CN103240420B - A kind of method of purification of golden double cone structure nano particle - Google Patents
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- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
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Abstract
Description
技术领域 technical field
本发明涉及一种纳米材料的提纯方法，特别涉及一种对采用合成方法得到的金双锥纳米粒子混合溶液的提纯方法，属于纳米材料制备技术领域。 The invention relates to a method for purifying nanomaterials, in particular to a method for purifying a gold biconical nanoparticle mixed solution obtained by a synthesis method, and belongs to the technical field of nanomaterial preparation.
背景技术 Background technique
近年来，基于纳米粒子的技术被广泛应用，因为其具有依赖于纳米结构的独特的光学、电场、磁场特性。对于充分利用纳米粒子的性质来说，寻找一种快速有效的制备特定形状和尺寸的高纯度的纳米粒子的方法是非常关键的。金棒和金双锥都表现出两个等离子体共振峰，即横向等离子体共振峰和纵向等离子体共振峰。目前，已经有许多种方法可以制得高纯度的金棒纳米粒子，并将其广泛应用于双光子吸收、生物血管成像、生物传感和药物释放等领域。但一般来说，较大的电场增强和消光截面更有利于光学和生物技术领域的应用。金双锥具有一个五角基底和两个尖锐的顶点，与金棒相比，在相近的纵向等离子体共振峰的条件下，金双锥的消光截面是金棒的6倍，金双锥产生的电场强度的增强是金棒的3.6倍。如此明显的优势使得金双锥在表面增强拉曼基质和增强非线性光学性质的复合材料的应用中极具吸引力。 In recent years, nanoparticle-based technologies have been widely used because of their unique optical, electric, and magnetic properties that depend on nanostructures. To make full use of the properties of nanoparticles, it is very critical to find a fast and efficient method to prepare high-purity nanoparticles of specific shape and size. Both the gold rod and the gold bicone exhibit two plasmon resonances, the transverse plasmon resonance and the longitudinal plasmon resonance. At present, there are many methods to prepare high-purity gold rod nanoparticles, which are widely used in the fields of two-photon absorption, biological blood vessel imaging, biosensing and drug release. But in general, larger electric field enhancement and extinction cross sections are more beneficial for applications in the fields of optics and biotechnology. Gold bicones have a pentagonal base and two sharp vertices. Compared with gold rods, under the condition of similar longitudinal plasmon resonance peaks, the extinction cross section of gold bicones is 6 times that of gold rods, and the electric field intensity generated by gold bicones The reinforcement is 3.6 times that of the gold rod. Such obvious advantages make Au bicones attractive for applications in surface-enhanced Raman matrices and composites with enhanced nonlinear optical properties.
由于制得的金双锥纯度不高及副产品的存在，制约了金双锥纳米粒子的应用。通常使用的提纯手段主要是离心分离，其依据的原理是纳米粒子的质量或尺寸有一定程度的差别，然而，对于质量或大小相近的纳米粒子，离心无法实现有效的分离。从已有的研究中得知，通过改变生长液中所用的表面活性剂，可以达到提高产率的目的，如文献Small,2007(3),2103–2113通过采用具有更大端基的十六烷基三丁基溴化铵（CTBAB），使产率达到50～60%，但是，这样的纯度仍然不能满足金双锥的充分应用。 Due to the low purity of the prepared gold bicone and the existence of by-products, the application of gold bicone nanoparticles is restricted. The commonly used purification method is mainly centrifugation, which is based on the principle that there is a certain degree of difference in the quality or size of nanoparticles. However, for nanoparticles with similar quality or size, centrifugation cannot achieve effective separation. It is known from existing studies that by changing the surfactant used in the growth solution, the purpose of increasing the yield can be achieved, such as the literature Small, 2007 (3), 2103-2113 by using hexadecanoids with larger end groups Alkyl tributylammonium bromide (CTBAB), the yield can reach 50-60%, however, such purity still cannot meet the full application of gold bicone.
