CN116948640A - Method for preparing green light carbon quantum dots with ultrahigh fluorescence quantum yield by one-step hydrothermal method and application - Google Patents
Method for preparing green light carbon quantum dots with ultrahigh fluorescence quantum yield by one-step hydrothermal method and application Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 30
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
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- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000001022 rhodamine dye Substances 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
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- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 5
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- UPZKDDJKJWYWHQ-UHFFFAOYSA-O [6-amino-9-(2-carboxyphenyl)xanthen-3-ylidene]azanium Chemical compound C=12C=CC(=[NH2+])C=C2OC2=CC(N)=CC=C2C=1C1=CC=CC=C1C(O)=O UPZKDDJKJWYWHQ-UHFFFAOYSA-O 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- TUFFYSFVSYUHPA-UHFFFAOYSA-M rhodamine 123 Chemical compound [Cl-].COC(=O)C1=CC=CC=C1C1=C(C=CC(N)=C2)C2=[O+]C2=C1C=CC(N)=C2 TUFFYSFVSYUHPA-UHFFFAOYSA-M 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 31
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 240000001829 Catharanthus roseus Species 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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Classifications
-
- 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
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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"
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/169—Nanoparticles, e.g. doped nanoparticles acting as a gain material
Abstract
The invention discloses a method for preparing green light carbon quantum dots with ultrahigh fluorescence quantum yield by a one-step hydrothermal method and application thereof. Belongs to the field of nanometer material preparing technology and optoelectronics. The method comprises the steps of taking aqueous solution of rhodamine dye and strong alkali as precursors, transferring the precursor into a reaction kettle with para-polyphenol as a lining, carrying out hydrothermal reaction for a certain time at a certain temperature, and filtering the reaction product by a 0.22 mu m filter screen to obtain the green light carbon quantum dot with ultrahigh fluorescence quantum yield. The carbon quantum dot prepared by the invention has the fluorescence radiation center wavelength of 520nm and the particle size distribution of 3-5 nm, and has good stability and ultrahigh fluorescence quantum yield. The carbon quantum dot prepared by the method can be used as a laser gain medium to realize green laser radiation with a low threshold value, and can also be used as a probe molecule to realize detection of the pH value of a solution and heavy metal ions.
Description
Technical Field
The invention relates to the field of nano material preparation technology and optoelectronics, in particular to a method for preparing green light carbon quantum dots with ultrahigh fluorescence quantum yield by a one-step hydrothermal method and application thereof.
Background
Since 2004, xu et al have separated carbon quantum dots (Carbon Quantum Dots, abbreviated as CQDs) from carbon nanotubes by electrophoresis, and researchers have found that CQDs have the advantages of unique fluorescence emission characteristics, good biocompatibility, water solubility, and the like. CQDs are widely used in bioimaging, heavy metal ions (e.g., mercury Hg) as excellent fluorescent materials 2+ Pb of Pb 2+ Fe of iron 2+ Or Fe (Fe) 3+ Etc.), detection, photovoltaic devices, and photocatalysis, etc. (A review on advancements in carbon quantum dots and their application in photovoltaics; applications of Carbon Quantum Dots (CQDs) in membrane technologies A review; review of carbon and graphene quantum dots for sensing). Besides the common advantages of the traditional fluorescent materials, such as tunable emission spectrum, easy functionalization and the like, the CQDs also have the characteristics of low toxicity, good water solubility, photo-bleaching resistance, environmental protection, low manufacturing cost and the like.
In addition, CQDs have a broad excitation spectrum, and simultaneous excitation of a plurality of CQDs having different radiation wavelengths can be achieved by using a single excitation wavelength. Therefore, the CQDs have wide application prospect in the aspect of being used as a laser gain medium. In 2012, siu Fung Yu group enhanced CQDs fluorescence intensity by surface passivationThe CQDs passivated by polyethylene glycol (PEG 200) are coated on the surface of the optical fiber, and the CQDs are subjected to interference modulation in a deep blue region (Whispering Gallery Mode, WGM) laser radiation (Observation of lasing emission from carbon nanodots in organic solvents) by adopting a lateral (perpendicular to the axial direction of the optical fiber) optical pumping mode for the first time; in 2017, the study group prepared CQDs with four photon absorption, achieving conversion of the CQDs to random laser radiation over the deep blue region (Realization of multiphoton lasing from carbon nanodot microcavities). In 2014, the institute of science, catharanthus roseus, shen Dezhen taught the subject group by changing the nitrogen atoms and sp of the doping 2 Carbon content, green laser radiation (Amplified spontaneous green emission and lasing emission from carbon nanoparticles) with fluorescence Quantum Yield (QY) of only 36% aqueous ethanol CQDs was achieved in a Fabry-Perot (F-P) cavity. The laser radiation produced by CQDs in the green region is further enhanced, both from QY and solvent, than the WGM laser radiation that is interferometrically modulated in the blue region.
