CN114604853B - Method for preparing nitrogen-doped carbon quantum dots in large quantity and carbon quantum dots - Google Patents
Method for preparing nitrogen-doped carbon quantum dots in large quantity and carbon quantum dots Download PDFInfo
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- CN114604853B CN114604853B CN202210328770.3A CN202210328770A CN114604853B CN 114604853 B CN114604853 B CN 114604853B CN 202210328770 A CN202210328770 A CN 202210328770A CN 114604853 B CN114604853 B CN 114604853B
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Abstract
The invention discloses a method for preparing a large amount of nitrogen-doped carbon quantum dots, which comprises the following steps: mixing terephthalaldehyde and terephthalonitrile, adding alkaline solution, and carrying out hydrothermal reaction at 120-160 ℃ to obtain the nitrogen doped carbon quantum dots. According to the preparation method, the large-scale preparation of the nitrogen-doped carbon quantum dots is realized by a one-step hydrothermal method, the raw materials required by the preparation method are cheap and easy to obtain, the toxicity is low, the yield is high, no impurity is introduced in the whole reaction process, a complex post-treatment purification process is not needed, and the generated carbon quantum dots can be purified by simple centrifugal cleaning after the hydrothermal reaction is finished, so that the operation is simple.
Description
Technical Field
The invention relates to the technical field of carbon quantum dot preparation, in particular to a method for preparing nitrogen-doped carbon quantum dots in a large quantity and the carbon quantum dots.
Background
In the past decades, carbon-based nano materials such as carbon nanotubes, fullerenes, graphene and the like have been widely studied due to their superior properties, and have shown good application prospects in various fields. Carbon Dots (CDs) have been discovered since 2004 as an emerging Carbon nanomaterial, generally referred to as zero-dimensional Carbon nanoparticles, which have three dimensions of less than 10nm, and generally have fluorescent properties. Compared with the traditional semiconductor quantum dot and organic dye, the carbon quantum dot has the advantages of low toxicity, abundant sources, easy functionalization, good biocompatibility, good light stability, adjustable wavelength of applied light and the like, and has potential application value in the fields of biomedicine, environmental protection, photoelectrocatalysis, energy storage, conversion and the like. The synthesis and preparation methods of the carbon quantum dots can be divided into a top-down method and a bottom-up method. The former includes graphite direct current arc, ball milling graphite powder, electrolytic graphite electrode, laser cutting graphite, oxidation cutting and the like, and is used for decomposing the existing large carbon material into small nano particles; the latter includes high temperature calcination, vapor deposition, microwave digestion, electrochemical synthesis, etc. and is prepared through chemical reaction condensation and carbonization of small molecule to form carbon dot.
However, these methods have low stall yields and efficiencies, usually over several days of reaction and purification, with the final one-pot reaction product being only a few milligrams to tens of milligrams. In addition, during the reaction, washing and purification processes, particularly the column chromatography separation, a large amount of solvent is required, and the organic solvent cannot be recycled, so that the emission can cause pollution. This severely limits their practical application. Therefore, there is a need to develop a method for mass production of CDs with high quality and cost performance, which is simple in process, low in cost, and high in yield.
Disclosure of Invention
Based on the method, the invention provides a method for preparing a large amount of nitrogen-doped carbon quantum dots, the preparation method realizes the large-scale preparation of the nitrogen-doped carbon quantum dots by a one-step hydrothermal method, the raw materials required by the preparation method are cheap and easy to obtain, the toxicity is low, the yield is high, no impurities are introduced in the whole reaction process, a complex post-treatment purification process is not needed, and the generated carbon quantum dots can be purified by only needing simple centrifugal cleaning after the hydrothermal reaction is finished.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a method for mass production of nitrogen-doped carbon quantum dots, comprising the steps of:
mixing terephthalaldehyde and terephthalonitrile, adding alkaline solution, and carrying out hydrothermal reaction at 120-160 ℃ to obtain the nitrogen doped carbon quantum dots.