发明内容 Contents of the invention
本发明的目的在于克服现有技术存在的不足，提供一种简单有效提纯金双锥纳米粒子的方法。 The purpose of the present invention is to overcome the deficiencies in the prior art and provide a simple and effective method for purifying gold biconical nanoparticles.
本发明所采用的技术方案是：对采用合成方法得到的金双锥纳米粒子混合溶液初产品进行离心浓缩处理，再加入相同体积的浓度为0.1M～0.6M的十六烷基三甲基溴化铵水溶液，混合均匀，静置24小时后分离上下层，得到的下层即为等离子体共振波长为700nm～1300nm的纯金双锥纳米粒子产品。 The technical scheme adopted in the present invention is: carry out centrifugal concentration treatment to the initial product of the gold biconical nanoparticle mixed solution obtained by the synthesis method, and then add the same volume of cetyl trimethyl bromide with a concentration of 0.1M to 0.6M Ammonium chloride aqueous solution, mixed uniformly, separated upper and lower layers after standing for 24 hours, and the obtained lower layer is a pure gold biconical nanoparticle product with a plasmon resonance wavelength of 700nm-1300nm.
在上述技术方案中，所述纯金双锥纳米粒子产品的纯度为90%以上。 In the above technical solution, the purity of the pure gold biconical nanoparticle product is above 90%.
当所加入的十六烷基三甲基溴化铵水溶液浓度分别为0.1M、0.2M、0.3M、0.4M、0.5M、0.6M时,得到的金双锥纳米粒子的等离子体共振波长对应为1300nm、1070nm、1000nm、950nm、850nm、740nm附近。 When the added cetyltrimethylammonium bromide aqueous solution concentration is 0.1M, 0.2M, 0.3M, 0.4M, 0.5M, 0.6M respectively, the plasmon resonance wavelength of the obtained gold bipyramidal nanoparticles corresponds to Around 1300nm, 1070nm, 1000nm, 950nm, 850nm, 740nm.
传统的提纯纳米粒子的方法主要是依据粒子的尺寸与质量的离心分离，而十六烷基三甲基溴化铵（CTAB）作为阳离子型表面活性剂，在现有技术中主要用作化妆品的杀菌剂、柔软剂，乳化剂和抗静电剂。本发明采用CTAB用于对金双锥纳米粒子的提纯，其原理是：在制备过程中，由于得到的金双锥纳米粒子与副产物金球纳米粒子的晶面不同，它们对十六烷基三甲基溴化铵（CTAB）的吸附量也不同，金双锥对CTAB的吸附能力优于金球，通过调节十六烷基三甲基溴化铵（CTAB）的浓度，使金双锥纳米粒子产生絮凝，聚集，沉降，在静置的过程中优先沉降下来，从而方便地对金双锥纳米粒子实现提纯。 The traditional method of purifying nanoparticles is mainly based on the centrifugal separation of particle size and mass, while cetyltrimethylammonium bromide (CTAB), as a cationic surfactant, is mainly used as a cosmetic agent in the prior art. Bactericide, softener, emulsifier and antistatic agent. The present invention adopts CTAB to be used for the purification of gold biconical nanoparticles, and its principle is: in the preparation process, because the crystal face of the gold biconical nanoparticles obtained is different from that of the by-product gold spherical nanoparticles, they have no effect on hexadecyl The adsorption capacity of trimethylammonium bromide (CTAB) is also different. The adsorption capacity of gold bipyramid to CTAB is better than that of gold balls. By adjusting the concentration of cetyltrimethylammonium bromide (CTAB), the gold bipyramid Nanoparticles produce flocculation, aggregation, and sedimentation, and preferentially settle down during the standing process, so that the gold biconical nanoparticles can be purified conveniently.
与现有技术相比，本发明的不同之处在于直接将制得的金双锥纳米粒子离心浓缩后，加入相同体积一定浓度的CTAB水溶液，静置24h以上，沉降在底部的为纯度很高的金双锥产品，上层清液中的产品为金球。其显著的优点是：方法简便、易操作；对产品的尺寸易控制，提纯效率高，可实现工业化生产。 Compared with the prior art, the difference of the present invention is that after directly centrifuging and concentrating the prepared gold biconical nanoparticles, adding the same volume of CTAB aqueous solution with a certain concentration, standing for more than 24 hours, and those that settle at the bottom are of high purity The product of the gold bicone, the product in the supernatant is the gold ball. Its remarkable advantages are: the method is simple and easy to operate; the size of the product is easy to control, the purification efficiency is high, and industrial production can be realized.
附图说明 Description of drawings
图1是按本发明实施例1技术方案制备的金双锥纳米粒子提纯前后的扫描电镜（SEM）图； Fig. 1 is the scanning electron microscope (SEM) figure before and after purification of the gold biconical nanoparticles prepared by the technical scheme of embodiment 1 of the present invention;
图2是按本发明技术方案提纯金双锥纳米粒子的等离子体共振波长与CTAB浓度的关系图； Fig. 2 is the relation figure of the plasmon resonance wavelength and CTAB concentration of purifying gold bipyramidal nanoparticles according to the technical scheme of the present invention;
图3是按本发明制备的不同尺寸的金双锥纳米粒子的紫外-可见吸收光谱图； Fig. 3 is the ultraviolet-visible absorption spectrogram of the gold bipyramidal nanoparticles of different sizes prepared by the present invention;
图4是按本发明制备的等离子体共振波长约为1066nm的金双锥纳米粒子提纯前后的紫外-可见吸收光谱图； Fig. 4 is the ultraviolet-visible absorption spectrogram before and after purification of the gold biconical nanoparticle of about 1066nm by the plasmon resonance wavelength prepared by the present invention;
图5是按本发明实施例2技术方案制备的金双锥纳米粒子（等离子体共振波长约为738nm）的提纯前后的扫描电镜（SEM）图。 Fig. 5 is a scanning electron microscope (SEM) image before and after purification of gold biconical nanoparticles (plasmon resonance wavelength is about 738nm) prepared according to the technical solution of Example 2 of the present invention.
具体实施方式 Detailed ways
下面结合附图和实施例对本发明技术方案作进一步的阐述。 The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and embodiments.
实施例1： Example 1:
采用种子生长方法制备得到金双锥纳米粒子，其步骤为：第一步，配制种子溶液：将0.125ml0.01M氯金酸溶液、0.25ml0.01M柠檬酸钠溶液加入9.625ml的超纯水中，再加入新配制的、冰的0.15ml0.01M硼氢化钠溶液，放置4h。第二步，配制生长溶液：将1.2ml0.01M氯金酸溶液、0.06ml0.01M硝酸银溶液和0.402ml0.1M抗坏血酸溶液依次加入到28.5ml0.01M十六烷基三丁基溴化铵溶液中，然后再加入0.2ml柠檬酸钠稳定的种子溶液，在65℃下放置6h，合成得到金双锥纳米粒子混合溶液初产品。 Adopt seed growth method to prepare gold biconical nanoparticles, the steps are: the first step, prepare seed solution: add 0.125ml0.01M chloroauric acid solution, 0.25ml0.01M sodium citrate solution into 9.625ml ultrapure water , then add freshly prepared, iced 0.15ml of 0.01M sodium borohydride solution, and let stand for 4h. The second step is to prepare the growth solution: add 1.2ml0.01M chloroauric acid solution, 0.06ml0.01M silver nitrate solution and 0.402ml0.1M ascorbic acid solution to 28.5ml0.01M cetyltributylammonium bromide solution , and then add 0.2ml sodium citrate stabilized seed solution, place it at 65°C for 6h, and synthesize the initial product of gold bipyramidal nanoparticle mixed solution.
将合成的金双锥纳米粒子混合溶液初产品进行提纯：将得到的金双锥纳米粒子离心浓缩，倾去上层清液后，分别加入相同体积的浓度为0.1M、0.2M、0.3M、0.4M、0.5M、0.6M的CTAB水溶液，混合均匀，常温下静置24h；将上下层分离，下层即为得到的高纯度的金双锥纳米粒子。 Purify the initial product of the synthesized gold biconical nanoparticle mixed solution: centrifuge and concentrate the obtained gold biconical nanoparticles, pour off the supernatant, and add the same volume of concentrations of 0.1M, 0.2M, 0.3M, 0.4 M, 0.5M, and 0.6M CTAB aqueous solutions were mixed evenly, and stood at room temperature for 24 hours; the upper and lower layers were separated, and the lower layer was obtained high-purity gold biconical nanoparticles.
对提纯前后的金双锥纳米粒子进行形貌分析，其结果参见附图1，其中，a图是金双锥纳米粒子初产品，b图是采用浓度为0.3M的CTAB水溶液提纯后下层液中的金双锥纳米粒子纯产品，c图是提纯后上层液中的副产物金球纳米粒子。由图中结果可以看出，提纯后的金双锥纳米粒子纯度很高，达到90%以上，在SEM图中基本上没有金球纳米粒子的存在，提纯效果好。 The morphology analysis of the gold biconical nanoparticles before and after purification is carried out, and the results are shown in accompanying drawing 1, wherein, the figure a is the initial product of the gold bicone nanoparticles, and the figure b is the concentration in the lower layer after purification by a CTAB aqueous solution with a concentration of 0.3M. The pure product of the gold biconical nanoparticles, c figure is the by-product gold spherical nanoparticles in the supernatant after purification. It can be seen from the results in the figure that the purity of the purified gold biconical nanoparticles is very high, reaching more than 90%. There are basically no gold spherical nanoparticles in the SEM image, and the purification effect is good.
参见附图2，它是按本实施例所述的提纯技术方案得到的金双锥纳米粒子的等离子体共振波长、体积与CTAB浓度的关系图；由图中结果可以看出，随着金双锥纳米粒子的等离子体共振波长的减小或体积的减小，所需的CTAB浓度增大。 Referring to accompanying drawing 2, it is the relationship diagram of the plasmon resonance wavelength, volume and CTAB concentration of the gold bipyramid nanoparticle that obtains by the purification technical scheme described in the present embodiment; As can be seen from the figure result, along with gold bipyramid As the plasmon resonance wavelength or volume of cone nanoparticles decreases, the required CTAB concentration increases.
参见附图3，它是本实施例制备的不同尺寸的金双锥纳米粒子的紫外-可见吸收光谱图；图中GBP1～GBP6样品是所合成的等离子体共振波长分别为1244nm、1069nm、1006nm、883nm、855nm、738nm附近的金双锥纳米粒子。从紫外谱图可以看出，金双锥纳米粒子初产品中有一定量的副产物金球存在。 Referring to accompanying drawing 3, it is the ultraviolet-visible absorption spectrogram of the gold biconical nanoparticles of different sizes prepared in the present embodiment; GBP1～GBP6 sample among the figure is that the synthesized plasmon resonance wavelength is respectively 1244nm, 1069nm, 1006nm, Gold biconical nanoparticles near 883nm, 855nm, and 738nm. It can be seen from the ultraviolet spectrogram that there is a certain amount of by-product gold balls in the initial product of gold biconical nanoparticles.
参见附图4，它是本实施例制备的等离子体共振波长为1066nm附近的金双锥纳米粒子提纯前后的紫外-可见吸收光谱图，其中，曲线a是合成得到的金双锥纳米粒子初产品，即未经提纯处理的金双锥纳米粒子的紫外谱图；曲线b是按本发明提纯方法处理后得到的下层沉淀即金双锥纳米粒子纯产品的紫外谱图，曲线c是提纯方法处理后得到的上层清液即合成中产生的副产品金球的紫外谱图；由图中结果可以看出，提纯后的金双锥的紫外谱图中没有了金球的紫外特征峰，与初制备的金双锥纳米粒子相比，纯度得到了很大的提高。 Referring to accompanying drawing 4, it is that the plasmon resonance wavelength prepared by the present embodiment is the ultraviolet-visible absorption spectrogram before and after purification of the gold biconical nanoparticles near 1066nm, wherein, curve a is the initial product of the gold biconical nanoparticles synthesized , the ultraviolet spectrogram of the unpurified gold biconical nanoparticle; Curve b is the lower layer precipitation obtained after the purification method of the present invention is processed, i.e. the ultraviolet spectrogram of the gold biconical nanoparticle pure product, and curve c is after the purification method is processed The obtained supernatant is the ultraviolet spectrogram of the by-product gold spheres produced in the synthesis; as can be seen from the results in the figure, there is no ultraviolet characteristic peak of gold spheres in the ultraviolet spectrogram of the purified gold bicone, which is different from that of the initially prepared Compared with gold biconical nanoparticles, the purity has been greatly improved.
实施例2： Example 2:
金双锥纳米粒子的制备：将0.125ml0.01M氯金酸溶液、0.25ml0.01M柠檬酸钠溶液加入9.625ml的超纯水中，再加入新配制的、冰的0.15ml0.01M硼氢化钠溶液，放置4h，配制种子溶液。将1.2ml0.01M氯金酸溶液、0.06ml0.01M硝酸银溶液和0.402ml0.1M抗坏血酸溶液依次加入到28.5ml0.01M十六烷基三丁基溴化铵溶液中，配制生长溶液。在生长溶液加入0.6ml柠檬酸钠稳定的种子溶液，在65℃下放置6h，得到金双锥纳米粒子初产品。 Preparation of gold biconical nanoparticles: add 0.125ml0.01M chloroauric acid solution and 0.25ml0.01M sodium citrate solution to 9.625ml ultrapure water, then add freshly prepared, iced 0.15ml0.01M sodium borohydride Solution, placed for 4h, the preparation of seed solution. Add 1.2ml of 0.01M chloroauric acid solution, 0.06ml of 0.01M silver nitrate solution and 0.402ml of 0.1M ascorbic acid solution to 28.5ml of 0.01M hexadecyltributylammonium bromide solution to prepare a growth solution. Add 0.6 ml sodium citrate stabilized seed solution to the growth solution, and place it at 65° C. for 6 hours to obtain the primary product of gold bipyramidal nanoparticles.
将合成的金双锥纳米粒子进行提纯：将得到的金双锥纳米粒子初产品离心浓缩，倾去上层清液，加入相同体积的0.6MCTAB水溶液，混合均匀，常温下，静置24h；将上下层分离，下层即为高纯度的金双锥。将提纯前后的金纳米粒子进行形貌分析，结果参见附图5，其中，d图是未提纯的金双锥纳米粒子初产品，e图是提纯后下层液中的高纯度的金双锥纳米粒子，f图是提纯后的上层液中的副产物金球纳米粒子。由图中结果可以看出，提纯后的金双锥纳米粒子中基本上看不到金球，纯度很高。 Purify the synthesized gold biconical nanoparticles: centrifuge and concentrate the obtained gold biconical nanoparticles primary product, pour off the supernatant, add the same volume of 0.6MCTAB aqueous solution, mix well, and stand at room temperature for 24 hours; put the upper and lower The layers are separated, and the lower layer is the high-purity gold bicone. Analyze the morphology of the gold nanoparticles before and after purification, and the results are shown in accompanying drawing 5, wherein, figure d is the initial product of unpurified gold biconical nanoparticles, and figure e is the high-purity gold biconical nanoparticle in the lower layer after purification. Particles, figure f is the by-product gold spherical nanoparticles in the purified supernatant. It can be seen from the results in the figure that basically no gold balls can be seen in the purified gold biconical nanoparticles, and the purity is very high.
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