JPH02277705A - Method for preparing ultra fine gold particles - Google Patents
Method for preparing ultra fine gold particlesInfo
- Publication number
- JPH02277705A JPH02277705A JP9976889A JP9976889A JPH02277705A JP H02277705 A JPH02277705 A JP H02277705A JP 9976889 A JP9976889 A JP 9976889A JP 9976889 A JP9976889 A JP 9976889A JP H02277705 A JPH02277705 A JP H02277705A
- Authority
- JP
- Japan
- Prior art keywords
- gold
- solution
- water
- gold particles
- chitin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010931 gold Substances 0.000 title claims abstract description 39
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 39
- 239000002245 particle Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920002101 Chitin Polymers 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 230000000850 deacetylating effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 230000006196 deacetylation Effects 0.000 abstract 1
- 238000003381 deacetylation reaction Methods 0.000 abstract 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229950006780 n-acetylglucosamine Drugs 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は触媒、各種ペースト、コロイド溶液等金の超微
粒子を調製する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for preparing ultrafine gold particles such as catalysts, various pastes, and colloidal solutions.
（従来技術とその問題点）
従来、金の微粒子としては２００Å以上の大きさのもの
しか安定した微粒子として調製することが出来ていない
。(Prior art and its problems) Conventionally, only stable gold particles with a size of 200 Å or more have been able to be prepared.
その主な方法として、金の酸性溶液に保護コロイドとし
てゼラチン等を加え、金を水素やヒドラジン等の還元剤
で還元する方法や、金を有機溶媒に抽出したのち、該有
機溶媒を微細な粒子として不活性ガス気流中に分散させ
加熱分解して、金に還元し微粒子とする方法等がある。The main methods are to add gelatin as a protective colloid to an acidic gold solution and reduce the gold with a reducing agent such as hydrogen or hydrazine, or to extract gold into an organic solvent and then transform the organic solvent into fine particles. As a method, there is a method in which gold is dispersed in an inert gas stream, thermally decomposed, and reduced to gold to form fine particles.
しかし、金の溶液の濃度や保護コロイドの量や、他の高
分子の界面活性剤等の種類や量を変えても安定した微粒
子として調製できるのは粒子径が２００Ａ程度が限界で
あった。However, even if the concentration of the gold solution, the amount of protective colloid, and the type and amount of other polymeric surfactants are changed, stable fine particles can only be prepared at a particle diameter of about 200 Å.
（発明の目的）
本発明は、上記の欠点を解決するために成されたもので
、金の超微粒子として粒子径が３０〜２０ＯＡで粒子径
の範囲がせまく安定したのものを調製する方法を提供す
ることを目的とする。(Object of the Invention) The present invention has been made to solve the above-mentioned drawbacks, and provides a method for preparing ultrafine gold particles having a particle diameter of 30 to 20 OA, which has a narrow range of particle diameters, and is stable. The purpose is to provide.
（問題点を解決するための手段）
本発明は、金含有溶液と還元剤を含む溶液を反応させて
、金の超微粒子を調製するに際し、金含有溶液に水溶性
キチンを加えてのちに還元剤を含む溶液を加えて反応さ
せることを特徴とする金超微粒子の調製方法であり、水
溶性キチンがキチンを脱アセチル化した構造のものを含
む還元剤を含む溶液が水酸化アルカリを含むホルムアル
デヒド溶液である。(Means for Solving the Problems) In the present invention, when preparing ultrafine gold particles by reacting a gold-containing solution with a solution containing a reducing agent, water-soluble chitin is added to the gold-containing solution and then reduced. A method for preparing ultrafine gold particles characterized by adding and reacting a solution containing a reducing agent, in which the solution containing a reducing agent containing a structure in which water-soluble chitin has a structure in which chitin is deacetylated is formaldehyde containing an alkali hydroxide. It is a solution.
以下、本発明の詳細について説明する。The details of the present invention will be explained below.
本発明の金含有溶液は最も一般的である塩化金酸の水溶
液でよく、全濃度は０．０１〜０．５ｇ／ｌであること
が好ましい。The gold-containing solution of the present invention may be the most common aqueous solution of chloroauric acid, preferably with a total concentration of 0.01 to 0.5 g/l.
