WO2023159804A1 - Carbon quantum dot having high quantum yield and wide-spectrum photoelectric response, and preparation method - Google Patents

Carbon quantum dot having high quantum yield and wide-spectrum photoelectric response, and preparation method Download PDF

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WO2023159804A1
WO2023159804A1 PCT/CN2022/098058 CN2022098058W WO2023159804A1 WO 2023159804 A1 WO2023159804 A1 WO 2023159804A1 CN 2022098058 W CN2022098058 W CN 2022098058W WO 2023159804 A1 WO2023159804 A1 WO 2023159804A1
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carbon quantum
quantum dots
wide
photoelectric response
infrared
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皮付伟
刘婧涵
刘玲
李姝琦
王丽颖
李靖坤
万玉琪
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江南大学
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    • C09K11/65Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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  • the invention relates to a carbon quantum dot with high quantum yield and wide-spectrum photoelectric response and a preparation method, belonging to the technical field of nano-luminescent materials.
  • carbon quantum dots usually have a diameter of less than 10nm. According to the crystal structure size of carbon quantum dots, they can be divided into carbon quantum dots, graphene quantum dots and polymer dots. Compared with traditional quantum dots, carbon quantum dots are mainly synthesized from readily available metal-free carbon-based materials. Due to their good biocompatibility and optical properties, such as excellent photostability and photobleaching resistance, carbon quantum dots are widely used in bioimaging, fluorescence sensing and other fields.
  • Typical synthesis methods mainly include the "bottom-up” method of hydrothermal, solvothermal, and microwave synthesis, and the "top-down” method of redox cleavage and physical grinding.
  • Modifying the structure of carbon quantum dots can improve their optical properties.
  • Current research mainly focuses on the doping of carbon quantum dots and the modification of functional groups. Among them, the doping of heteroatoms can improve the optical properties of carbon quantum dots, but its specific enhanced fluorescence mechanism and doping position have not yet been explained uniformly, and the structure and function of doped carbon quantum dots still need to be changed. further exploration.
  • the regulation of the fluorescence performance of carbon quantum dots and the improvement of quantum yield are the basis for later applications in the fields of sensing and imaging; at present, the photoelectric response of carbon quantum dots is mainly concentrated in the deep ultraviolet to visible light region, and the range is small, so the preparation Carbon quantum dots with photoelectric response in the near-infrared region are of great significance.
  • the present invention provides a simple carbon quantum dot with high quantum yield and wide-spectrum photoelectric response and a preparation method thereof.
  • the first object of the present invention is to provide a kind of method for preparing carbon quantum dots with high quantum yield and visible to near-infrared broad-spectrum photoelectric response, comprising the steps:
  • the concentration of the m-phenylenediamine in ethanol is 8-12mg/mL
  • the concentration range of the solid acid in the precursor solution is 0.1-4M.
  • the ethanol is absolute ethanol.
  • the full dissolution is carried out by ultrasonic-assisted dissolution.
  • the reaction method is a solvothermal method, specifically reacting at 180° C. for 12 hours.
  • the dopant solid acid is crystalline orthophosphoric acid.
  • the purification is to filter the solution after the reaction through a microporous membrane and a chromatographic column, remove unreacted precursors and impurities, and obtain purified carbon quantum dots; Wherein the pore diameter of the microporous membrane is 0.22 microns.
  • the chromatographic column eluent is dichloromethane and methanol, and the volume ratio thereof is 8-12:1, more preferably 10:1.
  • the concentration is obtained by concentrating the purified carbon quantum dots using a rotary evaporator.
  • the drying is vacuum drying, specifically placing the concentrated sample in a vacuum drying oven at 60° C. for 12-24 hours.
  • the prepared carbon quantum dots need to be redissolved, and then stored in the dark at 4°C; wherein the solvent for redissolving includes one or both of water and absolute ethanol .
  • the second object of the present invention is the carbon quantum dots with high quantum yield and wide spectrum photoelectric response from visible to near infrared prepared by the method of the present invention.
  • the third object of the present invention is the application of the carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared in the fields of biological imaging, fluorescence sensing, solar cells, and photodetectors.
  • the carbon quantum dots of the present invention have better optical properties, including higher quantum yield, excellent photostability and photobleaching resistance, and still maintain better fluorescence properties after ultraviolet lamp irradiation for 24h, relatively
  • the quantum yield reaches more than 67.3%, and can be as high as 102%.
  • the quantum yield is increased by 40 times.
  • the present invention uses orthophosphoric acid as an acidity regulator and a dopant to make the carbon core structure more regular, and the doped phosphorus element is modified in the edge region of the carbon quantum dot in the form of dihydrogen phosphate, as a layer intercalation agent, A multi-layer carbon quantum dot structure is formed, and the interlayer potential energy is reduced to realize long-distance transport of electrons, thus improving the quantum yield of carbon quantum dots.
  • the carbon quantum dots of the present invention can excite electrons under the irradiation of visible light, have photoconductivity, and lay the foundation for further preparation of solar cells and photodetectors.
