CN112794297A - Synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics - Google Patents

Synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics Download PDF

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CN112794297A
CN112794297A CN202110022692.XA CN202110022692A CN112794297A CN 112794297 A CN112794297 A CN 112794297A CN 202110022692 A CN202110022692 A CN 202110022692A CN 112794297 A CN112794297 A CN 112794297A
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carbon nitride
quantum dots
synthetic method
nitride quantum
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计亚军
欧阳伟敏
谭淑芬
任富勇
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics, which comprises the following steps: s1, mixing AlCl3·6H2O and C3H6N6Mixing to form a precursor; s2, calcining the precursor at high temperature in air atmosphere to obtain dark yellow g-CN and Al2O3A mixture of (a); s3, adding a NaOH solution into the mixture, and heating in a water bath for a certain time until the mixture turns white; s4, washing and drying the obtained white sample; and S5, dispersing a certain amount of the white sample in the aqueous solution, and performing ultrasonic treatment for 30 minutes to obtain a uniformly dispersed g-CNQDS solution. THE ADVANTAGES OF THE PRESENT INVENTIONComprises the following steps: the preparation method is simple in preparation process, low in cost and environment-friendly, and has great potential in the aspect of preparing the carbon nitride quantum dots in a large scale in a short period.

Description

Synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics.
Background
g-CN QDs, a typical 0D material, attracts great interest of broad scholars due to unique boundary effect and quantum confinement effect. The method is widely applied to the fields of biological imaging, optical sensing, energy storage and conversion and the like.
So far, the common preparation methods of g-CN QDs mainly comprise strong acid stripping, hydrothermal stripping, strong ultrasonic stripping and the like. The methods have the defects of long synthesis period, low synthesis yield, unquantified quantum dot number and difficult recovery of synthesis raw materials in the process of preparing g-CN QDs, so that the methods are not favorable for further popularization and application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a synthesis method for preparing the carbon nitride quantum dots with the blue fluorescence characteristic, the method has the advantages of simple preparation process, low cost and environmental friendliness, and the method has great potential in the aspect of mass preparation of the carbon nitride quantum dots in a short period. To achieve the above objects and other advantages in accordance with the present invention, there is provided a synthesis method for preparing carbon nitride quantum dots having blue fluorescence characteristics, comprising:
s1, mixing AlCl3·6H2O and C3H6N6Mixing to form a precursor;
s2, calcining the precursor at high temperature in air atmosphere to obtain dark yellow g-CN and Al2O3A mixture of (a);
s3, adding a NaOH solution into the mixture, and heating in a water bath for a certain time until the mixture turns white;
s4, washing and drying the obtained white sample;
and S5, dispersing a certain amount of the white sample in the aqueous solution, and performing ultrasonic treatment for 30 minutes to obtain a uniformly dispersed g-CN QDS solution.
Preferably, the step S3 is performed by NaOH on g-CN and Al2O3Of the mixture ofRemoving Al2O3And performing cutting processing.
Preferably, the steps include:
S31、AlCl3·6H2o and C3H6N6Mixing according to the molar ratio of 3:10 to form a precursor;
s32, calcining the precursor in air at 550 ℃ for 4h to obtain g-CN and Al with dark yellow color2O3A mixture of (a);
s33, adding 2M NaOH into the mixture, and heating the mixture in a water bath at 80 ℃ for 6 hours until the mixture turns white;
and S34, washing and drying the obtained white sample, and dispersing a certain amount of sample in the aqueous solution for 30 minutes by ultrasonic treatment to obtain a uniformly dispersed g-CN QDS solution.
Preferably, in step S33, 2M NaOH is added to the mixture and heated in a water bath at 80 ℃ for 6h until the mixture turns white.
Preferably, said C3H6N6、AlCl3·6H2The molar ratio of O to NaOH was 10:3: 4.
Compared with the prior art, the invention has the beneficial effects that: the preparation process is simple, and the raw material AlCl is3·6H2The O can be recycled, and the large-scale preparation of the carbon nitride quantum dots can be realized. The prepared carbon nitride quantum dot has typical blue fluorescence characteristics and good hydrophilicity, and is expected to be widely applied in the fields of biological imaging, optical sensing, energy storage conversion and the like.
Drawings
FIG. 1 is a process diagram of the synthesis of carbon nitride quantum dots with blue fluorescence characteristics according to the present invention;
FIG. 2 is a HRTEM image and a crystal diffraction pattern image of a synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics according to the present invention;
FIG. 3 is a Fourier transform infrared spectrum of a synthetic method for making carbon nitride quantum dots with blue fluorescence characteristics according to the present invention;
FIG. 4 is a UV spectrum of a synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics according to the present invention;
FIG. 5 is a fluorescence spectrum of a visible light region under excitation of different wavelengths and a partial enlarged view thereof of a synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics according to the present invention;
fig. 6 is a comparative digital graph of deionized water (left) and carbon nitride quantum dots (right) under visible light and 365nm excitation for a synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-6, a synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics comprises the following steps: s1, mixing AlCl3·6H2O and C3H6N6Mixing to form a precursor;
s2, calcining the precursor at high temperature in air atmosphere to obtain dark yellow g-CN and Al2O3A mixture of (a);
s3, adding a NaOH solution into the mixture, and heating in a water bath for a certain time until the mixture turns white;
s4, washing and drying the obtained white sample;
s5, dispersing a certain amount of the white sample in the water solution, performing ultrasonic treatment for 30 minutes to obtain a uniformly dispersed g-CN QDS solution, and using NaOH and Al2O3The chemical reaction of (2) is to react g-CN with Al2O3Al in the composite2O3Removing, pore-forming, cutting g-CN with NaOH to obtain porous small-layer carbon nitride material, and ultrasonic treatingThis gave a high yield of a dispersion-stable solution of g-CN QDS.
Further, in the step S3, g-CN and Al are reacted by NaOH2O3Is subjected to Al removal2O3And performing cutting processing.
Further, the steps include:
S31、AlCl3·6H2o and C3H6N6Mixing according to the molar ratio of 3:10 to form a precursor;
s32, calcining the precursor in air at 550 ℃ for 4h to obtain g-CN and Al with dark yellow color2O3A mixture of (a);
s33, adding 2M NaOH into the mixture, and heating the mixture in a water bath at 80 ℃ for 6 hours until the mixture turns white;
and S34, washing and drying the obtained white sample, and dispersing a certain amount of sample in the aqueous solution for 30min by ultrasound to obtain the uniformly dispersed g-CN QDS solution.
Further, in said step S33, 2M NaOH was added to the above mixture, and heated in water bath at 80 ℃ for 6 hours until the mixture turned white.
Further, said C3H6N6、AlCl3·6H2The molar ratio of O to NaOH was 10:3: 4.
Example 1
Referring to FIG. 1, preparation of g-CN QDs
First weigh 3g C3H6N6Powder and 2g AlCl3·6H2Mixing and grinding the O evenly, and then transferring the mixture into a tubular furnace to calcine for 4 hours at 550 ℃; and mixing the obtained mixture with 2M NaOH solution, reacting for 6 hours at 80 ℃ under magnetic stirring, washing, collecting white precipitate, and carrying out ultrasonic treatment for about 30 minutes to obtain g-CN QDS.
Referring to fig. 2, HRTEM analysis: the resulting g-CNQDs are less than 5nm in size. The grain spacing was about 0.32nm, corresponding to the (002) crystal plane of carbon nitride.
Referring to fig. 3, FT-IR analysis: 800cm-1(triazine ring vidration)1400cm-1(C-N)，1600cm-1(C＝N)，1073cm-1(C-O) and 3400cm-1(O-H/N-H)。
Referring to fig. 4, UV-vis analysis: the absorption peak of 200to 360nm is pi-pi and N-pi transition of C-N bond and C-N bond in the triazine ring of the carbon nitride quantum dot.
Referring to fig. 5, PL analysis: as the excitation wavelength is increased from 290nm to 350nm, the intensity of the emission peak at 440nm is increased and then decreased, and the excitation wavelength corresponding to the strongest fluorescence peak is 320 nm. This phenomenon is related to the surface state of the material.
Referring to fig. 6, stability analysis: with the increase of time, the g-CN QDs solution does not have obvious coagulation phenomenon and the trend of reducing the luminous intensity, and shows better optical stability.
The number of devices and the scale of the processes described herein are intended to simplify the description of the invention, and applications, modifications and variations of the invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (5)

1. A synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics is characterized by comprising the following steps:
s1, mixing AlCl3·6H2O and C3H6N6Mixing to form a precursor;
s2, calcining the precursor at high temperature in air atmosphere to obtain dark yellow g-CN and Al2O3A mixture of (a);
s3, adding a NaOH solution into the mixture, and heating in a water bath for a certain time until the mixture turns white;
s4, washing and drying the obtained white sample;
and S5, dispersing a certain amount of the white sample in the aqueous solution, and performing ultrasonic treatment for 30 minutes to obtain a uniformly dispersed g-CN QDS solution.
2. The synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics according to claim 1, wherein g-CN and Al are treated by NaOH in step S32O3Is subjected to Al removal2O3And performing cutting processing.
3. The synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics according to claim 2, wherein the steps comprise:
S31、AlCl3·6H2o and C3H6N6Mixing according to the molar ratio of 3:10 to form a precursor;
s32, calcining the precursor in air at 550 ℃ for 4h to obtain g-CN and Al with dark yellow color2O3A mixture of (a);
s33, adding 2M NaOH into the mixture, and heating the mixture in a water bath at 80 ℃ for 6 hours until the mixture turns white;
and S34, washing and drying the obtained white sample, and dispersing a certain amount of sample in the aqueous solution for 30 minutes by ultrasonic treatment to obtain a uniformly dispersed g-CN QDS solution.
4. The synthetic method of claim 3 wherein in step S33, 2M NaOH is added to the mixture and heated in water bath at 80 ℃ for 6h until the mixture turns white.
5. The synthetic method for preparing carbon nitride quantum dots with blue fluorescence characteristics according to claim 3, wherein C is3H6N6、AlCl3·6H2The molar ratio of O to NaOH was 10:3: 4.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117187617A (en) * 2023-09-21 2023-12-08 上海理工大学 High-heat-conductivity composite material and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105670620A (en) * 2016-03-14 2016-06-15 山东农业大学 Preparation method of doped carbon nitride fluorescent quantum dots
CN106006581A (en) * 2016-05-20 2016-10-12 太原理工大学 Method for solvothermal preparation of fluorescent carbon nitride quantum dots
CN107746710A (en) * 2017-09-06 2018-03-02 郑州大学 One kind nitridation carbon quantum dot and its preparation method and application
CN111117607A (en) * 2019-12-03 2020-05-08 上海理工大学 Preparation method and application of graphene quantum dots with blue fluorescence characteristics
CN111498818A (en) * 2020-04-21 2020-08-07 中国科学院化学研究所 Carbon nitride quantum dot hydrocolloid and preparation method and application thereof
US10800971B1 (en) * 2019-06-21 2020-10-13 Guangdong Pharmaceutical University Biomass-based high-efficiency fluorescent graphene quantum dot and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105670620A (en) * 2016-03-14 2016-06-15 山东农业大学 Preparation method of doped carbon nitride fluorescent quantum dots
CN106006581A (en) * 2016-05-20 2016-10-12 太原理工大学 Method for solvothermal preparation of fluorescent carbon nitride quantum dots
CN107746710A (en) * 2017-09-06 2018-03-02 郑州大学 One kind nitridation carbon quantum dot and its preparation method and application
US10800971B1 (en) * 2019-06-21 2020-10-13 Guangdong Pharmaceutical University Biomass-based high-efficiency fluorescent graphene quantum dot and preparation method thereof
CN111117607A (en) * 2019-12-03 2020-05-08 上海理工大学 Preparation method and application of graphene quantum dots with blue fluorescence characteristics
CN111498818A (en) * 2020-04-21 2020-08-07 中国科学院化学研究所 Carbon nitride quantum dot hydrocolloid and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117187617A (en) * 2023-09-21 2023-12-08 上海理工大学 High-heat-conductivity composite material and preparation method thereof
CN117187617B (en) * 2023-09-21 2024-06-11 上海理工大学 High-heat-conductivity composite material and preparation method thereof

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Application publication date: 20210514