TW200538398A - Method of manufacturing metallic nanoparticles - Google Patents

Abstract

This invention provides a method of manufacturing metallic nanoparticles, which uses a chemical compound shown below in formula (I) as a reducing agent to be mixed with a metal salt in a solvent, which is then subject to heating until the reflux of solvent carrying out a reaction; wherein R is selected from a group consisting of C1-6 alkyl, C1-6 alkenyl and C1-6 alkynyl; and n is the integer between 1 to 1,000.

Description

200538398 五、發明說明α) 【發明所屬之技術領域】 本發明係關於一種製造金屬奈米粒子之方法，特別是 一種利用高分子化合物作為還原劑製造金屬奈米粒子之方 法。 【先前技術】 相較於一般金屬微米級粒子，金屬奈米粒子之比表面 積增大（surface-to-volume)、表面能提高、承受壓力 後延展性高、硬度高、比熱大等優良性質，使得金屬奈米 粒子的應用性，在過去十年來倍受以材料導向為主的工業 界及科學界矚目。例如現今以各類型金屬奈米粒子為主的 _丨 催化劑已被應用在多種的催化反應中，且對不飽和碳氫化 合物的催化反應有高轉化率的優點。 根據奈米粒子大小的不同，可有不同的電子能帶組態 (size-dependent property)，進而影響其物理及化學 性質，其對工業應用上非常重要。例如，在無電鍍鎳反應 中以鉑（P t)奈米粒子當催化觸媒時，隨著粒子大小的不 同，會有不同的無電鍵反應速率。因此，如何控制合成不 同粒徑金屬奈米粒子的製備方法已成為當前工業應用的熱 門話題。 目前在製備金屬奈米粒子的程序上可分成化學合成法鲁 及物理合成法，其中以化學還原法因其產量大、製備程序 簡單、成本低，最常為工業界使用。一般來說，化學還原 法是將無機金屬鹽類溶在内溶有高分子化合物或界面活性 劑之溶液内，再利用外加還原劑，如聯氨、N a B Η 4、乙醇200538398 V. Description of the invention α) [Technical field to which the invention belongs] The present invention relates to a method for manufacturing metal nano particles, particularly a method for manufacturing metal nano particles using a polymer compound as a reducing agent. [Previous technology] Compared with general metal micron-sized particles, metal nano particles have excellent surface properties such as increased surface-to-volume, improved surface energy, high ductility after pressure, high hardness, and high specific heat. As a result, the applicability of metallic nano-particles has attracted much attention in the industrial and scientific circles, which are mainly oriented by materials. For example, today, various types of metal nanoparticle-based catalysts have been used in a variety of catalytic reactions, and have the advantage of high conversion rates for the catalytic reactions of unsaturated hydrocarbons. Depending on the size of the nano-particles, there can be different size-dependent properties of the electronic band, which in turn affects its physical and chemical properties, which is very important for industrial applications. For example, in the electroless nickel reaction, when platinum (Pt) nano-particles are used as the catalytic catalyst, there will be different non-bond reaction rates with different particle sizes. Therefore, how to control the preparation method of synthesizing metallic nano-particles with different particle sizes has become a hot topic in current industrial applications. At present, the procedures for preparing metallic nano particles can be divided into chemical synthesis methods and physical synthesis methods. Among them, the chemical reduction method is most commonly used in industry because of its large output, simple preparation procedure, and low cost. Generally, the chemical reduction method is to dissolve inorganic metal salts in a solution containing a polymer compound or a surfactant, and then use an external reducing agent such as hydrazine, Na B Η 4, ethanol