An ultra-high fluorescence quantum yield carbon quantum dot, a carbon quantum dot/PVA fluorescent film, a preparation method thereof and an application invention patent (application number 201911271586.4) applied by the agricultural university of Qingdao in 2019 propose a method for preparing ultra-high quantum yield green luminescence CQDs, wherein QY is 84.96-85.37% in aqueous solution with pH of 6.7, and QY is 95.84-96.55% when pH is 9.0. The key of the method is that rhodamine B is dissolved in a mixed solution of polyethylene glycol and alkaline ultrapure water, then the mixture is subjected to hydrothermal reaction for 8 to 12 hours at 180 to 200 ℃, and the mixture is cooled to room temperature to obtain CQDs. The preparation method is characterized in that polyethylene glycol is used as a surfactant with steric hindrance and is dissolved into ultrapure water to form a mixed solution with high steric hindrance. Rhodamine B is then dispersed into the mixed solution to form liquid reaction spaces for synthesizing CQDs using the relatively isolated space formed by steric hindrance. CQDs that emit green light are then prepared hydrothermally in an environment below 200deg.C.
The company of scintillant nanotechnology, limited, su-state 2020, also filed an invention patent (application No. 202010535758.0) similar to the preparation method of the university of green island agriculture. Except that this patent is based on the molecular structure of the prepared CQDs as claimed in patent claims. The structure of CQDs is synthesized by crosslinking a luminescent group and a crosslinking group. Wherein the luminescent group is composed of or combined with the molecular structure of one or more dyes. While the crosslinking group is described by the molecular structure of various surfactants. The preparation method application comprises three methods of solvothermal synthesis (hydrothermal synthesis), microwave-assisted synthesis and thermal injection synthesis.
As can be seen from a comparison of the two patents, the basic concepts of both patents are the basic source of dye as the chromophore and surfactant as the crosslinking group. The luminescent groups are interconnected with the crosslinking groups. The luminescent group provides green emission light. The crosslinking groups reduce the steric hindrance of the CQDs. The CQDs are stabilized by the different electronegativity that the crosslinking groups exhibit under different detection environments (solutions of different pH values). The CQDs prepared by adding the additive has strong fluorescence scattering and the quantum dots are difficult to separate, so that industrialization is difficult to popularize.
In summary, how to provide a preparation method of green carbon quantum dots with ultra-high fluorescence quantum yield is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a method for preparing green light carbon quantum dots with ultrahigh fluorescence quantum yield by a one-step hydrothermal method and application thereof. The quantum yield (PLQY or QY) of the green light carbon quantum dots prepared by the one-step hydrothermal method is up to 97.7%. The laser gain medium does not need to be added with additives, has the characteristics of no agglomeration and no fluorescence scattering, can be used as the laser gain medium, and can effectively reduce the laser threshold. The CQDS is used as a laser of a laser gain medium, and can be applied to high-sensitivity laser detection, such as detection of solution pH value and trace heavy metal ions in water.
The technical scheme of the invention optimizes the carbon source and solution environment regulation on the basis of preparing CQDs by a hydrothermal method, and can be widely used for preparing CQDs.
The invention aims to provide a preparation method of green fluorescent carbon quantum dots with good water solubility and ultrahigh fluorescence quantum yield.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention prepares the water-soluble green light CQDs with ultrahigh fluorescence quantum yield by taking dye as a carbon source and performing hydrothermal reaction in deionized water.
A method for preparing green light carbon quantum dots with ultrahigh fluorescence quantum yield by a one-step hydrothermal method comprises the following steps:
(1) Mixing rhodamine dye with deionized water to obtain dye dispersion solution;
(2) Dispersing analytically pure strong base solid in the dye dispersion solution at 25 ℃, carrying out ultrasonic oscillation for half an hour, uniformly mixing, and regulating the pH value to be more than 10 to obtain a precursor solution;
(3) Placing the precursor solution into a reaction kettle, and reacting for 2-12 hours at 120-250 ℃ to obtain a carbon quantum dot solution;
(4) And filtering the carbon quantum dot solution by a 0.22 mu m filter screen to obtain the green light carbon quantum dot with ultrahigh fluorescence quantum yield.
