TWI419749B - Method for making gold nanoparticles - Google Patents
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本發明涉及一種金奈米粒子的製備方法，尤其涉及一種製備形貌可控的金奈米粒子的方法。 The invention relates to a method for preparing gold nano particles, in particular to a method for preparing gold nanoparticles with controllable morphology.
金奈米粒子由於具有小尺寸效應、表面效應、量子尺寸效應以及量子隧道效應而具有獨特的物理和化學性質，在光學、電學和磁學等方面具有廣闊的應用前景，可用做催化劑、部分醫藥製劑和生物感測器的傳感測定介質等。 Jinnai particles have unique physical and chemical properties due to their small size effect, surface effect, quantum size effect and quantum tunneling effect. They have broad application prospects in optics, electricity and magnetism, and can be used as catalysts and some medicines. Sensing assay media for formulations and biosensors.
金奈米粒子的性質取決於金奈米粒子的形狀和尺寸等因素，故在製備金奈米粒子的同時，能較好地控制金奈米粒子的形狀和尺寸具有極大的挑戰性。 The nature of the gold nanoparticles depends on the shape and size of the gold nanoparticles, so that it is extremely challenging to control the shape and size of the gold nanoparticles while preparing the gold nanoparticles.
先前技術中金奈米粒子的製備方法分為物理法和化學法，其中物理法主要有真空蒸鍍法、軟著陸法、電分散法和鐳射消融法，化學法主要有氧化還原法、範本法、光化學法、電化學法、相轉移法、溶膠法和微波法。目前化學法比較成熟，且化學法中氧化還原法最為常用。Turkevich法係比較經典的還原法製備金奈米粒子的方法之一(請參閱文獻“The Formation of Colloidal Gold,J Turkevich,P.C.Stevenson,J Hillier,The Journal of Physical Chemistry,Vol.57(1953)670-673”)，該方法中介紹了將檸檬酸鈉加入到沸騰的氯金酸溶液中反應來製備金奈米粒子，該方法反應速度較快，不利於金奈米粒子形貌的精確控制；另，2006年2月2日公開的、公開號為US20060021468的美國專利申請中也公開了一種用檸檬酸鈉還原製備金奈米粒子的方法，該方法在反應的過程中需要添加聚乙烯吡咯烷酮(PVP)等穩定劑，使得製備過程和條件更加複雜。 The preparation method of the gold nanoparticle in the prior art is divided into a physical method and a chemical method, wherein the physical method mainly includes a vacuum evaporation method, a soft landing method, an electric dispersion method and a laser ablation method, and the chemical method mainly includes a redox method and a template method. , photochemical method, electrochemical method, phase transfer method, sol method and microwave method. At present, the chemical method is relatively mature, and the redox method in the chemical method is most commonly used. The Turkevich method is one of the methods for preparing gold nanoparticles by the classical reduction method (see the literature "The Formation of Colloidal Gold, J Turkevich, P.C. Stevenson, J Hillier, The Journal of Physical Chemistry, Vol. 57 (1953) 670-673"), the method describes the addition of sodium citrate to a boiling chloroauric acid solution to prepare gold nanoparticles, the method is faster, which is not conducive to gold A method for the preparation of gold nanoparticles by reduction with sodium citrate is disclosed in US Patent Application Publication No. US20060021468, which is incorporated by reference. Stabilizers such as polyvinylpyrrolidone (PVP) are required in the process to make the preparation process and conditions more complicated.
有鑒於此，提供一種製備方法簡單且可精確控制形貌的金奈米粒子的製備方法實為必要。 In view of this, it is necessary to provide a preparation method of a gold nanoparticle which is simple in preparation method and can accurately control the morphology.
一種金奈米粒子的製備方法，該方法包括提供含金離子的溶液以及作為還原劑和穩定劑的含至少兩個羧基的羧基酸溶液，混合該含金離子的溶液以及該羧基酸溶液形成一混合溶液，在20℃~60℃下反應，生成金奈米粒子膠體溶液。 A method for preparing gold nanoparticle, comprising: providing a solution containing gold ions; and a carboxylic acid solution containing at least two carboxyl groups as a reducing agent and a stabilizer, mixing the gold ion-containing solution and the carboxylic acid solution to form a The mixed solution is reacted at 20 ° C to 60 ° C to form a colloidal solution of the gold nanoparticles.