  • the carbon quantum dots obtained in the present invention respond to laser light from the visible light region to the near-infrared region, and have the characteristics of wide band and fast response. This characteristic has unique advantages for the development of new optoelectronic devices in the future.
  • FIG. 1 is a high-resolution transmission electron micrograph of the carbon quantum dots of Example 1.
  • Fig. 2 is the carbon quantum dot fluorescence spectrogram of embodiment 1.
  • Fig. 3 is the carbon quantum dot photostability graph of embodiment 1.
  • Example 4 is an electrochemical test diagram of the carbon quantum dots of Example 1.
  • FIG. 5 is a photoelectric response test diagram of the carbon quantum dots in the visible light region of Example 1.
  • Example 6 is a photoelectric response test chart of the carbon quantum dots in Example 1 in the near-infrared region.
  • Transmission electron microscope test Take dry carbon quantum dots and dissolve them in absolute ethanol. After ultrasonication for 10 minutes, take 2.5 ⁇ L of the solution and drop it on the ultra-thin carbon film, and observe its morphology with a high-resolution transmission electron microscope (200kV).
  • the test of relative quantum yield with fluorescein isothiocyanate as a standard, the quantum yield of its 0.1M aqueous sodium hydroxide solution at 494nm excitation wavelength is 95%, according to the formula (1) can calculate the carbon quantum dot Relative quantum yield.
  • represents the quantum yield
  • k is the slope of the linear relationship graph based on the absorbance of the standard and carbon quantum dots at 494nm and the intensity of the emission wavelength at the corresponding wavelength
  • n is the refractive index of the solvent
  • s and r represent Analytes carbon quantum dots and standards.
  • Fluorescence performance test 4 mg/mL carbon quantum dot solution was placed in a micro-volume fluorescence cuvette, using a Shimadzu RF 6000 fluorescence spectrophotometer, the excitation and emission slits were set to 5nm, and the excitation and emission wavelengths were measured. test.
  • Fluorescence stability performance test After recording the fluorescence intensity of the 4mg/mL carbon quantum dot solution, place it under the ultraviolet lamp for continuous irradiation for 24 hours, and then test its fluorescence intensity under the same fluorescence test conditions.
  • Electrochemical test Take 2.5 ⁇ L carbon quantum dot solution with a concentration of 2mg/ml and drop it on the ground glassy carbon electrode. After drying with an infrared lamp, use the three-electrode method to perform an electrochemical test on it.
  • Photoelectric response test drop 1mg/mL carbon quantum dot aqueous solution on the silicon substrate with gold electrodes, and dry at 70°C to form carbon quantum dots into a film, evenly covering the middle of the gold electrodes, and apply 10mV between the two electrodes The photocurrent generated by carbon quantum dots was monitored in the dark and under different laser irradiation conditions.
  • a method for preparing carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared comprising the steps of:
  • step (2) After the carbon quantum dot solution in step (1) is absorbed by a disposable syringe, the large particulate matter is removed by a 0.22 ⁇ m organic microporous filter membrane, and the eluent of dichloromethane/methanol (volume ratio is 10:1) Perform chromatographic column filtration to remove unreacted precursors and impurities, and finally obtain purified carbon quantum dots;
  • Figure 1 is the morphological characterization. It can be seen from Figure 1 that the size of carbon quantum dots is uniformly dispersed, and the particle diameter is between 1-3nm.
  • Figure 2 shows the test results of fluorescence performance. It can be seen from Figure 2 that the optimal excitation wavelength of carbon quantum dots is 460nm, and the emission wavelength is 500nm.
  • Figure 3 shows the test results of fluorescence stability. It can be seen from Figure 3 that after long-time irradiation, carbon quantum dots still maintain good fluorescence performance, indicating the stability of their fluorescence.
  • Figure 4 shows the electrochemical performance test results. It can be seen from Figure 4 that the redox peak of carbon quantum dots increases under light conditions, indicating that they have photoconductivity.
  • Figure 5 and Figure 6 show the photoelectric response test results. It can be seen from Figure 5 and Figure 6 that carbon quantum dots produce photoelectric response in a wide spectral range from visible light to near infrared.
  • Step (1) in the adjustment embodiment 1 is:
  • Example 2 Others are consistent with Example 1, and the carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared are obtained.
  • Example 1 The absolute ethanol in Example 1 was adjusted to be ultrapure water, and the others were kept the same as in Example 1 to obtain carbon quantum dots.
  • Example 1 The crystalline orthophosphoric acid in Example 1 was omitted, and the others were kept the same as in Example 1 to obtain carbon quantum dots.
  • Example 1 The crystalline orthophosphoric acid in Example 1 was replaced by phosphoric acid aqueous solution, so that the final concentration of phosphoric acid in the precursor solution was 2M, and the others were kept the same as in Example 1 to obtain carbon quantum dots.
  • Example 1 The crystalline orthophosphoric acid in Example 1 was replaced with nitric acid solution, so that the final concentration of nitric acid in the precursor solution was 2M, and the others were consistent with Example 1 to obtain carbon quantum dots.
