TW200427505A

TW200427505A - Unary or multiple metal colloid and method of producing , unary or multiple metal colloid

Info

Publication number: TW200427505A
Application number: TW93104412A
Authority: TW
Inventors: Naoki Toshima; Yukihide Shiraishi; Hisayoshi Mukai; Toru Matsushita; Mamoru Mizogami
Original assignee: Tanaka Precious Metal Ind; Naoki Toshima
Priority date: 2003-02-28
Filing date: 2004-02-23
Publication date: 2004-12-16
Also published as: JP4145166B2; TWI314475B; WO2004076104A1; JP2004263222A

Abstract

The present invention provides a unary or multiple metal colloid comprising nanoparticles consisting of one or more metal species, and one or more protective agents for protecting the nanoparticles, characterized in that the protective agents are a lower molecular weight material having one or more static groups and molecular weight of 30-5000. As the static groups contained in the protective agents, any of carboxyl group, amino group, sulfo group, phosphoric acid group, silic acid group, or boric acid group is preferable.

Description

200427505200427505

【發明所屬之技術領域】凡系或多元系金屬膠體溶液及本發明係有關於一種一其製造方法。【先前所陶瓷等態，一所謂奈多的原應用於製造則雖的，而料電池以構成的理由的原子應用膠到期待作下觀點原子凝是多元技術】謂金屬的微小般習知米粒子子所形觸媒、正在研一般認其中作用觸媒膠體的 ° 一般態或分體的觸〇為膠體 :作為聚者，系金屬膠體係指將不粒子（奈米粒者係使用液體係指並非單原成的奈米級之光學·電氣· 討中.。為膠體應用於為受到期待的、汽車用廢氣奈米粒子作為認為載持奈米子態金屬之觸媒，藉由今後溶於溶劑的1〜lOOnm的金屬、子）分散、懸浮於溶劑中的狀作為溶劑的膠體溶液。此處，子，而是由2原子、3原子或更群體。金屬膠體係對於近年來兹〖生材料的各種領域的材料之各種材料之製造是相當有用領域之一，可舉出：應用於燃處理觸媒等的觸媒。此係基於觸媒粒子而能夠載持於載體上粒子的觸媒顯示出和載持先前媒有不同的反應行為。因而，的研究來找出更優異的特性受對於觸媒的製造是有效的另一個理膠體中的奈米粒子，利用作成複數種 =夠很容易地製造多元系金屬觸媒、特另化的觸媒。例如，在汽車等所使用的肩[Technical field to which the invention belongs] Any or multiple metal colloidal solution and the present invention relate to a method for manufacturing the same. [The ceramic isomorphism previously described is a kind of so-called Nido's original application in manufacturing, but the atomic coagulation is expected to be a multi-technology based on the atomic composition of the battery for the reason of the composition] It is called the tiny conventional rice particles of metal. The catalyst in the form of a particle, which is currently being researched, generally recognizes the role of the catalyst colloid. The general or split contact is colloid: as a polymer, the metal colloid system refers to the non-particles (nano-particles use the liquid system to indicate that they are not Nano-grade optical, electrical, and optical components under discussion ... For colloidal applications. Nanoparticles for automotive exhaust gas are expected to be used as catalysts that support nanoscale metallic metals. They will be dissolved in solvents in the future. A colloidal solution of 1 to 100 nm of metal as a solvent dispersed and suspended in a solvent. Here, the child is composed of 2 atoms, 3 atoms, or groups. Metal glue systems have been one of the most useful fields for the production of various materials in various fields of raw materials in recent years. Examples include catalysts used in fuel processing catalysts. This system is based on catalyst particles, and the catalysts capable of supporting particles on the carrier show different reaction behaviors from the previous catalysts. Therefore, the research to find out more excellent properties affected by nano particles in another colloid that is effective for the manufacture of catalysts, using a plurality of types = enough to easily produce multi-metal catalysts, special catalyst. For example, shoulders used in cars, etc.