上記の理由はｌｉ製した金の超微粒子が凝集せずまた調
製する量が経済的な範囲であるからである。The reason for the above is that the ultrafine gold particles made from Li do not aggregate and the amount to be prepared is within an economical range.
水溶性キチンはキチン（Ｎ−アセチル−Ｄ−グルコサミ
ンが約８５０連なったもの）を脱アセチル化した構造の
ものを含むものであり、水溶性の高分子化合物として金
の超微粒子が安定させる効果を有するものと考えられる
。Water-soluble chitin contains a deacetylated structure of chitin (approximately 850 chains of N-acetyl-D-glucosamine), and as a water-soluble polymer compound, ultrafine gold particles have a stabilizing effect. It is considered to have.
上記水溶性キチンの加える量は反応させる溶液中の濃度
を０．２〜３ｇ／ｌとすることにより、金の粒子径を３
０〜２００人に調製することができ、粒子径と水溶性キ
チンとの関係は水溶性キチンの濃度を高くするに従い粒
子径が小さくなり、粒子径の分布範囲は平均粒子径の±
２０％で８５％以上のものが得られる。The amount of water-soluble chitin added is adjusted so that the concentration in the reaction solution is 0.2 to 3 g/l, and the gold particle size is adjusted to 3 g/l.
The relationship between particle size and water-soluble chitin is that as the concentration of water-soluble chitin increases, the particle size becomes smaller, and the particle size distribution range is ± of the average particle size.
85% or more can be obtained with 20%.
還元剤を含む溶液は水酸化アルカリとして水酸化ナトリ
ウムまたは水酸化カリウムを加えであるホルムアルデヒ
ド３％前後の水溶液で、水酸化アルカリを加えるのは金
をホルムアルデヒドで還元させやすい反応条件とするた
めである。The solution containing the reducing agent is an aqueous solution containing around 3% formaldehyde, with sodium hydroxide or potassium hydroxide added as an alkali hydroxide.The reason for adding the alkali hydroxide is to create reaction conditions that facilitate the reduction of gold with formaldehyde. .
また、還元剤としてのホルムアルデヒドの加える量は金
に対して７０倍当量となるようにするのが好ましく、過
剰に加えると経済的でないばかりか金の超微粒子の粒子
径の分布が広くなってしまう等の問題が生ずる。Further, it is preferable that the amount of formaldehyde added as a reducing agent is 70 times equivalent to gold; adding too much will not only be uneconomical but also cause the particle size distribution of ultrafine gold particles to become wide. Problems such as this arise.
尚、反応させる溶液のそれぞれの液温は室温でよい。Note that the temperature of each solution to be reacted may be room temperature.
以下、本発明の実施例について言己載するが、該実施例
は本発明を限定するものではない。Examples of the present invention will be described below, but the examples are not intended to limit the present invention.
（実施例１）
塩化金酸溶液（Ａｕｇ、０５ｇ／ｌ）を５０ｍ１比色管
に取り、水溶性キチン（０，５ｇを水に溶解して５０ｒ
ｎ１にメスアップしたもの）を１ｍｌ加えて十分に攪拌
したのち、ホルムアルデヒド溶液（ＩＮ−ＫＯＨを５ｍ
ｊ！十水を２０ｍｆ＋３５％ホルムアルデヒドを２．
５ｍ１２）を１−加えて攪拌して反応させたところ、溶
液は赤紫に変化して金の微粒子が生成した。(Example 1) A chloroauric acid solution (Aug, 05 g/l) was placed in a 50 ml colorimetric tube, and water-soluble chitin (0.5 g was dissolved in water for 50 ml).
Add 1 ml of formaldehyde solution (IN-KOH to 5 ml) and stir well.
j! 20mf + 35% formaldehyde with ten water.
When the solution was stirred and reacted, the solution turned reddish-purple and fine gold particles were produced.
この微粒子を拡大して観察したところ、平均粒子径は２
００人で±２０％の範囲に８５％が入るもので、３０日
間凝集せずに安定していた。When we enlarged and observed these fine particles, we found that the average particle diameter was 2.
00 people, 85% fell within the range of ±20% and remained stable without aggregation for 30 days.
（実施例２）
水溶性キチンの加えた量が、２ｍｌ、５−１１５−の３
段階にした以外は実施例１と同様の方法で行ったと、こ
ろ下記の表−１の様な結果であった。(Example 2) The amount of water-soluble chitin added was 2 ml, 5-115-3
The procedure was carried out in the same manner as in Example 1, except that the procedure was carried out in stages, and the results were as shown in Table 1 below.
