CN114604853A - Method for preparing nitrogen-doped carbon quantum dots in large scale and carbon quantum dots - Google Patents

Method for preparing nitrogen-doped carbon quantum dots in large scale and carbon quantum dots Download PDF

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CN114604853A
CN114604853A CN202210328770.3A CN202210328770A CN114604853A CN 114604853 A CN114604853 A CN 114604853A CN 202210328770 A CN202210328770 A CN 202210328770A CN 114604853 A CN114604853 A CN 114604853A
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carbon quantum
quantum dots
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doped carbon
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CN114604853B (en
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纪效波
侯红帅
邹国强
邓文韬
张豪
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Central South University
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Abstract

The invention discloses a method for preparing nitrogen-doped carbon quantum dots in large scale, which comprises the following steps: mixing terephthalaldehyde and terephthalonitrile, adding an alkaline solution, and carrying out hydrothermal reaction at 120-160 ℃ to obtain nitrogen-doped carbon quantum dots. The preparation method realizes 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, the generated carbon quantum dots can be purified by simple centrifugal cleaning after the hydrothermal reaction is finished, and the operation is simple.

Description

Method for preparing nitrogen-doped carbon quantum dots in large scale and carbon quantum dots
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 scale and a carbon quantum dot.
Background
In the past decades, carbon-based nanomaterials 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 quantum dots (CDs), discovered since 2004, generally refer to zero-dimensional Carbon nanoparticles with three dimensions less than 10nm, as an emerging Carbon nanomaterial, and generally have fluorescent properties. Compared with the traditional semiconductor quantum dots and organic dyes, the carbon quantum dots have the advantages of low toxicity, rich sources, easy functionalization, good biocompatibility, good light stability, adjustable wavelength of applied light and the like, and have potential application values in the fields of biomedicine, environmental protection, photoelectrocatalysis, energy storage and 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 DC arc, ball milling graphite powder, electrolytic graphite electrode, laser cutting graphite, oxidation cutting, etc. the present carbon material is decomposed into small nanometer particle; the latter includes high temperature calcination, vapor deposition, microwave digestion, electrochemical synthesis and other technologies, and forms carbon dots by condensation and carbonization through chemical reaction starting from small molecules.
However, these methods have low synthetic yield and efficiency, and usually undergo several days of reaction and purification, and the final product of one-pot reaction is only several mg to several tens mg. Moreover, in the reaction, washing and purification processes, especially column chromatography, a large amount of solvent is consumed, and the organic solvent cannot be recycled, so that the emission causes pollution. This severely limited their practical application. Therefore, there is a need to develop a method for producing CDs with high quality and high cost performance, which is simple in process, low in cost, and high in yield, and can be used for mass production.
Disclosure of Invention
Based on the method, the preparation method realizes 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 simple centrifugal cleaning after the hydrothermal reaction is finished.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for mass production of nitrogen-doped carbon quantum dots, comprising the steps of:
mixing terephthalaldehyde and terephthalonitrile, adding an 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 concentration of the alkaline solution is 0.5-2 mol/L. Preferably, the concentration of the alkaline solution is 1 mol/L.
In some embodiments, the mass ratio of terephthalaldehyde to terephthalonitrile is: 0.6-1.05: 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 performing ultrasonic treatment to obtain a dispersion liquid;
s2, adding the terephthalaldehyde into the dispersion liquid obtained in the step S1, performing ultrasonic treatment, and uniformly mixing to obtain a mixed liquid;
s3, heating the mixed solution to 120-160 ℃ for hydrothermal reaction;
s4, after the reaction is finished, cooling to room temperature, then adding deionized water into the reacted solution, centrifuging, removing the supernatant, adding acetone, and centrifuging;
and S5, drying the carbon quantum dots cleaned by the acetone to obtain purified carbon quantum dots.
In some embodiments, in step S3, the hydrothermal reaction time is 1 to 2 hours. Preferably for 2 hours.
In some embodiments, the drying temperature in step S5 is 100 ℃.
The invention also provides a nitrogen-doped carbon quantum dot which is prepared by the method of any one of the embodiments, contains abundant aldehyde groups and cyano groups, and 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 conversion rate of raw materials 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 small. In addition, no impurities are introduced in the whole reaction process, a complex subsequent treatment and purification process is not needed, after the hydrothermal reaction is finished, complex dialysis and column chromatographic separation are not needed, the generated carbon quantum dots can be purified only by simple centrifugal cleaning, and the operation method is simple. The method for preparing the nitrogen-doped carbon quantum dots has the advantages of simple operation, low cost, suitability for industrialization and wide application prospect.