  • Example 1 The crystalline orthophosphoric acid in Example 1 was replaced with hydrochloric acid solution, so that the final concentration of hydrochloric acid in the precursor solution was 2M, and the others were consistent with Example 1 to obtain carbon quantum dots.
  • Example 1 The crystalline orthophosphoric acid in Example 1 was replaced with a sulfuric acid solution, so that the final concentration of sulfuric acid in the precursor solution was 2M, and the others were consistent with Example 1 to obtain carbon quantum dots.

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Abstract

The present invention relates to the technical field of nano luminescent materials. Disclosed are a carbon quantum dot having a high quantum yield and a wide-spectrum photoelectric response, and a preparation method. The method for preparing a carbon quantum dot of the present invention comprises the following steps: fully dissolving m-phenylenediamine in ethanol to obtain a precursor solution; then uniformly mixing the precursor solution and a dopant solid acid, and reacting at 175-185°C for 10-15 h; and after the reaction is finished, purifying, concentrating, and drying to obtain the carbon quantum dot having a visible-to-near-infrared wide-spectrum photoelectric response, wherein the concentration of m-phenylenediamine in ethanol is 8-12 mg/mL, and the concentration range of the solid acid in the precursor solution is 0.1-4 M. The carbon quantum dot of the present invention has good optical performance, comprises a high quantum yield, and excellent optical stability and anti-photobleaching effect, and has wide-spectrum photoelectric response performance from visible light to near infrared.

Description

一种高量子产率和宽光谱光电响应的碳量子点及制备方法A carbon quantum dot with high quantum yield and wide-spectrum photoelectric response and its preparation method 技术领域technical field
本发明涉及一种高量子产率和宽光谱光电响应的碳量子点及制备方法,属于纳米发光材料技术领域。The invention relates to a carbon quantum dot with high quantum yield and wide-spectrum photoelectric response and a preparation method, belonging to the technical field of nano-luminescent materials.
背景技术Background technique
碳量子点作为一种新型的纳米材料,通常直径小于10nm,根据碳量子点的晶型结构尺寸,可将其分为碳量子点、石墨烯量子点和聚合物点。与传统的量子点相比,碳量子点主要由易获得的无金属碳基材料合成。因其具有良好的生物相容性和光学性能,如优异的光稳定性、耐光漂白性等,碳量子点被广泛应用在生物成像、荧光传感等领域。As a new type of nanomaterial, carbon quantum dots usually have a diameter of less than 10nm. According to the crystal structure size of carbon quantum dots, they can be divided into carbon quantum dots, graphene quantum dots and polymer dots. Compared with traditional quantum dots, carbon quantum dots are mainly synthesized from readily available metal-free carbon-based materials. Due to their good biocompatibility and optical properties, such as excellent photostability and photobleaching resistance, carbon quantum dots are widely used in bioimaging, fluorescence sensing and other fields.
为提高碳量子点的荧光性能和量子产率,已经开发了一系列的合成和结构修饰方法。典型的合成方法主要包括水热、溶剂热、微波合成的“自下而上”法和氧化还原切割、物理研磨的“自上而下”法。对碳量子点的结构进行修饰,可提升其光学性能,目前的研究主要集中在对碳量子点进行掺杂及官能团的修饰等方面。其中杂原子的掺杂可提高碳量子点的光学性能,但其具体的增强荧光机理和掺杂位置还没有较为统一的解释,对掺杂后的碳量子点的结构和功能的改变也还需进一步的探究。To improve the fluorescence performance and quantum yield of carbon quantum dots, a series of synthesis and structural modification methods have been developed. Typical synthesis methods mainly include the "bottom-up" method of hydrothermal, solvothermal, and microwave synthesis, and the "top-down" method of redox cleavage and physical grinding. Modifying the structure of carbon quantum dots can improve their optical properties. Current research mainly focuses on the doping of carbon quantum dots and the modification of functional groups. Among them, the doping of heteroatoms can improve the optical properties of carbon quantum dots, but its specific enhanced fluorescence mechanism and doping position have not yet been explained uniformly, and the structure and function of doped carbon quantum dots still need to be changed. further exploration.
由于碳量子点在紫外到可见光区域具有较宽的光学吸收范围,优异的光电,包括较高的电子迁移率、较长的热电子寿命等特性,可显著提高能量转化效率和光响应率,在太阳能电池和光电探测器领域广泛应用。但由于近、中、远红外区域的光子激发能和光吸收性较低,基于碳量子点的光电响应主要是集中在深紫外到可见光区域,因此设计制备在近红外区域有光响应的碳量子点具有重要意义。Due to the wide optical absorption range of carbon quantum dots in the ultraviolet to visible region, excellent photoelectricity, including high electron mobility, long thermal electron lifetime and other characteristics, can significantly improve energy conversion efficiency and photoresponse rate, in solar energy It is widely used in the field of batteries and photodetectors. However, due to the low photon excitation energy and light absorption in the near, middle and far infrared regions, the photoelectric response based on carbon quantum dots is mainly concentrated in the deep ultraviolet to visible light region. Therefore, carbon quantum dots with photoresponse in the near infrared region are designed and prepared. is of great significance.