相較於先前技術，本發明在較低溫度下來製備金奈米粒子，該溫度下，所述含金離子的溶液與羧基酸之間的反應比較緩慢，利於精確控制生成的金奈米粒子的形貌；此外，所述羧基酸可同時作為還原劑和穩定劑，故在反應過程中不需要加入額外的化學試劑，降低了製備的成本。 Compared with the prior art, the present invention prepares gold nanoparticles at a lower temperature, and the reaction between the gold ion-containing solution and the carboxylic acid is relatively slow at this temperature, which is advantageous for precisely controlling the generated gold nanoparticles. In addition, the carboxylic acid can serve as both a reducing agent and a stabilizer, so that no additional chemical reagents need to be added during the reaction, which reduces the cost of preparation.
圖1為本發明實施例製備的金奈米片的透射電鏡(TEM)照片。 1 is a transmission electron microscope (TEM) photograph of a gold nanosheet prepared in accordance with an embodiment of the present invention.
圖2為本發明實施例製備的金奈米網的TEM照片。 2 is a TEM photograph of a gold mesh prepared in accordance with an embodiment of the present invention.
圖3為本發明實施例製備的金奈米鏈的TEM照片。 Figure 3 is a TEM photograph of a gold nanostrand prepared in accordance with an embodiment of the present invention.
以下將結合附圖詳細說明本發明實施例金奈米粒子的製備方法。 Hereinafter, a method for preparing the gold nanoparticle of the embodiment of the present invention will be described in detail with reference to the accompanying drawings.
本發明實施例提供一種金奈米粒子的製備方法，該方法包括以下步驟：S1，提供含金離子的溶液以及作為還原劑和穩定劑的含至少兩個羧基的羧基酸溶液，以及S2，混合該含金離子的溶液以及該羧基酸溶液形成一混合溶液，在20℃~60℃下反應，生成金奈米粒子膠體溶液。 Embodiments of the present invention provide a method for preparing gold nanoparticles, the method comprising the steps of: providing a solution containing gold ions and a carboxylic acid solution containing at least two carboxyl groups as a reducing agent and a stabilizer, and S2, mixing The gold ion-containing solution and the carboxylic acid solution form a mixed solution, and react at 20 ° C to 60 ° C to form a gold nanoparticle colloidal solution.
在上述步驟S1中，所述含金離子的溶液包括溶劑以及溶於該溶劑的金源。所述溶劑包括水、乙醇、丙酮以及氯仿中的一種或複數種，優選為水或乙醇，本發明實施例採用水作為溶劑。所述金源優選為氯金酸(HAuCl4)、氯化金(AuCl3)以及氯金酸鉀(KAuCl4)中的一種或複數種。本發明實施例採用HAuCl4作為所述金源。在較低溫度(≦60℃)下，該羧基酸可同時作為穩定劑和還原劑使用，且該羧基酸的穩定作用更強，利於減慢反應速度且可較穩定的保存生成的金奈米粒子。所述至少含兩個羧基的羧基酸可為檸檬酸(C6H8O7)、乙二酸(H2C2O4)、丙二酸(C3H4O4)以及丁二酸(C4H6O4)中的一種或複數種。本發明實施例中採用C6H8O7作為所述羧基酸。 In the above step S1, the gold ion-containing solution includes a solvent and a gold source dissolved in the solvent. The solvent includes one or more of water, ethanol, acetone, and chloroform, preferably water or ethanol, and the embodiment of the present invention uses water as a solvent. The gold source is preferably one or more of chloroauric acid (HAuCl 4 ), gold chloride (AuCl 3 ), and potassium chloroaurate (KAuCl 4 ). In the embodiment of the invention, HAuCl 4 is used as the gold source. At lower temperatures (≦60 °C), the carboxylic acid can be used as both a stabilizer and a reducing agent, and the carboxylic acid has a stronger stabilizing effect, which is advantageous for slowing down the reaction rate and for stably storing the formed gold nanoparticles. particle. The carboxylic acid having at least two carboxyl groups may be citric acid (C 6 H 8 O 7 ), oxalic acid (H 2 C 2 O 4 ), malonic acid (C 3 H 4 O 4 ), and succinic acid. One or more of (C 4 H 6 O 4 ). In the examples of the present invention, C 6 H 8 O 7 is used as the carboxylic acid.
在上述步驟S2中，所述含金離子的溶液中的金離子與所述羧 基酸的摩爾比優選為1：0.1~1：10；該摩爾比不同，生成的金奈米粒子形貌各異，故，可藉由調控所述金離子與羧基酸的摩爾比來控制生成的金奈米粒子的形貌，本發明實施例中所述摩爾比為1：1。該步驟中可將該兩種溶液同時加入到一反應器中混合或該兩種溶液相互滴加來混合。 In the above step S2, the gold ions in the gold ion-containing solution and the carboxyl group The molar ratio of the base acid is preferably 1:0.1 to 1:10; the molar ratio of the formed gold nanoparticles is different, so that the molar ratio of the gold ion to the carboxylic acid can be controlled to control the formation. The morphology of the gold nanoparticles is 1:1 in the embodiment of the present invention. In this step, the two solutions may be simultaneously added to a reactor for mixing or the two solutions may be added to each other to be mixed.
另，在所述混合的過程中可進一步包括攪拌的步驟使所述含金離子的溶液與所述羧基酸均勻混合。 Further, the step of stirring may further include a step of stirring to uniformly mix the gold ion-containing solution with the carboxylic acid.
上述步驟S2中所述反應溫度較低，在該溫度範圍內，所述金源與所述羧基酸之間的反應比較緩慢，利於精確地控制生成的金奈米粒子的形貌。優選地，所述反應溫度為30℃~50℃。本發明實施例中所述反應溫度為50℃。所述混合過程在一反應器中進行，可藉由水浴或沙浴等加熱方式在所述混合過程開始之前就加熱所述混合反應的反應器到預定溫度，然後再進行混合，並一直保持該溫度到反應結束。本發明實施例中採用水浴加熱的方式在所述混合反應開始之前就加熱所述混合反應的反應器到50℃，並一直保持該溫度到反應結束。本發明實施例所述金奈米粒子可為金奈米片、金奈米網、金奈米鏈以及單分散的金奈米顆粒中的一種或幾種。其中所述金奈米片、金奈米網以及金奈米鏈均由金奈米顆粒或金奈米顆粒團聚的粒子之間藉由所述羧基以化學鍵連接而成。 The reaction temperature in the above step S2 is relatively low, and the reaction between the gold source and the carboxylic acid is relatively slow in the temperature range, which facilitates precise control of the morphology of the formed gold nanoparticles. Preferably, the reaction temperature is from 30 ° C to 50 ° C. The reaction temperature in the examples of the present invention is 50 °C. The mixing process is carried out in a reactor, and the reactor of the mixed reaction can be heated to a predetermined temperature by heating in a water bath or a sand bath or the like before the start of the mixing process, and then mixed, and kept at all times. Temperature until the end of the reaction. In the embodiment of the present invention, the reactor of the mixed reaction is heated to 50 ° C before the start of the mixing reaction by means of water bath heating, and the temperature is maintained until the end of the reaction. The gold nanoparticles in the embodiments of the present invention may be one or more of a gold nanosheet, a gold mesh, a gold nanostrand, and a monodisperse gold nanoparticle. The gold nanosheet, the golden nanoweb and the golden nanochain are all formed by chemically bonding the particles agglomerated by the gold nanoparticles or the gold nanoparticles.
另，可在所述步驟S2反應的任一時刻藉由快速冷卻等方式令該混合溶液停止反應，以控制反應時間，從而獲得穩定的不同形貌的金奈米粒子。本發明實施例中每隔一定時間從該膠 體溶液中取樣，並用冷水(<5℃)冷卻該樣品從而獲得具有特定形貌的金奈米粒子。所述反應的時間優選為15分鐘~24小時。 Alternatively, the mixed solution may be stopped at any time during the reaction of the step S2 by means of rapid cooling or the like to control the reaction time, thereby obtaining stable gold nanoparticles having different morphologies. In the embodiment of the invention, the glue is taken from the glue at regular intervals. The body solution was sampled and the sample was cooled with cold water (<5 ° C) to obtain gold nanoparticles having a specific morphology. The reaction time is preferably from 15 minutes to 24 hours.
上述步驟S2可進一步包括：調節所述混合溶液的pH值。該pH值調節的範圍為2~12.7。調節該混合溶液的pH值可控制生成的金奈米粒子的形貌，且總體來說，隨著pH值的增大，金奈米顆粒之間的分散性變強。 The above step S2 may further comprise: adjusting the pH of the mixed solution. The pH adjustment range is from 2 to 12.7. Adjusting the pH of the mixed solution controls the morphology of the formed gold nanoparticles, and in general, as the pH increases, the dispersibility between the gold nanoparticles becomes stronger.
本發明實施例中所述pH值的調節均為在所述混合步驟的開始階段進行調節，並在所述反應的過程中控制該pH值不變直到反應結束。可藉由在所述混合溶液中滴加酸、堿、酸式鹽或鹼式鹽來調節該混合溶液的pH值。本發明實施例中採用鹽酸溶液和氫氧化鈉溶液來調節該混合溶液的pH值。 The adjustment of the pH in the examples of the present invention is carried out at the beginning of the mixing step, and the pH is controlled during the course of the reaction until the end of the reaction. The pH of the mixed solution can be adjusted by dropwise adding an acid, a hydrazine, an acid salt or a basic salt to the mixed solution. In the embodiment of the present invention, a hydrochloric acid solution and a sodium hydroxide solution are used to adjust the pH of the mixed solution.
該調節所述混合溶液pH值的步驟可進一步包括：調節該混合溶液的pH值為2~4.4以形成金奈米片。 The step of adjusting the pH of the mixed solution may further comprise: adjusting the pH of the mixed solution to 2 to 4.4 to form a gold nanosheet.
在該pH值為2~4.4範圍內所述混合溶液反應可生成金奈米片。該金奈米片主要包括四邊形金奈米片、三角形金奈米片、切頂三角形金奈米片以及六邊形金奈米片。所述切頂三角形金奈米片以及六邊形金奈米片均以三角形金奈米片為構形基礎。該金奈米片的邊長為20nm~100nm，厚度為5nm~8nm。 The mixed solution reacts to form a gold nanosheet in the range of pH 2 to 4.4. The Jinnai tablets mainly include quadrilateral gold nano tablets, triangular gold nano tablets, cut-top triangular gold nano tablets and hexagonal gold nano tablets. The cut-top triangular gold nanosheet and the hexagonal gold nanosheet are all based on a triangular gold nanosheet. The gold nanosheet has a side length of 20 nm to 100 nm and a thickness of 5 nm to 8 nm.