17790工研院.ptd 第4頁 200538398 五、發明說明（2) 或氫氣，還原無機金屬鹽類以形成金屬奈米粒子。 例如美國第4，5 9 3，0 1 6號專利即揭示將氯化鈀及氣化 亞錫分別溶於HC 1水溶液中，再將兩液混和升高溫度至1 〇 〇 °C，使亞錫離子能夠還原鈀離子，形成錫鈀合金奈米膠體 粒子。美國第5，1 8 7,2 0 9號專利揭示將^2?1：(：14溶於含有 1 · 1克之聯氨（h y d r a z i d e )官能基共聚合物的5 0毫升等比例 混和之水與乙醇溶液中，再用5 0 0 w高壓汞燈（h i gh pressure mercury 1 amp )照射兩小時，還原p t溶液合成約 3 nm之Pt奈米粒子。美國第5, 1 47, 84 1號專利揭示一種將 NaJtCl4或NazPdCl4溶於含有陽離子界面活性劑雙十二烧 基二曱基銨溴化物（D D A B )之正辛烧溶液中，再加入n a B Η 4 或聯氨還原溶液中的Pt2+或Pd2+，形成粒徑為1〇至2〇㈣之 Pt或Pd奈来粒子。美國第5, 75 9, 2 3 0號專利揭示將pdcl 2或 AgN〇3溶於乙醇溶液中，以乙醇當還原劑，迴流加熱12〇至 2 0 0°C，1至3小時合成1 0 nm之Pd奈米粒子及4〇 ^之Ag奈 米粒子。美國第5，3 3 2，6 4 6揭示利用氫氣還原溶於内含有 界面活性劑之有機溶劑中p d與P t之有機金屬鹽類，合成並 有效分散2至50 nm之Pd與Pt金屬奈米粒子。美國第5 5 8 4專利揭示利用6 9 0毫升0 · 1 Μ之四辛基銨溴化物之τ η F溶 液當做電解液，以兩片鈀金屬片分別當作陰、陽電極，/以 陽極氧化陰極還原離子之電化學的方式在溶液中合成出pd 奈米粒子’並且改變不同的電流密度，合成不同i徑的pd 奈米粒子。美國第6, 1 0 3, 8 6 8號專利揭示將ι5〇毫客HAuC1 • 3H2 0溶於25毫升去離子水中形成黃色水溶液，再將 417790 Industrial Research Institute. Ptd Page 4 200538398 5. Description of the invention (2) or hydrogen, reducing inorganic metal salts to form metal nano particles. For example, U.S. Patent No. 4,5 9 3,0 16 discloses that palladium chloride and stannous gas are separately dissolved in HC 1 aqueous solution, and then the two liquids are mixed to increase the temperature to 1000 ° C, so that Tin ions can reduce palladium ions to form nano colloidal particles of tin-palladium alloy. U.S. Patent No. 5,18,7,209 discloses that ^ 2? 1 :(: 14 is dissolved in 50 ml of an equal proportion of water mixed with 1.1 g of hydrazide functional copolymer. In an ethanol solution, it was irradiated with a 500 w high pressure mercury lamp (hi gh pressure mercury 1 amp) for two hours to reduce the pt solution to synthesize Pt nano particles of about 3 nm. US Patent No. 5, 1 47, 84 1 discloses A solution of NaJtCl4 or NazPdCl4 dissolved in n-octane solution containing cationic surfactant didodecyldifluorenyl ammonium bromide (DDAB), and then adding Pt2 + or Pd2 + in na B Η 4 or hydrazine reduction solution, Pt or Pd Nylen particles having a particle size of 10 to 20 Å are formed. US Patent No. 5,75,9,230 discloses that pdcl 2 or AgN03 is dissolved in an ethanol solution, and ethanol is used as a reducing agent. Heating under reflux at 120 to 200 ° C for 1 to 3 hours to synthesize Pd nano particles at 10 nm and Ag nano particles at 40 ^. The United States No. 5, 3 3 2, 6 4 6 reveals the use of hydrogen to reduce the solvent. Synthesize and effectively disperse Pd and Pt metal nano particles of 2 to 50 nm in organometallic salts of pd and P t in an organic solvent containing a surfactant U.S. Patent No. 5 5 8 4 discloses the use of 690 ml of a 0.1 μM tetraoctyl ammonium bromide τ η F solution as an electrolyte, and two pieces of palladium metal pieces as cathode and anode electrodes, respectively, and anode Electrochemical way to oxidize the cathode to reduce ions to synthesize pd nano particles' in solution and change different current densities to synthesize pd nano particles with different i diameters. US Patent No. 6, 1 0 3, 8 6 8 discloses Dissolve ι50 mM HAuC1 • 3H2 0 in 25 ml of deionized water to form a yellow aqueous solution.