In some embodiments, the temperature of the hydrothermal reaction is 160 ℃.
In some embodiments, the alkaline solution has a concentration of 0.5 to 2mol/L. Preferably, the concentration of the alkaline solution is 1mol/L.
In some embodiments, the mass ratio of terephthalaldehyde to terephthalacetonitrile is: 0.6 to 1.05:1.
in some embodiments, the alkaline solution is a sodium hydroxide solution.
In some embodiments, the method specifically comprises the steps of:
s1, grinding the terephthalonitrile, then adding the grinded terephthalonitrile into the sodium hydroxide solution, and carrying out ultrasonic treatment to obtain dispersion liquid;
s2, adding terephthalaldehyde into the dispersion liquid obtained in the step S1, and then carrying out ultrasonic treatment and uniform mixing to obtain a mixed liquid;
s3, heating the mixed solution to 120-160 ℃ for hydrothermal reaction;
s4, after the reaction is completed, cooling to room temperature, adding deionized water into the reacted solution, centrifuging, removing supernatant, adding acetone, and centrifuging;
and S5, drying the carbon quantum dots after being cleaned by the acetone to obtain the purified carbon quantum dots.
In some embodiments, in step S3, the hydrothermal reaction time is 1 to 2 hours. Preferably 2h.
In some embodiments, in step S5, the drying temperature is 100 ℃.
The invention also provides a nitrogen-doped carbon quantum dot which is prepared by the method in any embodiment, and the carbon quantum dot contains abundant aldehyde groups and cyano groups, has a particle size of less than 5nm and an average particle size of 2-3 nm.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method, the nitrogen-doped carbon quantum dots can be synthesized by a one-step hydrothermal method, the reaction time is short, and the yield is high (the yield can reach 76.48%); the raw material conversion rate is high, and the consumption is low; and the required raw materials are cheap and easy to obtain, the toxicity is low, the production cost is low, and the environmental pollution is less. In addition, the whole reaction process has no impurity introduction, no complex subsequent treatment and purification process is needed, after the hydrothermal reaction is finished, no complex dialysis and column chromatographic separation are needed, and the generated carbon quantum dots can be purified only by simple centrifugal cleaning, so that the operation method is simple. The method for preparing the nitrogen-doped carbon quantum dot has the advantages of simple operation, low cost, suitability for industrialization and wide application prospect.
In addition, the carbon quantum dot prepared by the method has rich aldehyde groups and cyano groups, and has small particle size (average particle size is 2-3 nm).
Drawings
FIG. 1 is a diagram of a nitrogen-doped carbon quantum dot prepared in example 1; wherein (a) is a diagram of weighing the product; (b) the figure is a product physical figure;
FIG. 2 is a graph showing the results of the solubility of the nitrogen-doped carbon quantum dots prepared in example 1 in ethanol and water;
in fig. 3, (a) and (b) are both the test results of a transmission electron microscope of the nitrogen-doped carbon quantum dots prepared in example 1;
FIG. 4 is a Zeta potential and an infrared spectrum of the nitrogen-doped carbon quantum dots prepared in example 1; wherein, (a) the graph is an infrared spectrogram of the carbon quantum dots; (b) graph is Zeta potential graph of carbon quantum dots;
FIG. 5 is the result of an X-ray photoelectron spectrum test of the nitrogen-doped carbon quantum dots prepared in example 1; wherein, (a) the graph is a full spectrum scanning result; (b) plot is a fine spectrum of C1 s; (c) the fine spectrogram of N1 s; and (d) the graph is a fine spectrogram of O1 s.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The starting materials or chemical reagents used in the examples of the present invention described below were obtained from conventional commercial sources unless otherwise specified.