請參閱圖1，該圖為調節所述混合溶液的pH=3，反應時間T=30分鐘、T=45分鐘、T=150分鐘和T=330分鐘時生成的金奈米片的透射電鏡照片。從圖中可看出，該金奈米片顏色較 淺，且重疊的金奈米片之間仍能看到被重疊部分的金奈米片的輪廓，表明該金奈米片厚度較小。具體地，請參閱圖1(a)，當反應時間T=30分鐘時形成了三角形金奈米片，該三角形金奈米片的邊長為20nm~40nm，此外，在形成三角形金奈米片的同時還形成有少量的四邊形金奈米片以及大量團聚的金奈米顆粒。請參閱圖1(b)，當反應時間T=45分鐘時，部分三角形金奈米片自組裝成切頂三角形以及六邊形金奈米片，該切頂三角形金奈米片以及六邊形金奈米片的邊長為50nm~100nm。請參閱圖1(c)，當反應時間T=150分鐘時，切頂三角形金奈米片以及六邊形金奈米片均減少，形成大量邊長為60~80nm的三角形金奈米片。請參閱圖1(d)，當反應時間T=330分鐘時，部分三角形金奈米片消失，出現由三角形金奈米片自組裝形成的五面體和六面體。該五面體和六面體的邊長為30nm~55nm。 Please refer to FIG. 1 , which is a transmission electron micrograph of the gold nanosheet produced by adjusting the pH of the mixed solution to 3, and the reaction time T=30 minutes, T=45 minutes, T=150 minutes, and T=330 minutes. . As can be seen from the figure, the color of the golden rice tablets is better than The outline of the overlapped portion of the gold nanosheet can still be seen between the shallow and overlapping gold nanosheets, indicating that the thickness of the golden nanosheet is small. Specifically, referring to FIG. 1( a ), when the reaction time T=30 minutes, a triangular gold nanosheet is formed, and the side length of the triangular gold nanosheet is 20 nm to 40 nm, and in addition, a triangular gold nanosheet is formed. At the same time, a small amount of quadrilateral gold nanoparticles and a large number of agglomerated gold nanoparticles are formed. Referring to Figure 1(b), when the reaction time is T=45 minutes, the partially triangular gold nanosheets self-assemble into a chopped triangle and a hexagonal gold nanosheet, which is a triangular pyramidal gold nanosheet and a hexagon. The side length of the gold nanosheet is 50 nm to 100 nm. Referring to Fig. 1(c), when the reaction time is T=150 minutes, the cut-top triangular gold nanosheet and the hexagonal gold nanosheet are reduced, and a large number of triangular gold nanosheets with a side length of 60-80 nm are formed. Referring to Fig. 1(d), when the reaction time T=330 minutes, the partially triangular gold nanosheet disappears, and the pentahedron and hexahedron formed by self-assembly of the triangular gold nanosheet appear. The pentahedron and the hexahedron have a side length of 30 nm to 55 nm.
該調節所述混合溶液pH值的步驟可進一步包括：調節該混合溶液的pH值為4.5~7.8以形成金奈米網。 The step of adjusting the pH of the mixed solution may further comprise: adjusting the pH of the mixed solution to 4.5 to 7.8 to form a gold mesh.
在該pH值為4.5~7.8範圍內所述混合溶液反應可生成金奈米網，該金奈米網由複數條金奈米鏈藉由所述羧基連接而成，該金奈米鏈由複數金奈米顆粒或複數金奈米顆粒團聚的粒子之間藉由所述羧基以化學鍵連接而成。在該pH值範圍內，不同反應時間下生成的所述金奈米網形狀各異，但以網狀結構為主，伴隨少量單獨的金奈米鏈。 The mixed solution reacts to form a gold mesh in the range of pH 4.5 to 7.8, and the golden mesh is formed by connecting a plurality of gold nanochains by the carboxyl group, and the golden nanochain is composed of plural The particles in which the gold nanoparticles or the plurality of gold nanoparticles are agglomerated are formed by chemical bonding of the carboxyl groups. Within this pH range, the shape of the gold mesh formed at different reaction times varies, but is dominated by a network structure with a small amount of individual gold nanochains.
請參閱圖2，該圖為在調節所述混合溶液的pH=5，反應時間 T=3分鐘和T=24小時，以及pH=7，T=450分鐘和T=24小時時生成的金奈米網的透射電鏡照片。該網狀結構疏密程度不同，並且伴隨有少量單獨的金奈米鏈的形成，但總體來看，反應生成的所述金奈米粒子以形成金奈米網為主。具體地，請參閱圖2(a)，當pH=5，T=3分鐘，即在所述混合溶液反應的初始階段，已形成了規則的金奈米網狀結構。請參閱圖2(b)，當pH=5，T=24小時，金奈米顆粒粒徑變小，形成的網變得較密。請參閱圖2(c)，當pH=7，T=450分鐘，得到的金奈米網比較離散，並伴隨著少量的金奈米鏈。請參閱圖2(d)，當pH=7，T=24小時，所述金奈米網與金奈米鏈自組裝為較密的網狀結構，連接該金奈米網的金奈米顆粒的粒徑為10nm~18nm。 Please refer to FIG. 2, which is to adjust the pH of the mixed solution to 5, and the reaction time. Transmission electron micrographs of the gold mesh produced at T = 3 minutes and T = 24 hours, and at pH = 7, T = 450 minutes and T = 24 hours. The network structure is different in degree of density, and is accompanied by the formation of a small amount of individual gold nanochains. However, in general, the gold nanoparticles formed by the reaction are mainly formed into a gold mesh. Specifically, referring to Fig. 2(a), when pH = 5, T = 3 minutes, that is, in the initial stage of the reaction of the mixed solution, a regular gold mesh network structure has been formed. Referring to Fig. 2(b), when pH = 5, T = 24 hours, the particle size of the gold nanoparticles becomes smaller, and the formed network becomes denser. Referring to Fig. 2(c), when pH=7, T=450 minutes, the obtained gold mesh is relatively discrete with a small amount of gold nanochain. Referring to FIG. 2(d), when pH=7, T=24 hours, the Jinnai net and the Jinnai chain self-assemble into a dense network structure, and the gold nanoparticles of the Jinnai net are connected. The particle size is from 10 nm to 18 nm.
該調節所述混合溶液pH值的步驟可進一步包括：調節該混合溶液的pH值為7.9~12.7以形成金奈米鏈。 The step of adjusting the pH of the mixed solution may further comprise: adjusting the pH of the mixed solution to 7.9 to 12.7 to form a gold nanochain.
在該pH值為7.9~12.7範圍內所述混合溶液反應可生成金奈米鏈，該金奈米鏈主要由複數金奈米顆粒或複數金奈米顆粒團聚的粒子之間藉由羧基以化學鍵連接而成，使該複數金奈米顆粒單向連成一串。請參閱圖3，該圖為在調節所述混合溶液的pH=9，反應時間T=90分鐘和T=450分鐘，以及pH=11，T=15分鐘和T=24小時時生成的金奈米鏈的透射電鏡照片。從圖中可看出，金奈米鏈由複數金奈米顆粒或複數金奈米顆粒團聚的粒子連接而成，而且形狀都比較規則。該金奈米鏈中金奈米顆粒的粒徑為10nm~55nm。 In the range of pH 7.9 to 12.7, the mixed solution reacts to form a gold nanochain, which is mainly composed of a plurality of gold nanoparticles or a plurality of gold nanoparticles, and a chemical bond is formed by a carboxyl group. Connected to make the plurality of gold nanoparticles unidirectionally connected into a string. Please refer to FIG. 3 , which is a Chennai produced when the pH of the mixed solution is adjusted to 9, the reaction time is T=90 minutes and T=450 minutes, and the pH is 11, T=15 minutes and T=24 hours. Transmission electron micrograph of the rice chain. As can be seen from the figure, the Jinnai chain is formed by connecting a plurality of gold nanoparticles or a plurality of particles of agglomerated gold nanoparticles, and the shape is relatively regular. The particle size of the gold nanoparticles in the gold nanochain is 10 nm to 55 nm.
上述步驟S2可進一步包括：在所述混合溶液中添加還原劑。該還原劑與所述金離子的摩爾比優選為3：1~7：1，該摩爾比範圍內，所述還原劑的添加利於生成分散性較好的金奈米顆粒，根據添加還原劑的量的不同，輔助控制生成的金奈米顆粒的形貌，還原劑的量越多，越趨向於生成金奈米鏈甚至單分散的金奈米顆粒。此外，生成的金奈米粒子的形貌也與加入所述還原劑的時機有關，如在生成的金奈米粒子為金奈米網時加入還原劑，金奈米網趨向於分解為金奈米鏈；在生成的金奈米粒子為金奈米鏈時加入還原劑，該金奈米鏈會趨向於分解為單分散的金奈米顆粒。可以理解，金奈米顆粒的分散性還與所述還原劑的還原性能的強弱有關，還原性越強，少量還原劑的添加也可生成分散性較好的金奈米顆粒。 The above step S2 may further include adding a reducing agent to the mixed solution. The molar ratio of the reducing agent to the gold ion is preferably from 3:1 to 7:1. In the range of the molar ratio, the addition of the reducing agent is favorable for forming a finely dispersed gold nanoparticle according to the addition of a reducing agent. The difference in the amount, the auxiliary control of the morphology of the gold nanoparticles produced, the more the amount of reducing agent, the more tend to produce gold nano-chain or even monodisperse gold nanoparticles. In addition, the morphology of the produced gold nanoparticles is also related to the timing of adding the reducing agent. For example, when the generated gold nanoparticle is a gold mesh, a reducing agent is added, and the golden mesh tends to be decomposed into Chennai. Rice chain; when the generated gold nanoparticle is a gold nanochain, a reducing agent is added, and the golden nano chain tends to decompose into monodisperse gold nanoparticle. It can be understood that the dispersibility of the gold nanoparticles is also related to the strength of the reducing performance of the reducing agent, and the stronger the reducing property, the addition of a small amount of the reducing agent can also produce the gold nanoparticles having better dispersibility.
所述生成的金奈米顆粒的粒徑為10nm~100nm。所述還原劑可為硼氫化鈉(NaBH4)、甲醛(CH2O)或抗壞血酸等。 The produced gold nanoparticles have a particle diameter of 10 nm to 100 nm. The reducing agent may be sodium borohydride (NaBH 4 ), formaldehyde (CH 2 O) or ascorbic acid or the like.
相較於先前技術，本發明在較低溫度下調節所述混合溶液的pH值來製備金奈米粒子，該溫度下，所述金源與所述羧基酸之間的反應比較緩慢，利於精確控制生成的所述金奈米粒子的形貌，且由於溫度較低，可僅藉由在反應初始階段調節所述混合溶液到相應的pH值範圍即可較容易地獲得不同形貌的金奈米粒子如金奈米片、金奈米網或金奈米鏈，無需額外添加穩定劑。獲得的該金奈米粒子的形貌經冷卻可保持較長時間(至少一週)。此外，本發明反應原料除所述金源和所述羧基酸之外不需要額外的化學試劑，降低了金奈米粒子的製 備成本。 Compared with the prior art, the present invention adjusts the pH of the mixed solution at a lower temperature to prepare a gold nanoparticle, and at this temperature, the reaction between the gold source and the carboxylic acid is relatively slow, which is advantageous for precision. Controlling the morphology of the formed gold nanoparticles, and because of the lower temperature, it is easier to obtain different morphologies of Chennai by adjusting the mixed solution to the corresponding pH range at the initial stage of the reaction. Rice particles such as Jinnai tablets, Jinnai nets or Jinnai chains do not require additional stabilizers. The morphology of the obtained gold nanoparticles can be maintained for a long time (at least one week) by cooling. In addition, the reaction raw material of the present invention does not require additional chemical reagents other than the gold source and the carboxylic acid, thereby reducing the production of the gold nanoparticles. Backup cost.
本發明實施例利用HAuCl4水溶液和C6H8O7溶液製備了不同形貌的金奈米粒子。 In the present invention, gold nanoparticles with different morphologies were prepared by using aqueous HAuCl 4 solution and C 6 H 8 O 7 solution.
實施例1 Example 1
金奈米片的製備 Preparation of Jinnai tablets
將反應器用王水浸洗，並用去離子水清洗複數次去除反應器中殘留的王水，50℃水浴加熱反應器，然後按所述金離子與所述羧基酸摩爾比1：1將C6H8O7溶液一次加入HAuCl4水溶液中形成混合溶液，並用鹽酸溶液調節該混合溶液的pH=3，藉由在不同時間取樣，獲得反應生成的金奈米粒子膠體溶液。取樣時間為T=30分鐘，T=45分鐘，T=150分鐘以及T=330分鐘，該取樣的樣品立刻用4℃冷水冷卻以停止反應，並放置2天後拍攝TEM照片，請參閱圖1(a)~(d)。 The reactor was dipped in aqua regia and washed with deionized water for several times to remove the aqua regia remaining in the reactor. The reactor was heated in a 50 ° C water bath, and then C 6 was added in a molar ratio of gold ions to the carboxylic acid of 1:1. The H 8 O 7 solution was added to the aqueous solution of HAuCl 4 at a time to form a mixed solution, and the pH of the mixed solution was adjusted to 3 with a hydrochloric acid solution, and the gold nanoparticle colloidal solution formed by the reaction was obtained by sampling at different times. The sampling time was T=30 minutes, T=45 minutes, T=150 minutes and T=330 minutes. The sampled sample was immediately cooled with 4°C cold water to stop the reaction, and the TEM photograph was taken after 2 days. Please refer to Figure 1. (a)~(d).