17790工研院_ptd 第5頁 200538398 五、發明說明（3) 0.3 6 5克之趴(：81117)461'溶於25毫升甲苯中，將水溶液與甲 苯溶液強烈攪拌，再加入0. 151克之NaBH4還原出金奈米粒 子。 然而，外加還原劑往往會影響粒子的大小，加得過 多，還原力強，成核速率太快，以致合成的金屬奈米粒子 過大且大小不均勻。若添加還原劑量過少，常會導致還原 速率過慢，粒子合成需要數天時間，甚至無法還原無機金 屬鹽類。因此，外加還原劑的劑量、攪拌方式及種類的選 擇都成了關鍵，增加製程上的複雜性。 綜上所述，如何開發出一種可以簡單地製造金屬奈米 j 粒子，並使所製得之金屬奈米粒子具有均勻粒徑以及穩定 分散性，確為此相關研發領域所需迫切面對之課題。 【發明内容】 本發明之一目的即在於提供一種直接使用高分子化合 物作為還原劑製造金屬奈米粒子之方法。 本發明之另一目的係在於提供一種使用高分子化合物 作為還原劑製造具有均勻粒徑分布之金屬奈米粒子之方 法。 本發明之又一目的係在於提供一種使用高分子化合物 作為還原劑製造可長時間分散於溶液中之金屬奈米粒子之馨 方法。 本發明之再一目的係在於提供一種使用簡單配方即可 大規模製造金屬奈米粒子之方法。 本發明之又一目的係在於提供一種以低成本製造金屬17790 工研院 _ptd Page 5 200538398 V. Description of the invention (3) 0.3 6 5 grams of lye (: 81117) 461 'dissolved in 25 ml of toluene, the aqueous solution was strongly stirred with the toluene solution, and then 0.151 g of NaBH4 was added The gold nano particles are reduced. However, the addition of reducing agents often affects the size of the particles. If they are added too much, the reducing power is strong, and the nucleation rate is too fast, so that the synthesized metal nano particles are too large and uneven in size. If the amount of reducing agent added is too small, the reduction rate is often too slow. It takes several days to synthesize the particles, and even the inorganic metal salts cannot be reduced. Therefore, the selection of the amount of external reducing agent, the stirring method and the type are all critical, increasing the complexity of the process. In summary, how to develop a kind of metal nano particles that can be easily manufactured, and make the obtained metal nano particles have a uniform particle size and stable dispersibility is indeed an urgent need for the relevant research and development field. Topic. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing metal nano particles by directly using a polymer compound as a reducing agent. Another object of the present invention is to provide a method for producing metallic nano particles having a uniform particle size distribution using a polymer compound as a reducing agent. Yet another object of the present invention is to provide a method for manufacturing metal nano particles which can be dispersed in a solution for a long time using a polymer compound as a reducing agent. Another object of the present invention is to provide a method for manufacturing metal nano particles on a large scale using a simple formula. Another object of the present invention is to provide a method for manufacturing metal at a low cost.

17790工研院.ptd 第6頁 20053839817790 ITRI.ptd page 6 200538398

劑子 式溶粒 下於米 如合奈 用混屬 使類金 種鹽造 一 屬製 供金以 提與應 明而反 發劑行 本原進 ，還， 的為流 目作迴 他以劑 。其物溶 法及合使 }方述化致 (4之前之熱 ξ子達示加 £粒為所並 Τ米 ， T1 S奈 C中 法 方 之 式中，R係選自C η烷基、C η烯基、及C η炔基所組成組群 之其中一者；以及η係介於1至1，0 0 0之整數。 不同於習知方法使用高分子化合物溶於溶劑所形成之 微泡作為保護劑，本發明之方法係直接利用高分子化合物 與金屬鹽類混合的自身還原能力，在不需額外使用還原劑 的條件下，直接使用式（I )所示之化合物作為還原劑。由 於本發明之方法不需其他複雜的配方，而具有製法簡單、 容易大規模量產、以及成本低廉等優點。另一方面，本發 明之方法適用製造於多種金屬元素之奈米粒子，利用特定 化合物作為還原劑，控制所形成之金屬奈米粒子的粒徑，鲁 使所製得之金屬奈米粒子具有粒徑分布均勻，可長時間分 散於溶液中等優點。 【實施方式】 以下係藉由特定的具體實例說明本發明之實施方式，Under the method of dissolving granules in Miruhe Nai, a mixed genus was used to make a gold-based salt to make a genus of gold for the purpose of mentioning the anti-inflammation agent and the original formulation of the anti-inflammatory agent. . Its physical solution method and synthesizer} Fang Huahua (The thermal ξ sub-Dashi plus grains before 4 are combined T rice, T1 S Na C in the French formula, R is selected from C η alkyl, C one of the groups consisting of an η alkenyl group and a C η alkynyl group; and η is an integer ranging from 1 to 1, 0 0. Different from the microbubbles formed by dissolving a polymer compound in a solvent in a conventional method As a protective agent, the method of the present invention directly utilizes the self-reducing ability of a mixture of a polymer compound and a metal salt, and directly uses a compound represented by the formula (I) as a reducing agent without using a reducing agent. Because The method of the present invention does not require other complicated formulas, but has the advantages of simple preparation method, easy large-scale mass production, and low cost. On the other hand, the method of the present invention is suitable for manufacturing nano particles of various metal elements, using specific compounds As a reducing agent, the particle size of the metal nano particles formed is controlled, so that the obtained metal nano particles have the advantages of uniform particle size distribution and long-term dispersion in the solution. [Embodiment] The following is based on special features. Specific examples illustrate embodiments of the present invention,