In addition, the carbon quantum dots prepared by the method have rich aldehyde groups and cyano groups, and are small in particle size (the average particle size is 2-3 nm).
Drawings
FIG. 1 is a schematic diagram of a nitrogen-doped carbon quantum dot prepared in example 1; wherein, (a) is a diagram of the weighing of the product; (b) the figure is a product object figure;
fig. 2 is a result of testing the solubility of the nitrogen-doped carbon quantum dots prepared in example 1 in ethanol and water;
in FIG. 3, both the (a) and (b) graphs are the transmission electron microscope test results of the nitrogen-doped carbon quantum dots prepared in example 1;
FIG. 4 is Zeta potential and infrared spectrum of nitrogen doped carbon quantum dots prepared in example 1; wherein, the picture (a) is an infrared spectrogram of a carbon quantum dot; (b) the figure is a Zeta potential diagram of carbon quantum dots;
FIG. 5 shows the result of X-ray photoelectron spectroscopy on the N-doped carbon quantum dots prepared in example 1; wherein, the graph (a) is a full spectrum scanning result; (b) the figure is a fine spectrogram of C1 s; (c) the figure is a fine spectrogram of N1 s; (d) the figure shows a fine spectrum 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. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
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 in the description of the invention herein 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 following examples of the present invention were obtained by conventional commercial methods unless otherwise specified.
Example 1
A method for preparing a large number of nitrogen-doped fluorescent carbon quantum dots comprises the following steps:
s1, weighing 15.6g of terephthalonitrile, putting the terephthalonitrile into a mortar, grinding the mixture for 15-20 min with force to ensure that the 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 10min 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, naturally cooling the reaction kettle to room temperature, adding 200mL of deionized water into the reacted mixed solution, and then transferring the mixed solution into a centrifugal tube for centrifugal cleaning, wherein the revolution is 10000r/min, and the time is 10 min; washing is repeated twice; then pouring out the supernatant liquid, and collecting the lower turbid liquid; adding acetone, centrifuging and cleaning twice, wherein the revolution per time of centrifugation is 10000r/min, and the time is 10 min;
and S5, drying the carbon quantum dots cleaned by the acetone in a vacuum drying oven at 100 ℃ for 8h to obtain the purified nitrogen-doped carbon quantum dots.
The prepared carbon quantum dots are orange yellow, the quality is as high as 22.18g, and the yield is 76.48 percent by calculation.
And carrying out related performance tests on the prepared carbon quantum dots, wherein the test results are shown in figures 1-5.
Fig. 1 is a picture of a prepared nitrogen-doped carbon quantum dot material object, wherein (a) is a picture of product weight weighing, and (b) is a picture of the product material object. It is clear from fig. 1 that the yield of the prepared carbon quantum dots is as high as 22.18g, the volume is more than 40mL, and the calculated yield is 76.48% by dividing the mass of the carbon dots by the total mass of the reactants. The method shows that the carbon quantum dots with high yield 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 for large scale manufacturing of the methods of the present invention, this will expand the application of carbon quantum dots in a variety of fields.
Fig. 2 is a result of solubility test of the prepared nitrogen-doped carbon quantum dot in ethanol and water, and the test method comprises the following steps: 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 into ethanol, a part of the carbon quantum dots are dispersed in ethanol, which indicates that the carbon quantum dots have a certain solubility in the organic solvent, which is caused by a large amount of non-polar benzene ring structures of the carbon quantum dots; by adding carbon quantum dots to water, we will find that the carbon quantum dots have very poor solubility in water and are hardly dispersed in deionized water, which means that the carbon quantum dots prepared by the method of the present invention are substantially insoluble in water. This shows that the carbon quantum dot has wide application prospect in non-aqueous or organic systems.
Fig. 3 shows the Transmission Electron Microscope (TEM) test results of the prepared nitrogen-doped carbon quantum dots. The specific sample preparation process comprises the following steps: adding a small amount of carbon quantum dots into ethanol, performing ultrasonic treatment for half an hour to uniformly disperse the carbon quantum dots in the ethanol solution, then dropping the dispersed 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 present invention have relatively uniform size distribution, and the diameter of the carbon quantum dots is less than 10nm, mainly concentrated around 2-3 nm. TEM test results show that the carbon quantum dots are successfully prepared.
Fig. 4(a) is an infrared spectrum of the prepared nitrogen-doped carbon quantum dot, and it can be seen from fig. 4(a) that the carbon quantum dot surface contains abundant functional groups. In particular, at 1687 and 2220cm-1The nearby strong absorption peak can be attributed to the stretching vibration of aldehyde group (-CHO) and cyano group (-CN); hydroxyl (-OH) is 3394cm-1Nearby wide stretching vibration peaks can also be detected. In order to further explore the charge state of the surface of the prepared carbon quantum dot, the Zeta potential of the carbon quantum dot is detected, and the detection result is shown as a graph (b) in fig. 4. The graph (b) in fig. 4 is a graph of the Zeta potential test result of the carbon quantum dots, and the Zeta potential approximately represents the potential of the electrostatic charge carried on the surface of the material in the liquid as in the graph (b) in fig. 4. As can be seen from the graph (b) in FIG. 4, the average Zeta potential of the carbon quantum dot measured six times is-34.55 mV, which indicates that 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 does not spontaneously aggregate.
