TW201330955A - Manufacturing method of precious metal nanoparticles - Google Patents
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本發明係提出一種貴金屬奈米粒子的製造方法，係利用光化學合成法，在不需額外添加晶種的條件下，使用一鍋式的反應溶液合成金或銀奈米粒子。The present invention provides a method for producing noble metal nanoparticles, which uses a photochemical synthesis method to synthesize gold or silver nanoparticles using a one-pot reaction solution without additional seeding.
金及銀奈米粒子因為具有獨特的物理化學性質，已經被廣泛的應用在抗菌、化學或生物感測、細胞或組織影像的標示、光電元件、催化反應以及表面增強拉曼光譜(Raman spectroscopy)上。Gold and silver nanoparticles have been widely used in antibacterial, chemical or biological sensing, cell or tissue imaging, photoelectric elements, catalytic reactions, and surface enhanced Raman spectroscopy because of their unique physicochemical properties. on.
有許多種合成金及銀奈米粒子的方法已經被開發出來，其中，濕式化學法具有大量製備均質性高的金及銀奈米粒子的特性。濕式化學法可依照其合成原理分成電化學法、化學還原法、聲波化學法及光化學法，在這之中，光化學法理論上可以通過照射日光達成反應之目的，而被認為具有環境友善的優勢。因此，開發奈米金或奈米銀的光化學合成方法實能符合當前綠色化學及環境永續的精神。A variety of methods for synthesizing gold and silver nanoparticles have been developed, among which the wet chemical method has a large number of properties for preparing highly homogeneous gold and silver nanoparticles. The wet chemical method can be divided into electrochemical method, chemical reduction method, sonophoresis method and photochemical method according to the principle of synthesis. Among them, photochemical method can theoretically achieve the purpose of reaction by irradiating sunlight, and is considered to have an environment. Friendly advantage. Therefore, the development of photochemical synthesis methods of nano gold or nano silver can meet the current spirit of green chemistry and environmental sustainability.
過去利用光化學法合成金及銀奈米粒子的技術中，由於需要與光作用的表面電漿子，因此需要先利用化學合成法產生適當大小的金屬奈米粒子作為晶種。此化學方法往往需要使用強還原劑(strong reductant)，例如，硼氫化鈉(NaBH4)，還原金屬離子以得到晶種，但這樣的晶種產生方式會遭遇到一些問題：(1)強還原劑不當的使用，可能造成操作者或者生態的危害；(2)強還原劑需要以適當的速率添加才會產生適當大小的晶種，此操作手法需要耐性及技術，造成每一批奈米粒子的品質(型態以及大小分佈)不穩定；(3)由於需要加入還原劑產生晶種這道費時費工的程序，此方法遭遇到無法大量產生的問題。In the past, in the technique of synthesizing gold and silver nanoparticles by photochemical method, since surface plasmons acting on light are required, it is necessary to first use chemical synthesis to produce metal nanoparticles of appropriate size as seed crystals. This chemical method often requires the use of a strong reductant, such as sodium borohydride (NaBH 4 ), to reduce the metal ions to obtain seed crystals, but such seed crystal production methods will encounter some problems: (1) strong reduction Improper use of the agent may cause operator or ecological hazard; (2) Strong reducing agent needs to be added at an appropriate rate to produce an appropriate size seed crystal. This operation requires resistance and technology, resulting in each batch of nano particles. The quality (type and size distribution) is unstable; (3) due to the need to add a reducing agent to produce seed crystals, which is a time-consuming and labor-intensive procedure, this method suffers from problems that cannot be generated in large quantities.
為了克服以上三項光化學合成法的缺點，本發明人成功的發展出不需要晶種的光化學合成法，此合成法兼具環保、可量產、簡單操作以及重複性高等特質。In order to overcome the shortcomings of the above three photochemical synthesis methods, the inventors succeeded in developing a photochemical synthesis method that does not require a seed crystal, and the synthesis method has the characteristics of environmental protection, mass production, simple operation, and high repeatability.
