JP4903932B2 - Method for producing binary metal particle colloidal dispersion - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、二元金属粒子コロイド分散液の製造方法に関する。
【０００２】
【従来の技術】
本発明者らは、先に一液中に存在する二種の貴金属を同時に還元すると、二元金属ナノクラスター分散液（いいかえれば二元金属粒子コロイド分散液）が得られること、この二元金属ナノクラスターは、一方の金属をコアに他の金属がシェルとなったコア／シェル型構造をもつものであることを発表した〔Ｎ．Ｔｏｓｈｉｍａ ａｎｄ Ｔ．Ｙｏｎｅｚａｗａ，Ｎｅｗ Ｊ．ｃｈｅｍ．，２２， １１７９（１９９８）〕。
【０００３】
前述の技術は、同じ液中で二種の金属が還元されて、二種の原子ができ、これがその場で結合し、固溶体化して合金状になるものや、金属の組合せによっては一方の金属がコア（核）になり他方の金属がシェル（殻）となってコア／シェル型クラスターとなったり、クラスターインクラスター（ｃｌｕｓｔｅｒ−ｉｎ−ｃｌｕｓｔｅｒ）構造、いいかえればそれぞれの金属がいくつか集合したものがさらに集ったような構造となっていることがわかってきた。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、新規な二元金属粒子コロイド分散液の製造方法を提供する点にある。なお、本発明における二元金属粒子コロイド分散液とは、前述のような構造のもののほか例えばコアとなる第一の金属粒子上に第二の金属が斑状、帯状あるいは殻状に被覆したもの、または金属粒子中に他の金属層が喰い込んだ状態のもの、さらには一部合金化したものなどを総称している。
【０００５】
【課題を解決するための手段】
従来、二元金属コロイドを調製するためには、二種の金属イオンが一液中に共通して存在している系において、二種の金属イオンを同時還元するか、または逐次還元することが不可欠であると考えられていたが、驚くべきことに、本発明者らは、金属毎に別々の液中で還元しておいたものを、ただ単に混合するだけで二元金属粒子コロイド分散液が調製できることを見出し、本発明を完成したものである。
【０００６】
本発明の第一は、（１）１種類の貴金属イオン含有液を還元して得られた金属コロイド液を二種類調製し、（２）前記（１）の方法で得られた、貴金属の種類が異なる金属コロイド液を混合する二元金属粒子コロイド分散液の製造方法であって、前記二種類の貴金属の組合せが、Ａｇ−Ｐｄ、Ａｇ−ＲｈまたはＡｇ−Ｐｔであり、前記金属コロイド液の調製にあたりコロイド保護剤を用いることを特徴とする二元金属粒子コロイド分散液の製造方法に関する。
【００１１】
本発明の第二は、前記コロイド保護剤が親水性高分子である請求項１記載の二元金属粒子コロイド分散液の製造方法に関する。
【００１２】
本発明における金属イオン供給源としては、とくに制限するものではないが、金属のハロゲン化物、酢酸金属塩、過ハロゲン酸金属塩、硫酸金属塩、硝酸金属塩、炭酸金属塩、修酸金属塩などの各種酸の金属塩などを挙げることができる。
【００１３】
前記金属としては、Ａｇ、Ｒｈ、Ｐｄ、Ｐｔを用いる。
【００１４】
二元金属コロイドを形成するための金属の組合せは、Ａｇ−Ｐｄ、Ａｇ−Ｒｈ、Ａｇ−Ｐｔが好ましく、金属コロイド液を高い温度ではなく、室温で混合しただけで、二元金属粒子コロイド分散液を得ることができる。
【００１５】
混合に供される金属コロイド液の金属粒子は、平均粒径が１００ｎｍ以下、好ましくは５０ｎｍ以下、とくに好ましくは１０ｎｍ以下である。下限はないが、好ましくは０．８ｎｍ以上である。
【００１６】