200427505 五、發明說明（2) 氣處理觸媒方面，近年來，係藉由在具有觸媒作用的翻粒、铑二?系觸媒。此在廢氣處理觸媒的使用過程配置者鍺粒子，由於夠抑制粒子成長之故。並且，^二f鉑粒子的移動，而能為有望使用鈾/釕二元系觸媒/此電池用觸媒，被認著具有親水性的釕，利用將屬;^自粒子的近傍配置 OH—將吸附於鉑上之一氧化浐:至屬s金化，與釕結合的於燃料氣體中的一氧化碳之二、毒去除，目而能夠防止基然而，對於金屬膠體，一妒孫: 合物。所謂保護劑係指在金屬‘體二為保護劑的化化學或物理性的結合、吸附之於奈未粒子的周邊以的凝臂，廿祕座丨a物’抑制奈米粒子之間即，，由二：:ΐ徑分布於適性範圍内使之穩定化者。亦態，：===劑1=粒徑的奈米粒子保持懸浮狀增大觸媒的有效表面iv、s小觸媒粒子的粒徑，而儘可能膠體溶的^姥;體的穩定性加以研討，確認此 i二以製造廢氣淨化觸媒時，可確認此廢氣相當穩定（i昭中粒子成長亦不致發生而 )。、寻]2000 279818 以及特開2〇〇〇一279824 ㈣先前的膠體對於粉末載體的吸附性雖為良好，仁對於施仃搪竟（可沖洗襯套）的蜂嵩式載體，則顯然有第8頁 2169-6175-PF(N2);Tcshiau.ptd 200427505 五、發明說明（3) 吸附困難的問題。使用吸附迷户媒的情形，則不但製造出活性二膠體溶液來製造觸效率降低。足的觸媒而且觸媒的製造本發明係在如上的背景下所研一種對於包含保護劑的膠體，不^ ，、目的在於提供性良好的膠體。戰體種類之不同而吸附【發明内容】諸位本發明者，於先前的膠，不同致吸附性不同的原因加以、；因载體的種類之係基於載體的細孔徑、與含有# =；；，則達成以下結論：小之間的關係。㈣，於：ί:體的大保護劑包圍的狀態懸浮著（以不米粒子係以被保護劑之間的結合體稱為膠體粒子；米= = 的細孔係比保護劑的大小還大的孔徑之細：體入 : = 載體的種類…粉末載體的細形，於粉末載體，膠體粒子先前膠體的情體則無法滲入細孔致吸附性很差^ 、、田〒，但對於搪瓷載諸位本發明者認為，作為即附性的膠體，必須得到由甚至失入^ _ -亦具有吸粒子所形成的膠體。此處；：細孔大小⑽ 可說係以如pvp的高分子材料Λ本、> 體所應用的保護劑士 LU . 门刀子材科為主，膠體粒子的大小亦較大。因此’諸位本發明者為了控制膠體粒子的大小，將保第9頁 2169-6175-PF(N2);Tcshiau.ptd 200427505 五、發明說明（4) 護劑的分子量控制在適當的範圍内，藉此可得到由甚至可滲入微小細孔的膠體粒子所形成的膠體。亦即，本發明係一種一元系或多元系金屬膠體，由一種或二種以上的金屬種所形成的奈米粒子、以及保護前述奈米粒子之一種或二種以上的保護劑，而對於由此奈米粒子與保護劑所形成的一元系或多元系金屬膠體，其特徵在於：前述保護劑係具有一個以上的靜電性基，分子量為 3 0〜5 0 0 〇的低分子量材料。本發明係藉由將保護劑作成低分子材料以減小膠體粒200427505 V. Description of the invention (2) In terms of gas treatment catalysts, in recent years, it has been used to turn the grains and rhodium difluoride catalysts that have catalyst function. The use of germanium particles in the process of using the exhaust gas treatment catalyst can suppress the growth of the particles. In addition, it is possible to use a uranium / ruthenium binary catalyst / the catalyst for this battery because of the movement of the platinum particles, and it is recognized that it has hydrophilic ruthenium, and it will use the genus; —Plutonium oxide, which is adsorbed on platinum, is satinized, and the carbon monoxide in the fuel gas combined with ruthenium is toxic and removed to prevent radicals. However, for metal colloids, a jealousy: compound . The so-called protective agent refers to the chemical or physical combination of the metal's body two as the protective agent, the condensed arm adsorbed on the periphery of the nano particles, and the ‘a substance’ inhibits the nano particles, that is, From two :: The diameter is distributed in the adaptive range to stabilize it. In a normal state: === agent 1 = nano particles with a particle size that remain suspended increase the effective surface of the catalyst iv, s the particle diameter of the small catalyst particles, and make the colloid as soluble as possible; the stability of the body Examine it and confirm that when i is used to produce exhaust gas purification catalyst, it can be confirmed that the exhaust gas is quite stable (i Zhaozhong particle growth does not occur). , Xun] 2000 279818 and JP 2000-1279824 虽 Although the previous colloid had good adsorption on the powder carrier, Ren has apparently no Page 8 2169-6175-PF (N2); Tcshiau.ptd 200427505 V. Description of the invention (3) The problem of difficult adsorption. In the case of using adsorption medium, not only the active dicolloid solution is produced to reduce the contact efficiency. The present invention is developed under the above background. A colloid containing a protective agent is not intended to provide a colloid with good properties. Different types of warfare and adsorption [Summary of the invention] The inventors of the present invention, in the previous gel, different reasons for different adsorptivity; because the type of carrier is based on the pore size of the carrier, and contains # = ;; , Then the following conclusions are reached: The relationship between small. ㈣，于： ί: The body is surrounded by a large protective agent suspended (the combination of particles protected by the protective agent is called colloidal particles; the pore system of rice = = is larger than the size of the protective agent The fineness of the pore size: body type: = the type of carrier ... the fine shape of the powder carrier. In the powder carrier, the colloidal particles of the colloidal particles cannot penetrate into the pores and cause poor adsorption. The present inventors believe that as a colloidal colloid, it is necessary to obtain a colloid formed by absorbing particles even if it is lost ^ _-here .: pore size ⑽ can be said to be a polymer material such as pvp Λ The protective agent used in this and the body is LU. The main category is Knife, and the size of the colloidal particles is also large. Therefore, in order to control the size of colloidal particles, the inventors will protect the page 9 2169-6175- PF (N2); Tcshiau.ptd 200427505 V. Description of the invention (4) The molecular weight of the protective agent is controlled within an appropriate range, whereby colloids formed by colloidal particles that can even penetrate into minute pores can be obtained. That is, the present The invention is a one-element or multi-element gold Colloid, nano particles formed of one or two or more metal species, and one or two or more kinds of protective agents for protecting the aforementioned nano particles, and for the unitary system or multiple elements formed by the nano particles and the protective agent Is a metal colloid, characterized in that the aforementioned protective agent is a low molecular weight material having one or more electrostatic groups and a molecular weight of 30 to 500. The present invention is to reduce the colloid by using the protective agent as a low molecular material. grain

子的大小，使能滲入微小細孔中，並能吸附於具有該細孔的載體。此處，為了製成具有作為本發明目的的特性之膠體’保護劑的分子量需要在3 0〜5 0 0 〇的範圍内。若為5 〇〇〇以上’膠體粒子整體的大小則較大，滲入微小細孔中有所困難。因此，以上的靜電子或陽離子有防止奈米中’要求靜是藉由保護力，而能夠作為此磷酸基、石夕斥力的觀點有關本發明的膠體之保護劑必須至少具有一個性基。所謂靜電性基係在溶劑中具有作為陰離的行為之官能基。如上述，對於保護劑，雖也粒子之間凝聚、粗大化的目的，但在本發明電性基的情形係為了更有效地達到此目的。即劑具有靜電性基，使在保護劑之間產生排斥抑制奈米粒子的凝聚。種保護劑的靜電性基，係羧基、氨基、礓美、酸基以及硼酸基之中任一種較佳。並且「由排看來’保護劑所含的靜電性基的數目也是多者The size of the ion allows penetration into the minute pores and can be adsorbed on the carrier having the pores. Here, in order to make the colloidal 'protective agent having the characteristics which are the object of the present invention, the molecular weight needs to be in the range of 30 to 500. If it is 5,000 or more, the size of the entire colloidal particles is large, and it is difficult to penetrate into the minute pores. Therefore, the above electrostatic particles or cations are required to prevent nano-particles from being protected by the protective force, and can be used as the phosphate group and the stone repulsive force. The protective agent for the colloid of the present invention must have at least one sex group. The electrostatic group has a functional group which acts as an anion in a solvent. As described above, the protective agent has the purpose of agglomeration and coarsening between particles, but in the case of the electric group of the present invention, it is to achieve this purpose more effectively. That is, the agent has an electrostatic group, which repels the protective agent and suppresses the aggregation of nano particles. The electrostatic group of the protective agent is preferably any one of a carboxyl group, an amino group, an amiami, an acid group, and a boric acid group. And "from the point of view, the number of electrostatic groups contained in the protecting agent is also large.