本發明之主要目的在於提出一種貴金屬奈米粒子的製造方法，以改善光化學法之合成步驟，並克服每次反應時貴金屬奈米粒子品質不一以及因晶種合成之過程導致其製造流程較化學還原法複雜等缺失，本發明免去強還原劑合成晶種之步驟，由於簡化其製程，更方便於工業大量生產，且因不需添加對環境較具危害性之強還原劑，使得本發明提供之方法更為環保。The main object of the present invention is to provide a method for producing noble metal nanoparticles, which can improve the synthesis steps of photochemical methods, and overcome the different quality of precious metal nanoparticles in each reaction and the manufacturing process due to the process of seed crystal synthesis. The chemical reduction method is complicated and the like, and the invention eliminates the step of synthesizing the seed crystal by the strong reducing agent, and is more convenient for industrial mass production because of simplifying the process thereof, and the present invention does not need to add a strong reducing agent which is harmful to the environment. The method provided by the invention is more environmentally friendly.
本發明之次要目的在於提出一貴金屬奈米粒子光化學合成方法，係合成之奈米粒子尺寸均一性高，並可保持其形態長達數月之久。A secondary object of the present invention is to propose a photochemical synthesis method of noble metal nanoparticles, wherein the synthesized nanoparticles have high uniformity of size and can maintain their morphology for several months.
為達上述所指稱之各目的，本發明提出一種貴金屬奈米粒子的製造方法，該方法包含下列步驟：In order to achieve the above-mentioned various objects, the present invention provides a method for producing noble metal nanoparticles, which comprises the following steps:
(a).製備一貴金屬離子溶液；(a) preparing a noble metal ion solution;
(b).製備一光還原劑；(b) preparing a photoreducing agent;
(c).混合貴金屬離子溶液與光還原劑形成一混合溶液；(c) mixing a precious metal ion solution with a photoreducing agent to form a mixed solution;
(d).將溶液控制在特定之反應溫度；(d) controlling the solution at a specific reaction temperature;
(e).提供一光源，使混合溶液中之貴金屬團簇被檸檬酸鈉還原成貴金屬奈米粒子。(e). Providing a light source to reduce the noble metal clusters in the mixed solution to the noble metal nanoparticles by sodium citrate.
上述構想之金屬離子溶液之金屬可為但不限於金(Au)或銀(Ag)。離子來源例如，四氯金酸(HAuCl4)、硝酸銀(AgNO3)等。溶液可為超純水或去離子水。光還原劑可為但不限於檸檬酸鈉(sodium citrate)。The metal of the metal ion solution contemplated above may be, but not limited to, gold (Au) or silver (Ag). The ion source is, for example, tetrachloroauric acid (HAuCl 4 ), silver nitrate (AgNO 3 ) or the like. The solution can be ultrapure water or deionized water. The photoreducing agent can be, but not limited to, sodium citrate.
上述構想之反應溫度控制在攝氏0至100度間，提供之光源波長在200至800nm間，在適當光源照射下，金屬離子可以被檸檬酸鈉所還原，此過程我們稱之為『光輔助檸檬酸根還原過程』，此過程可以在沒有金屬奈米晶種之情況下發生。持續的照光，將使晶種經過逐漸長大並進一步形成晶形良好的奈米粒子。當提供之光源波長位於400至500nm之區間時，擁有較佳的反應速度，而根據銀或金離子濃度之調控，其產物之形狀也可隨之改變。光源波長位於450nm，濃度為10-4時，銀奈米粒子以十面體為主，金奈米粒子則是球形，在濃度為10-3時，銀奈米粒子或金奈米粒子則都以球形為主。The above reaction temperature is controlled between 0 and 100 degrees Celsius, and the wavelength of the light source is between 200 and 800 nm. Under the illumination of a suitable light source, the metal ions can be reduced by sodium citrate. This process is called "light-assisted lemon". Acid reduction process, this process can occur without metal nanocrystals. Continuous illumination will cause the seed crystal to gradually grow and further form crystal nanoparticles with good crystal shape. When the wavelength of the light source provided is in the range of 400 to 500 nm, the reaction speed is better, and the shape of the product may be changed according to the regulation of the concentration of silver or gold ions. When the wavelength of the light source is at 450 nm and the concentration is 10 -4 , the silver nanoparticles are mainly decahedron, and the gold nanoparticles are spherical. At a concentration of 10 -3 , silver nanoparticles or gold nanoparticles are Focus on the sphere.