发明内容Contents of the invention
[技术问题][technical problem]
对碳量子点荧光性能的调控和量子产率的提高,是后期在传感、成像等领域的应用基础;目前,碳量子点的光电响应主要集中在深紫外到可见光区域,范围小,因此制备在近红外区域有光电响应的碳量子点具有重要意义。The regulation of the fluorescence performance of carbon quantum dots and the improvement of quantum yield are the basis for later applications in the fields of sensing and imaging; at present, the photoelectric response of carbon quantum dots is mainly concentrated in the deep ultraviolet to visible light region, and the range is small, so the preparation Carbon quantum dots with photoelectric response in the near-infrared region are of great significance.
[技术方案][Technical solutions]
为了解决上述问题,本发明提供了一种简便、高量子产率、具有宽光谱光电响应的碳量子点及其制备方法。In order to solve the above problems, the present invention provides a simple carbon quantum dot with high quantum yield and wide-spectrum photoelectric response and a preparation method thereof.
本发明的第一个目的是提供一种制备具有高量子产率和可见到近红外宽光谱光电响应的 碳量子点的方法,包括如下步骤:The first object of the present invention is to provide a kind of method for preparing carbon quantum dots with high quantum yield and visible to near-infrared broad-spectrum photoelectric response, comprising the steps:
将间苯二胺在乙醇中充分溶解,得到前驱体溶液;之后将前驱体溶液和掺杂剂固体酸混合均匀,在175-185℃下反应10-15h;反应结束后,纯化、浓缩、干燥,得到所述的可见到近红外宽光谱光电响应的碳量子点;Fully dissolve m-phenylenediamine in ethanol to obtain a precursor solution; then mix the precursor solution and dopant solid acid evenly, and react at 175-185°C for 10-15h; after the reaction, purify, concentrate, and dry , to obtain the carbon quantum dots with photoelectric response of the visible to near-infrared wide spectrum;
其中,所述的间苯二胺在乙醇中的浓度为8-12mg/mL;Wherein, the concentration of the m-phenylenediamine in ethanol is 8-12mg/mL;
所述的固体酸在前驱体溶液中的浓度范围为0.1-4M。The concentration range of the solid acid in the precursor solution is 0.1-4M.
在本发明的一种实施方式中,所述的乙醇为无水乙醇。In one embodiment of the present invention, the ethanol is absolute ethanol.
在本发明的一种实施方式中,所述的充分溶解是采用超声辅助溶解法进行。In one embodiment of the present invention, the full dissolution is carried out by ultrasonic-assisted dissolution.
在本发明的一种实施方式中,所述的反应的方法为溶剂热法,具体是在180℃下反应12h。In one embodiment of the present invention, the reaction method is a solvothermal method, specifically reacting at 180° C. for 12 hours.
在本发明的一种实施方式中,所述的掺杂剂固体酸为结晶态的正磷酸。In one embodiment of the present invention, the dopant solid acid is crystalline orthophosphoric acid.
在本发明的一种实施方式中,所述的纯化是将反应结束后的溶液经过微孔滤膜和层析柱过滤后,去除未反应的前驱体和杂质,得到纯化后的碳量子点;其中微孔滤膜的孔径为0.22微米。In one embodiment of the present invention, the purification is to filter the solution after the reaction through a microporous membrane and a chromatographic column, remove unreacted precursors and impurities, and obtain purified carbon quantum dots; Wherein the pore diameter of the microporous membrane is 0.22 microns.
在本发明的一种实施方式中,所述的层析柱洗脱液为二氯甲烷与甲醇,其体积比为8-12:1,进一步优选为10:1。In one embodiment of the present invention, the chromatographic column eluent is dichloromethane and methanol, and the volume ratio thereof is 8-12:1, more preferably 10:1.
在本发明的一种实施方式中,所述的浓缩是将纯化后的碳量子点利用旋转蒸发仪浓缩得到。In one embodiment of the present invention, the concentration is obtained by concentrating the purified carbon quantum dots using a rotary evaporator.
在本发明的一种实施方式中,所述的干燥是真空干燥,具体是将浓缩样品置于60℃真空干燥箱内12-24h。In one embodiment of the present invention, the drying is vacuum drying, specifically placing the concentrated sample in a vacuum drying oven at 60° C. for 12-24 hours.
在本发明的一种实施方式中,制备得到的碳量子点需要重新溶解,之后避光置于4℃条件下保存;其中重新溶解时的溶剂包括水和无水乙醇中的一种或两种。In one embodiment of the present invention, the prepared carbon quantum dots need to be redissolved, and then stored in the dark at 4°C; wherein the solvent for redissolving includes one or both of water and absolute ethanol .
本发明的第二个目的是本发明所述的方法制备得到的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点。The second object of the present invention is the carbon quantum dots with high quantum yield and wide spectrum photoelectric response from visible to near infrared prepared by the method of the present invention.