200427505 五、發明說明（5) 為較佳，具有二個以上的靜電性基者為較佳。於具備以上的低分子量、靜電性基的存在之條件的本發明，作為適當的保護劑之具體實例，可舉出：檸檬酸、磷酸、酒石酸、琥珀酸、多磷酸、雜多酸、矽酸、硼酸、 N -（2-乙酿胺基）-亞氣基二乙酸、乙快二魏酸、氣基酸、N-乙醯甘氨酸、N-乙醯基-L-賴氨酸、己二酸、草酸、順丁烯二酸、乙二胺四乙酸、2-氨基-2-曱基丁二酮酸、2 -氨基-4-甲基戊二酮酸、8 -氨基-1-萘酚基-3,6 -二磺酸、氨基丁二酸、壬二酸、苯-1，2, 3 -三羧酸、丁基丙二酸、泛酸、樟腦酸、N-节酯基-L-氨基丁二酸、S-魏曱基-L-半胱氨酸、檸苹酸、檸嗉酸、1，1-環己烷二乙酸、 1，2 -環己烷二胺-N，N，N’，N’-四乙酸、1,2 -環己烷二甲酸、1，4-環己烷二甲酸、二乙撐三胺五乙酸、苯醯酒石酸、2, 2 -二甲基戊二酸、2, 4 -二甲基戊二酸、3, 3 -二甲基戊二酸、鄰苯二曱酸、對苯二甲酸、戊二酸、2，2 -二甲基琥珀酸、2，3 -二曱基琥珀酸、2，2 ’ -二硫代二乙酸、5，5 ’ -二硫代雙（2 -硝基苯曱酸）、苯甲酸、2，2 ’ -二硫代水揚酸、水楊酸、乙二氧撐雙（乙胺）-N，Ν，Ν’，Ν’ -四乙酸、谷氨酸、六氟戊二酸、η- (2 -羥乙基）-乙二胺三乙酸、 5 -羥基間苯二甲酸、間苯二甲酸、順丁烯二酸、蘋果酸、丙二酸、酼基琥珀酸、Ν-甲基亞氨二乙酸、黏酸、3-硝基鄰苯二曱酸、草醋酸、2, 2’ -羥基二乙酸、庚二酸、2 -氧代戊二酸、三乙酸胺、5 -續基水揚酸、牛續酸、或是這些酸的驗金屬鹽或錢鹽、或是1，1’-聯-2 -奈酸、4，4 -聯苯二200427505 V. Description of the invention (5) is better, and those with more than two electrostatic bases are better. Specific examples of suitable protective agents in the present invention having the above-mentioned conditions of low molecular weight and the presence of an electrostatic group include citric acid, phosphoric acid, tartaric acid, succinic acid, polyphosphoric acid, heteropolyacid, and silicic acid. , Boric acid, N- (2-ethylamino) -acrylidene diacetic acid, ethanedioic acid, gas-based acid, N-acetamidine glycine, N-acetamyl-L-lysine, adipic acid Acid, oxalic acid, maleic acid, ethylenediaminetetraacetic acid, 2-amino-2-fluorenylbutanedioic acid, 2-amino-4-methylglutaric acid, 8-amino-1-naphthol -3,6-disulfonic acid, aminosuccinic acid, azelaic acid, benzene-1,2,3-tricarboxylic acid, butylmalonic acid, pantothenic acid, camphoric acid, N-benzyl ester-L- Aminosuccinic acid, S-weisyl-L-cysteine, citrate, citrate, 1,1-cyclohexanediacetic acid, 1,2-cyclohexanediamine-N, N, N ' , N'-tetraacetic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diethylenetriaminepentaacetic acid, phenyltartaric acid, 2, 2-dimethylglutaric acid, 2, 4-dimethylglutaric acid, 3, 3-dimethylglutaric acid, phthalic acid, terephthalic acid, glutaric acid Acid, 2,2-dimethylsuccinic acid, 2,3-difluorenylsuccinic acid, 2,2'-dithiodiacetic acid, 5,5'-dithiobis (2-nitrophenylarsinic acid) ), Benzoic acid, 2,2'-dithiosalicylic acid, salicylic acid, ethylenedioxanebis (ethylamine) -N, N, N ', N'-tetraacetic acid, glutamic acid, hexafluoro Glutaric acid, η- (2-hydroxyethyl) -ethylenediamine triacetic acid, 5-hydroxyisophthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, fluorenylsuccinic acid , N-methyliminodiacetic acid, mucinic acid, 3-nitrophthalic acid, oxalic acid, 2, 2'-hydroxydiacetic acid, pimelic acid, 2-oxoglutaric acid, triacetamide , 5-salicyl salicylic acid, tauric acid, or metal or salt salts of these acids, or 1,1'-bi-2-nanoic acid, 4,4-biphenyl dicarboxylic acid

