CN111269714A - Multi-fluorescence nitrogen-doped graphene quantum dot and preparation method and application thereof - Google Patents

Multi-fluorescence nitrogen-doped graphene quantum dot and preparation method and application thereof Download PDF

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CN111269714A
CN111269714A CN201811473237.6A CN201811473237A CN111269714A CN 111269714 A CN111269714 A CN 111269714A CN 201811473237 A CN201811473237 A CN 201811473237A CN 111269714 A CN111269714 A CN 111269714A
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graphene quantum
quantum dot
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fluorescence
doped graphene
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CN111269714B (en
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只金芳
付杨
高冠岳
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Technical Institute of Physics and Chemistry of CAS
University of Chinese Academy of Sciences
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Technical Institute of Physics and Chemistry of CAS
University of Chinese Academy of Sciences
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    • 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
    • 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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material

Abstract

The invention discloses a multi-fluorescence nitrogen-doped graphene quantum dot, which is a graphene quantum dot with hydroxyl and amino on the surface and obtained by modifying semicarbazide. The multi-fluorescence nitrogen-doped graphene quantum dot has uniform particle size, and can emit blue, green and red fluorescence in aqueous solution. The invention also discloses the multi-fluorescence nitrogen-doped graphene quantum dot and a preparation method and application thereof.

