JPH11246227A - Noble metal ultra-fine particle having egg shell structure - Google Patents
Noble metal ultra-fine particle having egg shell structureInfo
- Publication number
- JPH11246227A JPH11246227A JP10071469A JP7146998A JPH11246227A JP H11246227 A JPH11246227 A JP H11246227A JP 10071469 A JP10071469 A JP 10071469A JP 7146998 A JP7146998 A JP 7146998A JP H11246227 A JPH11246227 A JP H11246227A
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- ultra
- fine particles
- egg shell
- shell structure
- 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
- 239000011882 ultra-fine particle Substances 0.000 title claims abstract description 41
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 38
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 13
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 13
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 239000011162 core material Substances 0.000 claims abstract description 6
- 239000010948 rhodium Substances 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 6
- -1 polyoxyethylene cetyl ether Polymers 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- 239000004530 micro-emulsion Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- FBELJLCOAHMRJK-UHFFFAOYSA-L disodium;2,2-bis(2-ethylhexyl)-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCC(CC)CC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CC(CC)CCCC FBELJLCOAHMRJK-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、貴金属触媒等とし
て有用な貴金属超微粒子に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to noble metal ultrafine particles useful as a noble metal catalyst or the like.
【０００２】[0002]
【従来の技術】ロジウム等の貴金属は触媒金属としてシ
リカやアルミナ等の耐熱性の担体金属酸化物に超微粒子
状で担持させた状態で、各種の反応用触媒として広く用
いられている。しかしながら、従来の貴金属触媒の場
合、これを８００℃程度の高温に加熱すると、その貴金
属粒子が凝集（シンタリング）し、そのため、触媒の活
性点の減少や、活性点構造等の質的変化が起り、その結
果、触媒の活性や選択性が低下するという問題を生じ
る。2. Description of the Related Art A noble metal such as rhodium is widely used as a catalyst for various reactions as a catalyst metal supported on a heat-resistant carrier metal oxide such as silica or alumina in the form of ultrafine particles. However, in the case of a conventional noble metal catalyst, when it is heated to a high temperature of about 800 ° C., the noble metal particles aggregate (sinter), and therefore, a decrease in the active site of the catalyst and a qualitative change such as the active site structure are caused. As a result, there arises a problem that the activity and selectivity of the catalyst are reduced.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、耐熱性にす
ぐれた貴金属超微粒子を提供することをその課題とす
る。SUMMARY OF THE INVENTION An object of the present invention is to provide ultrafine precious metal particles having excellent heat resistance.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、貴金属超微粒子を芯
物質とし、その周囲をシリカ層で包囲してなるエッグシ
ェル構造を有する貴金属超微粒子が提供される。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a precious metal ultrafine particle having an egg shell structure in which the precious metal ultrafine particle is used as a core material and the periphery thereof is surrounded by a silica layer.
【０００５】[0005]
【発明の実施の形態】本発明のエッグシェル構造を有す
る貴金属超微粒子は、マイクロエマルジョン法を利用し
て製造することができる。本発明の貴金属超微粒子を製
造するには、貴金属塩化物の水溶液を界面活性剤を含む
有機溶媒溶液中に加え、撹拌し、油中水滴型のマイクロ
エマルジョンを作る。この場合、界面活性剤の選択は重
要で、エッグシェル構造の貴金属超微粒子を安定的に得
るためには、ポリオキシエチレンセチルエーテルを使用
するのが好ましい。このものとは異ったタイプの界面活
性剤を用いても、初期の貴金属超微粒子を得ることがで
きない。前記界面活性剤に含まれるポリオキシエチレン
基において、そのオキシエチレンの平均付加モル数は１
０〜２０、好ましくは４〜１６である。また、有機溶媒
としては、シクロヘキサンやシクロヘキサノール等の非
水溶性ないし難水溶性のものが用いられる。撹拌温度は
室温〜８０℃、好ましくは４０〜６０℃である。前記貴
金属塩化物の水溶液中濃度は０．１〜１モル／ｄｍ3、
好ましくは０．２〜０．５モル／ｄｍ3であり、界面活
性剤の有機溶媒中濃度は０．１〜１モル／ｄｍ3、好ま
しくは０．２〜０．８モル／ｄｍ3である。BEST MODE FOR CARRYING OUT THE INVENTION The noble metal ultrafine particles having an egg shell structure of the present invention can be produced by utilizing a microemulsion method. In order to produce the noble metal ultrafine particles of the present invention, an aqueous solution of a noble metal chloride is added to an organic solvent solution containing a surfactant and stirred to form a water-in-oil type microemulsion. In this case, the selection of the surfactant is important, and it is preferable to use polyoxyethylene cetyl ether in order to stably obtain the noble metal ultrafine particles having the egg shell structure. Even if a different type of surfactant is used, the initial noble metal ultrafine particles cannot be obtained. In the polyoxyethylene group contained in the surfactant, the average number of moles of oxyethylene added is 1
It is 0-20, preferably 4-16. As the organic solvent, a water-insoluble or hardly water-soluble organic solvent such as cyclohexane or cyclohexanol is used. The stirring temperature is from room temperature to 80 ° C, preferably from 40 to 60 ° C. The concentration of the noble metal chloride in the aqueous solution is 0.1 to 1 mol / dm 3 ,
The concentration is preferably 0.2 to 0.5 mol / dm 3 , and the concentration of the surfactant in the organic solvent is 0.1 to 1 mol / dm 3 , preferably 0.2 to 0.8 mol / dm 3 . .
【０００６】次に、前記マイクロエマルジョンに対し、
ヒドラジンハイドレートを加えて貴金属塩化物と反応さ
せ、貴金属とヒドラジン（Ｎ2Ｈ4）とのコンプレックス
を形成し、次いでテトラエチルオルソシリケート（ＴＥ
ＯＳ）とアンモニア水溶液を加えてそのＴＥＯＳを加水
分解させ、重縮合させる。この場合の温度は約５０℃で
ある。この操作により、貴金属−Ｎ2Ｈ4コンプレックス
超微粒子を含む沈殿が得られるが、このものは、液中か
ら濾別し、次いでエタノールで洗浄した後、乾燥し、さ
らに、空気流通過下で４００〜６００℃で焼成する。こ
の焼成により、超微粒子に付着する界面活性剤は焼失さ
れる。Next, with respect to the microemulsion,
Hydrazine hydrate is added and reacted with the noble metal chloride to form a complex of the noble metal and hydrazine (N 2 H 4 ), then tetraethyl orthosilicate (TE)
OS) and an aqueous ammonia solution are added to hydrolyze the TEOS to cause polycondensation. The temperature in this case is about 50 ° C. By this operation, a precipitate containing noble metal-N 2 H 4 complex ultrafine particles is obtained, which is separated from the liquid by filtration, washed with ethanol, dried, and further dried under a stream of air. Bake at ~ 600 ° C. By this firing, the surfactant attached to the ultrafine particles is burned off.
【０００７】次いで、前記のようにして得られる超微粒
子を４００〜５００℃で水素と接触させ、貴金属／Ｎ2
Ｈ4コンプレックスを貴金属微粒子とする。前記のよう
にして得られる貴金属超微粒子は、エッグシェル構造の
ものである。即ち、貴金属超微粒子を芯物質とし、その
周囲をシリカ層で包囲した構造を有する超微粒子であ
る。この超微粒子において、それ全体の粒径は３〜５０
ｎｍ、特に、８〜２５ｎｍであり、その芯物質を構成す
る貴金属超微粒子の粒径は１〜１０ｎｍ、特に、３〜５
ｎｍである。また、そのシリカ層の厚みは、１〜４０ｎ
ｍ、特に、３〜１０ｎｍである。微粒子中の貴金属含有
量は０．１〜３０ｗｔ％である。Next, the ultrafine particles obtained as described above are brought into contact with hydrogen at 400 to 500 ° C., and the noble metal / N 2
The H 4 complex is a noble metal particle. The noble metal ultrafine particles obtained as described above have an egg shell structure. That is, it is an ultrafine particle having a structure in which the precious metal ultrafine particle is used as a core material and the periphery thereof is surrounded by a silica layer. In these ultrafine particles, the total particle size is 3 to 50.
nm, particularly 8 to 25 nm, and the particle size of the noble metal ultrafine particles constituting the core substance is 1 to 10 nm, particularly 3 to 5 nm.
nm. The thickness of the silica layer is 1 to 40 n.
m, especially 3 to 10 nm. The noble metal content in the fine particles is 0.1 to 30 wt%.
【０００８】本発明のエッグシェル構造の貴金属超微粒
子において、その貴金属は、ロジウム（Ｒｈ）又はそれ
と同等の貴金属であるルテニウム（Ｒｕ）や白金（Ｐ
ｔ）等であることもできる。In the ultrafine particles of a noble metal having an egg shell structure of the present invention, the noble metal is rhodium (Rh) or ruthenium (Ru) or platinum (P) which is a noble metal equivalent thereto.
t) and the like.
【０００９】[0009]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００１０】実施例１ 塩化ロジウム（ＲｈＣｌ3）を０．３８モル／ｄｍ3の濃
度で含む水溶液３４重量部を、５０℃の温度でポリオシ
キエチレン（１５）セチルエーテルを０．５モル／ｄｍ
3の濃度で含むシクロヘキサン溶液１重量部に加え、撹
拌して、油中水滴型のマイクロエマルジョンを作った。
次に、このマイクロエマルジョンにヒドラジンハイドレ
ート０．１５重量部を添加混合し、Ｒｈ／Ｎ2Ｈ4コンプ
レックスからなる超微粒子を形成した。次に、テトラエ
チルオルソシリケート（ＴＥＯＳ）７重量部と２８ｗｔ
％のアンモニア水７重量部を５０℃で添加混合し、ＴＥ
ＯＳの加水分解と重縮合を行った。これにより、Ｒｈ／
Ｎ2Ｈ4超微粒子を含有する沈殿が得られた。次に、この
沈殿粒子を液中から濾別し、エタノールで洗浄し、８０
℃で一晩乾燥し、空気流通過下で５００℃で２時間焼成
した。次いで、水素ガスを用いて４５０℃で２時間還元
した。このようにして得られた超微粒子は、中心部に直
径約４ｎｍのＲｈ超微粒子を１個有し、その周囲が多孔
質のシリカ層で包囲された平均粒子約２０ｎｍの超微粒
子からなるエッグシェル構造のものであり、そのＲｈ含
有量は６．６ｗｔ％であった。このＲｈ超微粒子は、エ
ッグシェル構造を有することから、耐熱性のすぐれたも
ので、８００℃で加熱しても、Ｒｈ超微粒子のシンタリ
ングは実質的に生じなかった。EXAMPLE 1 34 parts by weight of an aqueous solution containing rhodium chloride (RhCl 3 ) at a concentration of 0.38 mol / dm 3 was added at a temperature of 50 ° C. to 0.5 mol / dm of polyoxyethylene (15) cetyl ether.
The resulting mixture was added to 1 part by weight of a cyclohexane solution containing a concentration of 3 and stirred to form a water-in-oil type microemulsion.
Next, 0.15 parts by weight of hydrazine hydrate was added to and mixed with the microemulsion to form ultrafine particles composed of a Rh / N 2 H 4 complex. Next, 7 parts by weight of tetraethylorthosilicate (TEOS) and 28 wt.
% Aqueous ammonia at 50 ° C. and mixed.
OS hydrolysis and polycondensation were performed. Thereby, Rh /
A precipitate containing N 2 H 4 ultrafine particles was obtained. Next, the precipitated particles are filtered out of the liquid, washed with ethanol,
C. overnight, and calcined at 500.degree. C. for 2 hours under flowing air. Next, reduction was carried out at 450 ° C. for 2 hours using hydrogen gas. The ultrafine particles thus obtained have one Rh ultrafine particle having a diameter of about 4 nm at the center, and an egg shell composed of ultrafine particles having an average particle size of about 20 nm surrounded by a porous silica layer. It had a structure, and its Rh content was 6.6 wt%. Since the Rh ultrafine particles have an egg shell structure, they have excellent heat resistance. Even when heated at 800 ° C., sintering of the Rh ultrafine particles did not substantially occur.
【００１１】比較例１ 実施例１において、界面活性剤としてポリオキシエチレ
ン（５）−ｐ−ノニルフェニルエーテルを用いた以外は
同様にして実験を行った。この場合に得られた粒子は、
比較的大きな直径（平均粒径：約３００ｎｍ）を有し、
エッグシェル構造のものではなく、シリカ粒子中に多数
のＲｈ超微粒子が分散した構造のもので、そのＲｈ含有
量は１．３ｗｔ％であった。Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that polyoxyethylene (5) -p-nonylphenyl ether was used as a surfactant. The particles obtained in this case are:
Has a relatively large diameter (average particle size: about 300 nm),
Rather than having an egg shell structure, it had a structure in which a number of Rh ultra-fine particles were dispersed in silica particles, and the Rh content was 1.3 wt%.