17790工研院.ptd 第7頁 200538398 五、發明說明（5) 熟悉此技藝之人士可由本說明書所揭示之内容輕易地瞭解 本發明之其他優點與功效。本發明亦可藉由其他不同的具 體實例加以施行或應用，本說明書中的各項細節亦可基於 不同觀點與應用，在不悖離本發明之精神下進行各種修飾 與變更。 本發明提供一種使用如下式（I )所示之化合物以作為 還原劑而與金屬鹽類混合於溶劑中，並加熱致使溶劑迴 流，進行反應以製造金屬奈米粒子之方法： (1) γ 丫0 式中，R係獨立地選自C Η烷基、C Η烯基、及C Η炔基所組 成組群之其中一者；以及η係介於1至1，0 0 0之整數。 該烷基可為直鏈、分支、或環狀烷基，其實例包括， 但不限於甲基、乙基、丙基、異丙基、丁基、第二丁基、 戊基、己基、及環己基等；該烯基的實例包括，但不限於 乙烯基、丙烯基、及丁烯基；該炔基的實例包括，但不限 於乙炔、及丙炔等。 於本發明一具體實例中，用作為還原劑之化合物係以 具有介於3，5 0 0至1，3 0 0，0 0 0分子量之高分子化合物較佳， 其實例可為具有介於3，5 0 0至1，3 0 0，0 0 0分子量之聚乙烯吡 咯烷酮（以下簡稱PVP)。較佳者，該用作為還原劑之高分17790 Industrial Research Institute.ptd Page 7 200538398 V. Description of the invention (5) Those skilled in the art can easily understand the other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific examples, and various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the spirit of the present invention. The present invention provides a method for producing metal nano particles by using a compound represented by the following formula (I) as a reducing agent, mixing it with a metal salt in a solvent, and heating to cause the solvent to reflux, and performing a reaction: In the formula, R is independently selected from one of the group consisting of C-alkyl, C-alkenyl, and C-alkynyl; and η is an integer ranging from 1 to 1,000. The alkyl group may be a linear, branched, or cyclic alkyl group, and examples thereof include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, second butyl, pentyl, hexyl, and Examples of the alkenyl group include, but are not limited to, vinyl, propenyl, and butenyl; examples of the alkynyl group include, but are not limited to, acetylene, propyne, and the like. In a specific example of the present invention, the compound used as the reducing agent is preferably a high molecular compound having a molecular weight between 3,500 and 1,300,000, and an example thereof may have a molecular weight between 3. Polyvinylpyrrolidone (hereinafter referred to as PVP) with a molecular weight of 500 to 1,300,000. Preferably, the high score used as a reducing agent