Description

Multi-fluorescence nitrogen-doped graphene quantum dot and preparation method and application thereof
Technical Field
The invention relates to the technical field of nano luminescent materials. More particularly, relates to a multi-fluorescence nitrogen-doped graphene quantum dot, and a preparation method and application thereof.
Background
In recent years, graphene, as a zero band gap nanomaterial, has attracted much attention in the electrochemical field due to its excellent electron transport ability, excellent conductivity, and high specific surface area. The unique physical and chemical properties endow the graphene with good potential application values in catalysis, batteries and super capacitors. However, since graphene is a zero band gap semiconductor material, it has certain limitations in the fields of biological imaging and photoelectronics. In addition, its hydrophobicity and certain biotoxicity also prevent its application in biological and pharmaceutical fields.
In order to make graphene have an energy band gap, graphene quantum dots have been gradually spotlighted by more and more researchers and exhibit desirable properties including good biocompatibility, superior chemical stability and high fluorescence properties. Researches show that the obvious optical luminescence property of the graphene quantum dots is caused by quantum size effect, edge and defect influence. Meanwhile, the low toxicity and water solubility exhibited by the graphene quantum dots are caused by the quantum size effect and the oxygen-containing functional groups modified on the surface of the graphene quantum dots. Therefore, in consideration of these unique physicochemical characteristics, graphene quantum dots have been widely used in the fields of catalysis, printing ink, biosensing, bioimaging, drug loading, and the like.
Up to now, more and more researchers have been dedicated to exploring different methods for synthesizing graphene quantum dots, mainly divided into top-down and bottom-up. The bottom-up strategy is mainly obtained based on micromolecular carbon synthesis, and the graphene quantum dots with easily controlled and uniformly dispersed appearance can be obtained by the method. In contrast, the top-down method is based on shearing large carbon materials, which has the advantages of environmental friendliness, simplicity, short reaction process time, and the like. Although there are a number of reports on graphene quantum dots, they still face significant challenges. On one hand, harsh reaction conditions, such as the use of a large amount of strong acid, an excessively long treatment time, a high cost, a complex preparation process, and the like, all limit the rapid synthesis of graphene quantum dots. Secondly, due to the low signal-to-noise ratio and the short fluorescence emission wavelength, the graphene quantum dots with monochromatic fluorescence (generally, blue light) are not attractive in the fields of analysis and detection, biological imaging and the like. In contrast, multi-channel detection and multi-color fluorescence imaging have higher signal-to-noise ratios due to the low bandwidth interference sum of the background. However, to date, there has been relatively little work on synthesizing polychromatic fluorescent graphene quantum dots.
Therefore, it is required to provide a simple method for preparing a multi-photoluminescence graphene quantum dot capable of covering the full visible spectrum to solve the above existing technical problems.
Disclosure of Invention
The first purpose of the present invention is to provide a multi-fluorescent nitrogen-doped graphene quantum dot, which has a relatively uniform particle size and can emit blue, green and red fluorescence respectively in an aqueous solution.
The second purpose of the invention is to provide a preparation method of the multi-fluorescence nitrogen-doped graphene quantum dots, wherein the multi-fluorescence nitrogen-doped graphene quantum dots prepared by the method have uniform particle size and can respectively emit blue, green and red fluorescence in an aqueous solution.
The third purpose of the invention is to provide an application of the multi-fluorescence nitrogen-doped graphene quantum dot.
In order to achieve the first object, the present invention provides a multi-fluorescent nitrogen-doped graphene quantum dot, wherein the multi-fluorescent nitrogen-doped graphene quantum dot is a graphene quantum dot modified by semicarbazide and having a hydroxyl group and an amino group on the surface.
Preferably, the average particle size of the graphene quantum dots is 20nm, and the particle size is uniform.
In order to achieve the second object, the invention provides a preparation method of a multi-fluorescence nitrogen-doped graphene quantum dot, which comprises the following steps:
1) taking a graphite rod as a cathode and an anode, taking a mixed solution of an alkaline aqueous solution and semicarbazide as an electrolyte, carrying out electrolysis, and continuing to electrolyze until the reaction is sufficient after the surface layer of the graphite rod expands;
2) and carrying out centrifugal separation on the electrolyzed electrolyte to obtain solid powder, and further carrying out separation and purification on the obtained solid powder to obtain the multi-fluorescence nitrogen-doped graphene quantum dot.
In the preparation method, the graphite rod is selected as a raw material, and the mixed solution of the alkaline aqueous solution and the semicarbazide is used as the electrolyte, so that the performance of the obtained quantum dot is greatly influenced. Namely, the multi-fluorescence nitrogen-doped graphene quantum dot can be obtained through electrolysis only under the specific condition.
Preferably, in the step 1), the concentration of the hydroxyl group in the alkaline aqueous solution is 0.05 to 0.15 mol/L.
Preferably, in step 1), the molar ratio of the semicarbazide to the hydroxyl groups in the aqueous alkaline solution is from 0.5 to 2: 1.
preferably, the aqueous alkaline solution is selected from the group consisting of aqueous NaOH solution, aqueous KOH solution, Ba (OH)2One kind of (1).
Preferably, in the step 1), the working power supply used for electrolysis is a direct-current constant-voltage power supply, and a high constant potential of 5-10V is used. The working voltage at the two ends of the electrode is greater than the oxygen evolution potential, so that the electrolysis process is actually a water electrolysis process, hydroxyl and oxygen free radicals are generated by electrolyzing water, the surface of the graphite rod can be effectively corroded and cut, and the intercalation and stripping of ions and the formation of oxygen-containing functional groups on the surface are facilitated.
Preferably, in the step 1), the time for continuing the electrolysis is 1-4 h.
Preferably, the purity of the graphite rod is 99.99% or more.
Preferably, in step 2), the centrifugation comprises: and sequentially centrifuging and vacuum-filtering the electrolyzed electrolyte to obtain yellow filtrate, and then carrying out rotary evaporation and dehydration on the yellow filtrate.
More preferably, the vacuum filtration adopts a polytetrafluoroethylene microporous filter membrane, and the pore diameter is 0.22 um. The residue in the solution can be removed more effectively.
Preferably, in step 2), the separation and purification comprises: and dissolving the solid powder in an ethanol solution, centrifuging, dialyzing the solution obtained after centrifugation at room temperature, and performing rotary evaporation to completely remove the solvent. In this case, the solute is precipitated in a dissolved state, i.e., in an unsaturated state.
More preferably, the dialysis is carried out in a dialysis bag with a molecular weight cut-off of 3000Da for a dialysis time of 24-48 hours. Can effectively remove sodium and hydroxide ions.
In order to achieve the third purpose, the invention provides an application of the multi-fluorescence nitrogen-doped graphene quantum dot in selectively determining iron ions in a solution.
