CN110317606B - Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product - Google Patents

Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product Download PDF

Info

Publication number
CN110317606B
CN110317606B CN201910701856.4A CN201910701856A CN110317606B CN 110317606 B CN110317606 B CN 110317606B CN 201910701856 A CN201910701856 A CN 201910701856A CN 110317606 B CN110317606 B CN 110317606B
Authority
CN
China
Prior art keywords
bromoacetonitrile
carbon dots
carbon
imidazole
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910701856.4A
Other languages
Chinese (zh)
Other versions
CN110317606A (en
Inventor
陈久存
蒲建林
金燕子
邓志琴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest University
Original Assignee
Southwest University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest University filed Critical Southwest University
Priority to CN201910701856.4A priority Critical patent/CN110317606B/en
Publication of CN110317606A publication Critical patent/CN110317606A/en
Application granted granted Critical
Publication of CN110317606B publication Critical patent/CN110317606B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Optics & Photonics (AREA)
  • External Artificial Organs (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and a product, and particularly relates to a method for preparing carbon dots by mixing bromoacetonitrile and 1-methylimidazole and directly reacting. The method disclosed by the invention is simple and green in synthesis process, and the synthesized carbon dots have good fluorescence property and light stability, so that a new method is provided for synthesis of the carbon dots.

Description

Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product
Technical Field
The invention relates to preparation of a nano luminescent material, in particular to a method for preparing carbon dots by using bromoacetonitrile and imidazole compounds, and also relates to a product prepared by using the method.
Background
Carbon dots are a new type of fluorescent nanoparticles that have attracted extensive attention from researchers due to their many advantages such as good fluorescence stability, low toxicity, high biocompatibility, and stable chemical properties. Compared with conventional fluorescent materials such as organic dyes and semiconductor quantum dots, carbon dots have many advantages such as very strong fluorescence, up-conversion luminescence property, chemical stability, very good dispersibility in water, low photobleaching, good biocompatibility, low cost, low toxicity, etc., and these excellent properties make them popular with scientists. Therefore, carbon dots have been widely used in many fields including electrochemical sensing, drug loading, photothermal and photodynamic therapy, photocatalysis, energy storage, and batteries.
Methods of synthesizing carbon dots can be roughly divided into two major categories: top-down methods and bottom-up methods. The top-down method mainly cuts macromolecular carbon materials such as carbon nanotubes, graphite, carbon powder, graphene and the like into small nanoparticles by a physical or chemical method, and most cutting processes are non-selective. The bottom-up method mainly uses organisms as precursors to finally obtain carbon dots by a certain method, the methods comprise a pyrolysis/chemical oxidation method/hydrothermal method, a template method, a microwave or ultrasonic method and the like, and the selection range of the precursors is very wide. Besides, there is also a method to tune the fluorescence properties of carbon dots by surface passivation and functionalization. However, the above synthesis methods all require additional energy, so a green and low-energy-consumption carbon dot synthesis method is urgently needed.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing carbon dots by using bromoacetonitrile and imidazole compounds; the second object of the present invention is to provide a carbon dot produced by the above method.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the method for preparing the carbon dot by using bromoacetonitrile and an imidazole compound is characterized in that the bromoacetonitrile and the imidazole compound are mixed and then directly react to prepare the carbon dot.
Preferably, the imidazole compound is at least one of 1-vinyl imidazole or 1-methyl imidazole.
Preferably, the volume ratio of bromoacetonitrile to imidazole compounds is 1: 1-1: 3, mixing.
Preferably, the reaction temperature is 5-40 ℃.
Preferably, the mixing can be carried out by any mixing method in the prior art, and more preferably by stirring.
Preferably, the time of the reaction is at least 1 s; more preferably, the reaction time is from 1s to 10 min.
Preferably, the reaction further comprises carbon dot collection, specifically, the reaction liquid is cooled, centrifuged, filtered, dialyzed, and lyophilized to obtain carbon dot powder.
Preferably, the centrifugation is carried out at 8000rpm for 10-20 min; the filtration is carried out by using a 0.22 mu m microporous filter membrane; and the dialysis is carried out for 24-48 h by using a dialysis bag with the molecular weight cutoff of 500 Da.
2. The carbon dots are prepared by the method.
Preferably, the average particle size is 17.9 nm; the particle size distribution range is 12-22 nm.
The invention has the beneficial effects that: the invention discloses a method for preparing carbon dots by using bromoacetonitrile and imidazole compounds, which can directly stir at room temperature to obtain the carbon dots, has the advantages of simple synthesis steps, controllable conditions, no energy consumption, environmental friendliness and short reaction time, can generate the carbon dots at the second level, finds a new synthesis method for carbon dot synthesis, and has the advantages of good fluorescence property, water solubility and the like.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a transmission electron microscope image of a carbon dot prepared according to the present invention.
FIG. 2 is a histogram of the particle size distribution of the carbon dots produced by the present invention.
FIG. 3 is a graph showing an ultraviolet absorption spectrum of a carbon dot produced by the present invention.
FIG. 4 shows the emission spectra of carbon dots prepared according to the present invention at different excitation wavelengths.
Fig. 5 is a graph of quantum yield data processing for quinine sulfate standards.
FIG. 6 is a graph of quantum yield data processing for carbon dots made according to the present invention.
FIG. 7 is a graph showing an ultraviolet absorption spectrum of a carbon dot obtained in example 4.
FIG. 8 is an emission spectrum of a carbon dot prepared in example 4 at different excitation wavelengths.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1
The method for preparing the carbon dots by using bromoacetonitrile and 1-methylimidazole comprises the following steps:
(1) respectively measuring 2mL of bromoacetonitrile and 6mL of 1-methylimidazole, pouring the materials into a 50mL beaker, quickly stirring the materials to uniformly mix the solutions, and standing the solutions for reaction to obtain a reaction solution, wherein the reaction solution contains carbon dots;
(2) naturally cooling the reaction liquid obtained in the step (1), and centrifuging the reaction liquid in a high-speed centrifuge at 8000rpm for 10min to obtain a supernatant; then filtering the supernatant with a microporous filter membrane with the filter membrane being 0.22 μm, dialyzing the filtrate with a dialysis bag with the molecular weight cutoff of 500Da for 48h, and freeze-drying to obtain carbon dot powder; and finally, dispersing a part of the carbon dot powder by using ultrapure water and ethanol respectively to obtain a carbon dot dispersion liquid, and storing at 4 ℃.