根據本發明所得之貴金屬奈米粒子，依照不同製造條件皆能有極佳的粒徑大小均一性，其粒徑大小也可穩定維持一年以上。此外，本發明因製造過程簡單、不同反應批次品質均一以及符合環境保護概念等優點，並克服一般光化學法合成時的三項缺點，使得光化學法在貴金屬奈米粒子的工業製造上更為可能。The noble metal nanoparticles obtained according to the present invention can have excellent particle size uniformity according to different manufacturing conditions, and the particle size can be stably maintained for more than one year. In addition, the invention has the advantages of simple manufacturing process, uniform quality of different reaction batches and conforming to the concept of environmental protection, and overcomes three shortcomings in the synthesis of general photochemical methods, so that the photochemical method is more industrially manufactured for noble metal nanoparticles. As possible.
圖一為本發明之貴金屬奈米粒子的製造方法流程圖，主要包括以下步驟：1 is a flow chart of a method for manufacturing precious metal nanoparticles of the present invention, which mainly comprises the following steps:
(a). 製備一貴金屬離子溶液，(a). Preparing a precious metal ion solution,
(b). 製備一光還原劑，(b). preparing a photoreducing agent,
(c). 混合貴金屬離子溶液與光還原劑形成一混合溶液，(c) mixing a precious metal ion solution with a photoreducing agent to form a mixed solution,
(d). 將混合溶液控制在特定之反應溫度，(d). Control the mixed solution at a specific reaction temperature,
(e). 提供一光源，使混合溶液中之貴金屬團簇被檸檬酸鈉還原成貴金屬奈米粒子。(e). Providing a light source to reduce the noble metal clusters in the mixed solution to the noble metal nanoparticles by sodium citrate.
上述步驟(a)之貴金屬離子溶液包含但不限於金離子或銀離子，離子來源包括四氯金酸(HAuCl4)、硝酸銀(AgNO3)等。溶劑可為超純水或去離子水。製備時將離子來源溶於溶劑中即可。The precious metal ion solution of the above step (a) includes, but is not limited to, gold ions or silver ions, and the ion source includes tetrachloroauric acid (HAuCl 4 ), silver nitrate (AgNO 3 ), and the like. The solvent can be ultrapure water or deionized water. The ion source can be dissolved in the solvent during preparation.
上述步驟(b)之光還原劑為檸檬酸鈉，本發明之方法中，檸檬酸鈉除作為光還原劑，還可作為反應所需之穩定劑使用。The photoreducing agent of the above step (b) is sodium citrate. In the method of the present invention, sodium citrate can be used as a stabilizer for the reaction, in addition to being a photoreducing agent.
在作為光還原劑方面，當沒有檸檬酸根存在的情況下，照光不會使銀離子或四氯金酸離子還原形成奈米粒子，在只有檸檬酸根以及銀離子或四氯金酸離子混合的情況下，保持溶液在室溫中一段時間仍然不能觀察到金屬奈米粒子的生成，當光以及檸檬酸根同時存在下，其協同作用才使銀離子或四氯金酸離子還原成銀奈米或金奈米晶種。我們稱這個協同作用叫做『光輔助檸檬酸根還原過程』(photo-assisted citrate reduction process)，在這個過程中，可能是金屬離子團簇或者是檸檬酸根與金屬離子所形成的錯合物可以和可見光作用，雖然其作用的係數很小，以致於在紫外光可見光光譜中沒辦法呈現可觀察到的吸收值，然而僅僅少部分的團簇或錯合物所捕獲光子的能量，就促使檸檬酸根的還原作用產生，於是檸檬酸根即在光的輔助下將金屬離子還原成奈米晶種。In the case of a photoreducing agent, when there is no citrate present, the illumination does not reduce the silver ion or the tetrachloroauric acid ion to form a nanoparticle, in the case where only citrate and silver ion or tetrachloroauric acid ion are mixed. Under the condition that the solution of the metal nanoparticles can not be observed for a while at room temperature, when the light and the citrate are simultaneously present, the synergistic effect is to reduce the silver ions or the tetrachloroauric acid ions into silver nanoparticles or gold. Nano seed crystals. We call this synergistic effect "photo-assisted citrate reduction process", in which a metal ion cluster or a complex formed by citrate and metal ions can be combined with visible light. The effect, although the coefficient of action is so small that there is no way to exhibit an observable absorption value in the ultraviolet visible spectrum, however, only a small fraction of the energy of the photon captured by the cluster or complex promotes citrate. The reduction occurs, so that the citrate reduces the metal ions to nanocrystals with the aid of light.