1779G工研院.ptd 第8頁 200538398 五、發明說明（6) 子化合物係以水溶液之型式使用。 本發明之方法係先使該用作為還原劑之高分子化合物 水溶液與金屬鹽類混和；接著’加熱致使溶劑迴流而&該 咼分子化合物還原劑與該金屬鹽進行反應，而形成金屬奈 米粒子。其可藉由抽取少許反應溶液利用光譜檢測是否2 反應完全，一般而言，迴流時間係介於1至2 〇小時，且較 佳係為3至1 0小時。 於本發明一具體實例中，該金屬鹽類係以貴金屬鹽類 較佳’例如Pd、Pt、Ag、或Au之鹽類。該等貴金屬鹽類的 實例包括，但不限於 Pd(0Ac)2、PdCl2、H2PtCl6· II 0、 Ag(OAc)、 Ag(N03)、以及 HAuC14· 3H2〇。 以下茲藉由具體實驗實例，進一步詳述本發明之特點 及功效。其中，係利用穿透式電子顯微鏡（以下簡稱 TEM)、能量分散光譜儀（energy dispersion spectra-EDX)、紫外光可見光光譜儀（uV-Visble spectra)鑑定合成之金屬奈米粒子之粒徑及元素成分。 實施例1 將0.1克之醋酸鈀（？(1((^〇2)溶於50毫升0.011^之聚乙 烯吡咯烷酮（P V P，分子量1 0，0 0 0 )水溶液中，在未添加其 他還原劑的條件下，以油浴迴流加熱，油浴溫度控制在 1 1 0°C至1 3 0°C之範圍，反應時間歷時1 6小時。當反應約1 小時後，反應液呈現澄清橘黃色，隨著反應時間增長’反 應液顏色由橘黃色轉為棕色，到反應時間為1 6小時後反應 液呈黑棕色。反應終止後利用1 5 0 0 0 r pm 2 0分鐘進行高&1779G Institute of Industry and Technology.ptd page 8 200538398 V. Description of the invention (6) The sub-compound is used in the form of an aqueous solution. The method of the present invention is to first mix the polymer compound aqueous solution used as a reducing agent with metal salts; then, 'heating causes the solvent to reflux and the amidine molecular compound reducing agent reacts with the metal salt to form metal nanometers. particle. It can be used to detect whether the 2 reaction is complete by extracting a small amount of the reaction solution. Generally, the reflux time is between 1 and 20 hours, and more preferably between 3 and 10 hours. In a specific embodiment of the present invention, the metal salt is preferably a noble metal salt, such as a salt of Pd, Pt, Ag, or Au. Examples of such precious metal salts include, but are not limited to, Pd (0Ac) 2, PdCl2, H2PtCl6 · II 0, Ag (OAc), Ag (N03), and HAuC14 · 3H2O. The characteristics and effects of the present invention are further detailed below by using specific experimental examples. Among them, the particle size and elemental composition of the synthesized metal nano-particles are identified using a transmission electron microscope (hereinafter referred to as TEM), energy dispersion spectra-EDX, and uV-Visble spectra. Example 1 0.1 g of palladium acetate (? (1 ((^ 〇2)) was dissolved in 50 ml of 0.011 ^ of polyvinylpyrrolidone (PVP, molecular weight 10, 0 0)) aqueous solution, without adding other reducing agents Then, the oil bath is heated under reflux, the temperature of the oil bath is controlled in the range of 110 ° C to 130 ° C, and the reaction time is 16 hours. When the reaction is about 1 hour, the reaction liquid appears clear orange, with Increase in reaction time 'The color of the reaction solution changed from orange to brown, and the reaction solution became black-brown after the reaction time was 16 hours. After the reaction was terminated, the temperature was increased by 15 0 0 r pm 20 minutes.

200538398 五、發明說明（7) 離心，結果分為上層液及離心沈澱物，該上層液為澄清透 明淡黃色水溶液，經原子吸收光譜儀（Atom Absorption200538398 V. Description of the invention (7) Centrifugation, the results are divided into a supernatant liquid and a centrifugal precipitate. The supernatant liquid is a clear and light yellow aqueous solution, which is subjected to atomic absorption spectrometer (Atom Absorption)

Spectrum )測定產率為9〇%。取出反應液測TEM其結果為粒 子大小均勻之Pci奈米粒子，°如第1圖所示。利用PVP來合成Spectrum) determined that the yield was 90%. The reaction solution was taken out and measured for TEM. As a result, Pci nano particles having a uniform particle size were shown in Fig. 1. Use PVP to synthesize

Pd奈米粒子之平均粒徑在6 1 γ nm，如第2圖所示，由第2 圖可知所合成之Pd奈米粒子大小相當均勻。經EDX之電子 束對準粒子測其經電子束激發之X-ray鑑定其化學成分為 純Pd。 將所製備之P d奈米粒子沈澱物，再度分散於水溶The average particle diameter of Pd nano particles is 6 1 γ nm. As shown in FIG. 2, it can be seen from FIG. 2 that the size of the synthesized Pd nano particles is quite uniform. The electron beam of EDX was used to align the particles and the X-ray excited by the electron beam was used to identify the chemical composition as pure Pd. Disperse the prepared P d nanoparticle precipitate in water