前記金属イオン含有液を形成するための溶媒としては、水、アルコール類、エチレングリコール類およびエーテル類よりなる群から選ばれた少なくとも１種を用いることが好ましい。
【００１７】
前記還元剤は、対象金属を還元できる還元剤であれば、とくに制限はなく、化学還元剤のほかに光還元、超音波還元、電気還元、Ｘ線還元、γ線還元なども使用することができる。また、化学還元剤としては、一級または二級アルコール類、グリコール類、酸素原子に隣接する炭素原子に水素原子が結合しているエーテル類、エタノールアミン類さらには水素化ホウ素類、ヒドラジンなどを挙げることができる。
【００１８】
金属イオン供給源としてＡｇＸ（Ｘはハロゲン）を、還元剤として、エタノールを用いたケースでみると、本発明における還元反応は
【化１】
【化２】
式中、Ａｇ（０）は、還元されて０価の金属になっていることを示す。
【００１９】
還元剤の使用量は、金属１モルに対し、１モル以上存在すればよく、好ましくは１〜１００モルである。
【００２０】
前記コロイド保護剤としては、親水性高分子、金属配位性分子、両親媒性分子および／またはアニオン性化合物を挙げることができる。
【００２１】
前記コロイド保護剤の使用量は、金属１モルに対し、０．１モル以上存在すればよく、好ましくは１〜５０モルである。なお、コロイド保護剤が高分子の場合には、そのモノマー単位当りのモル数に換算したものを適用する。
【００２２】
前記親水性高分子としては、ポリビニルピロリドン〔たとえばポリ（Ｎ−ビニル−２−ピロリドン）〕、ポリビニルアルコール、ポリ（メタ）アクリル酸塩のように、アミド基、水酸基、カルボキシル基および／またはアミノ基を含有するポリマーあるいはこれら親水性ホモ重合体形成用モノマーの共重合体などのほか、シクロデキストリン、アミノペクチン、メチルセルロース、ゼラチンなどの天然物を挙げることができる。
【００２３】
前記金属配位性分子としては、アミノ基、チオール基、ジスルフィド基、アミド基、カルボン酸基、ホスフィン基、スルホン酸基など金属に配位することのできる官能基を１つ以上持つ有機分子および一酸化炭素、一酸化窒素をあげることができる。
【００２４】
前記両親媒性分子としては、各種一官能性または多官能性界面活性剤（アニオン性、カチオン性、ノニオン性、両性いずれでも可）たとえばドデシル硫酸ナトリウム、ポリエチレングリコールモノラウレートなどを挙げることができる。
【００２５】
前記アニオン性化合物としては、塩化物などのハロゲン化物、過塩素酸塩、各種アルコキシドなどのほか修酸、酒石酸、クエン酸などのカルボン酸の塩を挙げることができ、その塩としてはアルカリ金属塩、アンモニウム塩、アミン塩などを挙げることができる。
【００２６】
本発明により得られた二元金属粒子コロイド分散液は、そのまま、あるいはそれを適当な担体に担持させて触媒として使用することができる。本発明の二元金属粒子コロイド分散液中の二元金属粒子は、本発明者らが先に発表した同時還元法で得られた二元金属粒子（同時還元以外の点は同じ方法、条件で得られたもの）より、やや大きい粒子となっているが、それにもかかわらず、同時還元法で得られたものより触媒活性が高い傾向を示すのは全く驚くべき現象である。
【００２７】
【実施例】
以下に、実施例、比較例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。
【００２８】
実施例１
（１）銀粒子コロイド分散液の調製
還流冷却器付き１００ミリリットルナス型フラスコに過塩素酸銀（小島化学製特級試薬）０．００６８ｇ（０．０３３ミリモル）およびポリ（Ｎ−ビニル−２−ピロリドン）（東京化成工業製特級試薬）０．１４７ｇ（１．３２ミリモル、単量体単位）を入れ、反応器の空気部分を窒素置換した。これに蒸留水５ミリリットルを加え、磁気撹拌機を用いて十分撹拌した後、さらにエタノール４５ミリリットルを加え、９０〜９５℃で２時間加熱還流した。溶液は黄色に変化し、銀粒子コロイド分散液が得られた。銀粒子コロイド分散液のＵＶ−Ｖｉｓ吸収スペクトルの結果、銀特有の表面プラズモン吸収による吸収極大が４００ｎｍ付近に現れた。この溶液を透過型電子顕微鏡により分析した結果、銀粒子の平均粒径は７．６ｎｍであった。
【００２９】
（２）ロジウム粒子コロイド分散液の調製
前記銀コロイド液の調製における過塩素酸銀に変えて、塩化ロジウム０．００８７ｇ（０．０３３ミリモル）を使用した以外は、銀粒子コロイド分散液の調製と同様に操作し、黒褐色の溶液を得た。ロジウム粒子コロイド分散液のＵＶ−Ｖｉｓ吸収スペクトルは、吸収極大は観察されず、滑らかな右下がりの曲線であった。この溶液を透過型電子顕微鏡により分析した結果、粒子の平均粒径は２．２ｎｍであった。
【００３０】
（３）パラジウム粒子コロイド分散液の調製
前記銀粒子コロイド分散液の調製における過塩素酸銀に変えて、酢酸パラジウム０．００７４ｇ（０．０３３ミリモル）を使用した以外は、銀粒子コロイド分散液の調製と同様に操作し、黒褐色の溶液を得た。パラジウム粒子コロイド分散液のＵＶ−Ｖｉｓ吸収スペクトルは、吸収極大は観察されず、滑らかな右下がりの曲線であった。この溶液を透過型電子顕微鏡により分析した結果、粒子の平均粒径は２．７ｎｍであった。
【００３１】
（４）銀／ロジウム 複合金属粒子コロイド分散液の調製
１００ミリリットルナス型フラスコに前記（１）記載の銀粒子コロイド分散液４ミリリットルと、前記（２）記載のロジウム粒子コロイド分散液１６ミリリットルとを磁気撹拌機を用いて十分撹拌した。銀／ロジウムコロイドのＵＶ−Ｖｉｓ吸収スペクトルの結果、銀とロジウムの単なる算術平均を示さず、混合後時間が経つと図１に示すような滑らかな右下がりの曲線を示した。この結果は、銀粒子およびロジウム粒子の単独コロイド分散液の混合物ではなく、銀／ロジウム複合金属粒子コロイド分散液の生成を示唆している。透過型電子顕微鏡写真からも、銀およびロジウムの単なる混合ではないことが観察された。
【００３２】
実施例２（銀／パラジウム複合金属粒子コロイド分散液の調製）
１００ミリリットルナス型フラスコに実施例１（１）記載の銀コロイド４ミリリットルと、実施例１（３）記載のパラジウムコロイド１６ミリリットルとを磁気撹拌機を用いて十分撹拌した。銀／パラジウムコロイドのＵＶ−Ｖｉｓ吸収スペクトルの結果、銀とパラジウムの単なる算術平均を示さず、滑らかな右下がりの曲線を示した。この結果は、銀およびパラジウムの単独コロイドの単なる混合物ではなく、銀／パラジウム複合金属粒子コロイド分散液の生成を示唆している。透過型電子顕微鏡写真からも、銀およびパラジウムの単なる混合ではないことが観察された。
【００３３】
実施例３（水素化触媒としての利用）
３０ミリリットルナス型フラスコに、実施例１（４）記載の銀／ロジウム複合金属粒子コロイド分散液を０．３ミリリットル（２．０×１０−４ミリモル）入れ、溶媒としてエタノール１８．７ミリリットルを加え、水素雰囲気下、磁気撹拌機を用いて２時間３０℃で十分撹拌した。２時間後、水素化反応の基質としてアクリル酸メチル１ミリリットル（０．５ミリモル）を加え、消費した水素の量をガスビュレットにより読みとった。水素化触媒活性は、水素化初速度を測定することにより評価した。調製した触媒の水素化触媒活性は、４．７モル−Ｈ２モル−Ｍ−１ｓ−１であった。
【００３４】
比較例１
同様に実施例１（１）記載の銀粒子コロイド分散液の水素化触媒活性を調べたところ、０．１モル−Ｈ２モル−Ｍ−１ｓ−１であった。
【００３５】
比較例２
同様に実施例１（２）記載のロジウム粒子コロイド分散液の水素化触媒活性を調べたところ、３．１モル−Ｈ２モル−Ｍ−１ｓ−１であった。
【００３６】
実施例４
（１）銀粒子コロイド分散液の調製
１００ミリリットル石英製シュリンク管に過塩素酸銀（小島化学製特級試薬）０．００６８ｇ（０．０３３ミリモル）およびポリアクリル酸ナトリウム（Ａｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ製特級試薬）０．１２４ｇ（１．３２ミリモル、単量体単位）を入れ、これに蒸留水２５ミリリットルを加え、さらにエタノール２５ミリリットルを加え、反応器の空気部分を窒素置換した。磁気撹拌機を用いて十分撹拌した後、５００Ｗ高圧水銀灯にて１時間紫外線照射した。溶液は黄色に変化し、銀コロイド溶液が得られた。銀粒子コロイド分散液のＵＶ−Ｖｉｓ吸収スペクトルの結果、銀特有の表面プラズモン吸収による吸収極大が４００ｎｍ付近に現れた。この溶液を透過型電子顕微鏡により分析した結果、銀粒子の平均粒径は３．７ｎｍであった。
【００３７】
（２）パラジウム粒子コロイド分散液の調製
実施例４（１）の過塩素酸銀に変えて、酢酸パラジウム０．００７４ｇ（０．０３３ミリモル）を使用した以外は、実施例４（１）と同様に操作し、黒褐色の溶液を得た。パラジウム粒子コロイド分散液のＵＶ−Ｖｉｓ吸収スペクトルは、吸収極大は観察されず、滑らかな右下がりの曲線であった。この溶液を透過型電子顕微鏡により分析した結果、粒子の平均粒径は３．０ｎｍであった。
【００３８】
（３）銀／パラジウム複合金属粒子コロイド分散液の調製
１００ミリリットルナス型フラスコに実施例４（１）記載の銀コロイド１８ミリリットルと、実施例４（２）記載のパラジウムコロイド２ミリリットルとを磁気撹拌機を用いて十分撹拌した。銀／パラジウムコロイドのＵＶ−Ｖｉｓ吸収スペクトルの結果、銀とパラジウムの単なる算術平均を示さず、滑らかな右下がりの曲線を示した。この結果は、銀およびパラジウムの単独コロイドの混合物ではなく、銀／パラジウム複合金属粒子コロイド分散液の生成を示唆している。透過型電子顕微鏡写真からも、銀およびパラジウムの単なる混合ではないことが観察された。
【００３９】
実施例５
還流冷却器付き１００ミリリットルナス型フラスコに、実施例４（３）記載の銀／パラジウム複合金属粒子コロイド分散液を３０ミリリットル入れ、凍結脱気した。エチレン：酸素（２：１）６００ミリリットルの雰囲気下に静置し、閉鎖系で磁気撹拌機を用いて十分撹拌した後、３時間、１７０℃で加熱した。３時間後反応温度を０〜５℃に冷却し、反応を停止した。反応溶液中の生成物をガスクロマトグラフ法（ＴＳＧ−１カラムにより６０℃、ＦＩＤ検出器）により分析定量したところ、調製した触媒のエチレン酸化触媒活性は、４．３モル−ＥＯモル−Ｍ−１ｈ−１であった。
【００４０】
比較例３
同様に実施例４（１）記載の銀粒子コロイド分散液のエチレン酸化触媒活性を調べたところ、２．７モル−ＥＯモル−Ｍ−１ｈ−１であった。
【００４１】
比較例４
同様に実施例４（２）記載のパラジウム粒子コロイド分散液のエチレン酸化触媒活性を調べたところ、０．４６モル−ＥＯモル−Ｍ−１ｈ−１であった。
【００４２】
【発明の効果】
本発明により、予期もできない二元金属粒子コロイド分散液の簡単な製法が提供でき、かつそのコロイド分散液は触媒としても有用であった。
【図面の簡単な説明】
【図１】銀粒子コロイド分散液にロジウム粒子分散液を混合したときの銀表面プラズモン吸収が時間の経過とともに滑らかな右下り曲線に収れんしてゆくことを示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a binary metal particle colloidal dispersion.
[0002]
[Prior art]
The inventors of the present invention can obtain a binary metal nanocluster dispersion (in other words, a binary metal particle colloid dispersion) by simultaneously reducing two kinds of precious metals existing in one liquid, and this binary metal. It has been announced that nanoclusters have a core / shell structure in which one metal is a core and the other metal is a shell [N. Toshima and T.A. Yonezawa, New J .; chem. , 22 , 1179 (1998)].
[0003]
In the above technique, two kinds of metals are reduced in the same liquid to form two kinds of atoms, which are combined in situ and become a solid solution into an alloy, or depending on the combination of metals, Becomes a core and the other metal becomes a shell, forming a core / shell cluster, or a cluster-in-cluster structure, in other words, a collection of several metals. It has been found that the structure is more like a gathering.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel process for producing bimetallic particle colloidal dispersion. In addition, the binary metal particle colloid dispersion in the present invention, in addition to the one having the structure as described above, for example, the first metal particles that become the core, the second metal is coated in the form of spots, strips or shells, Or, it is a generic term for a state in which another metal layer is engulfed in a metal particle, or a partially alloyed one.
[0005]
[Means for Solving the Problems]
Conventionally, in order to prepare a binary metal colloid, two kinds of metal ions can be simultaneously reduced or sequentially reduced in a system in which two kinds of metal ions are commonly present in one liquid. was thought to be essential, surprisingly, the present inventors have found that what had been reduced in separate liquid in each metal, simply by simply mixing binary metal particle colloidal dispersion The present invention has been completed.
[0006]
First the present invention, (1) one kind of a noble metal ion-containing solution the metal colloid solution obtained by reducing to two prepared, obtained by the method (2) above (1), precious metals A method for producing a binary metal particle colloidal dispersion in which different types of metal colloidal liquids are mixed , wherein the combination of the two types of noble metals is Ag-Pd, Ag-Rh or Ag-Pt, liquid process for producing bimetallic particle colloidal dispersion, which comprises using a colloidal protective agent in the preparation of.
[0011]
The second invention relates to a method for producing a bimetallic particle colloidal dispersion of
[0012]
The metal ion source in the present invention is not particularly limited, but metal halides, metal acetates, metal perhalogenates, metal sulfates, metal nitrates, metal carbonates, metal oxalates, etc. And metal salts of various acids.
[0013]
As the metal, Ag, Rh, Pd, or Pt is used.
[0014]
The combination of metal for forming the bimetallic colloid, Ag-Pd, Ag-Rh , Ag-Pt are preferred, rather than the higher temperature of the metal colloid solution, only by mixing at room temperature, bimetallic particles colloidal dispersion A liquid can be obtained.
[0015]
The metal particles of the metal colloid liquid to be mixed have an average particle size of 100 nm or less, preferably 50 nm or less, particularly preferably 10 nm or less. Although there is no lower limit, it is preferably 0.8 nm or more.
[0016]
As a solvent for forming the metal ion-containing liquid, it is preferable to use at least one selected from the group consisting of water, alcohols, ethylene glycols and ethers.
[0017]
The reducing agent is not particularly limited as long as it is a reducing agent capable of reducing the target metal, and in addition to the chemical reducing agent, photoreduction, ultrasonic reduction, electrical reduction, X-ray reduction, γ-ray reduction, etc. may be used. it can. Examples of the chemical reducing agent include primary or secondary alcohols, glycols, ethers in which a hydrogen atom is bonded to a carbon atom adjacent to an oxygen atom, ethanolamines, borohydrides, and hydrazine. be able to.
[0018]
In the case of using AgX (X is halogen) as the metal ion source and ethanol as the reducing agent, the reduction reaction in the present invention is
In the formula, Ag (0) indicates that it is reduced to a zero-valent metal.
[0019]
The reducing agent may be used in an amount of 1 mol or more, preferably 1 to 100 mol, per 1 mol of metal.
[0020]
Examples of the colloid protective agent include hydrophilic polymers, metal coordination molecules, amphiphilic molecules, and / or anionic compounds.
[0021]
The colloid protective agent is used in an amount of 0.1 mol or more, preferably 1 to 50 mol, per 1 mol of metal. In addition, when the colloid protective agent is a polymer, the one converted to the number of moles per monomer unit is applied.
[0022]
Examples of the hydrophilic polymer include an amide group, a hydroxyl group, a carboxyl group, and / or an amino group such as polyvinyl pyrrolidone [for example, poly (N-vinyl-2-pyrrolidone)], polyvinyl alcohol, and poly (meth) acrylate. In addition to polymers containing styrene or copolymers of monomers for forming these hydrophilic homopolymers, natural products such as cyclodextrin, aminopectin, methylcellulose, and gelatin can be used.
[0023]
Examples of the metal coordinating molecule include an organic molecule having one or more functional groups capable of coordinating to a metal such as an amino group, a thiol group, a disulfide group, an amide group, a carboxylic acid group, a phosphine group, and a sulfonic acid group. Examples thereof include carbon monoxide and nitric oxide.
[0024]
Examples of the amphiphilic molecule include various monofunctional or polyfunctional surfactants (which may be anionic, cationic, nonionic or amphoteric) such as sodium dodecyl sulfate, polyethylene glycol monolaurate, and the like. .
[0025]
Examples of the anionic compound include halides such as chlorides, perchlorates, various alkoxides, and salts of carboxylic acids such as oxalic acid, tartaric acid, and citric acid, and the salts include alkali metal salts. , Ammonium salts and amine salts.
[0026]
Binary metal particle colloidal dispersion obtained by the present invention can be used as such or it be supported on a suitable carrier as a catalyst. Two bimetallic particles bimetallic particle colloidal dispersion of the present invention, the present inventors have same way except for the points bimetallic particles (simultaneous reduction obtained by the co-reduction method previously announced, the condition It is a surprising phenomenon that the catalyst activity tends to be higher than that obtained by the simultaneous reduction method.
[0027]
【Example】
Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.
[0028]
Example 1
(1) Preparation of silver particle colloidal dispersion In a 100 ml eggplant type flask equipped with a reflux condenser, 0.0068 g (0.033 mmol) of silver perchlorate (special reagent manufactured by Kojima Chemical) and poly (N-vinyl-2-pyrrolidone) ) (Tokyo Chemical Industry special grade reagent) 0.147 g (1.32 mmol, monomer unit) was added, and the air portion of the reactor was purged with nitrogen. Distilled water (5 ml) was added thereto, and after sufficiently stirring using a magnetic stirrer, 45 ml of ethanol was further added, followed by heating to reflux at 90 to 95 ° C. for 2 hours. The solution turned yellow and a silver particle colloidal dispersion was obtained. As a result of the UV-Vis absorption spectrum of the silver particle colloidal dispersion, an absorption maximum due to surface plasmon absorption peculiar to silver appeared near 400 nm. As a result of analyzing this solution with a transmission electron microscope, the average particle diameter of the silver particles was 7.6 nm.
[0029]
(2) Preparation of rhodium particle colloid dispersion Preparation of silver particle colloid dispersion except that 0.0087 g (0.033 mmol) of rhodium chloride was used instead of silver perchlorate in the preparation of the silver colloid solution. The same operation was performed to obtain a dark brown solution. In the UV-Vis absorption spectrum of the rhodium particle colloidal dispersion, no absorption maximum was observed, and it was a smooth downward curve. As a result of analyzing this solution with a transmission electron microscope, the average particle diameter of the particles was 2.2 nm.
[0030]
(3) Preparation of palladium particle colloidal dispersion The silver particle colloidal dispersion liquid except that 0.0074 g (0.033 mmol) of palladium acetate was used instead of silver perchlorate in the preparation of the silver particle colloidal dispersion. The same operation as in the preparation was performed to obtain a dark brown solution. The UV-Vis absorption spectrum of the palladium particle colloidal dispersion was a smooth, downward-sloping curve with no absorption maximum observed. As a result of analyzing this solution with a transmission electron microscope, the average particle size of the particles was 2.7 nm.
[0031]
(4) Preparation of silver / rhodium composite metal particle colloid dispersion In a 100 ml eggplant type flask, 4 ml of silver particle colloid dispersion described in (1) above and 16 ml of rhodium particle colloid dispersion described in (2) above. Stir well using a magnetic stirrer. As a result of the UV-Vis absorption spectrum of the silver / rhodium colloid, it did not show a simple arithmetic average of silver and rhodium, and showed a smooth downward curve as shown in FIG. This result suggests the production of a colloidal dispersion of silver / rhodium composite metal particles rather than a mixture of single colloidal dispersions of silver and rhodium particles. It was also observed from transmission electron micrographs that it was not just a mixture of silver and rhodium.
[0032]
Example 2 (Preparation of colloidal dispersion of silver / palladium composite metal particles)
In a 100 ml eggplant type flask, 4 ml of silver colloid described in Example 1 (1) and 16 ml of palladium colloid described in Example 1 (3) were sufficiently stirred using a magnetic stirrer. As a result of the UV-Vis absorption spectrum of the silver / palladium colloid, it did not show a mere arithmetic mean of silver and palladium, but showed a smooth downward-sloping curve. This result suggests the formation of a colloidal dispersion of silver / palladium composite metal particles, not just a single colloid of silver and palladium. It was also observed from transmission electron micrographs that it was not just a mixture of silver and palladium.
[0033]
Example 3 (Utilization as a hydrogenation catalyst)
Into a 30 ml eggplant-shaped flask, 0.3 ml (2.0 × 10 −4 mmol) of the silver / rhodium composite metal particle colloid dispersion described in Example 1 (4) was added, and 18.7 ml of ethanol was added as a solvent. In a hydrogen atmosphere, the mixture was sufficiently stirred at 30 ° C. for 2 hours using a magnetic stirrer. Two hours later, 1 ml (0.5 mmol) of methyl acrylate was added as a substrate for the hydrogenation reaction, and the amount of hydrogen consumed was read with a gas burette. Hydrogenation catalyst activity was evaluated by measuring the initial hydrogenation rate. The hydrogenation catalytic activity of the prepared catalyst was 4.7 mol-H 2 mol-M −1 s −1 .
[0034]
Comparative Example 1
Similarly, when the hydrogenation catalytic activity of the silver particle colloidal dispersion described in Example 1 (1) was examined, it was 0.1 mol-H 2 mol-M −1 s −1 .
[0035]
Comparative Example 2
Similarly, when the hydrogenation catalytic activity of the rhodium particle colloidal dispersion described in Example 1 (2) was examined, it was 3.1 mol-H 2 mol-M −1 s −1 .
[0036]
Example 4
(1) Preparation of silver particle colloidal dispersion 0.0068 g (0.033 mmol) of silver perchlorate (special reagent manufactured by Kojima Chemical) and sodium polyacrylate (special reagent manufactured by Aldrich Chemical) 0 in a 100 ml quartz shrink tube .124 g (1.32 mmol, monomer unit) was added, 25 ml of distilled water was added thereto, and 25 ml of ethanol was further added, and the air portion of the reactor was purged with nitrogen. After sufficiently stirring using a magnetic stirrer, ultraviolet irradiation was performed for 1 hour with a 500 W high-pressure mercury lamp. The solution turned yellow and a silver colloid solution was obtained. As a result of the UV-Vis absorption spectrum of the silver particle colloidal dispersion, an absorption maximum due to surface plasmon absorption peculiar to silver appeared near 400 nm. As a result of analyzing this solution with a transmission electron microscope, the average particle diameter of the silver particles was 3.7 nm.
[0037]
(2) Preparation of colloidal dispersion of palladium particles As in Example 4 (1) except that 0.0074 g (0.033 mmol) of palladium acetate was used instead of silver perchlorate in Example 4 (1). To give a dark brown solution. The UV-Vis absorption spectrum of the palladium particle colloidal dispersion was a smooth, downward-sloping curve with no absorption maximum observed. As a result of analyzing this solution with a transmission electron microscope, the average particle diameter of the particles was 3.0 nm.
[0038]
(3) Preparation of silver / palladium composite metal particle colloid dispersion In a 100 ml eggplant type flask, 18 ml of silver colloid described in Example 4 (1) and 2 ml of palladium colloid described in Example 4 (2) were magnetically stirred. The mixture was sufficiently stirred using a machine. As a result of the UV-Vis absorption spectrum of the silver / palladium colloid, it did not show a mere arithmetic mean of silver and palladium, but showed a smooth downward-sloping curve. This result suggests the formation of a colloidal dispersion of silver / palladium composite metal particles rather than a single colloidal mixture of silver and palladium. It was also observed from transmission electron micrographs that it was not just a mixture of silver and palladium.
[0039]
Example 5
30 ml of the colloidal dispersion of silver / palladium composite metal particles described in Example 4 (3) was placed in a 100 ml eggplant-shaped flask equipped with a reflux condenser and freeze-deaerated. The mixture was allowed to stand in an atmosphere of 600 ml of ethylene: oxygen (2: 1), sufficiently stirred using a magnetic stirrer in a closed system, and then heated at 170 ° C. for 3 hours. After 3 hours, the reaction temperature was cooled to 0 to 5 ° C., and the reaction was stopped. When the product in the reaction solution was analyzed and quantified by gas chromatography (60 ° C. using a TSG-1 column, FID detector), the ethylene oxidation catalytic activity of the prepared catalyst was 4.3 mol-EO mol-M −1. h- 1 .
[0040]
Comparative Example 3
Similarly, when the ethylene oxidation catalytic activity of the silver particle colloidal dispersion described in Example 4 (1) was examined, it was 2.7 mol-EO mol-M −1 h −1 .
[0041]
Comparative Example 4
Similarly, when the ethylene oxidation catalyst activity of the colloidal dispersion of palladium particles described in Example 4 (2) was examined, it was 0.46 mol-EO mol-M −1 h −1 .
[0042]
【Effect of the invention】
The present invention, expected also simple method to provide a bimetallic particle colloidal dispersion that can not be, and the colloidal dispersion is useful as a catalyst.
[Brief description of the drawings]
FIG. 1 is a graph showing that silver surface plasmon absorption converges on a smooth downward curve over time when a rhodium particle dispersion is mixed with a silver particle colloid dispersion.
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| WO2005007328A1 (en) * | 2003-07-17 | 2005-01-27 | Asahi Kasei Medical Co., Ltd. | Metal colloid solution |
| CA2537806A1 (en) * | 2003-09-03 | 2005-03-17 | Shetech Co., Ltd. | Platinum nanocolloid solution, process for producing the same and drink containing platinum nanocolloid |
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| JP4485174B2 (en) * | 2003-11-26 | 2010-06-16 | 日揮触媒化成株式会社 | Composite metal fine particle dispersion and method for producing the same |
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| KR20060129090A (en) * | 2004-04-16 | 2006-12-14 | 도쿠리츠교세이호징 붓시쯔 자이료 겐큐키코 | Colloidal solution of fine metal particles, electroconductive pasty material, electroconductive ink material and method for producting them |
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| JP2007113059A (en) * | 2005-10-19 | 2007-05-10 | Fujifilm Corp | Method for producing dispersion of metal microparticles, dispersion of metal microparticles, coloring composition using the same, photosensitive printing material, substrate provided with light-shielding image, color filter and liquid crystal display |
| US7749300B2 (en) * | 2008-06-05 | 2010-07-06 | Xerox Corporation | Photochemical synthesis of bimetallic core-shell nanoparticles |
| JP5537024B2 (en) * | 2008-12-25 | 2014-07-02 | 株式会社新光化学工業所 | Binary Metal Nanoparticle Colloid, Binary Metal Nanoparticle, Binary Metal Nanoparticle Colloid Manufacturing Method, and Binary Metal Nanoparticle Manufacturing Method |
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