成しにくいという利点がある。 Since the synthesis of metal oxide nanoparticles in a polymer gel is performed inside a gel network having an effective pore size of several nanometers, the network prevents the particles from aggregating and growing. There is an advantage that it is difficult to generate.
非特許文献１の合成方法では、一旦、高分子ゲルに金属イオン溶液に浸漬させて金属イオンを取り込ませ、その後、塩基性溶液に浸漬させる必要があるため、工程が多くなり操作が煩雑となるとともに、別途塩基性溶液を準備しなければならず製造コストが高くなる。 In the synthesis method of Non-Patent Document 1, since it is necessary to immerse the polymer gel in a metal ion solution to take in metal ions and then immerse in a basic solution, the number of steps increases and the operation becomes complicated. At the same time, a basic solution must be prepared separately, which increases the manufacturing cost.
本発明は上記事項に鑑みてなされたものであり、その目的とするところは、塩基性溶液を必要とせずに、高分子ゲルネットワーク内部に金属酸化物ナノ粒子を合成することが可能な金属酸化物ナノ粒子の製造方法を提供することにある。 The present invention has been made in view of the above matters, and its object is to provide a metal oxide capable of synthesizing metal oxide nanoparticles inside a polymer gel network without the need for a basic solution. It is providing the manufacturing method of a product nanoparticle.
本発明に係る金属酸化物ナノ粒子の製造方法は、
末端のアミノ基とアクリルアミド基又はメタクリルアミド基との間に炭素数が２以上のアルキレン鎖を有するアクリルアミドモノマー又はメタクリルアミドモノマーが重合して得られた親水性の高分子ゲルに水分子の存在下で金属イオンを介在させて、前記高分子ゲルのネットワーク空間内にて金属酸化物のナノ粒子を生成させる、
ことを特徴とする。
The method for producing metal oxide nanoparticles according to the present invention includes:
In the presence of water molecules in a hydrophilic polymer gel obtained by polymerizing an acrylamide monomer or methacrylamide monomer having an alkylene chain having 2 or more carbon atoms between the terminal amino group and the acrylamide group or methacrylamide group. In order to generate metal oxide nanoparticles in the network space of the polymer gel, intervening metal ions in
It is characterized by that.
また、炭素数が３以上の前記アルキレン鎖を有する前記アクリルアミドモノマー又は前記メタクリルアミドモノマーが重合して得られた前記高分子ゲルを用いることが好ましい。 Moreover, it is preferable to use the polymer gel obtained by polymerizing the acrylamide monomer or the methacrylamide monomer having the alkylene chain having 3 or more carbon atoms.
また、前記金属イオンを含有する水溶液に乾燥された前記高分子ゲルを浸漬させてもよい。 The dried polymer gel may be immersed in an aqueous solution containing the metal ions.
また、水素イオンよりも酸化還元電位が大きい前記金属イオンと水酸化物イオンよりも陰イオン化傾向が大きい陰イオンとの金属塩が溶解された前記水溶液に前記高分子ゲルを浸漬させることが好ましい。 Moreover, it is preferable to immerse the polymer gel in the aqueous solution in which a metal salt of the metal ion having a higher redox potential than hydrogen ions and an anion having a larger anionization tendency than hydroxide ions is dissolved.
また、アクリルアミド系の架橋剤又はメタクリルアミド系の架橋剤と前記アクリルアミドモノマー又は前記メタクリルアミドモノマーとの共重合により得られた前記高分子ゲルを用い、
前記架橋剤に対して１．５モル以上の前記アクリルアミドモノマー又は前記メタクリルアミドモノマーを加えてもよい。
Further, using the polymer gel obtained by copolymerization of an acrylamide-based crosslinking agent or a methacrylamide-based crosslinking agent and the acrylamide monomer or the methacrylamide monomer,
You may add 1.5 mol or more of the said acrylamide monomer or the said methacrylamide monomer with respect to the said crosslinking agent.
本発明に係る金属酸化物ナノ粒子の製造方法では、水分子の解離によって生じる水素イオンがアミノ基に引き付けられ、一方の水酸化物イオンは高分子ゲルの外部に拡散しないので、高分子ゲル内が塩基性に保たれる。この塩基性環境下にて金属イオンから金属酸化物ナノ粒子が合成されるので、塩基性溶液を別途必要としない。 In the method for producing metal oxide nanoparticles according to the present invention, hydrogen ions generated by the dissociation of water molecules are attracted to amino groups, and one hydroxide ion does not diffuse outside the polymer gel. Is kept basic. Since metal oxide nanoparticles are synthesized from metal ions in this basic environment, a basic solution is not required separately.
金属酸化物ナノ粒子の製造方法は、金属酸化物ナノ粒子の合成の場として、末端のアミノ基とアクリルアミド基又はメタクリルアミド基との間に炭素数が２以上のアルキレン鎖を有するアクリルアミドモノマー又はメタクリルアミドモノマー（以下、主モノマーと記す）が重合して得られた親水性の高分子ゲルを用いる。そして、水分子の存在下でこの高分子ゲルと金属イオンを介在させることにより、高分子ゲルのネットワーク空間内にて金属酸化物のナノ粒子を生成させることができる。 In the method for producing metal oxide nanoparticles, an acrylamide monomer or methacrylic monomer having an alkylene chain having 2 or more carbon atoms between a terminal amino group and an acrylamide group or methacrylamide group is used as a place for synthesizing metal oxide nanoparticles. A hydrophilic polymer gel obtained by polymerizing an amide monomer (hereinafter referred to as a main monomer) is used. Then, by interposing the polymer gel and metal ions in the presence of water molecules, metal oxide nanoparticles can be generated in the network space of the polymer gel.
