JP2003013105A - Method for manufacturing carrier with metal fine particles - Google Patents
Method for manufacturing carrier with metal fine particlesInfo
- Publication number
- JP2003013105A JP2003013105A JP2001199727A JP2001199727A JP2003013105A JP 2003013105 A JP2003013105 A JP 2003013105A JP 2001199727 A JP2001199727 A JP 2001199727A JP 2001199727 A JP2001199727 A JP 2001199727A JP 2003013105 A JP2003013105 A JP 2003013105A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- metal
- liquid
- fine particles
- reducing
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 239000010419 fine particle Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- 229910001111 Fine metal Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 239000011343 solid material Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000006229 carbon black Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000002923 metal particle Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は表面に金属微粒子を
付着させた担体の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a carrier having metal fine particles attached to its surface.
【０００２】[0002]
【従来の技術】金属微粒子、特に粒径1〜１００ｎｍの
微粒子は、種々の特異な性能を有することから、触媒、
センサー用電極あるいは電子材料と言うような分野で盛
んに注目されており、それに伴なって、各種の製造方法
が考えられている。代表的な製造方法としては、金属イ
オンを還元剤の存在下で加熱還元して金属元素とした後
に微粒子まで成長させる方法や、金属分を高温で蒸発さ
せた後に、トラップ等で捕捉する方法等が挙げられる。2. Description of the Related Art Since metal fine particles, especially fine particles having a particle size of 1 to 100 nm, have various peculiar performances, catalysts,
In the field of sensor electrodes or electronic materials, attention is being paid to it, and various manufacturing methods are being considered. As a typical manufacturing method, a method of heating and reducing metal ions in the presence of a reducing agent to form a metal element and then growing into fine particles, a method of evaporating a metal component at a high temperature, and then trapping it with a trap etc. Is mentioned.
【０００３】しかし、前者の場合、微粒子の成長と凝集
の制御が難しく、また後者の場合は特殊な装置が必要で
かつ煩雑な工程を踏まなければ製造できない等の問題を
有していた。However, in the former case, it is difficult to control the growth and agglomeration of fine particles, and in the latter case, there is a problem that a special device is required and the production cannot be performed without complicated steps.
【０００４】更に、これらの方法等で得られた金属微粒
子を、触媒等として実用化するためには、固体物質から
なる担体の表面に付着させる必要がある。しかしなが
ら、一度生成した金属微粒子を更に担体に付着させる方
法は、煩雑かつ経済的ではなく、更に生成した微粒子が
二次凝集を起こし均一に付着できないという問題もあっ
た。Further, in order to put the fine metal particles obtained by these methods into practical use as a catalyst or the like, it is necessary to adhere them to the surface of a carrier made of a solid substance. However, the method of further adhering the metal fine particles once produced to the carrier is not complicated and economical, and there is also a problem that the fine particles produced further cause secondary aggregation and cannot be evenly attached.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
従来技術の欠点を解決し、簡単な操作で、安価に金属の
微粒子を生成させ、更にこれを固体物質表面に付着させ
た金属微粒子付着担体を製造する方法を提供することで
ある。DISCLOSURE OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art, to produce fine metal particles at low cost by a simple operation, and further to attach the fine metal particles to the surface of a solid substance. It is to provide a method for producing an adherent carrier.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、金属微粒
子および金属微粒子付着担体の製造に関して鋭意検討を
重ねた結果、特定の液体中に金属の化合物やイオンを含
有させ、ここにマイクロ波を照射すると液体中に金属微
粒子が生成し、その系にカーボン粒子または粉体等の固
体物質からなる担体を存在させると、容易に目的とする
金属微粒子付着担体を製造できることを見出して本発明
を完成するに至った。The inventors of the present invention have conducted extensive studies as to the production of metal fine particles and a carrier on which metal fine particles are adhered, and as a result, a metal compound or ion is contained in a specific liquid and microwaves are added to the liquid. The present invention was found to be able to easily produce a target metal fine particle-adhered carrier by the presence of a carrier made of a solid substance such as carbon particles or powder in the system when metal fine particles are generated in a liquid upon irradiation with It came to completion.
【０００７】即ち、本発明は、担体となる固体物質の存
在下、金属の化合物またはイオンを含有した、還元能を
有する液体または還元物質を溶解した液体に、マイクロ
波を照射させるか、或いは、金属の化合物またはイオン
を含有した、還元能を有する液体または還元物質を溶解
した液体に、マイクロ波を照射させた後に、担体となる
固体物質を存在させることを特徴とする、金属微粒子を
表面に付着させた金属微粒子付着担体の製造方法であ
る。That is, according to the present invention, in the presence of a solid substance serving as a carrier, a liquid containing a metal compound or ions and having a reducing ability or a liquid in which a reducing substance is dissolved is irradiated with microwaves, or A liquid containing a compound or ion of a metal, having a reducing ability or a liquid in which a reducing substance is dissolved, is irradiated with microwaves, and then a solid substance serving as a carrier is present on the surface of the metal fine particles. This is a method for producing a carrier having metal fine particles attached thereto.
【０００８】[0008]
【発明の実施の形態】以下に、本発明を詳細に説明す
る。
○還元能を有する液体または還元物質を溶解した液体
本発明において反応は、還元能を有する液体または還元
物質を溶解した液体中で行なわれる。還元能を有する液
体とは、還元性の基を有する、即ち自己が酸化され得る
有機溶剤等が挙げられる。還元性を有する基としては、
アルコール性水酸基、アルデヒド基、アミノ基、イミノ
基等が挙げられ、具体的な有機溶剤としては、メタノー
ル、エタノール、プロパノール、ブタノール、オクタノ
ール、シクロヘキサノール、デカノール等のアコール
類；エチレングリコール、グリセリン等の多価アルコー
ル類；アニリン、エタノールアミン等の有機アミン類；
Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシ
ド、アセトン等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. -Liquid having a reducing ability or liquid having a reducing substance dissolved therein In the present invention, the reaction is carried out in a liquid having a reducing ability or a liquid having a reducing substance dissolved therein. Examples of the liquid having a reducing ability include organic solvents having a reducing group, that is, capable of being self-oxidized. Examples of the reducing group include
Examples thereof include alcoholic hydroxyl group, aldehyde group, amino group, imino group, and the like. Specific organic solvents include alcohols such as methanol, ethanol, propanol, butanol, octanol, cyclohexanol, and decanol; ethylene glycol, glycerin, etc. Polyhydric alcohols; Organic amines such as aniline and ethanolamine;
Examples include N, N-dimethylformamide, dimethyl sulfoxide, acetone and the like.
【０００９】また、還元物質を溶解した液体としては、
ギ酸、シュウ酸、糖類等の水溶液または有機溶剤溶液が
挙げられる。本発明で用いる還元能を有する液体の中で
は、還元能を有する有機溶剤が反応性の高さおよび取り
扱い易さから好ましく、更に好ましくはアルコール類ま
たは多価アルコール類である。また、本発明で用いる還
元物質を溶解した液体の中では、還元性を有する糖類の
水溶液が反応性の高さおよび取り扱い易さから好まし
く、更に好ましくブドウ糖の水溶液である。Further, as the liquid in which the reducing substance is dissolved,
Examples thereof include aqueous solutions of formic acid, oxalic acid, sugars and the like, or organic solvent solutions. Among the liquids having a reducing ability used in the present invention, an organic solvent having a reducing ability is preferable because of its high reactivity and easy handling, and alcohols or polyhydric alcohols are more preferable. Further, among the liquids in which the reducing substance used in the present invention is dissolved, an aqueous solution of a reducing saccharide is preferable because of its high reactivity and easy handling, and a glucose aqueous solution is more preferable.
【００１０】本発明では、前記液体中に、金属の化合物
またはイオン（以下「金属成分」と称する。）を添加
し、マイクロ波を照射することを特徴とする。マイクロ
波は分子レベルで局部的な加熱を起こさせるため、マイ
クロ波の照射された前記液体中の還元性を有する基また
は還元物質は部分的に反応を開始する。アルコールを例
に採ると、アルコール性水酸基にマイクロ波が照射され
ると、該基はアルデヒド基あるいはカルボキシル基に酸
化される。The present invention is characterized in that a metal compound or ion (hereinafter referred to as "metal component") is added to the liquid and microwave is irradiated. Since the microwave causes localized heating at the molecular level, the reducing group or reducing substance in the liquid irradiated with the microwave partially starts the reaction. Taking alcohol as an example, when the alcoholic hydroxyl group is irradiated with microwaves, the group is oxidized to an aldehyde group or a carboxyl group.
【００１１】この時、系内に金属成分が存在している
と、アルコールが還元剤として働き、当該金属成分が金
属に還元される。その時、金属は非常に細かい微粒子と
して生成する。At this time, if a metal component is present in the system, the alcohol acts as a reducing agent and the metal component is reduced to a metal. At that time, the metal is generated as very fine particles.
【００１２】またその系に、カーボンの粒子または粉体
等の担体となる固体物質を添加しておくと、還元によっ
て生成した金属微粒子が当該固体物質表面に析出し、結
果として金属微粒子を表面に付着させた担体が製造でき
る。When a solid substance such as carbon particles or powder that serves as a carrier is added to the system, fine metal particles produced by reduction are deposited on the surface of the solid substance, and as a result, fine metal particles are formed on the surface. An attached carrier can be produced.
【００１３】担体となる固体物質は、マイクロ波を照射
する系に最初から存在させなくとも、金属成分を含有す
る液体にマイクロ波を照射させることにより液体中に金
属微粒子を生成させた後に、そこに担体となる固体物質
を存在させ、表面に金属微粒子を付着させてもよい。し
かし生成した金属微粒子の付着性や金属微粒子同士の凝
集の防止を考えると、担体となる固体物質は最初から同
じ系に存在させた方が好ましい。The solid substance serving as a carrier does not need to be present in the microwave irradiation system from the beginning, but after the liquid containing the metal component is irradiated with microwaves to form the metal fine particles in the liquid, the solid substance may be present there. It is also possible to allow a solid substance to be a carrier to exist and to attach the fine metal particles to the surface. However, considering the adhesion of the generated metal fine particles and the prevention of aggregation of the metal fine particles, it is preferable that the solid substance serving as the carrier be present in the same system from the beginning.
【００１４】○担体となる固体物質
金属微粒子を表面に付着させる担体としては、固体物質
であれば特に種類は問わないが、マイクロ波を反射させ
ない非金属物質が好ましい。また、形状としては、表面
積が大きくて金属微粒子を付着し易い粒子または粉体が
好ましく、更に好ましくは、カーボンまたはアルミナの
粒子または粉体である。The solid substance serving as a carrier The carrier to which the metal fine particles are attached on the surface is not particularly limited as long as it is a solid substance, but a non-metallic substance that does not reflect microwaves is preferable. Further, the shape is preferably particles or powder having a large surface area to which metal fine particles are easily attached, and more preferably carbon or alumina particles or powder.
【００１５】○金属成分
微粒子化させる金属は、例えば、Ｆｅ、Ｎｉ、Ｃｕ、Ａ
ｇ、Ｐｔ、Ｒｕ等が挙げられるが、空気の存在下におい
て安定なものであれば、どの金属であっても使用でき、
目的とする用途に応じて選択すれば良い。系内に投入す
る微粒子金属源としては、イオンだけでなく、酸化物ま
たは水酸化物等の化合物の形体でも使用できる。金属成
分は、イオンの形態で存在していると還元し易く好まし
い。金属の化合物の中でも、金属酸化物または水酸化物
も同様に好ましい。一部の金属酸化物または水酸化物
は、使用する還元能を有する液体または還元物質を溶解
した液体に不溶な場合もあるが、当該液体に分散させて
使用することができる。The metal to be made into fine particles is, for example, Fe, Ni, Cu or A.
g, Pt, Ru, etc., but any metal that is stable in the presence of air can be used,
It may be selected according to the intended use. As the particulate metal source to be charged into the system, not only ions but also compounds in the form of oxides or hydroxides can be used. It is preferable that the metal component is present in the form of an ion because it can be easily reduced. Among the metal compounds, metal oxides or hydroxides are also preferable. Some metal oxides or hydroxides may be insoluble in the liquid having the reducing ability or the liquid in which the reducing substance is dissolved, but can be used by dispersing in the liquid.
【００１６】微粒子化を目的とする金属がＡｇや白金族
元素以外の場合には、系内に、反応開始剤となるＡｇま
たは白金族元素のイオンを微量添加すると、反応が速や
かに進行するので好ましい。これら元素の中でもＰｔが
特に効果が大きく好ましい。また、開始剤の添加量は、
微粒子化を目的とする金属成分に対して１モル％以下が
その性能を発揮し易く好ましい。When the metal for atomization is other than Ag or a platinum group element, the reaction proceeds rapidly when a small amount of Ag or a platinum group element ion as a reaction initiator is added to the system. preferable. Among these elements, Pt is particularly preferable because it has a large effect. The amount of initiator added is
It is preferable that the amount is 1 mol% or less with respect to the metal component for the purpose of forming fine particles, because the performance is easily exhibited.
【００１７】微粒子化を目的とする金属に対する還元能
を有する液体または還元物質を溶解した液体の配合量は
特に規定はなく、金属成分のモル数以上の量を適宜選択
すれば良い。照射するマイクロ波の強さと時間は、還元
能を有する液体または還元物質を溶解した液体により適
宜選択するが、０．０１〜０．５Ｗ／ｃｍ3の強度のも
のを数秒〜数十分照射すれば良い。反応の温度は、還元
能を有する液体または還元物質を溶解した液体の沸点以
下であれば良い。There is no particular limitation on the amount of the liquid having the ability to reduce the metal to be made into fine particles or the liquid in which the reducing substance is dissolved, and the amount may be appropriately selected in an amount of at least the number of moles of the metal component. The intensity and time of the microwave to be irradiated are appropriately selected depending on the liquid having a reducing ability or the liquid in which the reducing substance is dissolved, but the one having an intensity of 0.01 to 0.5 W / cm 3 is irradiated for several seconds to several tens of minutes. Good. The reaction temperature may be equal to or lower than the boiling point of the liquid having reducing ability or the liquid in which the reducing substance is dissolved.
【００１８】[0018]
【作用】金属成分を含有した、還元能を有する液体また
は還元物質を溶解した液体にマイクロ波を照射させた場
合に、その系に固体物質が存在していると、金属微粒子
が表面に付着した担体が製造できる理由は定かでない
が、当該固体物質の表面が局部的に加熱されて、そこが
反応場になり、還元によって生成した金属微粒子が担体
となる固体物質表面に析出するためと推測される。[Function] When a liquid containing a metal component and having a reducing ability or a liquid in which a reducing substance is dissolved is irradiated with microwaves and a solid substance is present in the system, fine metal particles adhere to the surface. The reason why the carrier can be produced is not clear, but it is presumed that the surface of the solid substance is locally heated to serve as a reaction field, and the metal fine particles generated by the reduction are deposited on the surface of the solid substance to be the carrier. It
【００１９】[0019]
【実施例】以下、実施例を挙げて更に詳しく本発明を説
明する。EXAMPLES The present invention will be described in more detail with reference to examples.
【００２０】実施例１
塩化白金酸溶液７ｍｌ（Ｐｔ含有量０．１４ｇ）に粉砕
したカーボンブラック（電気化学工業（株）製ＡＢ−１
２）０．１４ｇを添加し、スターラーで１０分攪拌、混
合した。試薬特級エチレングリコールで全量を１５０ｍ
ｌにし、冷却管を取り付けたガラス製の反応器に全量を
注ぎ、マイクロ波テスト装置（四国計測工業（株）製）
にて０．０２２Ｗ／ｃｍ3の出力でマイクロ波を6分間照
射した。液温が室温になった後に、全量を吸引ろ過し、
得られた固形物を包埋用常温硬化型エポキシ樹脂に添加
して混ぜて包埋をおこなった後に、ウルトラミクロトー
ムにて厚さ７０ｎｍの超薄切片を作成して、透過型電子
顕微鏡観察した。その結果、カーボンブラックの表面に
は５〜１０ｎｍの大きさのＰｔ粒子が生成しているのが
確認できた。Example 1 Carbon black pulverized into 7 ml of chloroplatinic acid solution (Pt content 0.14 g) (AB-1 manufactured by Denki Kagaku Kogyo KK)
2) 0.14 g was added, and stirred and mixed for 10 minutes with a stirrer. Reagent grade ethylene glycol with a total volume of 150 m
1, and the whole amount was poured into a glass reactor equipped with a cooling tube, and a microwave test device (manufactured by Shikoku Instrument Co., Ltd.)
At a power of 0.022 W / cm 3 for 6 minutes. After the liquid temperature reaches room temperature, the whole amount is suction filtered,
The obtained solid matter was added to a room temperature curing type epoxy resin for embedding and mixed for embedding, and then an ultrathin section having a thickness of 70 nm was prepared with an ultramicrotome and observed with a transmission electron microscope. As a result, it was confirmed that Pt particles having a size of 5 to 10 nm were generated on the surface of carbon black.
【００２１】実施例２
白金０．０００１ｍｍｏｌを溶解した硝酸銀溶液７ｍｌ
（Ａｇ含有量０．１４ｇ）に、粉砕したカーボンブラッ
ク（電気化学工業（株）製ＡＢ−１２）０．１４ｇを添
加し、スターラーで１０分攪拌し、カーボンブラックと
白金を混合した。試薬特級エチレングリコールで全量を
１５０ｍｌにし、実施例１に示した装置にて、同様の操
作を行い生成した銀粒子を透過型電子顕微鏡で観察し
た。その結果、カーボンブラックの表面には５〜２０ｎ
ｍの大きさのＡｇ粒子が生成しているのが確認できた。Example 2 7 ml of a silver nitrate solution in which 0.0001 mmol of platinum was dissolved
0.14 g of pulverized carbon black (AB-12 manufactured by Denki Kagaku Kogyo KK) was added to (Ag content 0.14 g), and the mixture was stirred with a stirrer for 10 minutes to mix carbon black and platinum. The total amount of the reagent grade ethylene glycol was adjusted to 150 ml, and the silver particles produced by the same operation as in Example 1 were observed with a transmission electron microscope. As a result, the surface of carbon black is 5-20n
It was confirmed that Ag particles having a size of m were generated.
【００２２】実施例３
白金０．０００１ｍｍｏｌを溶解した水酸化ニッケル分
散液７ｍｌ（Ｎｉ含有量０．１４ｇ）に、実施例2に示
す操作を施した後に、透過型電子顕微鏡で観察したとこ
ろ、カーボンブラックの表面には５〜２０ｎｍの大きさ
のＮｉ粒子が生成しているのが確認できた。Example 3 7 ml of a nickel hydroxide dispersion liquid (Ni content 0.14 g) in which 0.0001 mmol of platinum was dissolved was subjected to the procedure shown in Example 2 and then observed with a transmission electron microscope. It was confirmed that Ni particles having a size of 5 to 20 nm were generated on the surface of the black.
【００２３】比較例１
塩化白金酸を溶解したブタノール３０ｍｌ（Ｐｔ含有量
０．１４ｇ）に粉砕したカーボンブラック（電気化学工
業（株）製ＡＢ−１２）０．１４ｇを添加し、スターラ
ーで１０分攪拌、混合した。カーボンブラックをブタノ
ールから濾別し、得られたカーボンブラックを２００℃
で1時間酸化分解した後に、２００℃の水素気流下で2時
間還元し、カーボンブラックの表面に白金を析出させ
た。透過型電子顕微鏡で観察したところ、カーボンブラ
ックの表面に析出しているＰｔの粒径は大きく、２０〜
２００ｎｍ程あった。中には１０ｎｍ程度の細かい粒子
も存在したが、その多くは二次凝集しており、全体とし
て大きな粒径の固まりとなっていた。Comparative Example 1 0.14 g of pulverized carbon black (AB-12 manufactured by Denki Kagaku Kogyo KK) was added to 30 ml of butanol (Pt content 0.14 g) in which chloroplatinic acid was dissolved, and the mixture was stirred for 10 minutes with a stirrer. Stir and mix. The carbon black is filtered off from butanol and the carbon black obtained is heated to 200 ° C.
After oxidative decomposition for 1 hour, the mixture was reduced for 2 hours under a hydrogen stream at 200 ° C. to deposit platinum on the surface of carbon black. Observation with a transmission electron microscope revealed that the particle size of Pt deposited on the surface of the carbon black was large and was 20 to 20.
It was about 200 nm. Although there were fine particles of about 10 nm, most of them were secondary agglomerated, and became a lump with a large particle size as a whole.
【００２４】[0024]
【発明の効果】本発明によれば、簡単な操作で、安価に
金属の微粒子を生成させ、更にこれを表面に担持させた
金属微粒子付着担体を製造することができ、得られた金
属微粒子付着担体は各種反応の触媒、センサー用電極或
いは電子材料として有用である。EFFECTS OF THE INVENTION According to the present invention, it is possible to produce metal fine particles at low cost by a simple operation and to produce a metal fine particle-adhered carrier having the metal particles supported on the surface thereof. The carrier is useful as a catalyst for various reactions, a sensor electrode, or an electronic material.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２２Ｆ 9/24 Ｂ２２Ｆ 9/24 Ｂ Ｃ Ｅ Ｆターム(参考） 4G069 AA01 AA03 AA08 BA01A BA08A BA08B BB02A BB02B BC32B BC68B BC75B DA05 EA01X EA01Y EA02X EA02Y EB19 FA01 FA02 FB14 FB18 FB46 FB58 4K017 AA03 BB02 BB05 BB06 CA08 DA01 DA09 EJ01 FB04 FB11 4K018 BA01 BA02 BA04 BA13 BC26 BC32 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B22F 9/24 B22F 9/24 B C EF term (reference) 4G069 AA01 AA03 AA08 BA01A BA08A BA08B BB02A BB02B BC32B BC68B BC75B DA05 EA01X EA01Y EA02X EA02Y EB19 FA01 FA02 FB14 FB18 FB46 FB58 4K017 AA03 BB02 BB05 BB06 CA08 DA01 DA09 EJ01 FB04 FB11 4K018 BA01 BA02 BA04 BA13 BC26 BC32 BC32
Claims (4)
合物またはイオンを含有した、還元能を有する液体また
は還元物質を溶解した液体に、マイクロ波を照射させる
か、或いは、金属の化合物またはイオンを含有した、還
元能を有する液体または還元物質を溶解した液体に、マ
イクロ波を照射させた後に、担体となる固体物質を存在
させることを特徴とする、金属微粒子を表面に付着させ
た金属微粒子付着担体の製造方法。1. In the presence of a solid substance serving as a carrier, a liquid containing a metal compound or ions and having a reducing ability or a liquid in which a reducing substance is dissolved is irradiated with microwaves, or a metal compound or A metal having metal fine particles adhered to the surface, characterized in that a solid substance serving as a carrier is present after microwave irradiation to a liquid containing an ion or having a reducing ability dissolved therein A method for producing a fine particle-attached carrier.
請求項１の金属微粒子付着担体の製造方法。2. The method for producing a carrier having metal fine particles adhered thereto according to claim 1, wherein the solid substance serving as a carrier is a non-metal substance.
ルミナからなる請求項２の金属微粒子付着担体の製造方
法。3. The method for producing a fine metal particle-attached carrier according to claim 2, wherein the solid substance serving as a carrier is carbon or alumina.
あり、かつ還元能を有する液体または還元物質を溶解し
た液体に分散させることを特徴とする請求項１乃至３の
金属微粒子付着担体の製造方法。4. The carrier according to claim 1, wherein the solid substance serving as a carrier is particles or powder, and a liquid having reducing ability or a liquid in which the reducing substance is dissolved is dispersed. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001199727A JP2003013105A (en) | 2001-06-29 | 2001-06-29 | Method for manufacturing carrier with metal fine particles |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001199727A JP2003013105A (en) | 2001-06-29 | 2001-06-29 | Method for manufacturing carrier with metal fine particles |
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|---|---|
| JP2003013105A true JP2003013105A (en) | 2003-01-15 |
Family
ID=19036980
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| JP (1) | JP2003013105A (en) |
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| JP2007179785A (en) * | 2005-12-27 | 2007-07-12 | Sanyo Chem Ind Ltd | Method of manufacturing conductive fine particles |
| JP2007179781A (en) * | 2005-12-27 | 2007-07-12 | Sanyo Chem Ind Ltd | Method of manufacturing conductive fine particles |
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