Example 1
A method for mass production of nitrogen-doped fluorescent carbon quantum dots, comprising the steps of:
s1, weighing 15.6g of terephthalonitrile, putting the terephthalonitrile into a mortar, forcibly grinding the terephthalonitrile for 15 to 20 minutes to ensure that raw material particles are uniform, then adding the raw material particles into 50mL of NaOH solution with the concentration of 1mol/L, and carrying out ultrasonic treatment for 10 minutes to ensure that the terephthalonitrile is uniformly dispersed;
s2, adding 13.4g of terephthalaldehyde into the dispersion liquid in the step S1, and performing ultrasonic treatment for 10min to uniformly disperse the mixed solution to obtain a mixed solution;
s3, transferring the mixed solution obtained in the step S2 into a 100mL polytetrafluoroethylene high-pressure reaction kettle, and reacting for 2 hours at 160 ℃ to obtain a mixed solution;
s4, after the reaction kettle is naturally cooled to room temperature, adding 200mL of deionized water into the mixed solution after reaction, and then transferring into a centrifuge tube for centrifugal cleaning, wherein the rotation speed is 10000r/min, and the time is 10min; repeating the washing twice; then pouring out supernatant liquid and collecting lower turbid liquid; adding acetone, and centrifugally cleaning for two times, wherein the centrifugal revolution is 10000r/min each time, and the time is 10min;
and S5, placing the carbon quantum dots after being cleaned by the acetone into a vacuum drying oven for drying, wherein the drying temperature is 100 ℃, the drying time is 8 hours, and the purified nitrogen-doped carbon quantum dots are obtained after drying.
The prepared carbon quantum dot is orange-yellow, the quality is up to 22.18g, and the yield is 76.48% through calculation.
And carrying out related performance test on the prepared carbon quantum dots, wherein the test results are shown in figures 1-5.
Fig. 1 is a pictorial view of a prepared nitrogen-doped carbon quantum dot, wherein (a) is a diagram for weighing a product, and (b) is a diagram for the product. As is clear from FIG. 1, the yield of the prepared carbon quantum dots was as high as 22.18g, the volume was greater than 40mL, and the calculated yield was 76.48% by dividing the mass of the carbon dots by the total mass of the reactants. The method has the advantages that high-yield carbon quantum dots can be obtained in a 100mL reaction kettle at one time, the reaction time is short, the post-treatment process is simple, and the carbon quantum dots can be purified only by simple centrifugal cleaning. Further illustrating the potential of the method of the present invention for large scale manufacturing, this would expand the application of carbon quantum dots in various fields.
Fig. 2 is a test result of solubility of the prepared nitrogen-doped carbon quantum dots in ethanol and water, and the test method is as follows: equal amounts of the nitrogen-doped carbon quantum dots prepared in example 1 were added to water and ethanol, respectively. As can be seen from fig. 2, when the carbon quantum dots are added to ethanol, a part of the carbon quantum dots are dispersed in ethanol, which means that the carbon quantum dots have a certain solubility in an organic solvent, which is caused by a large amount of nonpolar benzene ring structures of the carbon quantum dots; however, when carbon quantum dots are added to water, it was found that the carbon quantum dots have very poor solubility in water and are hardly dispersed in deionized water, indicating that the carbon quantum dots prepared by the method of the present invention are substantially insoluble in water. The carbon quantum dot has wide application prospect in a nonaqueous or organic system.
Fig. 3 is a Transmission Electron Microscope (TEM) test result of the prepared nitrogen-doped carbon quantum dots. The preparation process of the specific sample comprises the following steps: adding a small amount of carbon quantum dots into ethanol, carrying out ultrasonic treatment for half an hour to uniformly disperse the carbon quantum dots in an ethanol solution, then, dripping the dispersion liquid on an ultrathin carbon film, and naturally drying to obtain a sample. As can be seen from the graphs (a) and (b) of FIG. 3, the carbon quantum dots prepared by the method have relatively uniform size distribution, have diameters smaller than 10nm and are mainly concentrated at about 2-3 nm. TEM test results show that the carbon quantum dots are successfully prepared.
