CN117143598A - High-entropy carbon quantum dot nanomaterial and preparation method and application thereof - Google Patents
High-entropy carbon quantum dot nanomaterial and preparation method and application thereof Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The application provides a high-entropy carbon quantum dot nanomaterial, a preparation method and application thereof, wherein the nanomaterial consists of a carbon core and a polymer chain segment, the polymer chain segment surrounds the carbon core, and the carbon core is regularly gathered through the polymer chain segment to form a spherical high-entropy carbon quantum dot with secondary aggregation; the high-entropy carbon quantum dot nano material at least contains 5 nonmetallic elements; the particle size of the carbon quantum dots is between 1 and 4nm, and the lattice spacing of the carbon cores is between 0.15 and 0.3nm; the nano material provided by the application has various nonmetallic elements and rich functional group structures, and has excellent fluorescence performance when being applied as a fluorescent material.
Description
Technical Field
The application relates to the technical field of fluorescent nano materials, in particular to a high-entropy carbon quantum dot nano material and a preparation method and application thereof.
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 quantum dots are an emerging carbon nanomaterial, generally referred to as zero-dimensional carbon nanoparticles with 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 fluorescence wavelength and the like, and has potential application value in the fields of biomedicine, environmental protection, photoelectrocatalysis, energy storage, conversion and the like.
In recent years, carbon quantum dots are in a rapid development stage, and the number of related papers shows a rapid increase trend. Various novel carbon quantum dot preparation methods have been developed successively, and semi-quantitative analysis is also performed through theoretical calculation and advanced characterization techniques with respect to the formation mechanism and complex structure of the carbon quantum dot.
Generally, the synthesis methods of carbon quantum dots can be broadly classified into a "top-down" method and a "bottom-up" method. The "top-down" method is to cut a large-size carbon target (such as graphene, graphite carbon nitride, fullerene, coke, etc.) into small-size carbon quantum dots by a physical or chemical method. The bottom-up rule is that organic micromolecules (such as citric acid, glucose, acetaldehyde, phenylenediamine and the like) are used as precursors, and carbon quantum dots are obtained through a series of polymerization, carbonization and the like. In terms of the "top-down" method, the oxidation cutting method, the arc discharge method and the laser ablation method are the more commonly used carbon quantum dot preparation methods in early researches. The reaction utilizes external energy to decompose large-size carbon target precursor to form gas plasma so as to recombine, so as to obtain the carbon quantum dot, except that the carbon quantum dot is driven by ultrahigh external voltage, and the carbon quantum dot is driven by high-energy laser pulse. Generally, the carbon quantum dots prepared by the method have poor fluorescence performance and involve a complex purification and separation process. In addition, the method has the defects of high cost, severe equipment requirements and the like. The bottom-up method mainly comprises a pyrolysis method, a template method and the like. Pyrolysis refers to the process of carbonizing or polymerizing a carbon-containing precursor under external heating or self-exothermic conditions to produce carbon quantum dots. In principle all carbon-containing precursors (e.g. citric acid, phenylenediamine, biomass, etc.) can be used to generate carbon quantum dots by the pyrolysis process. The template method is a method of generating carbon quantum dots having a specific morphology with the aid of template molecules. Although carbon quantum dots can be synthesized by various methods, the yield of carbon quantum dots synthesized by most of the methods is still generally low, and the synthesized carbon quantum dots are usually doped with only 1 to 2 hetero atoms, so that the functions of the synthesized carbon quantum dots are limited. How to realize large-scale production and multi-functionalization of carbon quantum dots is still a problem to be solved.
Disclosure of Invention
Based on the technical problems in the prior art, the application provides a high-entropy carbon quantum dot nanomaterial, which comprises various nonmetallic elements and functional group structures and shows excellent fluorescence performance as a fluorescent material.
Specifically, the technical scheme of the application is as follows:
the high-entropy quantum dot nano material consists of a carbon core and a polymer chain segment, wherein the polymer chain segment surrounds the carbon core, and the carbon core is regularly aggregated through the polymer chain segment to form a spherical high-entropy carbon quantum dot with secondary aggregation; the high-entropy carbon quantum dot nano material at least contains 5 nonmetallic elements; the particle size of the carbon quantum dots is between 1 and 4nm, and the lattice spacing of the carbon cores is between 0.15 and 0.3nm.