2169-6175-PF(N2);Tcshiau.ptd 第11頁 200427505 五、發明說明（6) 醇 N，『~雙（2-氨乙基）-1，3 基）甲胺、癸二酸基己酯）、2, 2 -雙二脲、1，丁二醇胺、Ν，Ν- 中的保護劑並且，明的金屬膠中的金屬離具有還原作保護劑於溶製程。於本可舉出··擰鹽、EDTA · 作為構有關本發明金、釕、鍺且，此金屬鋇、鈽、鍅银、獨、鉞由上述金屬而成。有關本是水與有機劑加以混合可為單保護劑體，雖子還原用的情劑中則發明中檬酸鈉二納鹽成奈米的金屬、銥、種亦可、鈦、。有關之一種以旦以製成形，藉能夠製，作為、删氫粒子的膠體的鐵、鐵以下列釩、鈮本發明所形成乙氧基乙酯）基）-2, 2,，2, 丁二醇、1，4-可為含有複數原作用較佳。將金屬鹽溶解奈米粒子來加由在溶劑中未成奈未粒子，具有適當的還化鈉、Ν -甲基、癸二，-氮川丁二醇種的保如後述於溶劑以製造使用還因而能原作用吡咯烷雙（3〜氨丙酸雙（2〜乙三乙醇、聯。金屬膠體護劑。，有關本發中，使溶劑而保護齊|J 原劑而添加夠簡化膠體之保護劑，酮、草酸金屬種雖無特別限定用途，則可舉出··麵、鈷、鎳、銅、銦為金屬來構成··錳、銘、鈕、銖、鋅、鍺、的金屬膠體的奈米粒之外’亦可由複數種，但若考慮、鈀、銀、較佳。並、銷、嫣、錫、録、子係除了僅金屬種凝聚發明的溶劑所 ’藉由膠體之製造方法係，由貴金形成的混合溶劑，將此混合添加還原劑於此溶液中，還屬鹽與水或溶劑與保護原此貴金屬 200427505 五、發明說明（7) 鹽以作成膠體粒子的方法還原，利用將電極***、+二t +對於，今液中的貴金屬鹽之方法雖也能夠，施行電化學還原的仁猎由添加遥原齊J的士勻的還原處理。並且，I π +定=d的方法，可進行均溶液的電源、、電極、以=1匕學逛原的情形，用以還原液之裝置結構係相當Z其；制裝置：與用以製造膠體溶電流.電壓條件等的讯定氺，丄用以適當地進行還原的具有還原作用的 1:5，；：=力當=再者’對保護劑金屬鹽與保護劑，貝|]能夠製造膠體溶劑來混合此處所添加的還原劑係侧氫化納烷、三曱胺基硼烷為較佳。作，一甲妝基硼因還原力，、在短時間1能原劑理想的理由係並且，作為保護劑，在使用具有上劑時，以保讜密丨丨你么、晉店十，+ I你、作用的保護 W才隻剎作為遇原劑來加以利用，則可僅禾劑，亦可添加還原劑與保護劑兩種。於六…二’、農 :的保濩劑則作為被還原的奈米粒子之保護劑來發揮功 5且’對於溶劑亦可使用具有還原作用的溶劑此種情形的溶劑，可舉出：n，n，_二甲基曱醯胺、乙’，、、甲醇、丙醇、四氫呋喃。 - y因此，對於保護劑、溶劑應用具有還原作用者的愔 =丄即使使還原劑的添加量成為少量（相對於金屬鹽則在 §里X下）仍了還原金屬離子。有關本發明的方法，還2169-6175-PF (N2); Tcshiau.ptd Page 11 200427505 V. Description of the invention (6) Alcohol N, "~ bis (2-aminoethyl) -1,3 group) methylamine, sebacate Esters), 2, 2-bisdiurea, 1, butanediolamine, N, N-, and the metal ion in the clear metal glue has a reduction process as a protective agent. Examples of the present invention include salt, EDTA, and the like. The present invention relates to gold, ruthenium, and germanium, and the metals barium, osmium, osmium silver, solium, and osmium are made of the above metals. It is related to the fact that water and organic agents can be mixed as a single protective agent, although in the case of ion reduction, the sodium, sodium citrate, di-nano salt, nano-metals, iridium, titanium, and titanium can also be used in the invention. The related one is made of dendrite, which can be made into colloidal iron and iron which are hydrogen particles, and the following vanadium and niobium are formed by the following ethoxyethyl esters of the present invention: (2), 2 ,, 2, butane Diol and 1,4- may have multiple primary effects. The metal salt is dissolved in the nano particles to add the non-nano particles in the solvent, and the appropriate sodium sulfide, N-methyl, sebac, and azabutanediol are as described below in the solvent for production and use. It can act as pyrrolidine bis (3 ~ amino propionate bis (2 ~ ethylene triethanol, hydrazone. Metal colloid protective agent.) In the present invention, it is necessary to protect the solvent and protect it | J The original agent is added to simplify the colloidal protective agent Although metal ketones and oxalic acids are not particularly limited in use, they can be made of metal, metal, colloid, nickel, copper, indium, etc. A variety of rice grains can also be used in multiple species, but if considered, palladium, silver, and more are preferred. In addition to the solvent of the invention that condenses only metal species, the colloidal production method is used, A mixed solvent formed of precious gold, and the reducing agent is added to this solution, which is also a salt and water or a solvent and protection of the precious metal 200427505 V. Description of the invention (7) The method of reducing salt to form colloidal particles, using the electrode Insert + + T + For the method of precious metal salts in this solution, although the method of electrochemical reduction is performed by adding Shihara of Haruka Harahara J. and the method of I π + fixed = d, It can be used for the solution of the power source, electrode, and solution of the solution. The structure of the device used to reduce the liquid is equivalent; the manufacturing device: It is used to determine the current of the colloid and the voltage conditions.丄 1: 5 with a reducing effect for proper reduction;: = Lidang = Further, the metal salt of the protective agent and the protective agent, bei |] can produce a colloidal solvent to mix the reducing agent added here The side hydride and triammonium borane are more preferred. The reason why monomethyl boron is ideal due to its reducing power and the ability to act as an energetic agent in a short period of time is that, as a protective agent, it has an upper agent. At the time, you must keep the secret 丨丨 you, Jindian ten, + I you, the role of protection W can only be used as the original agent, you can only use the agent, you can also add reducing agents and protective agents two于 ... 二 ', Nong's tincture is used as a protective agent for the reduced nano particles Solvents that perform work 5 and 'can also be used with solvents that have a reducing effect. In this case, n, n, -dimethylamidamine, ethyl',, methanol, propanol, tetrahydrofuran.- Therefore, 愔 = 丄 for those who have a reducing effect for protective agents and solvents, even if the amount of reducing agent added is small (under X in § relative to metal salts), the metal ions are still reduced. Regarding the method of the present invention, also