例えば、金属酸化物ナノ粒子の製造方法は、高分子ゲルの乾燥体を、金属イオンを含有する水溶液（水に金属塩を溶解させて得られた水溶液）に浸漬させることにより行うことができる。 For example, the metal oxide nanoparticles can be produced by immersing the dried polymer gel in an aqueous solution containing metal ions (an aqueous solution obtained by dissolving a metal salt in water).
主モノマーとして、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミドを重合して得られ、乾燥させた高分子ゲルを硫酸銅水溶液に浸漬させて酸化銅のナノ粒子を合成する例をもってメカニズムについて説明する。 The mechanism will be described with an example of synthesizing copper oxide nanoparticles by immersing a dried polymer gel obtained by polymerizing N, N-dimethylaminopropylacrylamide as a main monomer in an aqueous copper sulfate solution.
乾燥した高分子ゲルを硫酸銅水溶液に浸漬させると、高分子ゲルが水を吸収して膨潤する。そして、下式１に示すように、水分子の解離により生じる水素イオンがアミノ基（−Ｎ（ＣＨ３）２）に引き付けられ、アミノ基がプロトン化される。一方の水酸化物イオンは、イオン化した高分子鎖のアミノ基とのイオン性相互作用により、高分子ゲルの外部に拡散しない（Ｄｏｎｎａｎ平衡）。このため、高分子ゲル内部が塩基性に保たれる。 When the dried polymer gel is immersed in an aqueous copper sulfate solution, the polymer gel absorbs water and swells. Then, as shown in the following formula 1, hydrogen ions generated by dissociation of water molecules are attracted to the amino group (—N (CH 3 ) 2 ), and the amino group is protonated. One hydroxide ion does not diffuse outside the polymer gel due to ionic interaction with the amino group of the ionized polymer chain (Donnan equilibrium). For this reason, the inside of the polymer gel is kept basic.
この性質により、塩基性となった高分子ゲル内にて、下式２に示すように、金属イオンと水酸化物イオンとの反応により、水酸化物が形成される。更に、式３に示すように、水酸化物が分解されて金属酸化物のナノ粒子が合成されると考えられる。 Due to this property, a hydroxide is formed by a reaction between a metal ion and a hydroxide ion in the polymer gel that has become basic, as shown in the following formula 2. Furthermore, as shown in Formula 3, it is considered that the hydroxide is decomposed to synthesize metal oxide nanoparticles.
このように、本実施の形態に係る金属酸化物ナノ粒子の製造方法では、水分子の解離によって生じた水酸化物イオンによって塩基性となった高分子ゲル内部にて、金属イオンが水酸化物を経由して、金属酸化物ナノ粒子の合成が行われるため、引用文献１のように塩基性溶液を必要としない。したがって、高分子ゲルに金属イオンを取り込んだ後に、塩基性溶液に浸漬させる工程が不要であり、製造コストの低下にもつながる。 Thus, in the method for producing metal oxide nanoparticles according to the present embodiment, the metal ions are hydroxides inside the polymer gel that is made basic by the hydroxide ions generated by the dissociation of water molecules. Since the synthesis of the metal oxide nanoparticles is carried out via, a basic solution is not required as in the cited document 1. Therefore, the step of immersing metal ions in the polymer gel and then immersing them in a basic solution is unnecessary, leading to a reduction in manufacturing cost.
また、高分子ゲルの３次元網目構造により、金属酸化物ナノ粒子の成長や凝集が制限されるため、金属酸化物ナノ粒子の粒径制御が可能になる。 In addition, since the growth and aggregation of the metal oxide nanoparticles are limited by the three-dimensional network structure of the polymer gel, the particle size of the metal oxide nanoparticles can be controlled.
上述した主モノマーとして、式４、式５で表される化合物が用いられる。 As the main monomer described above, compounds represented by Formula 4 and Formula 5 are used.
式４及び式５中のｎは２以上、より好ましくは３以上である。高分子ゲルにおけるアミノ基のプロトン化は、アミノ基（−Ｎ（ＣＨ３）２）の窒素原子の孤立電子対をプロトン（Ｈ＋）と共有することによって起こる。この孤立電子対は、ｓｐ３混成軌道に入っており、窒素の原子核からの引力がｓｐ軌道、ｓｐ２混成軌道より弱いので、カルボニル基が近くにあるとＨ＋はカルボニル基に流れ込みやすい。そのため、アルキレン鎖（−（ＣＨ２）ｎ−）の長さが短いと（ｎ＝０，１）、ＮがＮＨ＋になりにくい。ｎが２以上の場合であり、溶液が酸性でＨ＋が豊富に介在する場合では、Ｈ＋がアミノ基の窒素に作用しやすくなりアミノ基のプロトン化が可能になる。更に、ｎが３以上であれば、水などの中性溶液においてもアミノ基のプロトン化が生じる。 N in Formula 4 and Formula 5 is 2 or more, more preferably 3 or more. The protonation of the amino group in the polymer gel occurs by sharing the lone electron pair of the nitrogen atom of the amino group (—N (CH 3 ) 2 ) with the proton (H + ). This lone pair is in the sp 3 hybrid orbital, and the attractive force from the nitrogen nucleus is weaker than the sp orbit and sp 2 hybrid orbitals, so if the carbonyl group is close, H + tends to flow into the carbonyl group. Therefore, when the length of the alkylene chain (— (CH 2 ) n —) is short (n = 0, 1), N is unlikely to become NH + . In the case where n is 2 or more and the solution is acidic and H + is abundant, H + tends to act on the nitrogen of the amino group, and protonation of the amino group becomes possible. Further, when n is 3 or more, amino group protonation occurs even in a neutral solution such as water.