Fig. 5 shows the results of X-ray photoelectron spectroscopy (XPS) tests on the prepared nitrogen-doped carbon quantum dots. As can be seen from the full spectrum scanning result of the graph (a) in fig. 5, the carbon quantum dot mainly consists of C, N and O, which indicates that the carbon dot can be doped with nitrogen by using the method; further, as can be seen from the fine spectrum of C1s in the graph (b) of FIG. 5, the peak of C1s can be divided into three small peaks, and the peak at 284.8eV corresponds to sp in graphite2C (C-C), whereas the peak at 286.4eV indicates the presence of C ≡ N in the carbon quantum dot, and the peak at the last 288.3eV corresponds to C ≡ O in the carbon quantum dot; from the fine spectrum of N1s in the (C) diagram of 5, a distinct peak with 400eV can be seen, which corresponds to the cyano group (C.ident.N) in the carbon quantum dot; the oxygen-containing functional group component can be analyzed by the fine spectrum of O1s in the graph (d) of FIG. 5, and 531.1eV is a strong peak attributed to aldehyde group (H-C ═ O) in the carbon quantum dot, 532.4The peak at eV corresponds to the oxygen in the hydroxyl group (OH), and finally a broad peak around 535.5eV is attributed to the water molecule (H)2O) oxygen. The XPS result analysis of the carbon quantum dots is basically consistent with the infrared spectrum, and the surfaces of the carbon quantum dots prepared on the surfaces contain rich functional groups, particularly aldehyde groups and cyano groups. The functional groups endow the carbon quantum dots with special properties, so that the carbon quantum dots can show potential application prospects in different fields.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A method for mass production of nitrogen-doped carbon quantum dots, comprising the steps of:
mixing terephthalaldehyde and terephthalonitrile, adding an alkaline solution, and carrying out hydrothermal reaction at 120-160 ℃ to obtain the nitrogen-doped carbon quantum dots.
2. The method for preparing a nitrogen-doped carbon quantum dot according to claim 1, wherein the concentration of the alkali solution is 0.5 to 2 mol/L.
3. The method for mass production of nitrogen-doped carbon quantum dots according to claim 1, wherein the mass ratio of terephthalaldehyde to terephthalonitrile is: 0.6-1.05: 1.
4. the method for mass production of nitrogen-doped carbon quantum dots according to claim 1, wherein the alkaline solution is a sodium hydroxide solution.
5. The method for mass production of nitrogen-doped carbon quantum dots according to claim 1, comprising the steps of:
s1, grinding the terephthalonitrile, then adding the grinded terephthalonitrile into the sodium hydroxide solution, and performing ultrasonic treatment to obtain a dispersion liquid;
s2, adding the terephthalaldehyde into the dispersion liquid obtained in the step S1, performing ultrasonic treatment, and uniformly mixing to obtain a mixed liquid;
s3, heating the mixed solution to 120-160 ℃ for hydrothermal reaction;
s4, after the reaction is finished, cooling to room temperature, then adding deionized water into the reacted solution, centrifuging, removing the supernatant, adding acetone, and centrifuging;
and S5, drying the carbon quantum dots cleaned by the acetone to obtain purified carbon quantum dots.
6. The method for mass production of nitrogen-doped carbon quantum dots according to claim 5, wherein in the step S3, the hydrothermal reaction time is 1-2 h.
7. The method for mass production of nitrogen-doped carbon quantum dots according to claim 5, wherein the drying temperature is 100 ℃ in step S5.
8. A nitrogen-doped carbon quantum dot, which is prepared by the preparation method of any one of claims 1 to 7, contains both aldehyde groups and cyano groups, and has a particle size of less than 5 nm.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115092909A (en) * 2022-07-12 2022-09-23 中南大学 High-concentration fluorine-doped carbon dot and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US20170110672A1 (en) * 2015-10-20 2017-04-20 Korea Institute Of Science And Technology N-doped nanocarbon materials and method for manufacturing the same
US20190300786A1 (en) * 2018-03-30 2019-10-03 Institute Of Process Engineering, Chinese Academy Of Sciences Fluorescent nanomaterial and preparation method and applications thereof
CN111205859A (en) * 2020-01-19 2020-05-29 国家纳米科学中心 Quantum dot and preparation method thereof
CN111808602A (en) * 2020-06-12 2020-10-23 苏州星烁纳米科技有限公司 Carbon quantum dot, method for synthesizing same, thin film, and electronic device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170110672A1 (en) * 2015-10-20 2017-04-20 Korea Institute Of Science And Technology N-doped nanocarbon materials and method for manufacturing the same
US20190300786A1 (en) * 2018-03-30 2019-10-03 Institute Of Process Engineering, Chinese Academy Of Sciences Fluorescent nanomaterial and preparation method and applications thereof
CN111205859A (en) * 2020-01-19 2020-05-29 国家纳米科学中心 Quantum dot and preparation method thereof
CN111808602A (en) * 2020-06-12 2020-10-23 苏州星烁纳米科技有限公司 Carbon quantum dot, method for synthesizing same, thin film, and electronic device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115092909A (en) * 2022-07-12 2022-09-23 中南大学 High-concentration fluorine-doped carbon dot and preparation method thereof

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