原劑的添加量以範圍較佳。配成金屬鹽的500分之1當量〜1〇倍當量的再者 > 、拄沾a p ’對於作為成為原料的金屬鹽，作為製造鉑膠體日守的金屬鴎r &扣石肖美—^義可應用：六氯合麵酸、二硝基二氨合翻、二二水人^合翻确酸鹽、順—二氨二水合鉑硝酸鹽、反—二氨 =、自確酸鹽、四亞硝酸根合鉑酸、四酸、順〜一占 — 氧B®肖基一水合鉑、四氨合鉑氫氧鹽、六氨合鉑氫化翻，化四氣合翻、氣化六氨合翻、六經基合翻酸、氧、氯化亞麵、氯化鉑、四氯合鉑酸卸。作為製造把膠體時的金屬鹽，可應用：氯化鈀、四亞 ^ ^合鈀酸、硝酸鈀、二氯二氨合鈀、四氨合鈀硝酸二&氯化四氨合鈀、四氨合鈀氫氧鹽、反—二水二氨合鈀 f |、二硝基二氨合鈀、雙（乙撐二氨）合鈀硝酸鹽、水（乙樓二氣）合把硝酸鹽。八作為製造金膠體時的金屬鹽，可應用：氣金酸、氰化至（111 )鉀、氰化金鉀、四氨合金硝酸鹽、四硝酸根合金叙鹽、二水（1，1 〇 —菲繞啉）合金硝酸鹽。The amount of the original agent added is preferably in the range. 1/500 equivalent to 10 times the equivalent of the metal salt is formulated, >, 拄 ap 'For the metal salt used as the raw material, as the metal 制造 r & 石石肖美 — ^ Applicable: Hexachlorofacial acid, dinitrodiammine, dihydrazine, heptadiate, cis-diammine dihydrate, platinum nitrate, trans-diammine =, self-acidate , Tetra nitrite platinum acid, tetra acid, cis ~ one-octane — oxygen B® Shawki monohydrate platinum, tetraammine platinum hydroxide, hexaammine platinum hydrogenation, hydration of four gases, hydration of six Ammonia conversion, hexadecyl acid conversion, oxygen, subchloride, platinum chloride, and tetrachloroplatinic acid. As metal salts used in the manufacture of colloids, palladium chloride, tetrachloropalladium acid, palladium nitrate, dichlorodiamine palladium, tetraamminepalladium nitrate di & tetraamminepalladium chloride, Ammonium palladium hydroxide, trans-diammonium diammine palladium f |, dinitrodiammine palladium, bis (ethylene diamine) palladium nitrate, and water (Yellow Gas) combined nitrate. As a metal salt in the production of gold colloids, it can be applied: gas gold acid, cyanide to (111) potassium, gold potassium cyanide, tetraammonium alloy nitrate, tetranitrate alloy salt, dihydrate (1, 1 〇 —Phenanthroline) alloy nitrate.

作為製造銀膠體時的金屬鹽，可應用：氯酸銀、硝酸銀、乙酸銀、乳酸銀。作為製造釕膠體時的金屬鹽，可應用：氣化釕、硝酸釕、四亞硝恭二水合釕、乙酸釕、六氨合釕硝酸鹽、五氨水合釕硝酸费、亞硝基五氨合釕硝酸鹽、羥基亞硝基四氨合釘硝酸鹽。作為製造錄膠體時的金屬鹽，可應用：氣化铑、硝酸As a metal salt for producing a silver colloid, silver chlorate, silver nitrate, silver acetate, and silver lactate can be applied. As metal salts used in the manufacture of ruthenium colloids, it can be applied: gaseous ruthenium, ruthenium nitrate, ruthenium tetranitrosium dihydrate, ruthenium acetate, hexaammine ruthenium nitrate, ruthenium pentaammonium nitrate, nitrite pentaammine ruthenium Nitrate, hydroxynitrosotetraammonium nail nitrate. As a metal salt in the manufacture of colloids, it can be applied: vaporized rhodium, nitric acid

2169-6175-PF(N2);Tcshiau.Ptd2169-6175-PF (N2); Tcshiau.Ptd

200427505 五、發明說明（9) 铑、乙酸铑、五氨水合鍺硝酸鹽、五氨硝基合铑、三水合铑硝酸鹽、六氨水合鍺硝酸鹽。作為製造銥膠體時的金屬鹽，可應用··六氯合銥酸、三氯化銥、六硝基合銥酸、三（草酸根）合銥酸、五氨水合銥石肖酸鹽、破基五氨合銥亞硝酸鹽、六氨合銥硝酸鹽。作為製造鐵膠體時的金屬鹽，可應用氧化餓。作為製造鐵膠體時的金屬鹽，可應用··氯化鐵、硝> 酸200427505 V. Description of the invention (9) Rhodium, rhodium acetate, pentammine hydrated germanium nitrate, pentammine nitrorhodium, trihydrate rhodium nitrate, hexaammonium hydrated germanium nitrate. As the metal salt used in the manufacture of iridium colloids, hexachloroiridium acid, iridium trichloride, hexanitroiridium acid, tris (oxalate) iridium acid, pentaammonium hydrated iridium oxalite salt, Pentammine iridium nitrite, hexaammine iridium nitrate. As a metal salt in the production of iron colloids, oxidation starvation can be applied. As a metal salt for the production of iron colloids, ferric chloride, nitrate > acid can be applied

鐵、富馬酸鐵、葡萄酸鐵、草酸鐵、硫酸鐵、幾基鐵。作為製造鈷膠體時的金屬鹽，可應用：氯化鈷、富馬酸錯、鼠乳化銘、靖酸敍、硫酸始、幾基始。作為製造鎳膠體時的金屬鹽，可應用：乙酸鎳、鎳-乙醯丙酮·二水合物、演化鎳、氯化鎳、氫氧化鎳、硝酸鎳、硫酸鎳。作為製造銦膠體時的金屬鹽，可應用：氯化銦、氫氧化銦、硝酸銦、填酸銦、硫酸錮。並且，對於銦、鎢、鋇、鈽、锆、鈦、釩、鈮、组、銖、鋅、鍺、錫、銻、鉍、硼、鈥的膠體之製造，這些金屬種的氯化物、硝酸鹽、硫酸鹽能夠適用作金屬鹽。Iron, iron fumarate, iron gluconate, iron oxalate, iron sulfate, iron. As metal salts in the manufacture of cobalt colloids, it can be applied: cobalt chloride, fumaric acid, rat emulsified inscription, jing acid, sulfuric acid, and several bases. As the metal salt used in the production of nickel colloids, nickel acetate, nickel-acetoneacetone · dihydrate, evolved nickel, nickel chloride, nickel hydroxide, nickel nitrate, and nickel sulfate can be used. As metal salts used in the manufacture of indium colloids, indium chloride, indium hydroxide, indium nitrate, indium acid filler, and thallium sulfate can be used. In addition, for the manufacture of colloids of indium, tungsten, barium, hafnium, zirconium, titanium, vanadium, niobium, groups, baht, zinc, germanium, tin, antimony, bismuth, boron, and the metal chlorides, nitrates Sulphate can be used as metal salt.