中。經長時間實驗觀察，發現所製備之金屬奈米粒子 ^ 2年後仍可有效地分散於水溶液中。 施例2 重複實施例i之步驟，以同樣方法，將pd(〇Ac 〇 5克之p d Γ 1 & 2 ’合成黑棕色P d奈米粒子溶液。經長時間實 驗觀察，發現所制# κ 八I x τ 斤製備之金屬奈米粒子約1至2年後仍可有效 分散於水溶液中。 β从 實jfe例3 n nR. ^ 1之步驟，以同樣方法，將Pd(0Ac)jit為 子，如第3圖^)，合成黑掠色Pt奈米粒 不 ，、平均粒徑為2·36ηπι，如第4圖所 將所製借 中。鲈异眭=以奈米粒子沈殿物，再度分散於水溶 至？、間實驗觀察’發現所製備之金屬奈米粒子 可有效分散於水溶液中。in. After a long period of experimental observation, it was found that the prepared metal nano particles can be effectively dispersed in an aqueous solution after 2 years. Example 2 The steps of Example i were repeated, and in the same way, pd (〇Ac 〇5 g of pd Γ 1 & 2 'was synthesized as a dark brown P d nanoparticle solution. After long-term experimental observation, it was found that the produced # κ The metal nano particles prepared by Ba I x τ kg can still be effectively dispersed in an aqueous solution after about 1 to 2 years. Β From the steps of Example 3 n nR. ^ 1, in the same way, Pd (0Ac) jit is As shown in Figure 3 ^), the synthetic black-sweet Pt nanoparticle is not, with an average particle size of 2.36ηπι, as borrowed from Figure 4. Perch 眭 = Shen Dianwu with nano particles, disperse in water again? Experimental observations' found that the prepared metal nanoparticle can be effectively dispersed in an aqueous solution.

Π790工研院.ptd 第10頁 200538398 五、發明說明（8) ''''~ ---一^' t Μ Μ 此一實施例係為確定不同濃度之金屬鹽類變化（金屬 鹽類之添加量）對於、製備金屬奈米粒子之影響。改變金屬 鹽類之濃度而固定向分子化合物還原劑之濃迴流反應 溫度皆控制於纖，反應條件係如表i所載，所製得之金 屬奈米粒子的粒徑亦記載於表J。 表1 組別 PdCl2濃度 (克/50毫升） P VP濃度 (5克/5〇毫升） 平均粒徑統計 (nm) 4a 0.4 0.01M 6.32 4b 0.08 '0.01M 5.46 4c 0.04 0.01M 6.08 4d 0.01 0.01M 4.62 實驗結果由UV-Vi S光譜及TEM測定，發現PdC1 2濃度不管降 至0_01克/50宅升或增加至q· 4克/50宅升都可合成出奈米 粒子。就不同濃度PdCl 2所合成Pd奈米粒子溶液而言，由 於是由系統内高分子還原pd 2+，反應較外加還原劑溫和， 因此金屬離子濃度對粒子粒徑之影響不大。 —實—麵倒5 此一實例係為確定使用不同濃度之高分子化合物作為 還原劑對於合成金屬奈米粒子之影響。改變高分子化合物 還原劑之濃度同時固定金屬鹽類濃度，其結果係如表2所Π790 Industrial Research Institute.ptd Page 10 200538398 V. Description of the invention (8) '' '' ~ --- ^^ t Μ Μ This example is to determine the changes of metal salts with different concentrations (the Addition amount) on the preparation of metal nano particles. Change the concentration of metal salts to fix the concentrated reflux reaction temperature of the molecular compound reducing agent. The temperature is controlled in fiber. The reaction conditions are as shown in Table i. The particle size of the prepared metal nano particles is also described in Table J. Table 1 Group PdCl2 concentration (g / 50 ml) P VP concentration (5 g / 50 ml) Average particle size statistics (nm) 4a 0.4 0.01M 6.32 4b 0.08 '0.01M 5.46 4c 0.04 0.01M 6.08 4d 0.01 0.01M 4.62 The experimental results were measured by UV-Vi S spectroscopy and TEM. It was found that nano particles could be synthesized no matter whether the concentration of PdC12 was reduced to 0_01 g / 50 liters or increased to q · 4 g / 50 liters. For Pd nanoparticle solutions synthesized with different concentrations of PdCl 2, pd 2+ is reduced from the polymer in the system, and the reaction is milder than the addition of a reducing agent, so the effect of metal ion concentration on particle size is not significant. —Solid—Top 5 This example is to determine the effect of using different concentrations of high molecular compounds as reducing agents on the synthesis of metallic nano particles. The concentration of the polymer compound reducing agent was changed while the metal salt concentration was fixed. The results are shown in Table 2.