用上述方法所產生的晶種比一般化學還原法所產生的晶種具有更好的結晶性，再進一步的照光，結晶性較佳的晶種即可以透過電漿子媒介光化學反應逐漸長大。由於表面電漿子與入射光作用產生空間非等向性的局部電場，促使周圍液體中的離子的濃度分佈不均勻，因此此晶體會成長成非球形的奈米結構。這些奈米結構的型態及大小可以透過控制溫度、以及光照波長等方式調控。The seed crystal produced by the above method has better crystallinity than the seed crystal produced by the general chemical reduction method, and further crystallizing, the crystal crystal having better crystallinity can be gradually grown by the photochemical reaction of the plasmonic medium. Since the surface plasmons react with the incident light to generate a spatially anisotropic local electric field, which promotes uneven distribution of ions in the surrounding liquid, the crystal grows into a non-spherical nanostructure. The shape and size of these nanostructures can be controlled by controlling temperature and wavelength of illumination.
另一方面，檸檬酸鈉提供之檸檬酸根離子和其他帶電產物，會吸附在金屬奈米粒子表面，使其帶負電荷，因而使奈米粒子因電荷相同而互相排斥，故能穩定金屬奈米粒子懸浮於溶液中而避免其聚集、沉澱。On the other hand, the citrate ion and other charged products provided by sodium citrate will adsorb on the surface of the metal nanoparticles to make it negatively charged, thus making the nanoparticles repel each other due to the same charge, so that the metal nanoparticle can be stabilized. The particles are suspended in the solution to avoid aggregation and precipitation.
上述步驟(d)之反應溫度控制在0到100度之間，可依照不同實施方式進行調整。The reaction temperature of the above step (d) is controlled between 0 and 100 degrees, and can be adjusted according to different embodiments.
上述步驟(e)之光源由可由LED、鹵素燈、鈉燈或UV燈提供，本發明中所使用之光源波長位於200至800nm間，因LED為一價格便宜且性能優越之單一波長光源提供者，故列舉之較佳實施例以LDE燈源為反應所使用之光源，由於表面電漿子形成的電場具有方向性，使得金屬奈米粒子的生長會呈現空間非勻向的生長，此時提供的光源波長更可進一步控制合成金屬奈米粒子的大小及形狀，因此依照不同實施方式可給予不同波長進行反應。本發明之貴金屬奈米粒子的製造方法可由以下列舉二較佳實施例說明得到充分瞭解，並使本技術領域中具有通常知識者可據以完成。然本發明之實施型態並不以下列實施例為限。The light source of the above step (e) may be provided by an LED, a halogen lamp, a sodium lamp or a UV lamp. The wavelength of the light source used in the present invention is between 200 and 800 nm, since the LED is a single wavelength light source provider which is inexpensive and superior in performance. Therefore, the preferred embodiment cited is a light source used for the reaction of the LDE lamp source. Since the electric field formed by the surface plasmon has directionality, the growth of the metal nanoparticle will exhibit spatial non-uniform growth, which is provided at this time. The source wavelength further controls the size and shape of the synthetic metal nanoparticles, and thus different wavelengths can be reacted in accordance with various embodiments. The method for producing the noble metal nanoparticles of the present invention can be fully understood from the following description of the preferred embodiments, and can be accomplished by those of ordinary skill in the art. However, the embodiments of the present invention are not limited to the following embodiments.
(a1)以電子天秤量取17mg硝酸銀(AgNO3)粉末，並溶於10ml去離子水(H2O)中均勻混合，形成濃度為10-2M之硝酸銀溶液。(a1) 17 mg of silver nitrate (AgNO 3 ) powder was weighed by an electronic balance and uniformly mixed in 10 ml of deionized water (H 2 O) to form a silver nitrate solution having a concentration of 10 -2 M.
(b1)以電子天秤量取1.32g檸檬酸鈉，並溶於990ml去離子水(H2O)中均勻混合，配製4.53x10-3M檸檬酸鈉水溶液。(b1) 1.32 g of sodium citrate was weighed by an electronic balance, and uniformly dissolved in 990 ml of deionized water (H 2 O) to prepare an aqueous solution of 4.53 x 10 -3 M sodium citrate.
(c1)混合硝酸銀溶液及檸檬酸鈉水溶液並以磁石攪拌器攪拌5分鐘，使檸檬酸鈉與硝酸銀充分混合。(c1) A silver nitrate solution and an aqueous sodium citrate solution were mixed and stirred with a magnetic stirrer for 5 minutes to sufficiently mix sodium citrate with silver nitrate.
(d1)將反應溫度控制在室溫。(d1) The reaction temperature was controlled at room temperature.
(e1)將混合溶液放置於波長為450nm之LED光源下，持續照光約1.5小時後溶液變為粉紅色即完成反應。(e1) The mixed solution was placed under an LED light source having a wavelength of 450 nm, and the reaction became pink after the illumination was continued for about 1.5 hours to complete the reaction.
本實施例所得之穿透式電子顯微鏡影像如圖二所示，其係為放大倍率12000倍下所見之銀奈米粒子放大照片，由圖二可明顯看出，本發明方法於此實施例上可獲得極多的銀十面體奈米粒子，並具有高度的粒子形狀專一性及粒徑大小均一性。The transmission electron microscope image obtained in this embodiment is shown in FIG. 2, which is a magnified photograph of the silver nanoparticle particles seen at a magnification of 12000 times. As is apparent from FIG. 2, the method of the present invention is on this embodiment. A large number of silver decahedral nanoparticles are obtained with high particle shape specificity and particle size uniformity.
本實施例溶液顏色變化過程請參閱圖三，其係隨時間取樣之紫外-可見光吸收光譜圖，可觀察到在照光時間1.5小時溶液會擁有最高的500nm吸收峰，此吸收峰為銀十面體奈米粒子所提供的長軸訊號。Refer to Figure 3 for the color change process of the solution in this example. It is a UV-visible absorption spectrum sample taken over time. It can be observed that the solution will have the highest absorption peak of 500 nm at 1.5 hours of illumination time. This absorption peak is a silver decahedron. The long axis signal provided by the nanoparticle.
本實施例合成之銀奈米粒子之穩定性可用圖四表明，圖四(A)係本實施例合成之十面體銀奈米粒子放置2個月之穿透式電子顯微鏡影像，圖四(B)係本實施例合成之十面體銀奈米粒子放置1年之穿透式電子顯微鏡影像，可以看到其仍擁有一定之十面體外型及粒徑大小，顯示本方法合成之銀奈米粒子擁有良好的穩定性。The stability of the silver nanoparticle synthesized in this embodiment can be shown in FIG. 4, and FIG. 4(A) is a transmission electron microscope image of the decahedral silver nanoparticle synthesized in this embodiment for 2 months, FIG. 4 ( B) The decahedral silver nanoparticle synthesized in this embodiment is placed in a transmission electron microscope image for one year, and it can be seen that it still has a certain ten-faced in vitro type and particle size, indicating that the method is synthesized by the silver mine. Rice particles have good stability.
(a2)以電子天秤量取394mg四氯金酸(HAuCl4‧3H2O)粉末，並溶於100ml去離子水(H2O)中均勻混合，形成濃度為10-2M之四氯金酸溶液。(a2) 394 mg of tetrachloroauric acid (HAuCl 4 ‧3H 2 O) powder was weighed by electronic balance and uniformly mixed in 100 ml of deionized water (H 2 O) to form tetrachlorogold at a concentration of 10 -2 M. Acid solution.
(b2)以電子天秤量取1.32g檸檬酸鈉，並溶於900ml去離子水(H2O)中均勻混合，配製4.99x10-3M檸檬酸鈉水溶液。(b2) 1.32 g of sodium citrate was weighed by an electronic balance, and uniformly dissolved in 900 ml of deionized water (H 2 O) to prepare an aqueous solution of 4.99 x 10 -3 M sodium citrate.
(c2)混合四氯金酸溶液及檸檬酸鈉水溶液並以磁石攪拌器攪拌5分鐘，使四氯金酸與硝酸銀充分混合。(c2) A tetrachloroauric acid solution and an aqueous solution of sodium citrate were mixed and stirred with a magnetic stirrer for 5 minutes to sufficiently mix tetrachloroauric acid with silver nitrate.
(d2)將反應溫度控制在室溫。(d2) The reaction temperature was controlled at room temperature.
(e2)將混合溶液放置於波長為450nm之LED光源下，持續照光約1.5小時後溶液變為粉紅色即完成反應。(e2) The mixed solution was placed under an LED light source having a wavelength of 450 nm, and the reaction was turned into pink after the illumination was continued for about 1.5 hours to complete the reaction.
本實施例所得之穿透式電子顯微鏡影像如圖五所示，其係為放大倍率20000倍下所見之金奈米粒子放大照片，由圖五可明顯看出，本發明方法於此實施例上可獲得極多的金奈米球，其粒徑大小約平均在10nm左右。The transmission electron microscope image obtained in this embodiment is shown in FIG. 5, which is an enlarged photograph of the gold nanoparticle particles seen at a magnification of 20,000 times. As apparent from FIG. 5, the method of the present invention is on this embodiment. A large number of gold nanospheres are available, and the particle size is about 10 nm on average.
綜合上述二較佳實施例，本發明方法可提供具有高度形狀專一性及粒徑大小均一性之金屬奈米粒子，且具有良好之穩定性，本發明方法與先前光化學合成技術相比，有以下優點：In combination with the above two preferred embodiments, the method of the present invention can provide metal nanoparticles having high shape specificity and uniformity of particle size, and has good stability. Compared with the prior photochemical synthesis technology, the method of the present invention has The following advantages:
(1)不需要事先合成晶種，使得光化學合成技術中較複雜之晶種合成步驟得以省略，並去除因晶種合成過程時產生的些微差異，導致每一批金屬奈米粒子的品質(型態以及大小分佈)不穩定。(1) It is not necessary to synthesize seed crystals in advance, so that the more complicated seed crystal synthesis steps in the photochemical synthesis technology are omitted, and the slight differences caused by the seed crystal synthesis process are removed, resulting in the quality of each batch of metal nanoparticles ( Type and size distribution) are unstable.
(2)本發明方法使用的合成步驟及使用之儀器以及藥劑都較為簡單，不需額外添加保護劑及還原劑，並減輕對環境之影響，使得合成過程更為環保。(2) The synthesis step and the apparatus and the medicament used in the method of the invention are relatively simple, no additional protective agent and reducing agent are added, and the environmental impact is alleviated, so that the synthesis process is more environmentally friendly.
惟以上方法僅為本發明之較佳實施例而已，並非用以限定本發明；凡其他未脫離本發明所揭示之精神下而完成的等效修飾或置換，均應包含於後述申請專利範圍內。The above-mentioned methods are only the preferred embodiments of the present invention, and are not intended to limit the present invention; all other equivalent modifications or substitutions that are not departing from the spirit of the present invention should be included in the scope of the following claims. .
圖 一：本發明之貴金屬奈米粒子的製造方法流程圖。Figure 1 is a flow chart showing a method for producing noble metal nanoparticles of the present invention.
圖 二：實施例一之穿透式電子顯微鏡影像。Figure 2: Transmissive electron microscope image of Example 1.
圖 三：實施例一之隨時間取樣之紫外-可見光吸收光譜圖。Figure 3: UV-visible absorption spectrum of the sample taken over time in Example 1.
圖四(A)：實施例一之銀奈米粒子放置一段時間後之穿透式電子顯微鏡影像(一)。Figure 4 (A): A transmission electron microscope image (I) of the silver nanoparticle of Example 1 after being left for a period of time.
圖四(B)：實施例一之銀奈米粒子放置一段時間後之穿透式電子顯微鏡影像(二)。Figure 4 (B): Transmissive electron microscope image of the silver nanoparticle of Example 1 after being placed for a period of time (2).
圖 五：實施例二之穿透式電子顯微鏡影像。Figure 5: Transmissive electron microscope image of Example 2.
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