本发明的第三个目的是本发明所述的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点在生物成像、荧光传感、太阳能电池、光电探测器领域中的应用。The third object of the present invention is the application of the carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared in the fields of biological imaging, fluorescence sensing, solar cells, and photodetectors.
[有益效果][beneficial effect]
(1)本发明的碳量子点有较好的光学性能,包括较高的量子产率、优异的光稳定性和抗光漂白作用,在紫外灯照射24h后仍保持较好的荧光性能,相对量子产率达到67.3%以上,可以高达102%,与磷酸调控前的碳量子点相比,量子产率提高40倍。(1) The carbon quantum dots of the present invention have better optical properties, including higher quantum yield, excellent photostability and photobleaching resistance, and still maintain better fluorescence properties after ultraviolet lamp irradiation for 24h, relatively The quantum yield reaches more than 67.3%, and can be as high as 102%. Compared with the carbon quantum dots before phosphoric acid regulation, the quantum yield is increased by 40 times.
(2)本发明采用正磷酸作为酸度调节剂和掺杂剂,使碳核结构更加规整,掺杂的磷元素 以磷酸二氢根的形式修饰于碳量子点的边缘区域,作为层插剂,构成多层碳量子点结构,并降低层间势能,实现电子的远距离运输,因此提高了碳量子点的量子产率。(2) The present invention uses orthophosphoric acid as an acidity regulator and a dopant to make the carbon core structure more regular, and the doped phosphorus element is modified in the edge region of the carbon quantum dot in the form of dihydrogen phosphate, as a layer intercalation agent, A multi-layer carbon quantum dot structure is formed, and the interlayer potential energy is reduced to realize long-distance transport of electrons, thus improving the quantum yield of carbon quantum dots.
(3)本发明的碳量子点在可见光的照射下即可激发电子,具有光致导电性,为进一步制备太阳能电池、光电探测器打下基础。(3) The carbon quantum dots of the present invention can excite electrons under the irradiation of visible light, have photoconductivity, and lay the foundation for further preparation of solar cells and photodetectors.
(4)本发明得到的碳量子点对从可见光区域到近红外区域的激光有响应,具有宽波段、快速响应的特征,在这一特性对未来发展新型的光电子器件有独特优势。(4) The carbon quantum dots obtained in the present invention respond to laser light from the visible light region to the near-infrared region, and have the characteristics of wide band and fast response. This characteristic has unique advantages for the development of new optoelectronic devices in the future.
附图说明Description of drawings
图1是实施例1的碳量子点的高分辨透射电镜照片。FIG. 1 is a high-resolution transmission electron micrograph of the carbon quantum dots of Example 1.
图2是实施例1的碳量子点荧光光谱图。Fig. 2 is the carbon quantum dot fluorescence spectrogram of embodiment 1.
图3是实施例1的碳量子点光稳定性图。Fig. 3 is the carbon quantum dot photostability graph of embodiment 1.
图4是实施例1的碳量子点的电化学测试图。4 is an electrochemical test diagram of the carbon quantum dots of Example 1.
图5是实施例1的碳量子点的在可见光区的光电响应测试图。FIG. 5 is a photoelectric response test diagram of the carbon quantum dots in the visible light region of Example 1. FIG.
图6是实施例1的碳量子点的在近红外区的光电响应测试图。6 is a photoelectric response test chart of the carbon quantum dots in Example 1 in the near-infrared region.
具体实施方式Detailed ways
以下对本发明的优选实施例进行说明,应当理解实施例是为了更好地解释本发明,不用于限制本发明。Preferred embodiments of the present invention are described below, and it should be understood that the embodiments are for better explaining the present invention, and are not intended to limit the present invention.
测试方法:Test Methods:
透射电镜的测试:取干燥的碳量子点溶解在无水乙醇中,超声10分钟后,取2.5μL溶液滴在超薄碳膜上,用高分辨透射电镜(200kV)观察其形貌。Transmission electron microscope test: Take dry carbon quantum dots and dissolve them in absolute ethanol. After ultrasonication for 10 minutes, take 2.5 μL of the solution and drop it on the ultra-thin carbon film, and observe its morphology with a high-resolution transmission electron microscope (200kV).
相对量子产率的测试:以异硫氰酸荧光素作为标准物,其0.1M的氢氧化钠水溶液在494nm激发波长下的量子产率为95%,根据公式(1)可计算碳量子点的相对量子产率。The test of relative quantum yield: with fluorescein isothiocyanate as a standard, the quantum yield of its 0.1M aqueous sodium hydroxide solution at 494nm excitation wavelength is 95%, according to the formula (1) can calculate the carbon quantum dot Relative quantum yield.
Figure PCTCN2022098058-appb-000001
Figure PCTCN2022098058-appb-000001
其中,Φ表示量子产率,k为以标准物和碳量子点在494nm处的吸光度和在对应波长下的发射波长强度作线性关系图的斜率,n为溶剂的折射率,s和r分别代表待测物碳量子点和标准物。Among them, Φ represents the quantum yield, k is the slope of the linear relationship graph based on the absorbance of the standard and carbon quantum dots at 494nm and the intensity of the emission wavelength at the corresponding wavelength, n is the refractive index of the solvent, and s and r represent Analytes carbon quantum dots and standards.