金属イオンを含有する水溶液として、金属塩を水に溶解した水溶液が用いられる。金属塩として、水素イオンよりも酸化還元電位の高い金属イオンと水酸化物イオンよりも陰イオン化傾向が大きい陰イオンとの塩であることが好ましい。 As an aqueous solution containing metal ions, an aqueous solution in which a metal salt is dissolved in water is used. The metal salt is preferably a salt of a metal ion having a higher redox potential than hydrogen ions and an anion having a greater anionization tendency than hydroxide ions.
水酸化物イオンよりも陰イオン化傾向が小さい陰イオンが介在した場合、金属イオンと水酸化物イオンとの反応が進行しない結果、金属酸化物のナノ粒子が生成されないためである。また、金属イオンは、水素イオンよりも酸化還元電位が大きい金属イオンであれば、金属酸化物のナノ粒子が合成されやすい。 This is because when an anion having a smaller anionization tendency than a hydroxide ion is present, the reaction between the metal ion and the hydroxide ion does not proceed, so that metal oxide nanoparticles are not generated. Further, if the metal ion is a metal ion having a higher oxidation-reduction potential than the hydrogen ion, the metal oxide nanoparticles are easily synthesized.
また、高分子ゲルとして、上記の主モノマーとアクリルアミド系の架橋剤又はメタクリルアミド系の架橋剤とを共重合させて得られたものを用いてもよい。この場合、主モノマーと架橋剤との配合比が６：４〜１０：０であることが好ましい。架橋剤が多い場合、後述の実施例に示すように、金属イオンと陰イオンが結晶として析出しやすくなり、金属酸化物のナノ粒子が合成されにくくなるためである。アクリルアミド系の架橋剤として、メチレンビスアクリルアミド等、メタクリルアミド系の架橋剤としてエチレングリコールジメタクリレート等が挙げられる。 Alternatively, a polymer gel obtained by copolymerizing the main monomer and an acrylamide-based crosslinking agent or a methacrylamide-based crosslinking agent may be used. In this case, the blending ratio of the main monomer and the crosslinking agent is preferably 6: 4 to 10: 0. When there are many crosslinking agents, as shown in the below-mentioned Example, it becomes easy to precipitate a metal ion and an anion as a crystal | crystallization, and it becomes difficult to synthesize | combine the metal oxide nanoparticle. Examples of the acrylamide-based crosslinking agent include methylene bisacrylamide, and examples of the methacrylamide-based crosslinking agent include ethylene glycol dimethacrylate.
（実施例１：主モノマー濃度が金属酸化物ナノ粒子の合成に及ぼす影響） (Example 1: Effect of main monomer concentration on synthesis of metal oxide nanoparticles)
（高分子ゲルの合成）
メスフラスコ内に主モノマーであるＮ，Ｎ−ジメチルアミノプロピルアクリルアミド（N,N-dimethylaminopropyl acrylamid（ＤＭＡＰＡＡ））、架橋材のＮ，Ｎ’−メチレンビスアクリルアミド（N,N’-methylenbisacrylamid（ＭＢＡＡ））、重合促進剤としてテトラメチルエチレンジアミン（N,N,N’,N’-tetraethylmethylendiamine（ＴＥＭＥＤ））を加え、蒸留水で所定の濃度に調整した。
(Synthesis of polymer gel)
N, N-dimethylaminopropyl acrylamide (N, N-dimethylaminopropyl acrylamid (DMAPAA)), the main monomer in the volumetric flask, N, N'-methylenebisacrylamide (N, N'-methylenbisacrylamid (MBAA)) Then, tetramethylethylenediamine (N, N, N ′, N′-tetraethylmethylendiamine (TEMED)) was added as a polymerization accelerator and adjusted to a predetermined concentration with distilled water.
別のメスフラスコ内に開始剤の過硫酸アンモニウム（Ammonium peroxodisulfate（ＡＰＳ））を加えた水溶液を調製した。 An aqueous solution containing ammonium peroxodisulfate (APS) as an initiator was prepared in a separate volumetric flask.
両水溶液をそれぞれ１時間室温で窒素曝気したのち窒素雰囲気下で素早く混合し、内径６ｍｍのポリプロピレン管に注入して、パラフィルムで密閉した。 Both aqueous solutions were each aerated with nitrogen at room temperature for 1 hour, then quickly mixed under a nitrogen atmosphere, poured into a polypropylene tube having an inner diameter of 6 mm, and sealed with parafilm.
このポリプロピレン管を温度７℃の恒温水槽で４時間保持し重合を行った。重合により得られたゲルをポリプロピレン管から取り出し、長さ３ｍｍに切断して円柱状の金属酸化物ナノ粒子担持用高分子ゲル（高分子ゲル１〜６）を合成した。合成した高分子ゲル１〜６の合成に用いた原料を表１に記す。 The polypropylene tube was kept in a constant temperature water bath at a temperature of 7 ° C. for 4 hours for polymerization. The gel obtained by the polymerization was taken out from the polypropylene tube and cut into a length of 3 mm to synthesize columnar metal oxide nanoparticle-supporting polymer gels (polymer gels 1 to 6). The raw materials used for the synthesis of the synthesized polymer gels 1 to 6 are shown in Table 1.