The beneficial effects are that: firstly, preparing nitrogen doped CQDs by using dye as a carbon source; and (II) the pH value of the solution is adjusted to ensure the effective separation of the prepared CQDs.
Further, the rhodamine dye is any one of rhodamine B, rhodamine 123, rhodamine 560 or rhodamine 6G.
Further, the rhodamine dye is rhodamine 6G.
Further, the analytically pure strong base is sodium hydroxide, potassium hydroxide, ammonia water, tetraethylammonium hydroxide.
Further, the molar concentration of rhodamine dye in the dye dispersion solution is 1 mM-5 mM.
Further, in the step (3), the reaction kettle is a reaction kettle with para-polyphenol as a lining.
Further, the pH of the deionized water in step (1) is greater than 10 (deionized water is NaOH-adjusted deionized water).
Further, the fluorescence radiation center wavelength of the green light carbon quantum dot with the ultra-high fluorescence quantum yield is 520nm.
The carbon quantum dots prepared by the method are applied to laser gain media.
The carbon quantum dot prepared by the method is used as a probe molecule in the detection of the pH value of a solution and heavy metal ions.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method of the invention can prepare the CQDs which provide stable green fluorescence. Because the solution is aqueous solution, the application of the fluorescent probe in the aspect of biological fluorescence indication is ensured. The CQDs aqueous solution prepared by the method is used as a laser gain medium, and a mode of evanescent wave excitation along the axial direction of the optical fiber is adopted, so that low-threshold laser radiation can be realized, and the application of the CQDs in the aspect of novel laser sources is enriched.
(2) The photoluminescence wavelength of the CQDs prepared by the method is in a green light region, and the fluorescence radiation center wavelength is 520nm. In the case of using rhodamine 6G methanol solution as a standard solution, the highest value of QY in the prepared CQDs was calculated to be 97%.
(3) The CQDs prepared by the method of the invention have the size range of 3-5 nm. And still ensure its optical properties when left at room temperature for 1 month.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation process of the carbon quantum dots of the invention;
FIG. 2 is a TEM morphology of the carbon quantum dots prepared in example 2 of the present invention;
FIG. 3 is a graph showing the particle size distribution of the carbon quantum dots prepared in example 2 of the present invention;
fig. 4 is an infrared spectrum of the carbon quantum dot prepared in example 2 of the present invention;
FIG. 5 is an ultraviolet-visible absorption and fluorescence emission spectrum of the carbon quantum dots prepared in example 2 of the present invention;
FIG. 6 is an XPS spectrum of the carbon quantum dot prepared in example 2 of the present invention, wherein (A) is XPS full spectrum; (B) a high resolution spectrum of C1 s; (C) a high resolution spectrum of N1 s; (D) a high resolution spectrum of O1 s;
FIG. 7 is a graph showing the laser characteristics of the carbon quantum dots prepared in the embodiment 2 of the present invention as a laser gain medium, wherein (A) is a spectrum corresponding to different pumping energy densities; (B) Is the spectral intensity as a function of pump energy density, inset in (B): luminous material object diagrams corresponding to different pumping energy densities;
FIG. 8 is a laser spectrum of the carbon quantum dots prepared in example 2 of the present invention stored for different times;
FIG. 9 is a graph showing the relative light intensity of CQDs as a sensing probe according to the pH value of the carbon quantum dots prepared in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The required medicament is a conventional experimental medicament and is purchased from a commercial channel; the test methods not mentioned are conventional test methods and will not be described in detail herein.
Example 1
(1) Mixing rhodamine B with deionized water to obtain a dye dispersion solution;
the molar concentration of the dye in the dye dispersion solution is 1mM;
(2) Weighing analytically pure sodium hydroxide solid at 25 ℃, adding the analytically pure sodium hydroxide solid into the dye dispersion solution in the step (1), carrying out ultrasonic oscillation for half an hour, uniformly mixing, and measuring the pH value of the mixed solution to be 12 to obtain a precursor solution;
(3) Placing the precursor solution into a reaction kettle lined with para-polyphenolic material, and reacting at 250 ℃ for 10 hours to obtain CQDs solution;
(4) And filtering the CQDs solution by a 0.22 mu m filter screen to obtain a finished product.