荧光性能测试:将4mg/mL的碳量子点溶液放置在微量荧光比色皿中,利用岛津RF 6000荧光分光光度计,激发和发射狭缝均设定为5nm,对其激发和发射波长进行测试。Fluorescence performance test: 4 mg/mL carbon quantum dot solution was placed in a micro-volume fluorescence cuvette, using a Shimadzu RF 6000 fluorescence spectrophotometer, the excitation and emission slits were set to 5nm, and the excitation and emission wavelengths were measured. test.
荧光稳定性能测试:将4mg/mL的碳量子点溶液在记录荧光强度后,放置在紫外灯下连续照射24小时,随后在荧光测试条件一致情况下,测试其荧光强度。Fluorescence stability performance test: After recording the fluorescence intensity of the 4mg/mL carbon quantum dot solution, place it under the ultraviolet lamp for continuous irradiation for 24 hours, and then test its fluorescence intensity under the same fluorescence test conditions.
电化学测试:取2.5μL浓度为2mg/ml碳量子点溶液滴在磨好的玻碳电极上,红外灯干 燥后采用三电极法对其进行电化学测试。Electrochemical test: Take 2.5 μL carbon quantum dot solution with a concentration of 2mg/ml and drop it on the ground glassy carbon electrode. After drying with an infrared lamp, use the three-electrode method to perform an electrochemical test on it.
光电响应测试:将1mg/mL碳量子点水溶液滴在制成的有金电极的硅基底上,70℃干燥,使碳量子点成膜,均匀覆盖在金电极中间,在两电极之间施加10mV的电压,在黑暗和不同激光照射条件下监测碳量子点产生的光电流。Photoelectric response test: drop 1mg/mL carbon quantum dot aqueous solution on the silicon substrate with gold electrodes, and dry at 70°C to form carbon quantum dots into a film, evenly covering the middle of the gold electrodes, and apply 10mV between the two electrodes The photocurrent generated by carbon quantum dots was monitored in the dark and under different laser irradiation conditions.
实施例1Example 1
一种制备具有高量子产率和可见到近红外宽光谱光电响应的碳量子点的方法,包括如下步骤:A method for preparing carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared, comprising the steps of:
(1)将0.3g间苯二胺置于30mL无水乙醇中,得到前驱体溶液;之后加入结晶态的正磷酸,使得正磷酸在前驱体溶液中的终浓度为2M,通过超声辅助(功率为200W,时间为30分钟)溶解后作为反应溶液;之后将反应溶液放入反应釜中,在鼓风干燥箱内180℃加热12h,冷却得到反应后的碳量子点溶液;(1) Place 0.3g of m-phenylenediamine in 30mL of absolute ethanol to obtain a precursor solution; then add crystalline orthophosphoric acid so that the final concentration of orthophosphoric acid in the precursor solution is 2M. 200W, the time is 30 minutes) as the reaction solution after dissolving; then put the reaction solution into the reaction kettle, heat at 180°C for 12h in the blast drying oven, and cool to obtain the reacted carbon quantum dot solution;
(2)将步骤(1)的碳量子点溶液利用一次性注射器吸取后通过0.22μm有机微孔滤膜除去大颗粒物质,以二氯甲烷/甲醇(体积比为10:1)的洗脱液进行层析柱过滤,去除未反应的前驱体和杂质,最终得到纯化后的碳量子点;(2) After the carbon quantum dot solution in step (1) is absorbed by a disposable syringe, the large particulate matter is removed by a 0.22 μm organic microporous filter membrane, and the eluent of dichloromethane/methanol (volume ratio is 10:1) Perform chromatographic column filtration to remove unreacted precursors and impurities, and finally obtain purified carbon quantum dots;
(3)将纯化后的碳量子点溶液利用旋转蒸发仪浓缩至5mL,之后在真空干燥箱60℃干燥12小时,得到所述的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点固体样品。(3) Concentrate the purified carbon quantum dot solution to 5 mL using a rotary evaporator, and then dry it in a vacuum oven at 60° C. for 12 hours to obtain the carbon with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared. Quantum dot solid samples.
将得到的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点进行测试,测试结果如下:The obtained carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared were tested, and the test results are as follows:
图1为形貌表征,从图1可以看出:碳量子点尺寸均匀分散,颗粒直径在1-3nm之间。Figure 1 is the morphological characterization. It can be seen from Figure 1 that the size of carbon quantum dots is uniformly dispersed, and the particle diameter is between 1-3nm.
图2为荧光性能测试结果,从图2可以看出:碳量子点的最佳激发波长为460nm,发射波长为500nm。Figure 2 shows the test results of fluorescence performance. It can be seen from Figure 2 that the optimal excitation wavelength of carbon quantum dots is 460nm, and the emission wavelength is 500nm.
图3为荧光稳定性测试结果,从图3可以看出:在长时间照射后,碳量子点仍保持良好的荧光性能,表明其荧光的稳定性。Figure 3 shows the test results of fluorescence stability. It can be seen from Figure 3 that after long-time irradiation, carbon quantum dots still maintain good fluorescence performance, indicating the stability of their fluorescence.
图4为电化学性能测试结果,从图4可以看出:在光照条件下,碳量子点的氧化还原峰会有增加,表明其具有光致导电性。Figure 4 shows the electrochemical performance test results. It can be seen from Figure 4 that the redox peak of carbon quantum dots increases under light conditions, indicating that they have photoconductivity.
图5、图6为光电响应测试结果,从图5、图6可以看出:碳量子点在可见光到近红外的宽光谱范围下产生光电响应。Figure 5 and Figure 6 show the photoelectric response test results. It can be seen from Figure 5 and Figure 6 that carbon quantum dots produce photoelectric response in a wide spectral range from visible light to near infrared.
实施例2Example 2
调整实施例1中步骤(1)为:Step (1) in the adjustment embodiment 1 is:
将0.15g间苯二胺置于15mL无水乙醇中,加入结晶磷酸,使得正磷酸在前驱体溶液中的终浓度为2M,通过超声辅助溶解(功率为200W,时间为30分钟)后作为反应液;之后将前驱体溶液放入反应釜中,鼓风干燥箱180℃加热15h,冷却得到反应后的溶液;Put 0.15g of m-phenylenediamine in 15mL of absolute ethanol, add crystalline phosphoric acid so that the final concentration of orthophosphoric acid in the precursor solution is 2M, and dissolve it with the aid of ultrasound (power 200W, time 30 minutes) as a reaction solution; then put the precursor solution into the reaction kettle, heat it in a blast drying oven at 180°C for 15 hours, and cool it to obtain the reacted solution;
其他和实施例1保持一致,得到所述的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点。Others are consistent with Example 1, and the carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared are obtained.
实施例3Example 3
调整实施例1中步骤(1)正磷酸相对于前驱体溶液的浓度为1M;其他和实施例1保持一致,得到所述的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点。Adjust the concentration of step (1) orthophosphoric acid in Example 1 relative to the precursor solution to be 1M; Others are consistent with Example 1, and the carbon quantum with high quantum yield and visible to near-infrared wide-spectrum photoelectric response is obtained. point.
对比例1Comparative example 1
调整实施例1中无水乙醇为超纯水,其他和实施例1保持一致,得到碳量子点。The absolute ethanol in Example 1 was adjusted to be ultrapure water, and the others were kept the same as in Example 1 to obtain carbon quantum dots.
对比例2Comparative example 2
省略实施例1中结晶态的正磷酸,其他和实施例1保持一致,得到碳量子点。The crystalline orthophosphoric acid in Example 1 was omitted, and the others were kept the same as in Example 1 to obtain carbon quantum dots.
对比例3Comparative example 3
将实施例1中的结晶态的正磷酸替换成磷酸水溶液,使得磷酸在前驱体溶液中终浓度为2M,其他和实施例1保持一致,得到碳量子点。The crystalline orthophosphoric acid in Example 1 was replaced by phosphoric acid aqueous solution, so that the final concentration of phosphoric acid in the precursor solution was 2M, and the others were kept the same as in Example 1 to obtain carbon quantum dots.
对比例4Comparative example 4
调整实施例1中步骤(1)正磷酸相对于前驱体溶液的浓度为8M,其他和实施例1保持一致,得到碳量子点。Adjust the concentration of orthophosphoric acid relative to the precursor solution in step (1) in Example 1 to 8M, and keep the others consistent with Example 1 to obtain carbon quantum dots.
对比例5Comparative example 5
调整实施例1中步骤(1)正磷酸相对于前驱体溶液的浓度为0.001M,其他和实施例1保持一致,得到碳量子点。Adjust the concentration of orthophosphoric acid relative to the precursor solution in step (1) in Example 1 to 0.001M, and keep the others consistent with Example 1 to obtain carbon quantum dots.
对比例6Comparative example 6
将实施例1中的结晶态的正磷酸替换成硝酸溶液,使得硝酸在前驱体溶液中终浓度为2M,其他和实施例1保持一致,得到碳量子点。The crystalline orthophosphoric acid in Example 1 was replaced with nitric acid solution, so that the final concentration of nitric acid in the precursor solution was 2M, and the others were consistent with Example 1 to obtain carbon quantum dots.
对比例7Comparative example 7
将实施例1中的结晶态的正磷酸替换成盐酸溶液,使得盐酸在前驱体溶液中终浓度为2M,其他和实施例1保持一致,得到碳量子点。The crystalline orthophosphoric acid in Example 1 was replaced with hydrochloric acid solution, so that the final concentration of hydrochloric acid in the precursor solution was 2M, and the others were consistent with Example 1 to obtain carbon quantum dots.
对比例8Comparative example 8
将实施例1中的结晶态的正磷酸替换成硫酸溶液,使得硫酸在前驱体溶液中终浓度为2M, 其他和实施例1保持一致,得到碳量子点。The crystalline orthophosphoric acid in Example 1 was replaced with a sulfuric acid solution, so that the final concentration of sulfuric acid in the precursor solution was 2M, and the others were consistent with Example 1 to obtain carbon quantum dots.