（高分子ゲルとナノ粒子の複合体の作製）
高分子ゲル１〜６の乾燥体をそれぞれ、０．０１ｍｏｌ／Ｌの銅イオン溶液（０．０１ｍｏｌ／Ｌ ＣｕＳＯ４水溶液）中に浸漬させ（２０℃、２４時間）、高分子ゲル１〜６内部に酸化銅のナノ粒子を合成させ、酸化銅のナノ粒子を含有する高分子ゲル複合体（高分子複合体１〜６）を得た。酸化銅のナノ粒子の生成はＸＲＤ測定により確認した。
(Production of polymer gel and nanoparticle composite)
The dried bodies of the polymer gels 1 to 6 were each immersed in a 0.01 mol / L copper ion solution (0.01 mol / L CuSO 4 aqueous solution) (20 ° C., 24 hours), and the inside of the polymer gels 1 to 6 was inside. Then, copper oxide nanoparticles were synthesized to obtain polymer gel composites (polymer composites 1 to 6) containing copper oxide nanoparticles. The formation of copper oxide nanoparticles was confirmed by XRD measurement.
図１に、高分子ゲル複合体１，３，６のＸＲＤ測定結果を示す。また、図２に、高分子ゲル複合体１〜６の写真を示す。 In FIG. 1, the XRD measurement result of the polymer gel composites 1, 3, and 6 is shown. Moreover, the photograph of the polymer gel composites 1-6 is shown in FIG.
図１をみると、高分子ゲル複合体６では、ＣｕＯの生成を表すピーク（３３°、３６°）に現れており、ＣｕＯが合成されていることがわかる。また、高分子ゲル３では、ＣｕＯの生成を表すピークのほか、Ｃｕ（ＯＨ）２の生成を表すピークが現れている。また、高分子ゲル１では、ＣｕＯ、Ｃｕ（ＯＨ）２の生成を表すピークはいずれも現れなかった。 As shown in FIG. 1, in the polymer gel composite 6, it appears in peaks (33 °, 36 °) representing the formation of CuO, and it can be seen that CuO is synthesized. Moreover, in the polymer gel 3, in addition to the peak representing the production of CuO, a peak representing the production of Cu (OH) 2 appears. Moreover, in the polymer gel 1, none of the peaks representing the formation of CuO and Cu (OH) 2 appeared.
また、図２をみると、高分子ゲル４〜６では、高分子ゲル複合体は黒色であり、ＣｕＯが合成されていることがわかった。一方、高分子ゲル２，３では、高分子ゲル複合体は薄青色であり、水酸化銅が生成していることを確認した。また、高分子ゲル複合体１の色は変化がなく、ＣｕＯ、Ｃｕ（ＯＨ）２のいずれも生成されておらず、水溶液中の銅イオンはそのままであることを確認した。 Moreover, when FIG. 2 was seen, in the polymer gels 4-6, it turned out that a polymer gel composite is black and CuO is synthesize | combined. On the other hand, in the polymer gels 2 and 3, the polymer gel composite was light blue, and it was confirmed that copper hydroxide was generated. In addition, it was confirmed that the color of the polymer gel composite 1 was not changed, neither CuO nor Cu (OH) 2 was produced, and the copper ions in the aqueous solution remained as they were.
この結果から、架橋剤を用いて得られた高分子ゲルを利用する場合、架橋剤に対し、主モノマーを１．５モル以上加えて得られた高分子ゲルであれば、これを用いて酸化銅のナノ粒子を合成できることがわかった。 From this result, when using a polymer gel obtained using a cross-linking agent, a polymer gel obtained by adding 1.5 mol or more of the main monomer to the cross-linking agent is used to oxidize. It was found that copper nanoparticles can be synthesized.
（実施例２：水溶液中の銅イオン濃度が金属酸化物ナノ粒子の合成に及ぼす影響１）
実施例１と同様の手法で、高分子ゲル７を合成した。高分子ゲル７の合成で用いた原料を表２に示す。
(Example 2: Effect of copper ion concentration in aqueous solution on the synthesis of metal oxide nanoparticles 1)
Polymer gel 7 was synthesized in the same manner as in Example 1. The raw materials used in the synthesis of the polymer gel 7 are shown in Table 2.
銅イオン濃度０．０１ｍｏｌ／Ｌ、０．１０ｍｏｌ／Ｌの硫酸銅水溶液に、高分子ゲル７をそれぞれ浸漬（２０℃、２４時間）させて、酸化銅ナノ粒子を高分子ゲル７内部で合成させ、酸化銅のナノ粒子を含有する高分子ゲル複合体を得た。そして、酸化銅のナノ粒子の生成をＸＲＤ測定により確認した。 The polymer gel 7 is immersed (20 ° C., 24 hours) in copper sulfate aqueous solutions having copper ion concentrations of 0.01 mol / L and 0.10 mol / L, respectively, and the copper oxide nanoparticles are synthesized inside the polymer gel 7. A polymer gel composite containing copper oxide nanoparticles was obtained. And the production | generation of the copper oxide nanoparticle was confirmed by the XRD measurement.
０．１ｍｏｌ／Ｌ水溶液、０．０１ｍｏｌ／Ｌ水溶液を用いて得られた高分子ゲル複合体のＸＲＤ測定結果を図３に、写真を図４に示す。 FIG. 3 shows the XRD measurement results of the polymer gel composite obtained using the 0.1 mol / L aqueous solution and the 0.01 mol / L aqueous solution, and FIG. 4 shows the photograph.
０．０１ｍｏｌ／Ｌ水溶液では、ＣｕＯの生成を示すピークが見られ、ＣｕＯの純度が高いことがわかる。一方、０．１ｍｏｌ／Ｌ水溶液では、ＣｕＯの生成を示すピークのほか、Ｃｕ（ＯＨ）２の生成を示すピークが見られた。 In the 0.01 mol / L aqueous solution, a peak indicating the formation of CuO is observed, indicating that the purity of CuO is high. On the other hand, in the 0.1 mol / L aqueous solution, in addition to the peak indicating the formation of CuO, a peak indicating the generation of Cu (OH) 2 was observed.
高分子ゲル７を用いた場合、硫酸銅水溶液の濃度は、０．１ｍｏｌ／Ｌよりも０．０１ｍｏｌ／Ｌの方が酸化銅のナノ粒子を得られる結果となった。 When the polymer gel 7 was used, the concentration of the aqueous copper sulfate solution was 0.01 mol / L rather than 0.1 mol / L, which resulted in obtaining copper oxide nanoparticles.
（実施例３：水溶液中の銅イオン濃度が金属酸化物ナノ粒子の合成に及ぼす影響２）
実施例１と同様の手順で、高分子ゲル８を合成した。高分子ゲル８の合成で用いた原料を表３に示す。
(Example 3: Effect 2 of copper ion concentration in aqueous solution on synthesis of metal oxide nanoparticles 2)
A polymer gel 8 was synthesized by the same procedure as in Example 1. Table 3 shows the raw materials used in the synthesis of the polymer gel 8.
高分子ゲル８の乾燥体と実施例２で合成した高分子ゲル７の乾燥体を、それぞれ各種濃度の銅イオン水溶液（ＣｕＳＯ４水溶液）に浸漬させて（２０℃，２４時間）、酸化銅ナノ粒子を高分子ゲル７、８内部で合成させ、酸化銅のナノ粒子を含有する高分子ゲル複合体（高分子ゲル複合体７，８）を得た。 The dried polymer gel 8 and the dried polymer gel 7 synthesized in Example 2 were immersed in aqueous solutions of copper ions (CuSO 4 aqueous solution) of various concentrations (20 ° C., 24 hours), respectively. The particles were synthesized inside the polymer gels 7 and 8 to obtain polymer gel composites (polymer gel composites 7 and 8) containing copper oxide nanoparticles.
そして、高分子ゲル複合体７，８中の粒子含有率を熱量測定により求め、高分子ゲルの膨潤度を下式６に基づいて算出した。 And the particle content rate in the polymer gel composites 7 and 8 was calculated | required by calorimetry, and the swelling degree of the polymer gel was computed based on the following Formula 6.
粒子含有率の結果を図５に、膨潤度の結果を図６にそれぞれ示す。高分子ゲル７では、水溶液中の銅イオン濃度が高くなるにつれて粒子含有率が高くなっているが、０．１ｍｏｌ／Ｌあたりで頭打ちになっている。一方の、高分子ゲル８についても、銅イオン濃度が高くなるにつれて粒子含有率が高くなっているが、０．０７ｍｏｌ／Ｌあたりで頭打ちになっている。 The result of particle content is shown in FIG. 5, and the result of swelling degree is shown in FIG. In the polymer gel 7, the particle content increases as the copper ion concentration in the aqueous solution increases, but reaches a peak around 0.1 mol / L. On the other hand, as for the polymer gel 8, the particle content increases as the copper ion concentration increases, but reaches a peak around 0.07 mol / L.
図６を見ると、粒子含有率が頭打ちになっている点の銅イオン濃度と膨潤度が低下する点の銅イオン濃度が凡そ一致していることがわかる。銅イオン濃度が濃くなると高分子ゲルが膨潤しなくなり、高分子ゲルが銅イオンを取り込みにくくなるため、粒子含有率が頭打ちになったと考えられる。 As can be seen from FIG. 6, the copper ion concentration at the point where the particle content reaches a peak and the copper ion concentration at the point where the degree of swelling decreases substantially coincide. When the copper ion concentration is increased, the polymer gel does not swell and the polymer gel is less likely to take up copper ions, so it is considered that the particle content has reached its peak.
実施例２、３から、高分子ゲル内の粒子含有率を向上させるためには、銅イオン濃度が高くても膨潤する高分子ゲルを用いるとよく、高分子ゲルを合成する際の主モノマー濃度及び膨潤度に応じ、水溶液の銅イオン濃度を設定する必要がある。 From Examples 2 and 3, in order to improve the particle content in the polymer gel, it is preferable to use a polymer gel that swells even if the copper ion concentration is high, and the main monomer concentration when synthesizing the polymer gel It is necessary to set the copper ion concentration of the aqueous solution according to the degree of swelling.
（実施例４：種々の銅イオン溶液が金属酸化物ナノ粒子の合成に及ぼす影響）
実施例２で合成した高分子ゲル７を、酢酸銅（Ｃｕ（ＣＨ３ＣＯＯ）２）水溶液、塩化銅（ＣｕＣｌ２）水溶液、硫酸銅（ＣｕＳＯ４）水溶液にそれぞれ浸漬させて（２０℃，２４時間）、酸化銅ナノ粒子を高分子ゲル７内部で合成させ、酸化銅のナノ粒子を含有する高分子ゲル複合体を得た。なお、それぞれの水溶液の銅イオン濃度は０．１ｍｏｌ／Ｌである。
(Example 4: Effect of various copper ion solutions on the synthesis of metal oxide nanoparticles)
The polymer gel 7 synthesized in Example 2 was immersed in a copper acetate (Cu (CH 3 COO) 2 ) aqueous solution, a copper chloride (CuCl 2 ) aqueous solution, and a copper sulfate (CuSO 4 ) aqueous solution (20 ° C., 24 Time), copper oxide nanoparticles were synthesized inside the polymer gel 7 to obtain a polymer gel composite containing copper oxide nanoparticles. In addition, the copper ion concentration of each aqueous solution is 0.1 mol / L.
そして、それぞれの高分子ゲル複合体中の粒子含有率を熱量測定により求めた。また、粒子の結晶子サイズを下式７に基づいて算出した。 The particle content in each polymer gel composite was determined by calorimetry. Further, the crystallite size of the particles was calculated based on the following formula 7.
図７に、それぞれのＸＲＤ測定結果を示す。また、表４に結晶子サイズ及び粒子含有率を示す。また、図８に、酢酸銅水溶液に浸漬させて得られた高分子ゲル複合体のＴＥＭ画像を示す。 FIG. 7 shows each XRD measurement result. Table 4 shows the crystallite size and particle content. FIG. 8 shows a TEM image of a polymer gel composite obtained by immersing in a copper acetate aqueous solution.
酢酸銅水溶液及び硫酸銅水溶液に高分子ゲル７を浸漬させると、ＣｕＯの生成を示すピークが見られ、酸化銅のナノ粒子が合成された。また、硫酸銅水溶液よりも酢酸銅水溶液の方が、小さな粒子が得られるとともに、粒子含有率も高い結果であった。 When the polymer gel 7 was immersed in an aqueous copper acetate solution and an aqueous copper sulfate solution, a peak indicating the formation of CuO was observed, and copper oxide nanoparticles were synthesized. In addition, the copper acetate aqueous solution was smaller in size than the copper sulfate aqueous solution, and the particle content was higher.
一方で、塩化銅水溶液に浸漬させた場合、ＣｕＯの生成を示すピークがみられず、酸化銅は合成されなかった。 On the other hand, when immersed in an aqueous copper chloride solution, no peak indicating the formation of CuO was observed, and copper oxide was not synthesized.
陰イオン化傾向は、ＣＨ３ＣＯＯ−＞ＳＯ４ ２−＞ＯＨ−＞Ｃｌ−であることから、陰イオン化傾向がＯＨ−よりも小さい塩化物イオンと銅イオンの金属塩の水溶液では、塩化物イオンが銅イオンと結合し、塩化銅として結晶化していると考えられる。一方、陰イオン化傾向がＯＨ−よりも大きい陰イオンと銅イオンの金属塩の水溶液の場合では、酸化銅ナノ粒子が合成されることがわかった。 Negative ionization tendency, CH 3 COO -> SO 4 2-> OH -> Cl - since it is, negative ionization tendency OH - in aqueous solution of from less chloride ions and copper ions metal salt, chloride ions Is believed to be bonded to copper ions and crystallized as copper chloride. On the other hand, it was found that in the case of an aqueous solution of a metal salt of an anion and a copper ion having a larger anionization tendency than OH − , copper oxide nanoparticles were synthesized.
（実施例５：種々の金属イオン溶液が金属酸化物ナノ粒子の合成に及ぼす影響） (Example 5: Effect of various metal ion solutions on the synthesis of metal oxide nanoparticles)
主モノマーとしてＤＭＡＰＡＡＮ、架橋剤としてイソプロピルアクリルアミド（N-Isopropylacrylamide：ＮＩＰＡ）を用い、実施例１と同様の手法で高分子ゲル（高分子ゲル９）を合成した。高分子ゲル９の合成で用いた原料を表５示す。 A polymer gel (polymer gel 9) was synthesized in the same manner as in Example 1 using DMAPAAN as the main monomer and isopropylacrylamide (NIPA) as the crosslinking agent. Table 5 shows the raw materials used in the synthesis of the polymer gel 9.
この高分子ゲル９と実施例１で合成した高分子ゲル１の乾燥体を、各種硝酸塩水溶液に浸漬（２０℃，２４時間）させて、各種金属酸化物ナノ粒子を高分子ゲル内部で合成させ、金属酸化物ナノ粒子を含有する高分子ゲル複合体を得た。 The polymer gel 9 and the dried polymer gel 1 synthesized in Example 1 were immersed in various nitrate aqueous solutions (20 ° C., 24 hours) to synthesize various metal oxide nanoparticles inside the polymer gel. A polymer gel composite containing metal oxide nanoparticles was obtained.
用いた硝酸塩水溶液は、硝酸銅（Ｃｕ（ＮＯ３）２）水溶液、硝酸銀（ＡｇＮＯ３）水溶液、硝酸鉛（Ｐｂ（ＮＯ３）２）水溶液、硝酸ニッケル（Ｎｉ（ＮＯ３）２）水溶液であり、それぞれついて、０．１ｍｏｌ／Ｌ、１．０ｍｏｌ／Ｌ、５ｍｏｌ／Ｌに調製して用いた。 The nitrate aqueous solution used is a copper nitrate (Cu (NO 3 ) 2 ) aqueous solution, a silver nitrate (AgNO 3 ) aqueous solution, a lead nitrate (Pb (NO 3 ) 2 ) aqueous solution, or a nickel nitrate (Ni (NO 3 ) 2 ) aqueous solution. , About 0.1 mol / L, 1.0 mol / L, and 5 mol / L, respectively.
それぞれの高分子ゲル複合体の写真を図９に示す。硝酸銅水溶液、硝酸銀水溶液の場合は、高分子ゲル複合体は着色されており、高分子ゲル内に微粒子が生成している様子が確認できた。一方、硝酸鉛水溶液、硝酸ニッケル水溶液の場合は、高分子ゲル複合体は着色されておらず、肉眼では微粒子の生成は確認できなかった。 A photograph of each polymer gel composite is shown in FIG. In the case of an aqueous copper nitrate solution or an aqueous silver nitrate solution, the polymer gel composite was colored, and it was confirmed that fine particles were generated in the polymer gel. On the other hand, in the case of a lead nitrate aqueous solution and a nickel nitrate aqueous solution, the polymer gel composite was not colored, and the generation of fine particles could not be confirmed with the naked eye.
酸化還元電位は、Ｆｅ＜Ｎｉ＜Ｐｂ＜Ｈ＜Ｃｕ＜Ｈｇ＜Ａｇ＜Ａｕであり、式１に示した高分子ゲルの反応機構から、水素イオンより酸化還元電位の大きい金属イオンの場合は、イオン状態のままとどまり、微粒子化しにくく、水素イオンより酸化還元電位の大きい金属イオンの場合は、イオン化により生じた水酸化物イオン（ＯＨ−）と反応し、水酸化物を形成した後、金属酸化物として微粒子化しやすいことがわかった。 The oxidation-reduction potential is Fe <Ni <Pb <H <Cu <Hg <Ag <Au. From the reaction mechanism of the polymer gel shown in Formula 1, in the case of a metal ion having a greater oxidation-reduction potential than hydrogen ion, In the case of a metal ion that remains in an ionic state, is difficult to be finely divided, and has a higher redox potential than hydrogen ion, it reacts with hydroxide ion (OH-) generated by ionization to form a hydroxide, and then metal oxide It turned out that it is easy to make fine particles as a product.
（実施例６：種々の金属塩の溶液が金属酸化物ナノ粒子の合成に及ぼす影響） (Example 6: Effect of various metal salt solutions on the synthesis of metal oxide nanoparticles)
ＡｇＣｌ水溶液（９．２６ｍｍｏｌ／Ｌ）、ＣｕＮＯ３水溶液（１５．７ｍｍｏｌ／Ｌ）、ＰｂＣｌ２水溶液（４．８２ｍｍｏｌ／Ｌ）、ＳｎＣｌ２水溶液（８．４２ｍｍｏｌ／Ｌ）、ＮｉＣｌ２水溶液（１７．０ｍｍｏｌ／Ｌ）、ＣｄＮＯ３水溶液（８．８９ｍｍｏｌ／Ｌ）、ＭｎＳＯ４水溶液（１８．２ｍｍｏｌ／Ｌ）
の各種金属塩を水に溶解した水溶液を調製した。
AgCl aqueous solution (9.26 mmol / L), CuNO 3 aqueous solution (15.7 mmol / L), PbCl 2 aqueous solution (4.82 mmol / L), SnCl 2 aqueous solution (8.42 mmol / L), NiCl 2 aqueous solution (17.0 mmol) / L), CdNO 3 aqueous solution (8.89 mmol / L), MnSO 4 aqueous solution (18.2 mmol / L)
An aqueous solution prepared by dissolving various metal salts of the above in water was prepared.
実施例２で合成した高分子ゲル７の乾燥体を、上記の各種金属塩を水に溶解した水溶液に浸漬（２０℃，２４時間）させて、各種金属酸化物ナノ粒子を高分子ゲル内部で合成させ、金属酸化物ナノ粒子を含有する高分子ゲル複合体を得た。 The dried polymer gel 7 synthesized in Example 2 was immersed (20 ° C., 24 hours) in an aqueous solution in which the above various metal salts were dissolved in water, and the various metal oxide nanoparticles were placed inside the polymer gel. A polymer gel composite containing metal oxide nanoparticles was obtained by synthesis.
高分子ゲル複合体の写真を図１０に示す。図１０（Ａ）がＡｇＣｌ水溶液、図１０（Ｂ）がＣｕＮＯ３水溶液、図１０（Ｃ）がＰｂＣｌ２水溶液、図１０（Ｄ）がＳｎＣｌ２水溶液、図１０（Ｅ）がＮｉＣｌ２水溶液、図１０（Ｆ）がＣｄＮＯ３水溶液、図１０（Ｇ）がＭｎＳＯ４水溶液に浸漬させた結果である。 A photograph of the polymer gel composite is shown in FIG. 10A is an AgCl aqueous solution, FIG. 10B is a CuNO 3 aqueous solution, FIG. 10C is a PbCl 2 aqueous solution, FIG. 10D is a SnCl 2 aqueous solution, FIG. 10E is a NiCl 2 aqueous solution, FIG. 10 (F) is the result of immersion in a CdNO 3 aqueous solution, and FIG. 10 (G) is the result of immersion in a MnSO 4 aqueous solution.