【００１２】なお、界面活性剤として他のもの、例え
ば、ポリオキシエチレン（２３）ラウリルエーテル、セ
チルトリメチルアンモニウムブロミド、ナトリウムビス
（２−エチルヘキシル）スルホサクシネート等を用いた
場合にも、エッグシェル構造の超微粒子は得られず、前
記比較例１で得られたのと同様の構造の粒子が得られる
だけであった。Incidentally, when other surfactants such as polyoxyethylene (23) lauryl ether, cetyltrimethylammonium bromide, sodium bis (2-ethylhexyl) sulfosuccinate and the like are used, an egg shell structure is also used. Was not obtained, and only particles having the same structure as that obtained in Comparative Example 1 were obtained.
【００１３】[0013]
【発明の効果】本発明の貴金属超微粒子は、その周囲が
シリカ層で被覆されたエッグシェル構造のものであるた
め、高い熱安定化を有し、８００℃程度の高温に加熱し
てもシンタリングを殆んど生じない。従って、本発明の
貴金属超微粒子は、耐熱性の良い貴金属触媒として有利
に用いることができる。The precious metal ultrafine particles of the present invention have a high heat stabilization because they have an egg shell structure whose periphery is covered with a silica layer. Almost no rings. Therefore, the noble metal ultrafine particles of the present invention can be advantageously used as a noble metal catalyst having good heat resistance.
Claims (4)
をシリカ層で包囲してなるエッグシェル構造を有する貴
金属超微粒子。1. Noble metal ultrafine particles having an egg shell structure in which noble metal ultrafine particles are used as a core material and the periphery thereof is surrounded by a silica layer.
ある請求項１の貴金属超微粒子。2. The noble metal ultrafine particle according to claim 1, wherein the noble metal ultrafine particle has a particle size of 1 to 10 nm.
求項１又は２の貴金属超微粒子。3. The noble metal ultrafine particle according to claim 1, wherein the noble metal ultrafine particle is metal rhodium.
子からなる貴金属触媒。4. A noble metal catalyst comprising the noble metal ultrafine particles according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07146998A JP4200202B2 (en) | 1998-03-05 | 1998-03-05 | Noble metal ultrafine particles with egg shell structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07146998A JP4200202B2 (en) | 1998-03-05 | 1998-03-05 | Noble metal ultrafine particles with egg shell structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11246227A true JPH11246227A (en) | 1999-09-14 |
| JP4200202B2 JP4200202B2 (en) | 2008-12-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07146998A Expired - Fee Related JP4200202B2 (en) | 1998-03-05 | 1998-03-05 | Noble metal ultrafine particles with egg shell structure |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006064684A1 (en) * | 2004-12-14 | 2006-06-22 | Nissan Motor Co., Ltd. | Catalyst, exhaust gas clarifying catalyst, and method for producing catalyst |
| JP2007229594A (en) * | 2006-02-28 | 2007-09-13 | Nissan Motor Co Ltd | Catalyst for cleaning exhaust gas and its manufacturing method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101591640B1 (en) | 2014-10-13 | 2016-02-05 | 한림대학교 산학협력단 | Core containing platinum nanodots assemblies and silica shell nanoparticles and synthetic method thereof |
| KR101877262B1 (en) * | 2016-10-26 | 2018-07-11 | 한림대학교 산학협력단 | Assemblies of Au and core-shell Au/Pt Nanoparticles within Silica Nanotubes and synthetic methods thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006064684A1 (en) * | 2004-12-14 | 2006-06-22 | Nissan Motor Co., Ltd. | Catalyst, exhaust gas clarifying catalyst, and method for producing catalyst |
| JP2008212935A (en) * | 2004-12-14 | 2008-09-18 | Nissan Motor Co Ltd | Catalyst for purification of exhaust gas |
| JP4631934B2 (en) * | 2004-12-14 | 2011-02-16 | 日産自動車株式会社 | Exhaust gas purification catalyst |
| US8080494B2 (en) | 2004-12-14 | 2011-12-20 | Nissan Motor Co., Ltd. | Catalyst, exhaust gas purifying catalyst, and method of producing the catalyst |
| JP2007229594A (en) * | 2006-02-28 | 2007-09-13 | Nissan Motor Co Ltd | Catalyst for cleaning exhaust gas and its manufacturing method |
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| Publication number | Publication date |
|---|---|
| JP4200202B2 (en) | 2008-12-24 |
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