CN100463748C - Chemical Preparation Method of Silver Nanoparticles - Google Patents
Chemical Preparation Method of Silver Nanoparticles Download PDFInfo
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- CN100463748C CN100463748C CNB2006101351227A CN200610135122A CN100463748C CN 100463748 C CN100463748 C CN 100463748C CN B2006101351227 A CNB2006101351227 A CN B2006101351227A CN 200610135122 A CN200610135122 A CN 200610135122A CN 100463748 C CN100463748 C CN 100463748C
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title description 37
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 33
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Abstract
Description
技术领域： Technical field:
本发明属于溶液化学方法合成技术，特别是涉及一种采用化学的方法制备银纳米微粒。The invention belongs to the synthesis technology of solution chemical method, in particular to a chemical method for preparing silver nanoparticles.
背景技术： Background technique:
由于银纳米微粒可以在可见或近红外波段产生特征吸收峰。因此在过去二十几年的时间内，有关银纳米材料的研究在世界范围内引起了广泛重视。目前银纳米微粒已经在制备有机/无机纳米杂化发光器件、纳米生物传感器和具有抗菌功能的高分子材料中展示了很好的应用前景。Since silver nanoparticles can produce characteristic absorption peaks in the visible or near-infrared band. Therefore, in the past two decades, research on silver nanomaterials has attracted widespread attention worldwide. At present, silver nanoparticles have shown good application prospects in the preparation of organic/inorganic nano-hybrid light-emitting devices, nano-biosensors and polymer materials with antibacterial functions.
根据银纳米微粒所处的不同化学环境，其制备方法可以分为有机相、水相和两相反应三大类。第一种方法主要采用硼氢化钠为还原剂，在特定表面活性剂分子的作用下，于室温(或低温)条件下，进行化学反应得到银纳米微粒，虽然反应可以在常温下顺利完成，但由于硼氢化钠的较强还原作用，使得该反应的进行难于控制，而这一点对于制备不同形貌和尺寸的银纳米微粒是一个不利因素。第二种方法采用特殊的反应前驱体，在耐高温表面活性剂存在下，采用有机胺等作为还原剂，在高温条件下，合成制备银纳米微粒。该方法存在的主要问题是需要制备结构复杂的反应前驱体，并且要使用高沸点的有机溶剂作为反应介质，从而使进一步的应用受到了限制。第三种方法的制备过程中采用相转移催化剂，使银离子由水相转移至有机相，然后再加入硼氢化钠还原剂，在有机相中制备银纳米微粒，虽然目前这一方法在制备金属银纳米微粒的过程中仍被大量采用，但该方法在制备过程中需要耗费大量价格昂贵的相转移催化剂，从而增加了原材料成本。According to the different chemical environments in which silver nanoparticles are located, their preparation methods can be divided into three categories: organic phase, aqueous phase and two-phase reaction. The first method mainly uses sodium borohydride as a reducing agent. Under the action of specific surfactant molecules, under room temperature (or low temperature) conditions, a chemical reaction is carried out to obtain silver nanoparticles. Although the reaction can be successfully completed at room temperature, but Due to the strong reducing effect of sodium borohydride, it is difficult to control the reaction, which is an unfavorable factor for the preparation of silver nanoparticles with different shapes and sizes. The second method uses a special reaction precursor, in the presence of a high-temperature-resistant surfactant, and uses an organic amine as a reducing agent to synthesize and prepare silver nanoparticles under high-temperature conditions. The main problem of this method is that it needs to prepare the reaction precursor with complex structure, and the organic solvent with high boiling point is used as the reaction medium, which limits the further application. In the preparation process of the third method, a phase transfer catalyst is used to transfer silver ions from the aqueous phase to the organic phase, and then sodium borohydride reducing agent is added to prepare silver nanoparticles in the organic phase. Although this method is currently used in the preparation of metal The process of silver nanoparticles is still widely used, but this method needs to consume a lot of expensive phase transfer catalysts in the preparation process, thereby increasing the cost of raw materials.
发明内容： Invention content:
发明目的：本发明提供一种银纳米微粒的化学制备方法，其目的是解决现有的生产方法在反应难于控制、需要制备结构复杂的反应前驱体和高沸点的有机溶剂作为反应介质及生产成本大等方面存在的问题。Purpose of the invention: the present invention provides a chemical preparation method of silver nanoparticles, the purpose of which is to solve the problem that the existing production method is difficult to control the reaction and needs to prepare a complex reaction precursor and a high-boiling organic solvent as the reaction medium and production cost. Problems in large and other aspects.
技术方案：本发明是通过以下技术方案来实现的：Technical solution: the present invention is achieved through the following technical solutions:
一种银纳米微粒的化学制备方法，其特征在于：选择硝酸银、高氯酸银或醋酸银中的一种作为起始反应物，油酸钠或亚油酸钠作为表面活性剂，任意比例混合，以甲苯、二甲苯、临二氯苯或氯仿为反应介质，得溶液，将溶液缓慢升温，反应温度控制在80-200℃范围内，在电磁搅拌的反应条件下，恒定温度，反应时间为1～2小时，将上述反应得到的初产物进行离心分离，弃去上层清液，用丙酮和去离子水洗涤沉淀物2-3次，然后在40℃条件下，将沉淀物真空烘干12小时，即可得到由表面活性剂油酸钠作为包裹剂的银纳米微粒。A chemical preparation method for silver nanoparticles, characterized in that: one of silver nitrate, silver perchlorate or silver acetate is selected as an initial reactant, sodium oleate or sodium linoleate is used as a surfactant, and any proportion Mix, use toluene, xylene, dichlorobenzene or chloroform as the reaction medium to obtain a solution, slowly raise the temperature of the solution, and control the reaction temperature within the range of 80-200°C. Under the reaction conditions of electromagnetic stirring, the temperature is constant and the reaction time is Centrifuge the primary product obtained from the above reaction for 1 to 2 hours, discard the supernatant, wash the precipitate with acetone and deionized water for 2-3 times, and then dry the precipitate in vacuum at 40°C After 12 hours, silver nanoparticles with surfactant sodium oleate as encapsulating agent can be obtained.
起始反应物硝酸银与表面活性剂油酸钠的摩尔比为10:1～1:10；起始反应物硝酸银在反应介质中的浓度范围在1.0-50mmol/L之间。The molar ratio of the starting reactant silver nitrate to the surfactant sodium oleate is 10:1-1:10; the concentration range of the starting reactant silver nitrate in the reaction medium is between 1.0-50mmol/L.
所得到油酸钠修饰的银纳米微粒既可以较好地分散于非极性介质中，也可以较好地分散于极性介质中。The obtained silver nanoparticles modified with sodium oleate can be well dispersed in non-polar medium, and can also be well dispersed in polar medium.
优点及效果：本发明采用硝酸银为起始反应物，油酸钠为表面活性剂，通过控制反应温度和反应时间，制备得到了银纳米微粒。近些年的研究表明：油酸分子(或油酸根离子)对半导体及金属纳米微粒的表面具有较好的修饰作用。这种两亲性的有机分子可以为纳米微粒的自组装提供很好的化学受限环境，从而形成纳米微粒的三维或二维有序结构。另外，油酸钠是一种常见的工业表面活性剂，价廉易得，来源丰富。因此在本发明中，我们选用油酸钠作为反应过程的表面活性剂。Advantages and effects: the present invention adopts silver nitrate as a starting reactant, sodium oleate as a surfactant, and prepares silver nanoparticles by controlling the reaction temperature and reaction time. Studies in recent years have shown that oleic acid molecules (or oleate ions) have a good modification effect on the surface of semiconductor and metal nanoparticles. This amphiphilic organic molecule can provide a good chemically restricted environment for the self-assembly of nanoparticles, thereby forming a three-dimensional or two-dimensional ordered structure of nanoparticles. In addition, sodium oleate is a common industrial surfactant, which is cheap and easy to get, and has abundant sources. Therefore in the present invention, we select sodium oleate for use as the tensio-active agent of reaction process.
本发明寻找到了一种纳米银微粒的化学制备方法。通过选用硝酸银、油酸钠等基本化工原料作为反应物，在不同的反应温度、反应时间和反应物浓度条件下，通过采用价廉易得的基本化工原料，在有机相中制备得到了银纳米微粒。在本发明过程中，表面活性剂油酸钠起到了双重作用：一方面它为纳米银微粒的生长提供了良好的化学受限环境，从而可以使银纳米微粒尺寸得到较好的控制；另一方面它也起到了还原剂的作用，从而使起始反应物硝酸银被还原为纳米银微粒。同时由于油酸钠这种表面活性剂的特殊性质，使得所得到的银纳米微粒既可以较好地分散于甲苯、氯仿等非极性介质中，也可以较好地分散于水、乙醇等极性介质中。这一点对纳米银材料的进一步应用具有重要的意义。The present invention finds a chemical preparation method of nano-silver particles. By using basic chemical raw materials such as silver nitrate and sodium oleate as reactants, under different reaction temperature, reaction time and reactant concentration conditions, by using cheap and easy-to-obtain basic chemical raw materials, silver was prepared in the organic phase. nanoparticles. In the process of the present invention, the surfactant sodium oleate has played a dual role: on the one hand it provides a good chemically limited environment for the growth of nano-silver particles, so that the size of silver nanoparticles can be controlled better; on the other hand On the one hand, it also acts as a reducing agent, so that the starting reactant silver nitrate is reduced to nano-silver particles. At the same time, due to the special properties of the surfactant sodium oleate, the obtained silver nanoparticles can be well dispersed in non-polar media such as toluene and chloroform, and can also be well dispersed in polar media such as water and ethanol. in the sexual medium. This point is of great significance to the further application of nano-silver materials.
附图说明： Description of drawings:
附图1为本发明离心分离前银纳米粒子在甲苯中的紫外-可见吸收光谱检测依据示意图；Accompanying drawing 1 is that the ultraviolet-visible absorption spectrum detection basis schematic diagram of silver nanoparticles in toluene before centrifugation of the present invention;
附图2为本发明离心分离后银纳米粒子在甲苯中的紫外-可见吸收光谱检测依据示意图；Accompanying drawing 2 is that the ultraviolet-visible absorption spectrum detection basis schematic diagram of silver nanoparticles in toluene after centrifugal separation of the present invention;
附图3为本发明离心分离后银纳米粒子在水中的紫外-可见吸收光谱检测依据示意图；Accompanying drawing 3 is the ultraviolet-visible absorption spectrum detection basis schematic diagram of silver nanoparticle in water after centrifugal separation of the present invention;
附图4为本发明离心分离后银纳米粒子在乙醇中的紫外-可见吸收光谱检测依据示意图；Accompanying drawing 4 is the detection basis schematic diagram of the ultraviolet-visible absorption spectrum of silver nanoparticles in ethanol after centrifugation of the present invention;
附图5为本发明离心分离后银纳米粒子在氯仿中的紫外-可见吸收光谱检测依据示意图；Accompanying drawing 5 is the ultraviolet-visible absorption spectrum detection basis schematic diagram of silver nanoparticles in chloroform after centrifugal separation of the present invention;
附图6为本发明银纳米粒子的透射电子显微镜照片。Accompanying drawing 6 is the transmission electron micrograph of the silver nanoparticle of the present invention.
具体实施方式： Detailed ways:
本发明通过选择硝酸银、高氯酸银或醋酸银中的一种作为起始反应物，油酸钠或亚油酸钠作为表面活性剂，任意比例混合，甲苯、二甲苯、临二氯苯或氯仿为反应介质，在有机相中得到银纳米微粒。只是在不同反应条件下所得到的银纳米微粒所具有的特征吸收峰有些不同，但采用上述方法是完全能够达到发明目的的。下面通过具体的实施例来加以说明，但不因具体的实施例限制本发明。In the present invention, one of silver nitrate, silver perchlorate or silver acetate is selected as the initial reactant, sodium oleate or sodium linoleate is used as the surfactant, mixed in any proportion, toluene, xylene, and dichlorobenzene Or chloroform is used as the reaction medium, and silver nanoparticles are obtained in the organic phase. Only the characteristic absorption peaks of the silver nanoparticles obtained under different reaction conditions are somewhat different, but the above method can fully achieve the purpose of the invention. The following is illustrated by specific examples, but the present invention is not limited by the specific examples.
实施例1：Example 1:
将122mg油酸钠，34mg硝酸银，20ml甲苯加入到250ml的三口反应瓶内，温度缓慢升高到80℃后，在电磁搅拌的条件下，恒定温度反应1小时，即可得到黄色的含有银米金微粒的水溶胶。将上述反应得到的初产物进行离心分离，弃去上层清液，用丙酮和去离子水洗涤沉淀物2-3次，然后在40℃条件下，将沉淀物进行真空烘干12小时，即可得到由表面活性剂油酸钠作为包裹剂的纳米银微粒。所得到的银纳米微粒可以较好分散于甲苯、氯仿等非极性介质中，也可以较好地分散于水、乙醇等极性介质中。紫外-可见光谱测定的结果表明，银纳米微粒的在上述非极性和极性的分散体系中，于420-430nm处可以产生明显的纳米银所具有的特征吸收峰。Add 122mg of sodium oleate, 34mg of silver nitrate, and 20ml of toluene into a 250ml three-necked reaction flask. After the temperature is slowly raised to 80°C, react at a constant temperature for 1 hour under the condition of electromagnetic stirring to obtain a yellow silver-containing Hydrosol of rice gold particles. Centrifuge the initial product obtained from the above reaction, discard the supernatant, wash the precipitate with acetone and deionized water 2-3 times, and then dry the precipitate under vacuum for 12 hours at 40°C. The nano-silver particles with surfactant sodium oleate as encapsulating agent are obtained. The obtained silver nanoparticles can be preferably dispersed in non-polar media such as toluene and chloroform, and can also be preferably dispersed in polar media such as water and ethanol. The results of ultraviolet-visible spectrum measurement show that silver nanoparticles in the above non-polar and polar dispersion systems can produce obvious characteristic absorption peaks of nano-silver at 420-430 nm.
实施例2：Example 2:
将61mg油酸钠，17mg硝酸银，20ml甲苯加入到250ml的三口反应瓶内，温度缓慢升高到90℃后，在电磁搅拌的条件下，恒定温度反应1小时，即可得到黄色的含有银米金微粒的水溶胶。将上述反应得到的初产物进行离心分离，弃去上层清液，用丙酮和去离子水洗涤沉淀物2-3次，然后在40℃条件下，将沉淀物进行真空烘干12小时，即可得到由表面活性剂油酸钠作为包裹剂的纳米银微粒。所得到的银纳米微粒可以较好分散于甲苯、氯仿等非极性介质中，也可以较好地分散于水、乙醇等极性介质中。紫外-可见光谱测定的结果表明，银纳米微粒的在上述非极性和极性的分散体系中，于420-430nm处可以产生明显的纳米银所具有的特征吸收峰。Add 61mg of sodium oleate, 17mg of silver nitrate, and 20ml of toluene into a 250ml three-necked reaction flask. After the temperature is slowly raised to 90°C, react at a constant temperature for 1 hour under the condition of electromagnetic stirring to obtain a yellow silver-containing Hydrosol of rice gold particles. Centrifuge the initial product obtained from the above reaction, discard the supernatant, wash the precipitate with acetone and deionized water 2-3 times, and then dry the precipitate under vacuum for 12 hours at 40°C. The nano-silver particles with surfactant sodium oleate as encapsulating agent are obtained. The obtained silver nanoparticles can be preferably dispersed in non-polar media such as toluene and chloroform, and can also be preferably dispersed in polar media such as water and ethanol. The results of ultraviolet-visible spectrum measurement show that silver nanoparticles in the above non-polar and polar dispersion systems can produce obvious characteristic absorption peaks of nano-silver at 420-430 nm.
实施例3：Example 3:
将31mg亚油酸钠，10mg高氯酸银，20ml二甲苯加入到250ml的三口反应瓶内，温度缓慢升高到120℃后，在电磁搅拌的条件下，恒定温度反应2小时，即可得到黄色的含有银米金微粒的水溶胶。将上述反应得到的初产物进行离心分离，弃去上层清液，用丙酮和去离子水洗涤沉淀物2-3次，然后在40℃条件下，将沉淀物进行真空烘干12小时，即可得到由表面活性剂油酸钠作为包裹剂的纳米银微粒。所得到的银纳米微粒可以较好分散于甲苯、氯仿等非极性介质中，也可以较好地分散于水、乙醇等极性介质中。紫外-可见光谱测定的结果表明，银纳米微粒的在上述非极性和极性的分散体系中，于420-430nm处可以产生明显的纳米银所具有的特征吸收峰。Add 31mg of sodium linoleate, 10mg of silver perchlorate, and 20ml of xylene into a 250ml three-necked reaction flask. After the temperature is slowly raised to 120°C, react at a constant temperature for 2 hours under the condition of electromagnetic stirring to obtain A yellow hydrosol containing silver, rice and gold particles. Centrifuge the initial product obtained from the above reaction, discard the supernatant, wash the precipitate with acetone and deionized water 2-3 times, and then dry the precipitate under vacuum for 12 hours at 40°C. The nano-silver particles with surfactant sodium oleate as encapsulating agent are obtained. The obtained silver nanoparticles can be preferably dispersed in non-polar media such as toluene and chloroform, and can also be preferably dispersed in polar media such as water and ethanol. The results of ultraviolet-visible spectrum measurement show that silver nanoparticles in the above non-polar and polar dispersion systems can produce obvious characteristic absorption peaks of nano-silver at 420-430 nm.
实施例4：Example 4:
将16mg油酸钠，5mg醋酸银，20ml临二氯苯加入到250ml的三口反应瓶内，温度缓慢升高到180℃后，恒定温度反应1小时，可得到黄色的含有银米金微粒的水溶胶。将初产物进行离心分离，弃去上层清液，用丙酮和去离子水洗涤沉淀物2-3次，然后在40℃条件下，将沉淀物烘干12小时，即可得到由表面活性剂油酸钠作为包裹剂的纳米银微粒。所得到的银纳米微粒可以较好分散于甲苯、氯仿等非极性介质中，也可以较好地分散于水、乙醇等极性介质中。紫外-可见光谱测定的结果表明，银纳米微粒的在上述非极性和极性的分散体系中，于420-430nm处可以产生明显的纳米银所具有的特征吸收峰。Add 16mg of sodium oleate, 5mg of silver acetate, and 20ml of dichlorobenzene into a 250ml three-necked reaction flask. After the temperature is slowly raised to 180°C, react at a constant temperature for 1 hour to obtain yellow water containing silver rice gold particles. Sol. Centrifuge the initial product, discard the supernatant, wash the precipitate with acetone and deionized water for 2-3 times, and then dry the precipitate for 12 hours at 40°C to obtain the surfactant oil Sodium phosphate as the nano-silver particles of the encapsulation agent. The obtained silver nanoparticles can be preferably dispersed in non-polar media such as toluene and chloroform, and can also be preferably dispersed in polar media such as water and ethanol. The results of ultraviolet-visible spectrum measurement show that silver nanoparticles in the above non-polar and polar dispersion systems can produce obvious characteristic absorption peaks of nano-silver at 420-430 nm.
附图1、2、3、4、5分别显示为本发明离心分离前银纳米粒子在甲苯中的紫外-可见吸收光谱检测依据示意图、离心分离后银纳米粒子在甲苯中的紫外-可见吸收光谱检测依据示意图、离心分离后银纳米粒子在水中的紫外-可见吸收光谱检测依据示意图、离心分离后银纳米粒子在乙醇中的紫外-可见吸收光谱检测依据示意图离心分离后银纳米粒子在氯仿中的紫外-可见吸收光谱检测依据示意图。其中，附图1中a、b、c、d、e、f曲线分别代表反应时间为5min、10min、15min、20min、25min、30min离心分离前银纳米粒子在甲苯中的紫外-可见吸收光谱图；在附图2中a、b、c、d、e、f曲线分别代表反应时间为5min、10min、15min、20min、25min、30min的曲线为离心分离后所得到的银纳米粒子在甲苯中的紫外-可见吸收光谱图。附图6为本发明银纳米粒子的透射电子显微镜照片。Accompanying drawing 1,2,3,4,5 show respectively the UV-visible absorption spectrum detection basis schematic diagram of silver nanoparticle in toluene before centrifugal separation of the present invention, the ultraviolet-visible absorption spectrum of silver nanoparticle in toluene after centrifugal separation Schematic diagram of detection basis, schematic diagram of detection basis of UV-visible absorption spectrum of silver nanoparticles in water after centrifugation, schematic diagram of detection basis of UV-visible absorption spectrum of silver nanoparticles in ethanol after centrifugation Schematic diagram of the basis for the detection of ultraviolet-visible absorption spectroscopy. Wherein, a, b, c, d, e, f curves represent reaction time respectively in accompanying drawing 1 and be the ultraviolet-visible absorption spectrogram of silver nanoparticles in toluene before centrifugation of 5min, 10min, 15min, 20min, 25min, 30min In accompanying drawing 2, a, b, c, d, e, f curve represent reaction time respectively and be that the curve of 5min, 10min, 15min, 20min, 25min, 30min is the silver nanoparticle that obtains after centrifugation in toluene UV-Vis absorption spectrum. Accompanying drawing 6 is the transmission electron micrograph of the silver nanoparticle of the present invention.
结论：通过实验证明，选择硝酸银为起始反应物，油酸钠为表面活性剂，甲苯为反应介质，在有机相中得到银纳米粒子。在于不同反应条件下得到的银纳米粒子的紫外-可见吸收光谱于420-430nm范围表现出纳米银所具有的特征吸收峰。且所得到油酸钠修饰的银纳米粒子既可以较好地分散于甲苯、氯仿等非极性介质中，也可以较好地分散于水、乙醇等极性介质中。Conclusion: It is proved by experiments that silver nitrate is selected as the initial reactant, sodium oleate is used as the surfactant, and toluene is used as the reaction medium, and silver nanoparticles are obtained in the organic phase. The ultraviolet-visible absorption spectra of the silver nanoparticles obtained under different reaction conditions show the characteristic absorption peaks of nano silver in the range of 420-430 nm. Moreover, the obtained silver nanoparticles modified with sodium oleate can be well dispersed in non-polar media such as toluene and chloroform, and can also be well dispersed in polar media such as water and ethanol.
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