Fig. 4 (a) shows an infrared spectrum of the prepared nitrogen-doped carbon quantum dot, and as can be seen from fig. 4 (a), the surface of the carbon quantum dot contains abundant functional groups. In particular, at 1687 and 2220cm -1 The strong absorption peaks in the vicinity can be attributed to the stretching vibration of aldehyde groups (-CHO) and cyano groups (-CN); hydroxyl (-OH) at 3394cm -1 A very wide stretching vibration peak in the vicinity can also be detected. In order to further explore the charge state of the surface of the prepared carbon quantum dots, zeta potential of the carbon quantum dots was detected, and the detection result is shown in (b) diagram of fig. 4. Fig. 4 (b) is a graph of Zeta potential test results of carbon quantum dots, and the Zeta potential, as shown in fig. 4 (b), approximately represents the potential of electrostatic charges carried on the surface of the material in the liquid. As can be seen from the graph (b) in FIG. 4, the average Zeta potential measured six times by the carbon quantum dots is34.55mV, the surface of the carbon quantum dot has a certain negative charge, and the carbon quantum dot has a certain stability in ethanol solution and can not be agglomerated spontaneously.
Fig. 5 is an X-ray photoelectron spectrum (XPS) test result of the prepared nitrogen-doped carbon quantum dot. As can be seen from the full spectrum scan result of the graph (a) in fig. 5, the carbon quantum dot mainly comprises C, N and O, which indicates that the method can be used for doping nitrogen element in the carbon dot; further, as can be seen from the fine spectrum of C1s in the graph (b) of FIG. 5, the peak of C1s can correspond to sp in graphite at a peak divided into three small peaks, 284.8eV 2 C (C-C), whereas the peak at 286.4eV indicates the presence of c≡n for the carbon quantum dot, and the peak at 288.3eV corresponds to c=o in the carbon quantum dot; from the fine spectrum of N1s in (C) plot of 5, a distinct peak is seen at 400eV, which corresponds to cyano groups (c≡n) in carbon quantum dots; from the fine spectrum of O1s in the graph (d) of FIG. 5, it was possible to analyze the component of the oxygen-containing functional group, 531.1eV a strong peak was ascribed to the aldehyde group (H-C=O) in the carbon quantum dot, 532.4eV peak was corresponding to the oxygen in the hydroxyl group (OH), and finally a broad peak was ascribed to the water molecule (H) around 535.5eV 2 O) oxygen. The XPS result analysis of the carbon quantum dot is basically consistent with infrared spectrum, and the surface of the carbon quantum dot prepared by the surface contains rich functional groups, specifically aldehyde groups and cyano groups. The special properties of the carbon quantum dots are endowed by the functional groups, so that the carbon quantum dots can show potential application prospects in different fields.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (3)
1. A method for mass production of nitrogen-doped carbon quantum dots, comprising the steps of:
s1, grinding terephthalonitrile, adding the ground terephthalonitrile into a sodium hydroxide solution, and performing ultrasonic treatment to obtain a dispersion liquid;
s2, adding terephthalaldehyde into the dispersion liquid obtained in the step S1, and then carrying out ultrasonic treatment and uniform mixing to obtain a mixed liquid;
s3, heating the mixed solution to 120-160 ℃ for hydrothermal reaction;
s4, after the reaction is completed, cooling to room temperature, adding deionized water into the reacted solution, centrifuging, removing supernatant, adding acetone, and centrifuging;
s5, drying the carbon quantum dots after being cleaned by the acetone to obtain purified carbon quantum dots;
the mass ratio of terephthalaldehyde to terephthalonitrile is as follows: 0.6 to 1.05:1, a step of;
the concentration of the sodium hydroxide solution is 0.5-2 mol/L;
in the step S3, the hydrothermal reaction time is 1-2 hours;
the carbon quantum dot contains aldehyde groups and cyano groups at the same time, and the particle size is smaller than 5nm.
2. The method for mass production of nitrogen-doped carbon quantum dots according to claim 1, wherein in step S5, the drying temperature is 100 ℃.
3. A nitrogen-doped carbon quantum dot, characterized in that it is produced by the production method according to any one of claims 1 to 2.
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