Example 2
In the step (1), the adjusting dye is rhodamine 6G. In the step (2), the analytically pure strong base is adjusted to potassium hydroxide, and the pH value is 10. The hydrothermal reaction in step (3) was adjusted to 220℃for 12 hours, and the rest was the same as in example 1.
Example 3
In the step (1), rhodamine 560 is used as a solute to obtain a 1mM dye dispersion solution. In step (3), the reaction was carried out at 240℃for 8 hours, and the rest was the same as in example 1.
Example 4
In the step (1), rhodamine 123 was used as a solute to obtain a 1mM dye dispersion solution. In the step (2), the pH was adjusted to 13, and in the step (3), the reaction was carried out at 220℃for 10 hours, and the rest was the same as in example 1.
Experiment 1
TEM morphology, particle size distribution, infrared spectrum, ultraviolet-visible absorption spectrum, fluorescence emission spectrum and XPS spectrum of the CQDs prepared in example 2 were measured, and the results are shown in FIGS. 2 to 7.
Experimental results show that the prepared CQDs are uniformly distributed in the range of 3.0-5.0 nm in size. CQDs have carbon, nitrogen, oxygen and sodium as the main elements. As is known from infrared spectroscopic analysis, extra-nuclear electrons forming the main material atoms of CQDs undergo transition relaxation at energy levels mainly formed by c= C, C =n and c—n vibrations, and fluorescence is generated. And (3) using 488nm as excitation light to excite the prepared CQDs aqueous solution, wherein the fluorescence radiation center wavelength is 520nm. When rhodamine 6G methanol solution was used as a standard solution, the highest value of QY in the prepared CQDs was calculated to be 97.7%. The prepared CQDs aqueous solution is used as a laser gain medium, the radiation spectrum of CQDs under different pumping energy densities is recorded by adopting a mode of evanescent wave excitation along the axial direction of an optical fiber, and the pumping energy is lowBulk Density (1.00. Mu.J/mm) 2 ) The spectrum collected does not have any modal structure when the pump energy density is 2.00. Mu.J/mm 2 When laser radiation is generated, the spectrum has a modal structure. By recording the radiation spectrum at different pump amounts, a plot of laser radiation intensity versus pump energy density is then drawn.
Experiment 2
The QY of CQDs prepared in example 2 was determined. In the experiment, the QY of CQDs is calculated by adopting a method of measuring the relative quantum yield, and the QY of the CQDs can be calculated by the following formula
Wherein the subscripts "x" and "ref" denote the sample to be tested and the standard reference solution, respectively. Phi represents QY, F is the integral area of the fluorescence radiation spectrum, n is the refractive index of the solvent, f=1-10 -A A is the absorbance at the excitation wavelength. Wherein the standard reference solution is rhodamine 6G methanol solution (phi) ref ＝0.93)。
Experiment 3
The optical stability of the prepared CQDs was investigated by recording the laser spectra of the CQDs solutions prepared in example 2 stored for different times, and the results are shown in fig. 8. The resulting aqueous CQDs still achieved low threshold laser irradiation without wavelength drift by standing at room temperature for 1 month.
Experiment 4
The optical properties of CQDs under different preparation conditions were investigated.
(1) The concentration of rhodamine 6G was kept at 1mM, the reaction temperature was fixed at 250℃and the reaction times were changed to 1,2,4,6,8, 10, and 12 hours, respectively, to obtain CQDs at different reaction times. The fluorescence radiation center wavelength was blue shifted from 560 to 520nm, and the peak value did not drift with the change of the reaction duration after the reaction time exceeded 4 hours, and the relative quantum yields of CQDs prepared at different reaction times were calculated using the method of experiment 2, and the results are shown in table 1.
TABLE 1 relative quantum yields of CQDs prepared at different reaction times
| Reaction time | 1 | 2 | 4 | 6 | 8 | 10 | 12 |
| Quantum Yield (QY) | 0.250 | 0.266 | 0.805 | 0.844 | 0.923 | 0.977 | 0.955 |
(2) The reaction temperature is kept at 250 ℃ and the reaction time is kept unchanged for 10 hours, and the concentrations of rhodamine 6G are respectively 0.5,1.0,2.0 and 4.0mM, so that CQDs with different concentrations of dye serving as precursor solutions are obtained. The peak of fluorescence radiation was about 520nm, and the peak did not drift with the change in rhodamine 6G concentration, and the relative quantum yields of CQDs prepared with rhodamine 6G at different concentrations were calculated using the method of experiment 2, and the results are shown in Table 2.