Preferably, the application comprises the steps of:
dissolving the multi-fluorescence nitrogen-doped graphene quantum dots in deionized water to prepare a graphene quantum dot aqueous solution;
and (3) taking the same volume of prepared different metal ion solutions with the same concentration into the same volume of graphene quantum dot aqueous solution, fixing the volume, and obtaining a corresponding fluorescence spectrum by using a fluorescence spectrometer after the solution is stable.
More preferably, the application comprises the steps of:
a. dissolving the multi-fluorescence nitrogen-doped graphene quantum dots in deionized water to prepare a graphene quantum dot aqueous solution with the concentration of 1-10mg/mL, and stabilizing for 0.5-1 hour;
b. respectively taking 500 mu L of equivalent solution from the solution obtained in the step a into 13 volumetric flasks with the same size and volume and 10 mL;
c. preparing 12 common metal ion solutions with the concentration of 4mM/L, respectively taking 500 mu L of the metal ion solutions into the volumetric flask in the step b, and then fixing the volume by using deionized water;
d. and D, after stabilization, using a fluorescence spectrometer to obtain corresponding fluorescence spectra of the solution in the 13 volumetric flasks subjected to constant volume in the step H.
The invention has the following beneficial effects:
according to the preparation method, the graphite rod is used as a raw material, the specific electrolyte is adopted to prepare the multicolor fluorescent nitrogen-doped graphene quantum dots through an electrochemical method, and the problem that most of the existing works can only synthesize the monochromatic fluorescent graphene quantum dots is solved.
The multi-fluorescence nitrogen-doped graphene quantum dot can emit blue, green and red fluorescence in an aqueous solution, can realize the selective detection of iron ions, and provides a new material for the application in the fields of biological imaging and analysis and detection.
The method for preparing the multi-fluorescence nitrogen-doped graphene quantum dots has the advantages of simplicity in operation, low cost, environmental friendliness, low requirement on equipment and the like, and is easy to realize large-scale and large-batch production and application.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a transmission electron microscope picture of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1.
Fig. 2 shows a fourier transform infrared spectrum of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1.
Fig. 3 shows fluorescence emission spectra corresponding to different excitation wavelengths of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1.
Fig. 4 shows a fluorescent photograph of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1 emitted under an excitation light source with three wavelengths.
Fig. 5 shows a fluorescence spectrum of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1 after different metal ions are added.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The preparation method of the multi-fluorescence nitrogen-doped graphene quantum dot comprises the following steps:
taking graphite rods (with the purity of 99.99%) as an anode and a cathode, and adding semicarbazide into a 0.1mol/L NaOH aqueous solution to ensure that the molar ratio of the semicarbazide to the NaOH is 1: 1, carrying out electrolytic stripping treatment on an electrolytic cell through a 5V constant potential to enable the surface of a graphite rod to expand; maintaining the working voltage, and continuously electrolyzing for 4 hours, wherein the electrolyte changes from colorless to yellow and finally changes to dark brown. Then, the obtained electrolyte is firstly subjected to centrifugal separation at the rotating speed of 2000rpm, and large insoluble substances are removed; then, continuing to carry out centrifugal separation at the rotating speed of 10000 rpm; and finally, carrying out vacuum filtration on the centrifugate to obtain yellow filtrate. The yellow filtrate was dehydrated by rotary evaporation to give a solid powder. For further separation and purification, dissolving the obtained solid powder in an ethanol solution, further centrifuging to remove insoluble substances, dialyzing the solution in a dialysis bag with the molecular weight cutoff of 3000Da for 24 hours at room temperature to remove impurities such as redundant salt ions, and desolventizing the obtained solution by a rotary evaporation method after dialysis is finished to obtain the multi-fluorescence nitrogen-doped graphene quantum dot powder.
Fig. 1 is a transmission electron microscope picture of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1, and shows that the graphene quantum dot is spherical at a size of 20 nm.
Fig. 2 is a fourier transform infrared spectrum of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1, and as shown in the figure, the surface of the graphene quantum dot contains a large amount of oxygen-containing functional groups. The surface of the material has abundant hydroxyl and amino functional groups, so that the material has good hydrophilicity. At the same time, at 2340cm-1The very strong peaks belong to the C-N bond and are at 1760 and 1579cm, respectively-1Two sharp peaks are attributed to vibration of C ═ O and N-H in carbonyl, and the result shows that the surface of the obtained graphene quantum dot is successfully subjected to passivation reaction, namely semicarbazide is modified on the surface of the graphene quantum dot through a chemical bond.
Example 2
The multi-fluorescence nitrogen-doped graphene quantum dots realize a multi-fluorescence emission test:
the multi-fluorescence nitrogen-doped graphene quantum dot powder prepared in example 1 was dissolved in deionized water to prepare a concentration of 10 mg/mL. After the solution is stabilized for 1 hour, the prepared graphene quantum dot solution is irradiated under laser light sources with wavelengths of 375 nm, 485 nm and 560nm respectively, and can emit corresponding blue, green and red fluorescence respectively, and can be observed by naked eyes.
Fig. 3 is fluorescence emission spectra corresponding to different excitation wavelengths of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1, and the fluorescence emission spectra are shown to have a wide range, can cover the ultraviolet region to the visible light region, and are red-shifted with increasing excitation wavelength. While the emitted fluorescence is strongest at an excitation wavelength of 340 nm.
Fig. 4 is a fluorescent photograph of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1 emitted by an excitation light source with three wavelengths.
Example 3
The multi-fluorescence nitrogen-doped graphene quantum dots realize the selective detection of iron ions:
the multi-fluorescence nitrogen-doped graphene quantum dot powder prepared in example 1 was dissolved in deionized water to prepare a concentration of 1 mg/mL. After the solution is stabilized for 1 hour, 500 μ L of graphene quantum dot solution with the same amount is respectively added into 13 volumetric flasks with the same size and volume and 10 mL. 500. mu.L of each of 12 kinds of common metal ion solutions prepared in advance and having a concentration of 4mM/L was put into the above volumetric flask, and then the volume was fixed with deionized water. And D, after the solution is stabilized for 1 hour, measuring the solution in the 13 volumetric flasks with constant volume in the step H by using a fluorescence spectrometer, and measuring the corresponding fluorescence spectrum at the maximum excitation wavelength of 340 nm.
Fig. 5 is a fluorescence spectrum of the multi-fluorescent nitrogen-doped graphene quantum dot prepared in example 1 after different metal ions are added, and when iron ions are added, the intensity of the corresponding fluorescence spectrum emission peak is obviously reduced.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (9)