将得到的碳量子点进行测试,测试结果如下:The obtained carbon quantum dots were tested, and the test results were as follows:
表1相对量子产率和光电范围的测试结果Table 1 The test results of relative quantum yield and photoelectric range
example 相对量子产率(%)Relative quantum yield (%) 光电响应范围Photoelectric response range
实施例1Example 1 102102 可见光-近红外Visible light - near infrared
实施例2Example 2 95.695.6 可见光-近红外Visible light - near infrared
实施例3Example 3 67.367.3 可见光-近红外Visible light - near infrared
对比例1Comparative example 1 1.611.61
对比例2Comparative example 2 2.622.62 可见光visible light
对比例3Comparative example 3 21.621.6
对比例4Comparative example 4 46.246.2 可见光-近红外Visible light - near infrared
对比例5Comparative example 5 31.131.1 可见光-近红外Visible light - near infrared
对比例6Comparative example 6 17.917.9
对比例7Comparative example 7 24.224.2
对比例8Comparative example 8 15.615.6
注:“—”代表量子产率低于30%,未进行光电响应测试。Note: "—" means that the quantum yield is lower than 30%, and the photoelectric response test has not been carried out.
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore The scope of protection of the present invention should be defined by the claims.

Claims (10)

  1. 一种制备具有高量子产率和可见到近红外宽光谱光电响应的碳量子点的方法,其特征在于,包括如下步骤:A method for preparing carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared, characterized in that it comprises the following steps:
    将间苯二胺在乙醇中充分溶解,得到前驱体溶液;之后将前驱体溶液和掺杂剂固体酸混合均匀,在175-185℃下反应10-15h;反应结束后,纯化、浓缩、干燥,得到所述的可见到近红外宽光谱光电响应的碳量子点;Fully dissolve m-phenylenediamine in ethanol to obtain a precursor solution; then mix the precursor solution and dopant solid acid evenly, and react at 175-185°C for 10-15h; after the reaction, purify, concentrate, and dry , to obtain the carbon quantum dots with photoelectric response of the visible to near-infrared wide spectrum;
    其中,所述的间苯二胺在乙醇中的浓度为8-12mg/mL;Wherein, the concentration of the m-phenylenediamine in ethanol is 8-12mg/mL;
    所述的固体酸在前驱体溶液中的浓度范围为0.1-4M。The concentration range of the solid acid in the precursor solution is 0.1-4M.
  2. 根据权利要求1所述的方法,其特征在于,所述的掺杂剂固体酸为结晶态的正磷酸。The method according to claim 1, characterized in that said dopant solid acid is crystalline orthophosphoric acid.
  3. 根据权利要求1所述的方法,其特征在于,所述的纯化是将反应结束后的溶液经过微孔滤膜和层析柱过滤后,去除未反应的前驱体和杂质,得到纯化后的碳量子点。The method according to claim 1, wherein the purification is to filter the solution after the reaction through a microporous membrane and a chromatographic column, remove unreacted precursors and impurities, and obtain purified carbon quantum dots.
  4. 根据权利要求3所述的方法,其特征在于,所述的层析柱洗脱液为二氯甲烷与甲醇,其体积比为8-12:1。The method according to claim 3, characterized in that, the chromatographic column eluent is dichloromethane and methanol, and its volume ratio is 8-12:1.
  5. 根据权利要求3所述的方法,其特征在于,所述的微孔滤膜的孔径为0.22微米。The method according to claim 3, characterized in that the pore diameter of the microporous membrane is 0.22 microns.
  6. 根据权利要求1所述的方法,其特征在于,所述的浓缩是将纯化后的碳量子点利用旋转蒸发仪浓缩得到。The method according to claim 1, wherein the concentration is obtained by concentrating the purified carbon quantum dots using a rotary evaporator.
  7. 根据权利要求1所述的方法,其特征在于,所述的干燥是真空干燥,具体是将浓缩样品置于60℃真空干燥箱内12-24h。The method according to claim 1, characterized in that the drying is vacuum drying, specifically placing the concentrated sample in a vacuum oven at 60° C. for 12-24 hours.
  8. 根据权利要求1所述的方法,其特征在于,所述的反应的方法为溶剂热法,具体是在180℃下反应12h。The method according to claim 1, characterized in that the reaction method is a solvothermal method, specifically reacting at 180° C. for 12 hours.
  9. 权利要求1-8任一项所述的方法制备得到的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点。The carbon quantum dots prepared by the method according to any one of claims 1-8 have high quantum yield and wide-spectrum photoelectric response from visible to near-infrared.
  10. 权利要求9所述的具有高量子产率和可见到近红外宽光谱光电响应的碳量子点在生物成像、荧光传感、太阳能电池、光电探测器领域中的应用。The application of the carbon quantum dots with high quantum yield and wide-spectrum photoelectric response from visible to near-infrared in claim 9 in the fields of biological imaging, fluorescence sensing, solar cells, and photodetectors.
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