Example 2
The method for preparing the carbon dots by using bromoacetonitrile and 1-methylimidazole comprises the following steps:
(1) respectively measuring 5mL of bromoacetonitrile and 10mL of 1-methylimidazole, pouring the materials into a 50mL beaker, quickly stirring the materials to uniformly mix the solutions, and standing the solutions for reaction to obtain a reaction solution, wherein the reaction solution contains carbon dots;
(2) naturally cooling the reaction liquid obtained in the step (1), and centrifuging the reaction liquid in a high-speed centrifuge at 8000rpm for 10min to obtain a supernatant; then filtering the supernatant with a microporous filter membrane with the filter membrane being 0.22 μm, dialyzing the filtrate with a dialysis bag with the molecular weight cutoff of 500Da for 48h, and freeze-drying to obtain carbon dot powder; and finally, dispersing a part of the carbon dot powder by using ultrapure water and ethanol respectively to obtain a carbon dot dispersion liquid, and storing at 4 ℃.
Example 3
The method for preparing the carbon dots by using bromoacetonitrile and 1-methylimidazole comprises the following steps:
(1) respectively measuring 5mL of bromoacetonitrile and 5mL of 1-methylimidazole, pouring the materials into a 50mL beaker, quickly stirring the materials to uniformly mix the solutions, and standing the solutions for reaction to obtain a reaction solution, wherein the reaction solution contains carbon dots;
(2) naturally cooling the reaction liquid obtained in the step (1), and centrifuging the reaction liquid in a high-speed centrifuge at 8000rpm for 10min to obtain a supernatant; then filtering the supernatant with a microporous filter membrane with the filter membrane being 0.22 μm, dialyzing the filtrate with a dialysis bag with the molecular weight cutoff of 500Da for 48h, and freeze-drying to obtain carbon dot powder; and finally, dispersing a part of the carbon dot powder by using ultrapure water and ethanol respectively to obtain a carbon dot dispersion liquid, and storing at 4 ℃.
The prepared carbon dots were characterized:
FIG. 1 is a transmission electron microscope image of a carbon dot prepared according to the present invention. From the morphology analysis of the carbon dots in fig. 1, it can be seen that the carbon dots are spheroidal and have uniform size.
FIG. 2 is a histogram of the particle size distribution of the carbon dots produced by the present invention, showing that the average particle size of the carbon dots is 17.9nm and the particle size distribution is 12-22 nm.
FIG. 3 is a diagram of the ultraviolet absorption spectrum of carbon dots prepared by the present invention, the carbon dots have a very obvious absorption peak around 285nm, which is pi-pi＊Of the core carbon of (a).
FIG. 4 shows the emission spectra of the carbon dots prepared by the present invention under different excitation wavelengths, wherein the maximum excitation wavelength is 380nm, the corresponding emission wavelength is 455nm, and the carbon dots exhibit strong blue fluorescence under ultraviolet excitation and show excitation-dependent fluorescence. As the excitation wavelength increases, the emission is red-shifted.
Quantum yield analysis:
measuring the relative quantum yield of the carbon dots prepared in the embodiments 1-3 of the invention, taking quinine sulfate as a reference substance, and dissolving quinine sulfate in 0.1M H2SO4In the solution, the fluorescence quantum yield at an excitation wavelength of 360nm was 54%. The specific method comprises the following steps: firstly, a certain low-concentration carbon dot solution and a certain low-concentration quinine sulfate solution are prepared, the ultraviolet-visible spectrum absorption value of the solutions at 360nm is tested, the concentration is adjusted to enable the absorption value to be less than 0.1, and then the corresponding fluorescence emission spectrum peak area is tested on a fluorescence spectrometer (figure 5 and figure 6). After five times of repeated tests of different concentrations, the fluorescence spectrum peak area and the ultraviolet-visible spectrum absorption value which correspond to each other can be obtained, and the slope of the fluorescence spectrum peak area and the ultraviolet-visible spectrum absorption value can be calculated by mapping. The relative quantum yield can be calculated by the following formula:
Φx＝Φst(Ix/Ist)(ηx/ηst)2
wherein Φ represents the quantum yield; eta is the correlation coefficient of the solvent (absolute ethyl alcohol is 1.36, and 0.1M dilute sulfuric acid solution is 1.33); i represents the peak area of the fluorescence emission spectrum and the slope ratio of the corresponding absorption value of the ultraviolet-visible spectrum; the lower subscripts "x" and "st" correspond to the carbon dot sample and the fluorescent reference standard, respectively, and the results are shown in Table 1.
TABLE 1 Quantum yield test data for carbon dots
Figure BDA0002151045840000041
The results show that carbon dots with an average particle size of 17.9nm and a quantum yield of 21% can be obtained using the methods of examples 1 to 3 of the present invention. The method can directly react at room temperature (5-40 ℃), does not need additional energy consumption, is green and friendly, has short reaction time, can react to generate carbon dots in seconds under the condition that the reaction system is more than 30ml, and shortens the reaction time along with the increase of the volume of the reaction system, so that the aim of the invention can be fulfilled by controlling the reaction time to be more than 1s, and a new synthesis method is found for carbon dot synthesis.
Example 4
The method for preparing the carbon dots by using bromoacetonitrile and 1-vinyl imidazole comprises the following steps:
(1) respectively measuring 5mL of bromoacetonitrile and 5mL of 1-vinylimidazole, pouring the materials into a 50mL beaker, quickly stirring the materials to uniformly mix the solutions, and standing the mixture for reaction to obtain a reaction solution, wherein the reaction solution contains carbon dots;
(2) naturally cooling the reaction liquid obtained in the step (1), and centrifuging the reaction liquid in a high-speed centrifuge at 8000rpm for 10min to obtain a supernatant; then filtering the supernatant with a microporous filter membrane with the filter membrane being 0.22 μm, dialyzing the filtrate with a dialysis bag with the molecular weight cutoff of 500Da for 48h, and freeze-drying to obtain carbon dot powder; and finally, dispersing a part of the carbon dot powder by using ultrapure water and ethanol respectively to obtain a carbon dot dispersion liquid, and storing at 4 ℃.
In the embodiment, the reaction time is controlled to be more than 1s, and the temperature can be controlled within the range of 5-40 ℃; the volume ratio of bromoacetonitrile to 1-vinyl imidazole is controlled to be 1: 1-1: 3 can be realized.
The prepared carbon dots were characterized:
FIG. 7 is a graph of the UV absorption spectrum of the carbon dot prepared in this example, which has a very clear absorption peak at about 260nm, i.e., pi-pi＊Of the core carbon of (a).
Fig. 8 shows the emission spectra of the carbon dots prepared in this example under different excitation wavelengths, where the maximum excitation wavelength is 380nm, and the corresponding emission wavelength is 465nm, and the carbon dots exhibit strong blue fluorescence under ultraviolet excitation.
The quantum yield of the carbon dots prepared by the embodiment is equivalent to that of the carbon dots prepared by the embodiment 1, and the carbon dots can be prepared by bromoacetonitrile and imidazole compounds such as 1-vinyl imidazole or 1-methyl imidazole.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (4)