1. The multi-fluorescence nitrogen-doped graphene quantum dot is characterized in that the multi-fluorescence nitrogen-doped graphene quantum dot is a graphene quantum dot which is modified by semicarbazide and has hydroxyl and amino on the surface.
2. The preparation method of the multi-fluorescence nitrogen-doped graphene quantum dot according to claim 1, which is characterized by comprising the following steps:
1) taking a graphite rod as a cathode and an anode, taking a mixed solution of an alkaline aqueous solution and semicarbazide as an electrolyte, carrying out electrolysis, and continuing to electrolyze until the reaction is sufficient after the surface layer of the graphite rod expands;
2) and carrying out centrifugal separation on the electrolyzed electrolyte to obtain solid powder, and further carrying out separation and purification on the obtained solid powder to obtain the multi-fluorescence nitrogen-doped graphene quantum dot.
3. The method according to claim 1, wherein in step 1), the concentration of hydroxyl groups in the basic aqueous solution is 0.05 to 0.15 mol/L; the molar ratio of the semicarbazide to the hydroxyl in the aqueous alkaline solution is 0.5-2: 1.
4. the method according to claim 2 or 3, wherein the aqueous alkaline solution is selected from the group consisting of aqueous NaOH solution, aqueous KOH solution, Ba (OH)2One kind of (1).
5. The method according to claim 1, wherein in step 1), the working power supply for electrolysis is a DC constant voltage power supply, and a high constant potential of 5-10V is used.
6. The method according to claim 1, wherein in step 2), the centrifugation comprises: sequentially centrifuging and vacuum-filtering the electrolyzed electrolyte to obtain yellow filtrate, and then carrying out rotary evaporation and dehydration on the yellow filtrate; preferably, the vacuum filtration adopts a polytetrafluoroethylene microporous filter membrane, and the aperture is 0.22 um.
7. The method according to claim 1, wherein in step 2), the separation and purification comprises: dissolving the solid powder in an ethanol solution, centrifuging, dialyzing the solution obtained after centrifugation at room temperature, and performing rotary evaporation to completely remove the solution; preferably, the dialysis is carried out in a dialysis bag with a molecular weight cut-off of 3000Da for a dialysis time of 24-48 hours.
8. The application of the multi-fluorescence nitrogen-doped graphene quantum dot according to claim 1 and the multi-fluorescence nitrogen-doped graphene quantum dot prepared by the preparation method according to any one of claims 2 to 7 in selectively determining iron ions in a solution.
9. Use according to claim 8, characterized in that it comprises the following steps:
dissolving the multi-fluorescence nitrogen-doped graphene quantum dots in deionized water to prepare graphene quantum dot aqueous solutions with different concentrations;
and (3) taking the same volume of prepared different metal ion solutions with the same concentration into the same volume of graphene quantum dot aqueous solution, fixing the volume, and obtaining a corresponding fluorescence spectrum by using a fluorescence spectrometer after the solution is stable.
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CN104237192A (en) * 2014-06-26 2014-12-24 广西师范学院 Method for detecting ferric ions through graphene quantum dot probes
CN108117066A (en) * 2017-12-19 2018-06-05 浙江工业大学 A kind of nitrogen-doped graphene quantum dot electrochemical preparation method

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