（以下余白）
表−１
（比較例）
水溶性キチンの加えた量が、Ｏ，１ｍ、０． ２−１０
．５ｍｌの３段階にした以外は実施例１と同様の方法で
行ったところ下記の表−２の様な結果であった。(Margin below) Table 1 (Comparative example) The amount of water-soluble chitin added is O, 1 m, 0. 2-10
．． The same method as in Example 1 was carried out except that 5 ml was used in three stages, and the results were as shown in Table 2 below.
（発明の効果）
本発明は、以上の結果から明確なように、従来法では得
られなかった３０〜２００人の金超微粒子の粒子径を調
製することができ、反応条件等も極めて簡便であり、金
の超微粒子を金の特性を利用した触媒、ペースト、ある
いは薄膜形成用材料の原料等広く利用することが期待さ
れるものである。(Effects of the Invention) As is clear from the above results, the present invention makes it possible to prepare ultrafine gold particles with a particle size of 30 to 200, which could not be obtained using conventional methods, and the reaction conditions are extremely simple. It is expected that ultrafine gold particles will be widely used as raw materials for catalysts, pastes, and thin film forming materials that utilize the properties of gold.
出願人 田中貴金属工業株式会社 目黒謙次部 江角邦男Applicant: Tanaka Kikinzoku Kogyo Co., Ltd. Kenjibe Meguro Kunio Esumi
Claims (3)
の超微粒子を調製するに際し、金含有溶液に水溶性キチ
ンを加えたのちに還元剤を含む溶液を加えて反応させる
ことを特徴とする金超微粒子の調製方法。(1) When preparing ultrafine gold particles by reacting a gold-containing solution and a solution containing a reducing agent, it is recommended to add water-soluble chitin to the gold-containing solution and then add a solution containing a reducing agent to cause the reaction. Characteristic method for preparing ultrafine gold particles.
ものを含むことを特徴とする請求項１の金超微粒子の調
製方法。(2) The method for preparing ultrafine gold particles according to claim 1, wherein the water-soluble chitin includes a structure obtained by deacetylating chitin.
アルデヒド溶液であることを特徴とする請求項１の金超
微粒子の調製方法。(3) The method for preparing ultrafine gold particles according to claim 1, wherein the solution containing the reducing agent is a formaldehyde solution containing an alkali hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9976889A JP2684413B2 (en) | 1989-04-19 | 1989-04-19 | Method for preparing ultrafine gold particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9976889A JP2684413B2 (en) | 1989-04-19 | 1989-04-19 | Method for preparing ultrafine gold particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02277705A true JPH02277705A (en) | 1990-11-14 |
| JP2684413B2 JP2684413B2 (en) | 1997-12-03 |
Family
ID=14256150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9976889A Expired - Lifetime JP2684413B2 (en) | 1989-04-19 | 1989-04-19 | Method for preparing ultrafine gold particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2684413B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036316A (en) * | 2003-06-23 | 2005-02-10 | Mitsubishi Materials Corp | Metal particulate and production method therefor |
| JP2006152438A (en) * | 2004-11-02 | 2006-06-15 | Mitsubishi Materials Corp | Gold fine particle and producing method therefor |
| JP2011094234A (en) * | 2004-11-02 | 2011-05-12 | Mitsubishi Materials Corp | Gold nanoparticle |
-
1989
- 1989-04-19 JP JP9976889A patent/JP2684413B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005036316A (en) * | 2003-06-23 | 2005-02-10 | Mitsubishi Materials Corp | Metal particulate and production method therefor |
| JP4640570B2 (en) * | 2003-06-23 | 2011-03-02 | 三菱マテリアル株式会社 | Metal fine particles and production method thereof |
| JP2006152438A (en) * | 2004-11-02 | 2006-06-15 | Mitsubishi Materials Corp | Gold fine particle and producing method therefor |
| JP2011094234A (en) * | 2004-11-02 | 2011-05-12 | Mitsubishi Materials Corp | Gold nanoparticle |
| JP4706835B2 (en) * | 2004-11-02 | 2011-06-22 | 三菱マテリアル株式会社 | Method for producing gold fine particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2684413B2 (en) | 1997-12-03 |
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