In some embodiments, the nonmetallic elements include carbon, oxygen, fluorine, nitrogen, sulfur.
The application also provides a preparation method of the high-entropy carbon quantum dot nanomaterial of any embodiment, which comprises the following steps:
uniformly mixing the organic compound precursors, and reacting under alkaline conditions to obtain the high-entropy carbon quantum dots; wherein the organic compound precursor comprises an alpha-H-containing aldehyde or ketone, a fluorine-containing aromatic aldehyde and a sulfur-containing amino acid.
In some embodiments, the method comprises the steps of:
uniformly mixing the organic compound precursors to obtain a mixed solution; completely dispersing solid alkali in water to prepare an alkaline solution, adding the alkaline solution into the mixed solution while the alkaline solution is hot, and stirring for reaction; after the reaction is finished, solid-liquid separation is carried out, water is added into the solid product, ultrasonic dispersion is carried out, and then the solid product is transferred into a dialysis bag for dialysis until the solid product is neutral, and the high-entropy carbon quantum dot nano material is obtained.
In some embodiments, the solid base comprises at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide.
In some embodiments, the reaction time is 2 to 3 hours.
In some embodiments, the alkaline solution has a concentration of 0.5 to 12mol/L; preferably, it is 1 to 10mol/L.
In some embodiments, the alpha-H containing aldehyde comprises at least one of a mono-aliphatic aldehyde, a di-aliphatic aldehyde, a multi-aliphatic aldehyde, a mono-aromatic aldehyde, a di-aromatic aldehyde, a multi-aromatic aldehyde.
In some embodiments, the sulfur-containing amino acid comprises at least one of methionine, cystine, cysteine.
In some embodiments, the fluorine-containing aromatic aldehyde includes at least one of p-fluorobenzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, pentafluorobenzaldehyde, p-fluorobenzaldehyde, 2, 6-difluorobenzaldehyde, 3, 5-difluorobenzaldehyde, o-trifluoromethylbenzaldehyde, 3- (trifluoromethyl) benzaldehyde, 4- (trifluoromethyl) benzaldehyde, 2,3,4, 5-tetrafluorobenzaldehyde, 2-fluoro-3-methoxybenzaldehyde, 2,3, 5-trifluorobenzaldehyde, 3, 4-difluorobenzaldehyde, 3, 5-bis (trifluoromethyl) benzaldehyde, 2, 5-difluorobenzaldehyde, 2, 3-difluorobenzaldehyde, 2,4, 5-trifluorobenzaldehyde.
The application also provides the application of the high-entropy carbon quantum dot nanomaterial of any of the above embodiments or the high-entropy carbon quantum dot nanomaterial obtained by the preparation method of any of the above embodiments as a fluorescent material.
Compared with the prior art, the application has the following beneficial effects:
the application is based on aldol condensation reaction and dehydration condensation reaction of amino acid, and makes aldehyde or ketone precursor containing alpha hydrogen atom firstly convert into unsaturated aldehyde or ketone under alkaline condition in open system at room temperature and normal pressure, then the unsaturated aldehyde or ketone undergoes various substitution and condensation reaction with amino acid in the synthesis process to form polymer chain with different functional groups or branches and small clusters, and then further curls, crosslinks and dehydrates to form carbon core of carbon quantum dot; and the peripheral uncarbonized polymer chains surround the periphery of the carbon core and are provided with a plurality of heteroatom functional groups, so that the carbon quantum dots have a plurality of characteristics. As the reaction is completed, the mixture of carbon-containing quantum dots settles to the bottom of the reactor. After ultrasonic treatment in water environment, the carbon quantum dots are dispersed into water. In the dialysis process, small molecule precursors in the mixture enter the dialysis liquid, and the carbon quantum dots remain in the dialysis bag. Finally, removing solvent water through freeze drying to obtain the powdery high-entropy carbon quantum dot nano material.
The carbon quantum dot nano material obtained by the method provided by the application contains various nonmetallic elements and rich functional group structures, is used as a fluorescent material, shows excellent fluorescence performance, and can be applied to the fields of optical sensing, imaging and the like.
Drawings
FIG. 1 is a schematic diagram of a high entropy carbon quantum dot structure according to the present application;
FIG. 2 is a HRTEM diagram of the high entropy carbon quantum dots of the present application, wherein the (A) diagram is accompanied by a size distribution curve of the high entropy carbon quantum dots; (B) The diagram is attached with a schematic diagram of lattice spacing of high-entropy carbon quantum dots;
FIG. 3 is an infrared spectrogram of the high-entropy carbon quantum dot of the application;
FIG. 4 is a nuclear magnetic resonance spectrum of a high entropy carbon quantum dot according to the present application, wherein (A) is 1 H spectrum, (B) is 13 C spectrum;
FIG. 5 is an XPS diagram of a high entropy carbon quantum dot according to the present application;
FIG. 6 is a high resolution mass spectrum of the high entropy carbon quantum dots of the present application; A. b are peak intensities of different mass-to-charge ratio ranges, respectively.
FIG. 7 is a graph showing fluorescence emission spectra of the high-entropy carbon quantum dots according to the present application under excitation of 500nm wavelength excitation light.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The application 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 application, 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 application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Unless otherwise indicated, reagents, starting materials, and the like in the embodiments of the application are all commercially available.
Example 1
The preparation method of the high-entropy carbon quantum dot nano material comprises the following steps:
s1, dissolving 5g of cysteine with 15mL of deionized water, then adding 10mL of aqueous solution of acetaldehyde, continuously stirring until uniform, finally adding 10mL of p-fluorobenzaldehyde, and continuously and rapidly stirring;
s2, adding 5mL of deionized water into 6g of NaOH to dissolve the NaOH, adding the dissolved NaOH into the mixed solution obtained in the step S1 while the solution is hot, continuously stirring the solution for 2 to 3 hours, and finally standing the solution for 3 days; pouring out the supernatant, injecting deionized water into the precipitate, performing ultrasonic dispersion, transferring the dispersion into a 1000Da dialysis bag, dialyzing to neutrality, and freeze-drying to obtain yellowish powder.
The obtained product was subjected to a correlation performance test, and the test results are shown in fig. 2 to 6.
As shown in fig. 2, the carbon quantum dot nanomaterial obtained in this embodiment has a particle size of 1-4nm and an average particle size of 2.32±0.52nm; and the lattice spacing of the carbon cores in the carbon quantum dot nanomaterial is about 0.25nm.
As can be seen from fig. 3 and fig. 4, the nanomaterial obtained in the present application has constituent units shown in fig. 1, each unit is composed of a carbon core and a polymer segment, the polymer segment surrounds the carbon core and has a plurality of functional group structures such as-OH, -NH-, c= O, C = C, C-N, etc.
XPS analysis is carried out on the product, the obtained nano material contains C, N, O, F, S elements, and the specific content of each element is shown in figure 5 and table 1 below.
TABLE 1 high entropy carbon Quantum dot Material content of elements
And (3) performing fluorescence performance detection on the obtained carbon quantum dot nanomaterial, wherein the detection result is shown in fig. 7.
Example 2
The preparation method of the high-entropy carbon quantum dot nano material comprises the following steps:
s1, dissolving 5g of cysteine with 15mL of deionized water, then adding 10mL of aqueous solution of acetaldehyde, continuously stirring until uniform, finally adding 10mL of p-fluorobenzaldehyde, and continuously and rapidly stirring;
s2, adding 5mL of deionized water into 6g of NaOH to dissolve the NaOH, adding the dissolved NaOH into the mixed solution obtained in the step S1 while the dissolved NaOH is hot, and continuously stirring for 2-3 hours; immediately pouring out the supernatant, injecting deionized water into the precipitate, performing ultrasonic dispersion, transferring the dispersion into a 1000Da dialysis bag, dialyzing to neutrality, and finally performing freeze drying to obtain pale yellow powder.
XPS analysis is carried out on the product, the obtained nano material contains C, N, O, F, S elements, and the specific content of each element is shown in the following table 2.
TABLE 2 high entropy carbon Quantum dot Material content of elements
Through detection, the carbon quantum dot nano material obtained in the embodiment has the particle size of 2-4nm and the average particle size of 2.52+/-0.42 nm; and the lattice spacing of the carbon cores in the carbon quantum dot nanomaterial is about 0.23nm.
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 application, which are described in detail and are not to be construed as limiting the scope of the application. 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 application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. The high-entropy carbon quantum dot nano material is characterized by comprising a carbon core and a polymer chain segment, wherein the polymer chain segment surrounds the carbon core, and the carbon core is regularly aggregated through the polymer chain segment to form a spherical high-entropy carbon quantum dot with secondary aggregation; the high-entropy carbon quantum dot nano material at least contains 5 nonmetallic elements; the particle size of the carbon quantum dots is between 1 and 4nm, and the lattice spacing of the carbon cores is between 0.15 and 0.3nm.
2. The high entropy carbon quantum dot nanomaterial of claim 1, wherein the nonmetallic element comprises carbon, oxygen, fluorine, nitrogen, sulfur.
3. The method for preparing the high-entropy carbon quantum dot nanomaterial of claim 1 or 2, characterized by comprising the following steps:
uniformly mixing the organic compound precursors, and reacting under alkaline conditions to obtain the high-entropy carbon quantum dots; wherein the organic compound precursor comprises an alpha-H-containing aldehyde or ketone, a fluorine-containing aromatic aldehyde and a sulfur-containing amino acid.
4. The method for preparing the high-entropy carbon quantum dot nanomaterial according to claim 3, comprising the following steps:
uniformly mixing the organic compound precursors to obtain a mixed solution; completely dispersing solid alkali in water to prepare an alkaline solution, adding the alkaline solution into the mixed solution while the alkaline solution is hot, and stirring for reaction; after the reaction is finished, solid-liquid separation is carried out, water is added into the solid product, ultrasonic dispersion is carried out, and then the solid product is transferred into a dialysis bag for dialysis until the solid product is neutral, and the high-entropy carbon quantum dot nano material is obtained.
5. The method for preparing a high-entropy carbon quantum dot nanomaterial according to claim 4, wherein the solid alkali comprises at least one of potassium hydroxide, sodium hydroxide, and lithium hydroxide.
6. The method for preparing the high-entropy carbon quantum dot nanomaterial according to claim 3, wherein the reaction time is 2-3 hours.
7. The method for preparing the high-entropy carbon quantum dot nanomaterial according to claim 3, wherein the α -H-containing aldehyde comprises at least one of a mono-aliphatic aldehyde, a di-aliphatic aldehyde, a multi-aliphatic aldehyde, a mono-aromatic aldehyde, a di-aromatic aldehyde, and a multi-aromatic aldehyde.
8. The method for preparing high-entropy carbon quantum dot nanomaterial according to claim 3, wherein the sulfur-containing amino acid comprises at least one of methionine, cystine, and cysteine.
9. The method for preparing the high-entropy carbon quantum dot nanomaterial according to claim 3, wherein the fluorine-containing aromatic aldehyde comprises at least one of p-fluorobenzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, pentafluorobenzaldehyde, p-fluorobenzaldehyde, 2, 6-difluorobenzaldehyde, 3, 5-difluorobenzaldehyde, o-trifluoromethylbenzaldehyde, 3- (trifluoromethyl) benzaldehyde, 4- (trifluoromethyl) benzaldehyde, 2,3,4, 5-tetrafluorobenzaldehyde, 2-fluoro-3-methoxybenzaldehyde, 2,3, 5-trifluorobenzaldehyde, 3, 4-difluorobenzaldehyde, 3, 5-bis (trifluoromethyl) benzaldehyde, 2, 5-difluorobenzaldehyde, 2, 3-difluorobenzaldehyde, 2, 4-trifluorobenzaldehyde, and 2,4, 5-trifluorobenzaldehyde.
10. The use of the high-entropy carbon quantum dot nanomaterial of claim 1 or 2 or the high-entropy carbon quantum dot nanomaterial obtained by the preparation method of any one of claims 3 to 9 as a fluorescent material.
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| CN111100637A (en) * | 2020-02-14 | 2020-05-05 | 太原理工大学 | Green fluorescent carbon quantum dot based on high fluorescent quantum yield and preparation method thereof |
| 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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| CN111100637A (en) * | 2020-02-14 | 2020-05-05 | 太原理工大学 | Green fluorescent carbon quantum dot based on high fluorescent quantum yield and preparation method thereof |
| 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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