有關本發明的方法，能夠製造一元系膠體、=元系膠體兩種。對於製造多元系膠體的情形，作為溶解於溶劑的金屬鹽，使複數種作為目的之金屬的鹽溶解，藉由同時或依序使溶液中的複數種金屬離子還原，而能夠製造出包含由複數種金屬種所形成的奈米粒子之膠體。又對，製造多元系金屬膠體的情形，亦可各別製造複數種一兀系金屬膠體，再將這些金屬膠體加以混合。亦According to the method of the present invention, two types of colloidal colloids and = elementary colloids can be produced. In the case of producing a multi-component colloid, as a metal salt dissolved in a solvent, a plurality of salts of the intended metal are dissolved, and by reducing the plurality of metal ions in the solution simultaneously or sequentially, it is possible to produce A colloid of nano particles formed by a metal species. In the case of producing a plurality of metal colloids, a plurality of metal colloids may be separately produced, and these metal colloids may be mixed. also

200427505 五、發明說明（10) 即’藉由上述方法而製造複數種包含由不同的金屬種所形成的奈米粒子之金屬膠體，藉由混合所製造的複數種金屬膠體而可將金屬種加以複合化。再者，此處所謂的複合化係指除了使複數種金屬種隨機混合的結構之外，亦包含：複數種金屬種規則地排列混合的狀態，或以一種金屬為中心’其他的金屬包覆著此金屬而形成多層結構的端帶狀。【實施方式】以下對本發明的適合的實施例與比較例一起加以說明。第1實施例：於水中添加1 · 66 X 1 0_2M的氯酸銀溶液2mL、與3. 4 X 10_2M的檸檬酸鈉溶液(K2mL作為保護劑，並加以撥拌，再添加1· 65 X 1〇_2Μ的硼氫化鈉〇· 〇5mL於其中作為還原劑，而得到5 0mL的銀膠體溶液。第2實施例：於水中添加3. 88 X 1 0_2M的氯化铑溶液〇· 87mL、與3. 4 X 1 0_2M的檸檬酸鈉溶液2mL作為保護劑，並加以攪拌，再添加1· 65 X 10_2M的硼氫化鈉lmL於其中作為還原劑，而得到5 OmL的铑膠體溶液。比較例1 :200427505 V. Description of the invention (10) That is, 'the plurality of metal colloids containing nano particles formed by different metal species are produced by the above method, and the metal species can be added by mixing the plurality of metal colloids produced. Composite. In addition, the term "compositing" herein refers to a structure in which a plurality of metal species are randomly mixed, and includes a state in which a plurality of metal species are regularly arranged and mixed, or one metal is the center of the other metal coating. This metal forms an end band shape of a multilayer structure. [Embodiments] Suitable examples of the present invention and comparative examples will be described below. First Example: 2 mL of 1.66 X 1 0_2M silver chlorate solution and 3.4 X 10_2M sodium citrate solution (K2mL as a protective agent were added to water, and then stirred, and then added 1.65 X 1 〇_2M sodium borohydride 〇5mL was used as a reducing agent to obtain 50mL silver colloidal solution. Second Example: 3.88 X 1 0_2M rhodium chloride solution 0.887mL, and 2 mL of 3.4 X 1 0_2M sodium citrate solution was used as a protecting agent and stirred, and then 1.65 X 10_2M sodium borohydride 1 mL was added as a reducing agent to obtain 50 mL of a rhodium colloid solution. Comparative Example 1 :

採取PVP 0.1 476g，R=40，在氮氣流下，添加水3mL 並授拌1 0分鐘。授拌後’添加1. 6 6 X 1 〇-2 Μ的過氯酸銀溶液 2mL· ’再攪拌3〇分鐘。然後加入乙醇45mL於其中作為還原Take PVP 0.1 476g, R = 40, add 3mL of water under nitrogen flow, and mix for 10 minutes. After the instillation, '1.66 X 10-2 M silver perchlorate solution 2 mL ·' was added and stirred for 30 minutes. Then add 45mL of ethanol as a reduction

2169-6175-PF(N2);Tcshiau.ptd 200427505 五、發明說明（ll) 對此溶液以90〜95 °C回流2小時劑，將水：乙醇配成1 ·_ 而得到銀膠體溶液。比較例2 : 抓取PVP 〇.i 476g，r=40，在氮氣流下，添加水、& l、3mL亚授掉1〇分鐘。攪拌後，添加3, 8〇 X π的氯化铑 :8 7mL再稅拌3 0分鐘。然後加入乙醇45mL於其中作 ^還原劑，將水：乙醇配成i : 9。對此溶液以9 〇〜9 5回流2小時而得到鍺膠體溶液。、對於以第1實施例與比較例1所製造的銀膠體，測定對載體、f蜂窩上的搪瓷層）的吸附速度…及附試驗係，加水將銀濃度稀釋至5ppm為止的各別膠體，採取水溶液 1 50mL ’將塗上氧化鋁層的金屬蜂窩式載體（氧化鋁量： 2· 85g )浸潰於此水溶液中。然後，一邊攪拌溶液，一邊在每隔固定時間對溶液取樣並以lcp (感應耦合電漿發射光譜分析）來測定銀濃度。第1圖係表示浸潰載體時的各別溶液之銀濃度的變 =。由此圖可確認，吸附有關第i實施例的銀膠體時的銀濃度之減少速度（亦即銀吸附速度）較諸比較例丨者為更2169-6175-PF (N2); Tcshiau.ptd 200427505 V. Description of the invention (ll) The solution was refluxed at 90 ~ 95 ° C for 2 hours, and water: ethanol was mixed to make 1 · _ to obtain a silver colloid solution. Comparative Example 2: PVP 0.17g was grabbed, r = 40, and water, & 1, 3 mL was added under nitrogen flow for 10 minutes. After stirring, 3,80 x π rhodium chloride was added: 87 mL, and the mixture was stirred for 30 minutes. Then, 45 mL of ethanol was added as a reducing agent, and water: ethanol was formulated into i: 9. This solution was refluxed at 90-95 for 2 hours to obtain a germanium colloid solution. For the silver colloids produced in the first example and comparative example 1, the adsorption rate on the carrier and the enamel layer on the honeycomb f) was measured ... and the additional test system, each colloid was diluted by adding water to a silver concentration of 5 ppm, A 150 mL of aqueous solution was used to immerse a metal honeycomb support (alumina amount: 2.85 g) coated with an alumina layer in this aqueous solution. Then, while stirring the solution, the solution was sampled at regular intervals and the silver concentration was measured by lcp (inductively coupled plasma emission spectroscopy). Figure 1 shows the change in the silver concentration of each solution when the carrier was impregnated. From this graph, it can be confirmed that the decrease rate of the silver concentration (that is, the silver adsorption rate) when the silver colloid of the i-th example is adsorbed is more than that of the comparative examples.