200538398 五、發明說明（9) 示0 表2 組別 —PdCl2 濃度~ (克/50毫升） (克/50耷升） >均粒彳ΐ統計 fnm) 5a 0.4 5 6.32 5b 0.4 4 6.59 5 c 0.4 3 6.47 5d 0.4 2 7.69 5e 0.4 1 4.48200538398 V. Description of the invention (9) Shown 0 Table 2 Group—PdCl2 concentration ~ (g / 50ml) (g / 50ml) > Statistics of average grain size fnm) 5a 0.4 5 6.32 5b 0.4 4 6.59 5 c 0.4 3 6.47 5d 0.4 2 7.69 5e 0.4 1 4.48

在實驗結果中發現，實驗結果由uv —Vis光譜及TEM測定， 不同的高分子化合物還原劑濃度皆可製備出金屬奈米粒 子。 實施例6 為复清？(1((^(：)2在高分子水溶液中形成？(1奈米粒子是 否是由於Pd (0AC) 2受熱分解而非化學還原，故進行以下兩 個對照實驗： 6a: 1克之Pd(0Ac)2+ 〇·〇ιμ之PVP/5 0毫升H20，油浴溫度 ❿ 1 3 0°C ，時間1 6小時 6b: 0· 0 52克之 Pd(OAc)2/5〇毫升 H20，油浴溫度 12〇°C，時 間4小時It was found in the experimental results that the experimental results were determined by UV-Vis spectroscopy and TEM. Metal nanoparticle can be prepared with different concentrations of polymer compound reducing agent. Example 6 Is the restoration? (1 ((^ (:) 2 is formed in an aqueous polymer solution? (Is the 1nm particle due to thermal decomposition rather than chemical reduction of Pd (0AC) 2, the following two control experiments were performed: 6a: 1g of Pd ( 0Ac) 2+ 〇 · 〇μ PVP / 5 0ml H20, oil bath temperature ❿ 13 0 ° C, time 16 hours 6b: 0. 0 52 grams of Pd (OAc) 2 / 5ml H20, oil bath 12 ° C for 4 hours

17790工研院.ptd 第12頁 200538398 五、發明說明（ίο) 在6a力口入PVP之實驗中，溶液顏色變成黑棕色，Pd奈 米粒子光譜出現；另一方面，在6b未加PVP之實驗中 P d ( 0 A C ) 2對水的溶解度不佳，只能部分溶於水，油浴加熱 1 2 0°C，4小時後，Pd(OAC) 2仍然不溶於水。 由上述結果可知由本方法合成的奈米粒子不是由 Pd(0AC)2受熱分解所形成P d奈米粒子，而是由於PV P還原 金屬鹽類所形成者。17790 Industrial Research Institute.ptd Page 12 200538398 V. Description of Invention (ίο) In the experiment of entering PVP at 6a, the color of the solution became dark brown, and the spectrum of Pd nano particles appeared; on the other hand, in the case of 6b without PVP, In the experiment, P d (0 AC) 2 had poor solubility in water, and was only partially soluble in water. The oil bath was heated at 120 ° C. After 4 hours, Pd (OAC) 2 was still insoluble in water. From the above results, it can be seen that the nano particles synthesized by this method are not formed by P d nano particles formed by thermal decomposition of Pd (0AC) 2, but are formed by PV P reduction of metal salts.

17790工研院.ptd 第13頁 200538398 圖式簡單說明 【圖式簡單說明】 第1圖係使用本發明之方法所製得之Pd奈米粒子的TEM 照片（放大倍率為30萬倍，圖中0. 5公分即為20 nm); 第2圖係使用本發明之方法所製得之Pd奈米粒子的平 均粒徑分布； 第3圖係使用本發明之方法所製得之Pt奈米粒子的TEM 照片（放大倍率為30萬倍，圖中0. 5公分即為20 nm);以 及 第4圖係使用本發明之方法所製得之Pt奈米粒子的平 均粒徑分布。 (本案無元件符號）17790 Institute of Industry and Technology.ptd Page 13 200538398 Brief description of the drawings [Simplified description of the drawings] Figure 1 is a TEM photograph of Pd nano particles produced by the method of the present invention (magnification is 300,000 times, the figure 0.5 cm is 20 nm); Figure 2 is the average particle size distribution of Pd nano particles produced by the method of the present invention; Figure 3 is Pt nano particles produced by the method of the present invention TEM photo (magnification is 300,000 times, 0.5 cm in the figure is 20 nm); and FIG. 4 is the average particle size distribution of Pt nano particles produced by the method of the present invention. (No component symbol in this case)