TABLE 2 relative Quantum yields of CQDs prepared with rhodamine 6G at different concentrations
| Rhodamine 6G concentration (mM) | 0.5 | 1.0 | 2.0 | 4.0 |
| Quantum Yield (QY) | 0.404 | 0.977 | 0.955 | 0.935 |
(3) The concentration of rhodamine 6G was kept at 1mM, the reaction time was fixed for 10 hours, and the reaction temperatures were changed to 120, 150, 180, 200, 220, 250℃respectively, to obtain CQDs at different reaction temperatures. The fluorescence peak was blue shifted from 580 to 520nm, and the peak was not shifted with the change of the reaction duration after the reaction temperature exceeded 220 ℃, and the relative quantum yields of CQDs prepared at different reaction temperatures were calculated using the method of experiment 2, and the results are shown in table 3.
TABLE 3 relative quantum yields of CQDs prepared at different reaction temperatures
| Reaction temperature | 120 | 150 | 180 | 200 | 220 | 250 |
| Quantum Yield (QY) | 0.180 | 0.172 | 0.472 | 0.502 | 0.901 | 0.977 |
Experiment 5
The CQDs prepared in the first embodiment are used as probes, and the pH value sensing of the micro-solution is realized according to the change of the relative laser intensity of the CQDs along with the pH value.
The experimental results show that the laser intensity decreases with decreasing pH, and decreases as the pH of the solution decreases from 12.78 to 5.48. The laser sensitivity was improved by 2 orders of magnitude compared to the fluorescent signal under the same conditions, as shown in fig. 9.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The method for preparing the green light carbon quantum dot with the ultrahigh fluorescence quantum yield by the one-step hydrothermal method is characterized by comprising the following steps of:
(1) Mixing rhodamine dye with deionized water to obtain dye dispersion solution;
(2) Dispersing analytically pure strong base solid in the dye dispersion solution at 25 ℃, uniformly mixing after ultrasonic oscillation, and regulating the pH value to be more than 10 to obtain a precursor solution;
(3) Placing the precursor solution into a reaction kettle, and reacting for 2-12 hours at 120-250 ℃ to obtain a carbon quantum dot solution;
(4) And filtering the carbon quantum dot solution by a 0.22 mu m filter screen to obtain the green light carbon quantum dot with ultrahigh fluorescence quantum yield.
2. The method for preparing the green light carbon quantum dot with the ultrahigh fluorescence quantum yield by the one-step hydrothermal method according to claim 1, wherein the rhodamine dye is any one of rhodamine B, rhodamine 123, rhodamine 560 and rhodamine 6G.
3. The method for preparing the green carbon quantum dots with the ultra-high fluorescence quantum yield by the one-step hydrothermal method according to claim 1, wherein the analytically pure strong base is sodium hydroxide, potassium hydroxide or tetraethylammonium hydroxide.
4. The method for preparing the green light carbon quantum dots with the ultrahigh fluorescence quantum yield by the one-step hydrothermal method according to claim 1, wherein the molar concentration of the rhodamine dye in the dye dispersion solution is 1 mM-5 mM.
5. The method for preparing green light carbon quantum dots with ultrahigh fluorescence quantum yield by a one-step hydrothermal method as claimed in claim 1, wherein the reaction kettle in the step (3) is a reaction kettle lined with para-polyphenolic material.
6. The method for preparing green carbon quantum dots with ultrahigh fluorescence quantum yield by using a one-step hydrothermal method as claimed in claim 1, wherein the pH value of the deionized water in the step (1) is more than 10.
7. The method for preparing the green carbon quantum dot with the ultra-high fluorescence quantum yield by the one-step hydrothermal method according to claim 1, wherein the fluorescence radiation center wavelength of the green carbon quantum dot with the ultra-high fluorescence quantum yield is 520nm.
8. Use of the carbon quantum dots prepared by the method of any one of claims 1 to 7 as a laser gain medium.
9. The use of carbon quantum dots prepared by the method of any one of claims 1 to 7 as probe molecules in solution pH and heavy metal ion detection.
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