高，並且，約在4小時吸附完成，比起比較例，則吸間更短。 7于It is high and the adsorption is completed in about 4 hours, which is shorter than that in the comparative example. 7 in

2169-6175-PF(N2);Tcshiau.ptd 第17頁 200427505 圖式簡單說明第1圖係表示浸潰載體於第1實施例與比較例1的金屬膠體時的銀濃度之變化的圖。 iiiii 2169-6175-PF(N2);Tcshiau.ptd 第18頁2169-6175-PF (N2); Tcshiau.ptd Page 17 200427505 Brief Description of Drawings Figure 1 is a graph showing changes in the silver concentration when the carrier is impregnated with the metal colloids of the first and comparative examples 1. iiiii 2169-6175-PF (N2); Tcshiau.ptd page 18

Claims

200427505 六、申請專利範圍 "〜 -- I二種一元系或多元系金屬膠體，係由一種或二種以上的至屬種所形成的奈米粒子、以及保護前述奈米粒子之所3 ίί以ί:,蠖劑’❿對於由此奈米粒子與保護劑元系金屬膠體，其*徵在於··前述保農训係八有一個以上的靜電性基，分子量為30〜5000的低分子量材料。 2. 如申請專利範圍第1項所述的一元系或多元系金屬膝體，其中保護劑所包含的靜電性基係魏基、氨基、石黃基、磷酸基、矽酸基以及硼酸基之中的任一種。 3. 如申請專利範圍第1或2項所述的「凡系或多元系金屬膠體，其中保護劑係檸檬酸、磷酸、/酉石酸、琥珀酸、多磷酸、雜多酸、矽酸、硼酸、Ν-（ 2—乙醯，基）—亞氨基二乙酸、乙炔二羧酸、氨基酸、Ν一乙醯甘氨酸、Ν-乙醯基-L_賴氨酸、己二酸、草酸、順丁烯一酸、乙二胺四乙酸、2-氨基-2-曱基丁二酮酸、2-氨基一4_曱基戊二酮酸、 8-氨基-1-萘酚基-3, 6-二磺酸、氨基丁二酸、壬二酸、苯 -1，2, 3_三羧酸、丁基丙二酸、泛酸、樟腦+酸、N—苄酯基 -L-氨基丁二酸、S-羧甲基—L-半胱氨酸、挣苹酸、檸嗪酸、1，1-環己烷二乙酸、1，2-環己烷二胺—N，N，N’，N’一四乙酸、1，2-環己烷二曱酸、1，4-環己炫二T酸、二乙樓三胺五乙酸、苯醢酒石酸、2, 2-二甲基戍一酉夂、2, 4 —二曱基戊二酸、3, 3-二甲基戊二酸、鄰苯二甲酸、對苯二甲酸、戊二酸、2, 2-二甲基琥珀酸、2, 3-二甲基+琥珀酸、2, 2’ 一二硫代二乙酸、5，5，-二硫代雙（2 -硝基苯甲酸）、苯甲200427505 VI. Scope of Patent Application " ~-I Two types of mono- or polymetallic colloids, which are nano particles formed by one or two or more genus species, and the place to protect the aforementioned nano particles 3 ίί With ί :, 蠖剂 '❿ For this nano particle and protective agent element metal colloid, the * sign is that the aforementioned agricultural training department has a low molecular weight material with more than one electrostatic group and a molecular weight of 30 to 5000. . 2. The mono- or multi-metallic knee as described in item 1 of the scope of the patent application, wherein the electrostatic group contained in the protective agent is the group of weicyl, amino, xanthophyll, phosphate, silicic acid, and boric acid. Any of them. 3. As described in item 1 or 2 of the scope of the application for patent, "every or polymetallic colloids, wherein the protective agents are citric acid, phosphoric acid, ocheric acid, succinic acid, polyphosphoric acid, heteropolyacid, silicic acid, Boric acid, N- (2-acetamidine) -iminodiacetic acid, acetylene dicarboxylic acid, amino acid, N-acetamidine glycine, N-acetamyl-L_lysine, adipic acid, oxalic acid, cis Butene monoacid, ethylenediaminetetraacetic acid, 2-amino-2-fluorenylbutanedioic acid, 2-amino-4-fluorenylglutaronic acid, 8-amino-1-naphthol-3, 6 -Disulfonic acid, aminosuccinic acid, azelaic acid, benzene-1,2,3-tricarboxylic acid, butylmalonic acid, pantothenic acid, camphor + acid, N-benzyl ester-L-aminosuccinic acid , S-carboxymethyl-L-cysteine, malic acid, citrazine, 1,1-cyclohexanediacetic acid, 1,2-cyclohexanediamine—N, N, N ', N 'Tetraacetic acid, 1,2-cyclohexanediacetic acid, 1,4-cyclohexanedicarboxylic acid, diethyltriaminepentaacetic acid, phenylartaric acid, 2,2-dimethylarsine , 2, 4-Difluorenylglutaric acid, 3, 3-dimethylglutaric acid, phthalic acid, terephthalic acid, glutaric acid, 2, 2- Methyl succinic acid, 2,3-dimethyl succinic acid + 2, 2 'one dithiophosphoric acid, 5,5, - dithiobis (2 - nitrobenzoic acid), benzyl

2169-6175-PF(N2);Tcshiau.ptd 第19頁 2004275052169-6175-PF (N2); Tcshiau.ptd Page 19 200427505

六、申請專利範圍酸、2，2 ’ -二硫代水楊酸、水揚酸、乙二氧撐雙（乙胺）6. Scope of patent application Acid, 2,2'-dithiosalicylic acid, salicylic acid, ethylenedioxane (ethylamine)

