技术领域technical field
本发明属于碳量子点的制备领域，特别涉及一种以柠檬酸-脲为原料的超高量子产率碳量子点的制备方法。The invention belongs to the field of preparation of carbon quantum dots, in particular to a method for preparing carbon quantum dots with an ultra-high quantum yield using citric acid-urea as a raw material.
背景技术Background technique
近年来，由于传统提供荧光染料受到反复多次激发后很容易光漂白从而荧光性能减弱，与其有相似光转换性能的半导体量子点越来越多的被应用于生物标记和科研材料中。但是传统的半导体量子点往往是重金属量子点，其固有的生物相容性能差以及易“光眨眼”现象等缺点严重影响了其应用范围的拓展。除却这些缺点，传统的标记物质固有的生物毒性限制了其添加的量并且一些标记物质量子产率不高，所以这就严重影响了它们在生物标记中的应用。因此，越来越多的研究开始关注于无机非金属碳颗粒量子点。首先，碳颗粒量子点不仅克服了传统标记物质的缺点，而且具有良好的生物相容性和无光眨眼现象的等优点。因此，无机非金属碳颗粒量子点正是目前生物标记、生物检测、生物探针等科研应用方面的最优异的材料。In recent years, due to the fact that the traditional fluorescent dyes are easily photobleached after repeated excitations and the fluorescence performance is weakened, semiconductor quantum dots with similar photoconversion properties are more and more used in biomarkers and scientific research materials. However, traditional semiconductor quantum dots are often heavy metal quantum dots, and their inherent poor biocompatibility and easy "light blinking" phenomenon seriously affect the expansion of their application range. In addition to these shortcomings, the inherent biotoxicity of traditional markers limits the amount of addition and some markers have low quantum yields, so this seriously affects their application in biomarkers. Therefore, more and more studies have begun to focus on inorganic non-metallic carbon particle quantum dots. First of all, carbon particle quantum dots not only overcome the shortcomings of traditional labeling substances, but also have the advantages of good biocompatibility and no blinking phenomenon. Therefore, inorganic non-metallic carbon particle quantum dots are the most excellent materials for scientific research applications such as biomarkers, biodetections, and bioprobes.
目前无机非金属碳量子点的合成方法主要有两种，一种是从上到下的合成方法：粉碎碳源，通过聚合物表面钝化的方式使其有效发光，主要包括电弧放电法、激光法、电化学法、机械粉碎、球磨或化学氧化。这种方法制备的碳点虽然粒径均一度较高，但是耗能过高，除激光灼烧法之外其他方法制备的碳点荧光产率都较低。另外一种方法是从下到上的合成方法：热解或碳化合适前驱物直接合成荧光碳量子点，包括灰烬的氧化或腐蚀法、热解有机物法、微波合成法、超声法、掺杂法。但是通过这些方法中的大部分生产的碳量子点的量子产率往往较低，这就要在生物标记时增加投入量，致使毒性提高。因此，寻找一种能制备出具有超高量子产率、粒径均匀的碳点的方法具有相当重要的意义。At present, there are two main synthesis methods for inorganic non-metallic carbon quantum dots. One is the synthesis method from top to bottom: pulverize the carbon source and passivate the surface of the polymer to make it emit light effectively, mainly including arc discharge method, laser method, electrochemical method, mechanical pulverization, ball milling or chemical oxidation. Although the carbon dots prepared by this method have high particle size uniformity, the energy consumption is too high, and the fluorescence yield of carbon dots prepared by other methods except the laser burning method is low. Another method is a bottom-up synthesis method: pyrolysis or carbonization of suitable precursors to directly synthesize fluorescent carbon quantum dots, including oxidation or corrosion of ash, pyrolysis of organic matter, microwave synthesis, ultrasonication, and doping . However, the quantum yield of carbon quantum dots produced by most of these methods is often low, which requires an increase in the amount of input in biomarking, resulting in increased toxicity. Therefore, it is of great significance to find a method that can prepare carbon dots with ultra-high quantum yield and uniform particle size.
高温热解法是目前常用的荧光碳点制备方法。目前已有报道的，通过微波热解各种氨基酸来制备荧光碳点，但是存在着微波温度不可控(存在局部过热点)以及荧光效率不高等缺点。通过水热法制备荧光碳点不仅具有成核均匀，颗粒大小可控的优点，但是在目前的报道中通过此法碳颗粒量子点大多数荧光产率不高。High-temperature pyrolysis is currently the most commonly used method for the preparation of fluorescent carbon dots. It has been reported that fluorescent carbon dots are prepared by microwave pyrolysis of various amino acids, but there are disadvantages such as uncontrollable microwave temperature (local hot spots) and low fluorescence efficiency. The preparation of fluorescent carbon dots by hydrothermal method not only has the advantages of uniform nucleation and controllable particle size, but in the current reports, most of the fluorescence yields of carbon particle quantum dots by this method are not high.
发明内容Contents of the invention
本发明所要解决的技术问题是提供一种以柠檬酸钠-脲为原料的超高量子产率量子点的制备方法，该方法简便易行，成本较低；该方法制备得到的碳量子点具有量子效率高、单分散性好、发光性能稳定、不发生“眨眼”现象、生物相容性好等优势。The technical problem to be solved by this invention is to provide a kind of preparation method using sodium citrate-urea as raw material ultra-high quantum yield quantum dot, the method is simple and easy, and the cost is low; the carbon quantum dot prepared by the method has It has the advantages of high quantum efficiency, good monodispersity, stable luminescent performance, no "blinking" phenomenon, and good biocompatibility.
本发明的一种以柠檬酸-脲为原料的超高量子产率碳量子点的制备方法，包括：A kind of preparation method of the ultra-high quantum yield carbon quantum dot that takes citric acid-urea as raw material of the present invention comprises:
(1)以柠檬酸和脲为原料进行水热反应，得到水热产物；其中，水热反应温度为80～260℃，反应时间为0.5h～3h；(1) Using citric acid and urea as raw materials to perform a hydrothermal reaction to obtain a hydrothermal product; wherein, the hydrothermal reaction temperature is 80-260°C, and the reaction time is 0.5h-3h;
(2)将步骤(1)中的水热产物烘干后，进行热解煅烧，得到煅烧产物；其中，煅烧的温度为100～500℃，煅烧时间为0.1～2h；(2) After drying the hydrothermal product in step (1), perform pyrolysis and calcination to obtain a calcined product; wherein, the calcination temperature is 100-500° C., and the calcination time is 0.1-2 h;
(3)将步骤(2)中煅烧的产物进行研磨，过滤，得到以柠檬酸-脲为原料的超高量子产率碳量子点。(3) Grinding and filtering the product calcined in step (2) to obtain carbon quantum dots with an ultra-high quantum yield using citric acid-urea as a raw material.
用于生物方面应用时，用3000Da～3500Da透析膜透析，透析外液备用；其中透析时间为12h。For biological applications, use a 3000Da-3500Da dialysis membrane for dialysis, and dialyze the external fluid for standby; the dialysis time is 12 hours.
所述步骤(1)中柠檬酸、脲与蒸馏水的质量比为1～10g:0.01～100g:0.01～100g。In the step (1), the mass ratio of citric acid, urea and distilled water is 1-10g:0.01-100g:0.01-100g.
所述步骤(2)中烘干为60℃过夜烘干。The drying in the step (2) is overnight drying at 60°C.
所述步骤(2)中煅烧时升温速率为10℃/min。The heating rate during calcination in the step (2) is 10° C./min.
所述步骤(3)中过滤为0.22μm水系滤膜过滤。The filtration in the step (3) is 0.22 μm water membrane filtration.
本发明中运用柠檬酸为碳源、以尿素为氮源，在水环境下进行水热反应。由于此反应是均相反应，所以成核的大小均一。然后通过热解的方法使水热产物进一步的碳化使其吸湿性以及粘连性降低。通过此法得到的碳颗粒量子点具有超高量子产率，颗粒大小均一，无光眨眼现象，荧光稳定性极高，合成方法简单，反应材料廉价易得，成本较低等诸多优点。由于具有超高量子产率兼具低的细胞毒性，所以本专利方法制备的碳点只需少量添加即可得到完美的生物标记图。这些优点为柠檬酸-脲(尿素)碳量子点在生命科学、分析科学、材料科学、免疫医学、检验检疫等传统及新兴领域的应用打下了良好的基础。In the present invention, citric acid is used as carbon source, urea is used as nitrogen source, and hydrothermal reaction is carried out under water environment. Since this reaction is a homogeneous reaction, the size of the nucleation is uniform. Then the hydrothermal product is further carbonized by pyrolysis to reduce its hygroscopicity and adhesion. The carbon particle quantum dots obtained by this method have many advantages such as ultra-high quantum yield, uniform particle size, no blinking phenomenon, high fluorescence stability, simple synthesis method, cheap and easy-to-obtain reaction materials, and low cost. Due to its ultra-high quantum yield and low cytotoxicity, the carbon dots prepared by this patented method only need a small amount of addition to obtain a perfect biomarker map. These advantages have laid a good foundation for the application of citric acid-urea (urea) carbon quantum dots in traditional and emerging fields such as life science, analytical science, material science, immunology, inspection and quarantine.
本发明的方法中以柠檬酸-脲为原料水热法制备热解前体并完成初步的碳化以及氮的掺杂；将水热产物煅烧来完成继续碳化。In the method of the present invention, citric acid-urea is used as a raw material to prepare a pyrolysis precursor by a hydrothermal method and complete preliminary carbonization and doping of nitrogen; the hydrothermal product is calcined to complete further carbonization.
发明在中低温条件下水相中进行，反应条件较为温和，操作简便，原料易得便宜，绿色环保，水热反应产物本身具有较强荧光，产品产率较高，制备的碳量子点具有超高量子产率、无“光眨眼”现象、稳定性高、生物相容性好、pH性质优异等优势。The invention is carried out in the water phase under medium and low temperature conditions, the reaction conditions are relatively mild, the operation is simple, the raw materials are easy to obtain and cheap, green and environmentally friendly, the hydrothermal reaction product itself has strong fluorescence, the product yield is high, and the prepared carbon quantum dots have ultra-high Quantum yield, no "light blinking" phenomenon, high stability, good biocompatibility, excellent pH properties and other advantages.
有益效果Beneficial effect
(1)本发明的制备方法操作简单方便，重复性好，成本低，制备得到的碳量子点保存时间长；(1) The preparation method of the present invention is simple and convenient to operate, has good repeatability, low cost, and the prepared carbon quantum dots have a long storage time;
(2)本发明的制备方法得到的碳量子点具有量子效率高(可达78.8％，以硫酸奎宁硫酸溶液在其激发波长360nm处紫外吸收为0.05以下的发射强度为基准计算)、单分散性好、发光性能稳定、不发生“眨眼”现象、生物相容性好等优势。(2) The carbon quantum dots obtained by the preparation method of the present invention have high quantum efficiency (up to 78.8%, based on the emission intensity of quinine sulfuric acid solution at its excitation wavelength 360nm where the ultraviolet absorption is below 0.05), monodisperse Good performance, stable luminous performance, no "blinking" phenomenon, good biocompatibility and other advantages.
附图说明Description of drawings
图1为实施例1中的制备方法流程图；Fig. 1 is the preparation method flowchart in embodiment 1;
图2为实施例1中碳颗粒荧光量子点的透射电镜图；Fig. 2 is the transmission electron micrograph of carbon particle fluorescence quantum dot in embodiment 1;
图3为实施例1中碳颗粒荧光量子点的X射线衍射图；Fig. 3 is the X-ray diffraction figure of carbon particle fluorescent quantum dot in embodiment 1;
图4为实施例1中碳颗粒荧光量子点的荧光稳定性测试曲线；Fig. 4 is the fluorescent stability test curve of carbon particle fluorescent quantum dot in embodiment 1;
图5为实施例3碳颗粒荧光量子点在不同水热时间(0.5h、1.0h、1.5h、2.0h、2.5h、3.0h)下的荧光强度对比图；Fig. 5 is the comparison chart of the fluorescence intensity of the carbon particle fluorescent quantum dots of Example 3 under different hydrothermal times (0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h);
图6为实施例2中碳颗粒荧光量子点在不同环境pH下的荧光强度对比图。FIG. 6 is a comparison diagram of the fluorescence intensity of the carbon particle fluorescent quantum dots in Example 2 at different environmental pHs.
具体实施方式detailed description
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
(1)将柠檬酸、脲和蒸馏水(质量比为1.2g:0.8g:20g)混合，搅拌溶解，得到混合液；(1) Mix citric acid, urea and distilled water (mass ratio is 1.2g:0.8g:20g), stir and dissolve to obtain a mixed solution;
(2)将(1)中混合液置于100mL高压反应釜中，170℃环境下，水热反应1.5h，得到水热产物；(2) Put the mixture in (1) in a 100mL autoclave, and conduct a hydrothermal reaction at 170°C for 1.5h to obtain a hydrothermal product;
(3)将(2)中所得水热产物于60℃环境下过夜烘干；(3) drying the hydrothermal product obtained in (2) overnight at 60°C;
(4)将(3)中所得烘干产物置于250℃环境下煅烧0.5h，升温速率为10℃/min，得到煅烧产物；(4) Calcining the dried product obtained in (3) at 250° C. for 0.5 h at a heating rate of 10° C./min to obtain the calcined product;
(5)将(4)中得到的煅烧产物研磨充分蒸馏水溶解，用0.22μm水系滤膜过滤，得到粒径均一的碳点溶液。(5) The calcined product obtained in (4) is ground and fully dissolved in distilled water, and filtered with a 0.22 μm water filter membrane to obtain a carbon dot solution with uniform particle size.
制备方法流程图如图1所示。图2为实施例1中碳颗粒荧光量子点的透射电镜图，粒子平均粒径约为6.64nm。图3为碳颗粒荧光量子点的X射线衍射图，衍射峰位与标准石墨晶型标准峰位类似。图4为碳颗粒荧光量子点的荧光稳定性测试曲线，从图中可以看出制备的产品经过1个小时的照射荧光强度基本没有变化，说明产品的荧光性质非常稳定。The flow chart of the preparation method is shown in Figure 1. Fig. 2 is a transmission electron microscope image of carbon particle fluorescent quantum dots in Example 1, and the average particle size of the particles is about 6.64nm. Fig. 3 is an X-ray diffraction pattern of carbon particle fluorescent quantum dots, and the diffraction peak position is similar to the standard peak position of standard graphite crystal form. Figure 4 is the fluorescence stability test curve of carbon particle fluorescent quantum dots. It can be seen from the figure that the fluorescence intensity of the prepared product basically does not change after 1 hour of irradiation, indicating that the fluorescence properties of the product are very stable.
实施例2Example 2
(1)将柠檬酸、脲和蒸馏水(质量比为1.2g:0.8g:25g)混合，搅拌溶解，得到混合液；(1) Mix citric acid, urea and distilled water (mass ratio is 1.2g:0.8g:25g), stir and dissolve to obtain a mixed solution;
(2)将(1)中混合液置于100mL高压反应釜中，170℃环境下，水热反应1.5h，得到水热产物；(2) Put the mixture in (1) in a 100mL autoclave, and conduct a hydrothermal reaction at 170°C for 1.5h to obtain a hydrothermal product;
(3)将(2)中所得水热产物于60℃环境下过夜烘干；(3) drying the hydrothermal product obtained in (2) overnight at 60°C;
(4)将(3)中所得烘干产物置于250℃环境下煅烧0.5h，升温速率为10℃/min，得到煅烧产物；(4) Calcining the dried product obtained in (3) at 250° C. for 0.5 h at a heating rate of 10° C./min to obtain the calcined product;
(5)将(4)中得到的煅烧产物研磨充分蒸馏水溶解，用0.22μm水系滤膜过滤，得到粒径均一的碳点溶液。(5) The calcined product obtained in (4) is ground and fully dissolved in distilled water, and filtered with a 0.22 μm water filter membrane to obtain a carbon dot solution with uniform particle size.
图6为碳颗粒荧光量子点在不同环境pH下的荧光强度对比图，从图中可以看出碳点溶液在pH为4～6之间时荧光强度最强，具有pH特殊效应应用可能。Figure 6 is a comparison chart of the fluorescence intensity of carbon particle fluorescent quantum dots at different environmental pHs. It can be seen from the figure that the fluorescence intensity of the carbon dot solution is the strongest when the pH is between 4 and 6, and it has the possibility of applying pH special effects.
实施例3Example 3
(1)将柠檬酸、脲和蒸馏水(质量比为1.2g:0.8g:20g)混合，搅拌溶解，得到混合液；(1) Mix citric acid, urea and distilled water (mass ratio is 1.2g:0.8g:20g), stir and dissolve to obtain a mixed solution;
(2)将(1)中混合液置于100mL高压反应釜中，170℃环境下，水热反应0.5～3h，得到水热产物；(2) Put the mixture in (1) in a 100mL autoclave, and conduct a hydrothermal reaction at 170°C for 0.5-3 hours to obtain a hydrothermal product;
(3)将(2)中所得水热产物于60℃环境下过夜烘干；(3) drying the hydrothermal product obtained in (2) overnight at 60°C;
(4)将(3)中所得烘干产物置于300℃环境下煅烧1h，升温速率为10℃/min，得到煅烧产物；(4) Calcining the dried product obtained in (3) at 300° C. for 1 hour at a heating rate of 10° C./min to obtain the calcined product;
(5)将(4)中得到的煅烧产物研磨充分蒸馏水溶解，用0.22μm水系滤膜过滤，得到粒径均一的碳点溶液。(5) The calcined product obtained in (4) is ground and fully dissolved in distilled water, and filtered with a 0.22 μm water filter membrane to obtain a carbon dot solution with uniform particle size.
图5为水热-热解两步法制备柠檬酸-脲(尿素)碳颗粒荧光量子点在不同水热时间(0.5h、1.0h、1.5h、2.0h、2.5h、3.0h)下的荧光强度对比图，从图中可以看出即使已经减小了数十倍荧光设备功率，产物的荧光强度还是如此之强。Fig. 5 is the preparation of citric acid-urea (urea) carbon particle fluorescent quantum dots under different hydrothermal times (0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h) by hydrothermal-pyrolysis two-step method Fluorescence intensity comparison chart, it can be seen from the figure that even if the power of the fluorescence equipment has been reduced by dozens of times, the fluorescence intensity of the product is still so strong.
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20160127 |