水素イオンより酸化還元電位の大きい金属イオンが溶解しているＡｇＣｌ水溶液、ＣｕＮＯ３水溶液に加え、水素イオンより酸化還元電位の小さい金属イオンが溶解しているＭｎＳＯ４水溶液においても、金属酸化物ナノ粒子の形成が見られた。この結果から、水素イオンより酸化還元電位の小さい金属イオンであっても、高分子ゲル中に形成される弱塩基性場で、水酸化物イオンと反応して水酸化物を形成するもので、この水酸化物が熱的に不安定なものであれば、分解、脱水により金属酸化物のナノ粒子が形成されるものと考えられる。 In addition to an AgCl aqueous solution and a CuNO 3 aqueous solution in which metal ions having a higher redox potential than hydrogen ions are dissolved, a metal oxide nanoparticle also in an MnSO 4 aqueous solution in which metal ions having a lower redox potential than hydrogen ions are dissolved The formation of was seen. From this result, even a metal ion having a smaller redox potential than a hydrogen ion reacts with a hydroxide ion to form a hydroxide in a weak basic field formed in a polymer gel. If this hydroxide is thermally unstable, it is considered that metal oxide nanoparticles are formed by decomposition and dehydration.
（実施例７：高分子ゲル複合体中にて酸化銅ナノ粒子が分散して形成されていることの検証） (Example 7: Verification that copper oxide nanoparticles are dispersed and formed in a polymer gel composite)
Ｎａ２ＨＡｓＯ４・７Ｈ２Ｏを使用し、砒素濃度が２０，３０，４０，８０ｐｐｍの水溶液を調製した。この水溶液に、実施例２で得られた高分子ゲル複合体７（０．１ｇ）を添加し、室温で２４時間、砒素の吸着を行った。比較例１として、高分子ゲル７のみ（０．１ｇ）、比較例として高分子ゲル複合体７（０．１ｇ）に含まれるのと同量の酸化銅ナノ粒子のみを用い、上記と同様の実験を行った。 Na 2 HAsO 4 · 7H 2 O was used to prepare an aqueous solution having an arsenic concentration of 20, 30, 40, and 80 ppm. To this aqueous solution, the polymer gel composite 7 (0.1 g) obtained in Example 2 was added, and arsenic was adsorbed at room temperature for 24 hours. As Comparative Example 1, only polymer gel 7 (0.1 g) was used, and as a comparative example, only the same amount of copper oxide nanoparticles as contained in polymer gel composite 7 (0.1 g) was used. The experiment was conducted.
その結果を図１１に示す。比較例１（高分子ゲル７のみ）、比較例２（酸化銅微粒子のみ）のそれぞれの砒素の吸着量を合わせたよりも、高分子ゲル複合体７の砒素の吸着量が大きく上回っていることがわかる。これは、酸化銅ナノ粒子が高分子ゲル７内部で分散して形成されており、比表面積が著しく増加したために、吸着量が増加したことを示していると考えられる。 The result is shown in FIG. The arsenic adsorption amount of the polymer gel composite 7 is much higher than the combined arsenic adsorption amounts of Comparative Example 1 (polymer gel 7 only) and Comparative Example 2 (copper oxide fine particles only). Recognize. This is thought to indicate that the amount of adsorption increased because the copper oxide nanoparticles were dispersed and formed inside the polymer gel 7 and the specific surface area significantly increased.
塗料や吸着剤等、金属酸化物ナノ粒子が利用され得る種々の分野に利用可能である。 It can be used in various fields where metal oxide nanoparticles can be used, such as paints and adsorbents.
Claims (5)
ことを特徴とする金属酸化物ナノ粒子の製造方法。 In the presence of water molecules in a hydrophilic polymer gel obtained by polymerizing an acrylamide monomer or methacrylamide monomer having an alkylene chain having 2 or more carbon atoms between the terminal amino group and the acrylamide group or methacrylamide group. In order to generate metal oxide nanoparticles in the network space of the polymer gel, intervening metal ions in
The manufacturing method of the metal oxide nanoparticle characterized by the above-mentioned.
ことを特徴とする請求項１に記載の金属酸化物ナノ粒子の製造方法。 Using the polymer gel obtained by polymerizing the acrylamide monomer or the methacrylamide monomer having the alkylene chain having 3 or more carbon atoms,
The method for producing metal oxide nanoparticles according to claim 1.
ことを特徴とする請求項１又は２に記載の金属酸化物ナノ粒子の製造方法。 Immersing the dried polymer gel in an aqueous solution containing the metal ions;
The method for producing metal oxide nanoparticles according to claim 1 or 2.
ことを特徴とする請求項３に記載の金属酸化物ナノ粒子の製造方法。 Immersing the polymer gel in the aqueous solution in which a metal salt of the metal ion having a larger oxidation-reduction potential than hydrogen ions and an anion having a larger tendency to anionization than hydroxide ions is dissolved;
The method for producing metal oxide nanoparticles according to claim 3.
前記架橋剤に対して１．５モル以上の前記アクリルアミドモノマー又は前記メタクリルアミドモノマーを加える、
ことを特徴とする請求項１乃至４のいずれか一項に記載の金属酸化物ナノ粒子の製造方法。 Using the polymer gel obtained by copolymerization of an acrylamide-based crosslinking agent or a methacrylamide-based crosslinking agent and the acrylamide monomer or the methacrylamide monomer,
Add 1.5 moles or more of the acrylamide monomer or the methacrylamide monomer to the crosslinking agent,
The method for producing metal oxide nanoparticles according to any one of claims 1 to 4, wherein:
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