1. The method for preparing the carbon dots by using bromoacetonitrile and imidazole compounds is characterized by comprising the following steps: mixing bromoacetonitrile and an imidazole compound, directly reacting, cooling reaction liquid, centrifuging, filtering, dialyzing, and freeze-drying to obtain carbon dot powder; the reaction temperature is 5-40 ℃, the mixing adopts a stirring mode, and the reaction time is at least 1 s; the imidazole compound is at least one of 1-vinyl imidazole or 1-methyl imidazole.
2. The method for preparing the carbon dots by using bromoacetonitrile and imidazole compounds according to claim 1, which is characterized in that: the volume ratio of bromoacetonitrile to the imidazole compound is 1: 1-1: 3, mixing.
3. The method for preparing the carbon dots by using bromoacetonitrile and imidazole compounds according to claim 2, which is characterized in that: the centrifugation is carried out at 8000rpm for 10-20 min; the filtration is carried out by using a 0.22 mu m microporous filter membrane; and the dialysis is carried out for 24-48 h by using a dialysis bag with the molecular weight cutoff of 500 Da.
4. The carbon dot produced by the method according to any one of claims 1 to 3, characterized in that: the average grain diameter of the carbon dots is 17.9 nm; the particle size distribution range is 12-22 nm.
CN201910701856.4A 2019-07-31 2019-07-31 Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product Active CN110317606B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910701856.4A CN110317606B (en) 2019-07-31 2019-07-31 Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910701856.4A CN110317606B (en) 2019-07-31 2019-07-31 Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product