實施例2 Example 2
金奈米網的製備 Preparation of Jinnai Net
該金奈米網的製備過程與上述實施例1相同，區別僅在用鹽酸溶液調節該混合溶液的pH=5。取樣時間為T=3分鐘以及T=24小時，該取樣的樣品立刻用4℃冷水冷卻以停止反應，並放置2天後拍攝TEM照片，請參閱圖2(a)和圖2(b)。 The preparation process of the golden mesh was the same as in the above Example 1, except that the pH of the mixed solution was adjusted to 5 with a hydrochloric acid solution. The sampling time was T = 3 minutes and T = 24 hours. The sampled sample was immediately cooled with 4 ° C cold water to stop the reaction, and the TEM photograph was taken after 2 days of placement, see Fig. 2 (a) and Fig. 2 (b).
實施例3 Example 3
金奈米網的製備 Preparation of Jinnai Net
該金奈米網的製備過程與上述實施例1相同，區別僅在用氫氧化鈉溶液調節該混合溶液的pH=7。取樣時間為T=450分鐘以及T=24小時，該取樣的樣品立刻用4℃冷水冷卻以停止反應，並放置2天後拍攝TEM照片，請參閱圖2(c)和圖2(d)。 The preparation process of the golden mesh was the same as in the above Example 1, except that the pH of the mixed solution was adjusted to 7 with a sodium hydroxide solution. The sampling time was T = 450 minutes and T = 24 hours. The sampled sample was immediately cooled with 4 ° C cold water to stop the reaction, and the TEM photograph was taken after 2 days of placement, see Fig. 2 (c) and Fig. 2 (d).
實施例4 Example 4
金奈米鏈的製備 Preparation of Jinnai chain
該金奈米鏈的製備過程與上述實施例1相同，區別僅在用氫氧化鈉溶液調節該混合溶液的pH=9。取樣時間為T=90分鐘以及T=450分鐘，該取樣的樣品立刻用4℃冷水冷卻以停止反應，並放置2天後拍攝TEM照片，請參閱圖3(a)和圖3(b)。 The preparation process of the gold nanochain was the same as in the above Example 1, except that the pH of the mixed solution was adjusted to 9 with a sodium hydroxide solution. The sampling time was T = 90 minutes and T = 450 minutes. The sampled sample was immediately cooled with 4 ° C cold water to stop the reaction, and the TEM photograph was taken after 2 days of placement, see Fig. 3 (a) and Fig. 3 (b).
實施例5 Example 5
金奈米鏈的製備 Preparation of Jinnai chain
該金奈米鏈的製備過程與上述實施例1相同，區別僅在用氫氧化鈉溶液調節該混合溶液的pH=11。取樣時間為T=15分鐘以及T=24小時，該取樣的樣品立刻用4℃冷水冷卻以停止反應，並放置2天後拍攝TEM照片，請參閱圖3(c)和圖3(d)。 The preparation process of the gold nanochain was the same as in the above Example 1, except that the pH of the mixed solution was adjusted to 11 with a sodium hydroxide solution. The sampling time was T = 15 minutes and T = 24 hours. The sampled sample was immediately cooled with 4 ° C cold water to stop the reaction, and the TEM photograph was taken after 2 days of placement, see Fig. 3 (c) and Fig. 3 (d).
另，藉由實驗發現，當pH=1或pH=13時，反應24小時，均未發現有金奈米粒子形成。 Further, it was found by experiments that when pH = 1 or pH = 13, the reaction was carried out for 24 hours, and no gold nanoparticles were formed.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡習知本案技藝之人士援 依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Those who know the skills of this case Equivalent modifications or variations in accordance with the spirit of the invention are intended to be included within the scope of the following claims.
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