-Ν，Ν，Ν’，Ν’ -四乙酸、谷氨酸、六氟戊二酸、η- (2-羥乙基）—乙二胺三乙酸、5 -羥基間苯二甲酸、間苯二甲酸、順丁稀一酸、韻果酸、丙二酸、魏基破拍酸、曱基亞乳二乙酸、黏酸、3〜頌基鄰苯二曱酸、草醋酸、2，2，-羥基二乙酸、庚二酸、2 —氧代戊二酸、三乙酸胺、5〜磺基水揚酸、牛磺酸、或是這些酸的鹼金屬鹽或銨鹽、或是1，1，〜聯-2 -萘紛、4, 4—聯苯二醇、Ν，Ν，—雙（2一氨乙基）1 3 丙二胺、Ν，Ν-雙（3_氨丙基）甲胺、癸二酸雙（2〜乙氧乙醋，）、癸二酸雙（2-乙基己酯）、2, 2-雙（羥甲基^基 -2, 2’，2’ ’ -氮川三乙醇、聯二脲、ι 3_ 丁二醇、l 醇、1，4- 丁二醇。 Γ 二 4·如申請專利範圍第1、2或3項所述的一元系或客一系金屬膠體，*中至少-種保護劑具有還原能力。％膠體5: 利Ξ圍Γ項所述的一元系或多元系金屬 ^ LL八中至夕一種保護劑係檸檬酸鈉、硼氳化鈉、t 基吡咯烷酮、草酸鹽、EDTA ·二鈉鹽。 p ΐΐί專利範圍第卜2、3、4或5項所述的一元奉或夕凡糸金屬膠體，其中金屬種係翻、鈀、銀、糸-N, N, N ', N' -tetraacetic acid, glutamic acid, hexafluoroglutaric acid, η- (2-hydroxyethyl) -ethylenediaminetriacetic acid, 5-hydroxyisophthalic acid, m-benzene Dicarboxylic acid, maleic acid, rhodopic acid, malonic acid, weicyl acetic acid, fluorenyl lactic acid, mucoic acid, 3 ~ sodium phthalic acid, oxalic acid, 2, 2, -Hydroxydiacetic acid, pimelic acid, 2-oxoglutaric acid, amine triacetate, 5 ~ sulfosalicylic acid, taurine, or alkali or ammonium salts of these acids, or 1, 1 , ~ Bi-naphthalene, 4, 4-biphenyldiol, Ν, Ν,-bis (2-aminoaminoethyl) 1 3 Propanediamine, Ν, Ν-bis (3-aminopropyl) methyl Amine, sebacic acid bis (2 ~ ethoxyethyl acetate,), sebacic acid bis (2-ethylhexyl), 2, 2-bis (hydroxymethyl ^ -2, 2 ', 2' '- Nitrogen triethanol, biuret, i-butanediol, l-alcohol, 1,4-butanediol. Γ ２ · The unitary system or the unitary system described in item 1, 2 or 3 of the scope of patent application Metal colloids, at least one of the protective agents in * has reducing ability.% Colloid 5: Mono- or polymetallic metals as described in the item Γ Ξ LL 八A protective agent from mid to late is sodium citrate, sodium boronate, t-pyrrolidone, oxalate, EDTA disodium salt. P 范围专利 Monovalent or as described in item 2, 2, 3, 4 or 5 of the patent scope Xifan 糸 metal colloid, among which the metal species are palladium, palladium, silver, 糸

铑、欽、餓、鐵、銘、錄、銅、姻之中的任一種。了 ρ7元範圍第1、2、3、4或5項所述的-元夺或多兀糸金屬膠體，其中金屬種係糸筛、結、鈦、飢、錕、叙、銖、鋅、鍺、錫、錄、Μ鋇' 硼、鈥之中的任一種。 ’Rhodium, Chin, Hungry, Iron, Ming, Lu, Copper, Marriage. The metal colloids described in item 1, 2, 3, 4 or 5 of the range of ρ7 yuan are Yuanyuan or Vultures, in which the metal germplasm is sieve, knot, titanium, starved, hafnium, Syria, baht, zinc, germanium , Tin, Lu, M Barium 'Boron,' any one. ’

ZUU4Z/DUDZUU4Z / DUD

六、申請專利範圍 • 種一元系或多元系舍屬® M 請專利範圍第1、2、3、4、r :體之‘造方法，係如申元系金屬膠體之製造方法，、6或7項所述的一元系或多 ’、特欲在於：將一種咬二種以上的保護劑溶解於溶劑；，鹽與-種或二劑中的溶液；衣^金屬離子分散於溶以還原前述金屬離子並作添加還原劑於前述溶液中成奈米粒子。6. Scope of patent application • Kinds of mono- or multi-system genus ® M Please refer to patent scopes 1, 2, 3, 4, and r: the method of making the body, such as the method of making metal colloids of the Shenyuan system, 6 or The unitary system or more described in item 7, the special purpose is: dissolving one or more protection agents in a solvent; a solution of salt and one or two agents; dispersing metal ions in a solution to reduce the foregoing Metal ions are added as reducing agents to form nano particles in the aforementioned solution.

膝體9之:利ίΐΓ:所種述广-元系或多元系金屬 ,λτ /、甲至V 一種保護劑係檸檬酸鈉、硼崖化鈉、Ν-甲基吡咯烷，、草酸鹽、edta •二納鹽。 10.如申請專利範圍第8或9項所述的一元系或多元系、膠體之製造方法，其中還原劑係硼氫化鈉、聯氨、二甲胺基硼烷、三甲胺基硼烷。 / 11.如申請專利範圍第8、9或1 0項所述的一元系或多兀系金屬膠體之製造方法，其中溶劑係N，N，-二甲基甲醯胺、乙醇、曱醇、丙醇、四氳咲喃。Knee 9: Lee ΐΓ: All kinds of broad-elementary or multivalent metals, λτ /, A to V A protective agent is sodium citrate, sodium borate, N-methylpyrrolidine, oxalate Edta • two sodium salt. 10. The method for producing a mono- or multi-component or colloid according to item 8 or 9 of the scope of the patent application, wherein the reducing agent is sodium borohydride, hydrazine, dimethylaminoborane, trimethylaminoborane. / 11. The method for producing a mono- or polymetallic colloid according to item 8, 9 or 10 of the scope of the patent application, wherein the solvent is N, N, -dimethylformamide, ethanol, methanol, Propanol, tetramethylfuran.

1 2 ·如申請專利範圍第8、9、1 〇或i J項所述的一元系或多元系金屬膠體之製造方法，其中添加相對於金屬鹽 5 00分之1當量〜1 〇倍當量的還原劑來還原金屬離子。 1 3 · —種多元系金屬膠體之製造方法，係藉由如申請專利範圍第8、9、1 〇、11或1 2項所述的方法，製造複數種包含由不同的金屬種所形成的奈米粒子之金屬膠體，並藉由混合所製造的複數種金屬膠體而製成將金屬種加以複合1 2 · The method for producing a mono- or multi-metal colloid as described in item 8, 9, 10, or i J of the scope of the patent application, in which 1 to 500 times equivalent to 100 times equivalent of the metal salt is added. Reducing agent to reduce metal ions. 1 3 · — A method for producing a multi-element metal colloid, which is produced by a method as described in item 8, 9, 10, 11 or 12 of the scope of patent application, including a plurality of metal colloids formed by different metal species. Metal colloids of nano particles, and a plurality of metal colloids produced by mixing to compound metal species

2169-6175_PF(N2);Tcshiau.ptd 第21頁 200427505 六、申請專利範圍化的奈米粒子。 inn 2169-6175-PF(N2);Tcshiau.ptd 第 22 頁2169-6175_PF (N2); Tcshiau.ptd Page 21 200427505 6. Patented Nanoparticles. inn 2169-6175-PF (N2); Tcshiau.ptd page 22