17790工研院.ptd 第14頁17790 ITRI.ptd Page 14

Claims (1)

200538398 六、申請專利範圍 1. 一種製造金屬奈米粒子之方法，該方法係使用如下式 (I )所示之化合物作為還原劑而與金屬鹽類混合於溶 劑中，並加熱致使溶劑迴流，進行反應：200538398 VI. Scope of patent application 1. A method for manufacturing metal nano particles, the method is to use a compound represented by the following formula (I) as a reducing agent, mix it with a metal salt in a solvent, and heat to cause the solvent to reflux. reaction: 式中，R係選自C η烷基、C η烯基、及C η炔基所 組成組群之其中一者；以及η係介於1至1，0 0 0之整數。· 2. 如申請專利範圍第1項所述之方法，其中，該R係乙烯 基。 3. 如申請專利範圍第1項所述之方法，其中，該化合物之 分子量係介於3，5 0 0至1，3 0 0，0 0 0之間。 4. 如申請專利範圍第1項所述之方法，其中，該化合物之 分子量最佳係介於3，5 0 0至1 0，0 0 0之間。 5. 如申請專利範圍第4項所述之方法，其中，該溶劑係 水。 6. 如申請專利範圍第1項所述之方法，其中，該金屬鹽類 係選自Pd金屬鹽、Pt金屬鹽、Ag金屬鹽、以及Au金屬 ® 鹽所組成組群之其中一者。 7. 如申請專利範圍第6項所述之方法，其中，該Pd金屬鹽 係選自Pd(OAc) 2、以及PdCl 2之其中一者。 8. 如申請專利範圍第6項所述之方法，其中，該Pt金屬鹽In the formula, R is one selected from the group consisting of a C η alkyl group, a C η alkenyl group, and a C η alkynyl group; and η is an integer ranging from 1 to 1,000. · 2. The method according to item 1 of the scope of patent application, wherein the R is a vinyl group. 3. The method according to item 1 of the scope of patent application, wherein the molecular weight of the compound is between 3,500 and 1,300,000. 4. The method according to item 1 of the scope of patent application, wherein the molecular weight of the compound is preferably between 3,500 and 10,0 0. 5. The method according to item 4 of the scope of patent application, wherein the solvent is water. 6. The method according to item 1 of the scope of patent application, wherein the metal salt is one selected from the group consisting of Pd metal salt, Pt metal salt, Ag metal salt, and Au metal ® salt. 7. The method according to item 6 of the scope of patent application, wherein the Pd metal salt is selected from one of Pd (OAc) 2 and PdCl2. 8. The method according to item 6 of the scope of patent application, wherein the Pt metal salt 17790工研院.ptd 第15頁 200538398 六、申請專利範圍 係為 Η 2 P t C 1 6 · Η 2 0。 9.如申請專利範圍第6項所述之方法，其中，該Ag金屬鹽 係選自Ag(OAc)、以及Ag(N03 )之其中一者。 1 0 .如申請專利範圍第6項所述之方法，其中，該Au金屬鹽 係為 HAuCl 4 · 3H2 0。 1 1.如申請專利範圍第1項所述之方法，其中，加熱致使溶 劑迴流之迴流時間係介於1至2 0小時之間。17790 Industrial Research Institute.ptd Page 15 200538398 6. The scope of patent application is Η 2 P t C 1 6 · Η 2 0. 9. The method according to item 6 of the scope of patent application, wherein the Ag metal salt is one selected from the group consisting of Ag (OAc) and Ag (N03). 10. The method according to item 6 of the scope of patent application, wherein the Au metal salt is HAuCl 4 · 3H2 0. 1 1. The method according to item 1 of the scope of patent application, wherein the reflux time of the solvent caused by heating to reflux is between 1 and 20 hours. 17790工研院.ptd 第16頁17790 ITRI.ptd Page 16