Publications (2)

Publication Number Publication Date
CN110317606A CN110317606A (en) 2019-10-11
CN110317606B true CN110317606B (en) 2022-04-15

Family

ID=68125109

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910701856.4A Active CN110317606B (en) 2019-07-31 2019-07-31 Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product

Country Status (1)

Country Link
CN (1) CN110317606B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112113944A (en) * 2020-09-30 2020-12-22 江南大学 Preparation of emission spectrum variable carbon dots and application thereof in detection of pH value
CN114989820B (en) * 2022-05-31 2024-03-26 哈尔滨工程大学 Construction method of carbazolyl fluorescent carbon dots with large Stokes displacement

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105315993A (en) * 2014-07-22 2016-02-10 中国科学院兰州化学物理研究所 Preparation method for ionic-liquid-modified carbon quantum dot

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105315993A (en) * 2014-07-22 2016-02-10 中国科学院兰州化学物理研究所 Preparation method for ionic-liquid-modified carbon quantum dot

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Bottom-up electrochemical preparation of solid-state carbon nanodots directly from nitriles/ionic liquids using carbon-free electrodes and the applications in specific ferric ion detection and cell imaging;Fushuang Niu等;《Nanoscale》;20160205;第5470-5477页 *

Also Published As

Publication number Publication date
CN110317606A (en) 2019-10-11

Similar Documents

Publication Publication Date Title
CN110257060B (en) Method for preparing carbon dots by using resveratrol, product and application
US9642815B2 (en) Biocompatible graphene quantum dots for drug delivery and bioimaging applications
CN110317606B (en) Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product
Huo et al. Preparation and biomedical applications of multicolor carbon dots: recent advances and future challenges
CN106701069B (en) A kind of preparation method of controllable, longwave transmissions the carbon-based nano dot of fluorescence of wavelength
US9079837B2 (en) Water-soluble fluorescent fullerene derivative, and preparation method thereof
CN109321240B (en) Orange fluorescent carbon dot and preparation method thereof
Wu et al. Pentosan-derived water-soluble carbon nano dots with substantial fluorescence: properties and application as a photosensitizer
CN113620274B (en) Method for preparing lignin-based carbon quantum dots with high quantum yield quickly, simply and conveniently
CN102994080A (en) Method for preparing fluoresent carbon nanoparticles
CN107603612B (en) Preparation method and application of hollow orange fluorescent carbon nanoparticles
Saheeda et al. Investigation on the pH‐independent photoluminescence emission from carbon dots impregnated on polymer matrix
CN114574196B (en) Preparation method and application of carbon quantum dot with high fluorescence quantum yield
Mkhari et al. Supported carbon-dots: A review
CN110817843B (en) Eutectic solvent, application thereof, carbon quantum dot and preparation method thereof
CN113403068A (en) Fused carbon dot, preparation method and application thereof
CN107603608B (en) Method for preparing fluorescent carbon dots by taking gynostemma pentaphylla as carbon source
CN108329903B (en) Preparation method of color-changeable carbon quantum dot with photo-thermal effect, product and application thereof
CN110229665B (en) Method for preparing carbon dots by utilizing bromopropylene and imidazole compounds and product
CN113697850B (en) Perovskite nanocrystalline powder capable of being dispersed by polar solvent and large-scale preparation method thereof
JP5604835B2 (en) Semiconductor nanoparticles and manufacturing method thereof
CN111747398B (en) Red carbon dot material and preparation method and application thereof
Zhang et al. Preparation of highly luminescent and biocompatible carbon dots using a new extraction method
CN107812957A (en) A kind of method that fluorescence silver nano-grain is prepared based on silver mirror reaction
US20220241419A1 (en) Highly dispersible zinc phthalocyanine-silica nanotubes and preparation method therefor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant