CN112251218B - Preparation method of ethylenediamine functionalized carbon quantum dots and application of ethylenediamine functionalized carbon quantum dots in catechol detection - Google Patents
Preparation method of ethylenediamine functionalized carbon quantum dots and application of ethylenediamine functionalized carbon quantum dots in catechol detection Download PDFInfo
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Abstract
The invention provides a preparation method of ethylenediamine functionalized carbon quantum dots and application of the ethylenediamine functionalized carbon quantum dots in catechol detection. The ethylenediamine is introduced to the surface of the carbon quantum dot through an amidation reaction and a protection/deprotection method to synthesize the ethylenediamine functionalized carbon quantum dot, the preparation process is simple, the raw material source is wide, the price is low, and the obtained compound has the selective binding function of the target detection object. In a neutral environment, catechol can rapidly react with ethylenediamine on the surface of the ethylenediamine functionalized carbon quantum dot to generate a static compound, and the static compound causes synchronous quenching of nuclear state and surface state fluorescence of the ethylenediamine functionalized carbon quantum dot. The catechol concentration and the fluorescence quenching value of the ethylenediamine functionalized carbon quantum dot present a good linear relation, and the detection limit reaches 0.07mg/L. The invention establishes a simple and rapid catechol fluorescence quantitative analysis method, and has extremely high selectivity and anti-interference performance for detecting catechol.
Description
Technical Field
The invention belongs to the technical field of preparation of carbon nano material fluorescent probes and detection of organic pollutants, and particularly relates to a preparation method of ethylenediamine functionalized carbon quantum dots and application of the ethylenediamine functionalized carbon quantum dots in catechol detection.
Background
Catechol is widely used as an organic raw material for producing drugs, light stabilizers, insecticides, antioxidants, dyes, and the like. In the production and application process, the water-soluble nano-particles easily enter the environmental water body and cause serious harm to the health and the ecological environment of human bodies at very low concentration. The resorcinol and the hydroquinone which are taken as isomers of the catechol have similar structures with the catechol, and the resorcinol and the hydroquinone often coexist in water. Therefore, establishing a high-selectivity detection method for quantitatively analyzing catechol has important practical significance. At present, various analytical methods have been applied to the quantitative detection of catechol, such as high performance liquid chromatography, spectroscopy, gas chromatography/mass spectrometry, chemical fluorescence, electrochemical detection, and the like. Most of these methods require expensive instrumentation, time consuming and complex pre-treatment steps. Therefore, it is still necessary to develop a new quantitative analysis technique for catechol detection which is fast and convenient.
In recent years, fluorescence detection methods have gained increasing attention from researchers due to their extremely high detection sensitivity, simple analytical procedures, and the need for relatively inexpensive detection instruments. Compared with organic or inorganic fluorescent probes such as cadmium telluride quantum dots, furan red, calcium red and the like, carbon quantum dots with high fluorescence stability, photobleaching resistance, wide and continuous excitation light, adjustable emitted light, good biocompatibility and other excellent performances are favored in the field of fluorescence analysis. Carbon quantum dots have been used to detect various metal ions and organic molecules by analyzing changes in their fluorescence intensity, but studies on the analysis of catechol using carbon quantum dots have been rarely reported. The existence of isomers with similar structures is easy to interfere the detection of catechol; in addition, the maximum excitation wavelength (mostly around 360 nm) or the maximum emission wavelength is generally selected as the detection wavelength based on the design of the carbon quantum dot fluorescent probe. In fact, the fluorescence of carbon quantum dots has a plurality of complex sources, and the change of fluorescence signals has close relation with different luminescent sites (such as sp2 carbon nucleus, surface defect and the like) and corresponding excitation wavelengths. If the relationship between the change of the fluorescence of the carbon quantum dot caused by the target analyte and the fluorescence emission site inside the carbon quantum dot can be found, not only can better detection conditions be found conveniently, but also a more efficient and anti-interference detection method can be established.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of an ethylenediamine functionalized carbon quantum dot and an application of the ethylenediamine functionalized carbon quantum dot in catechol detection. Within a certain range, the catechol concentration and the fluorescence quenching value of the ethylenediamine functionalized carbon quantum dot show a good linear relationship, and the functionalized carbon quantum dot probe shows extremely high selectivity and anti-interference performance on a detection body of the catechol when other various organic pollutants and various anions and cations coexist.
The invention modifies ethylenediamine on the surface of the carbon quantum dot through a protection/deprotection method and an amidation reaction to obtain the functionalized carbon quantum dot. The ethylenediamine molecule reserved amino end on the ethylenediamine functionalized carbon quantum dot can rapidly and chemically react with pyrocatechol in a solution to generate a static compound, so that the fluorescence of the kernel state and the surface state of the ethylenediamine functionalized carbon quantum dot is effectively quenched, and a simple and rapid pyrocatechol fluorescence quantitative analysis method with high sensitivity and selectivity is successfully established on the basis of selecting the kernel state corresponding to the excitation wavelength which has the excitation wavelength independence and a narrower emission peak.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of ethylenediamine functionalized carbon quantum dots comprises the following steps:
(1) Dissolving citric acid and urea in ethylene glycol, stirring, heating, filtering, dialyzing with deionized water as dialysis external liquid, and freeze-drying the dialysate to obtain carbon quantum dot powder;
(2) Adding the carbon quantum dot powder obtained in the step (1) into a 2- (N-morpholine) ethanesulfonic acid buffer solution, and introducing nitrogen after ultrasonic dispersion;
(3) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and hydroxysuccinimide into the solution obtained in the step (2) at the environmental condition of 0 ℃, continuously introducing nitrogen, and stirring;
(4) Adding tert-butoxycarbonyl ethylenediamine into the solution obtained in the step (3) at 0 ℃ in the nitrogen atmosphere, adding a sodium hydroxide solution, adjusting the pH value, and stirring;
(5) Adding a certain amount of hydrochloric acid into the solution obtained in the step (4), and continuously stirring;
(6) Adding sodium bicarbonate powder into the solution obtained in the step (5), adjusting the pH of the solution, and dialyzing by taking deionized water as dialysis external liquid;
(7) And (4) freeze-drying the dialysate obtained in the step (6) to obtain ethylenediamine functionalized carbon quantum dot powder.
Preferably, in the step (1), the molar ratio of the citric acid to the urea to the glycol is 1: (1-3): (40 to 80), preferably, 1: (1.5-2.5): (50-60); the heating temperature is 120-240 ℃, the heating time is 2-24 h, and the preferable time is 8-16 h; the diameter of the filter membrane used for filtering is 0.1-0.5 μm, and the volume of the dialyzed external solution deionized water used for dialysis is 800-1500 mL; the dialysis time is 2 to 72 hours, preferably 12 to 48 hours; the time for replacing the dialysis external liquid is 2 to 4 times per 24 hours, and the time for freeze drying is 12 to 48 hours.
Preferably, in the step (2), the ratio of the mass of the carbon quantum dot powder to the volume of the 2- (N-morpholine) ethanesulfonic acid buffer solution is 1mg: (0.5-2.0) mL, preferably, the pH value of the ethanesulfonic acid buffer solution is 6, the ultrasonic time is 5-60 min, and the nitrogen gas is introduced for 10-60 min.
Preferably, in the step (3), the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the hydroxysuccinimide to the carbon quantum dot powder used in the step (2) is (2-5): (0.2-10): 1-the stirring time is from 2 to 24 hours, preferably from 8 to 16 hours.
Preferably, in the step (4), the mass ratio of the volume of the added tert-butoxycarbonyl ethylenediamine to the mass of the carbon quantum dots in the step (2) is (5-10) μ L:1mg, the adding amount of the sodium hydroxide solution depends on the pH value of the solution, the sodium hydroxide solution is stopped to be added when the pH value of the solution is 7.2 to 7.8, and the stirring time is 2 to 48 hours.
Preferably, in the step (5), the mass ratio of the volume of the added hydrochloric acid (1M) to the carbon quantum dots in the step two is (0.2-1) mL:1mg, and the stirring time is 1-6 h.
Preferably, in the step (6), the amount of sodium bicarbonate powder is added to adjust the pH to 6, the amount of deionized water used for dialyzing the external liquid is 800-1600 mL, and the dialysis time is 2-72 h; preferably, 12 to 48 hours.
Preferably, the freeze-drying time period in the step (7) is 12 to 48 hours.
The invention provides application of the ethylenediamine functionalized carbon quantum dot prepared by the preparation method in catechol detection.
Preferably, the fluorescence emission of the sample is tested using a fluorescence spectrometer with an excitation wavelength of 310 nm; preferably, the concentration of the ethylenediamine functionalized carbon quantum dots is 0.01-0.05g/L during detection.
The mechanism of the invention is as follows: after the surface of the carbon quantum dot is modified with ethylenediamine, the connected ethylenediamine can be combined with pyrocatechol in a solution through Michael addition reaction or Schiff base reaction to generate a static compound, and the static compound can be used as an electron donor to transfer electrons of the static compound to a surface luminescence site of the functionalized carbon quantum dot in an excited state and inhibit the radiative recombination of excited carriers. The ethylenediamine functional carbon quantum dot comprises three luminescent sites of a kernel state, an edge state and a surface state, after the kernel state is excited, an excited state electron of the kernel state is very easily captured by a defect of the surface state and is radiatively compounded, so that fluorescence generated by the kernel state and the surface state is easily influenced by the external environment, the surface state and the kernel state of the ethylenediamine functional carbon quantum dot are synchronously quenched under the action of catechol, and the excited state electron of the edge state is mainly compounded at the edge state, so that the ethylenediamine functional carbon quantum dot has certain fluorescent response inert characteristics.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) In the carbon quantum dot functionalization process, an amino group at one end of an ethylenediamine molecule is protected and then loaded on the surface of the carbon quantum dot through amidation reaction, and then deprotection is carried out, so that effective combination of ethylenediamine and the carbon quantum dot can be ensured, and free amino at the other end can be provided to combine with a target analyte.
(2) The ethylenediamine molecules on the prepared ethylenediamine functionalized carbon quantum dots can rapidly and chemically react with pyrocatechol in a solution to generate a static compound, so that the fluorescence of the carbon quantum dot probe is effectively quenched, and a simple and rapid pyrocatechol fluorescence quantitative analysis method is established based on the static compound.
(3) The 310nm which has stronger fluorescence intensity, excitation wavelength independence and narrower emission peak and corresponds to kernel-state luminescence is selected as the excitation wavelength, the fluorescence quenching rate of the functionalized carbon quantum dot and the concentration of catechol show good linear relation, and the detection effect of methods such as electrochemistry or HPLC can be achieved on the actual water body.
(4) The ethylene diamine functionalized carbon quantum dot based probe has extremely high selectivity for fluorescence detection of catechol, and has interference resistance to isomers of the catechol, other various organic matters and anions and cations.
Drawings
FIG. 1 is a three-dimensional fluorescence scanning spectrum of an ethylenediamine functionalized carbon quantum dot (excitation wavelength range: 200-500nm; emission wavelength range: 220-700 nm);
FIG. 2 (a) is a fluorescence emission spectrum curve of the ethylenediamine-functionalized carbon quantum dots after the addition of catechol with different concentrations, and (b) is a linear relationship between quenching rate (F0-F)/F and catechol concentration;
FIG. 3 shows quenching rates of catechol, resorcinol, and hydroquinone on ethylenediamine-functionalized carbon quantum dots at different excitation wavelengths;
FIG. 4 shows the effect of (a) different organic compounds and (b) different anions and pyrocatechol on the fluorescence quenching rate of ethylenediamine-functionalized carbon quantum dots.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
(1) Preparation of ethylenediamine functionalized carbon quantum dots
0.65g of citric acid and 0.42g of urea are dissolved in 25mL of ethylene glycol, magnetically stirred for 2 hours, heated at 200 ℃ for 10 hours, cooled to room temperature, filtered, dialyzed and freeze-dried to obtain carbon quantum dot powder. 20mg of the carbon quantum dot powder was added to 20mL of MES buffer (pH = 6), dispersed with ultrasound for 40 minutes and then purged with nitrogen for 30 minutes to remove dissolved oxygen in the solution, after which the solution was placed in an ice bath vessel and 120mg of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 60mg of hydroxysuccinimide were added in this order, and the reaction was continued under a nitrogen atmosphere and stirred at a constant speed for 12 hours using a magnetic stirrer to ensure the reaction. mu.L of t-butyloxycarbonyl ethylenediamine was added under nitrogen at low temperature of 0 ℃ and a little sodium hydroxide solution (1M) was slowly added dropwise to the solution to adjust the pH of the solution to neutral conditions of about 7.4. Stirring is continued for 24 hours at a constant speed to ensure that the tert-butoxycarbonyl ethylenediamine is fully and covalently connected to the surface of the carbon quantum dot. 10mL of hydrochloric acid (1M) was then added to the solution and stirring was continued at room temperature for 3 hours. Adding sodium bicarbonate powder to neutralize excessive hydrochloric acid in the solution, dialyzing with 800mL of deionized water as external liquid for 48 hours to remove various solutes in the mixed solution after the pH value of the solution reaches 6, and freeze-drying after dialysis to obtain the ethylenediamine functionalized carbon quantum dot powder. Fig. 1 is a three-dimensional fluorescence scanning spectrum of the ethylenediamine functionalized carbon quantum dot, and it can be seen that the quantum dot has three fluorescence regions corresponding to a core state, an edge state and a surface state respectively.
(2) Detection of ethylenediamine functionalized carbon quantum dots on catechol
Injecting 1mL of ethylenediamine functionalized carbon quantum dot dispersion into a 10mL sample bottle, diluting with 8mL of PBS buffer solution (0.01M, pH = 7.4), adding 1mL of catechol solutions with different concentrations into the bottle, shaking uniformly, and standing at room temperature for 30min. Fluorescence measurements (excitation wavelength 310 nm) were performed on different samples using a fluorescence spectrometer.
Example 1
1mL of ethylenediamine-functionalized carbon quantum dot dispersion (0.1 g/L) was injected into a 10mL sample bottle, 8mL of PBS buffer (0.01M, pH = 7.4) was added, 1mL of catechol solutions with different concentrations were injected, the mixture was shaken uniformly and then allowed to stand at room temperature for 30min, and fluorescence was measured using a fluorescence spectrometer.
Example 2
1mL of ethylenediamine-functionalized carbon quantum dot dispersion (0.2 g/L) was injected into a 10mL sample bottle, 8mL of PBS buffer (0.01M, pH = 7.4) was added, 1mL of catechol solutions with different concentrations was injected, the mixture was shaken uniformly and then allowed to stand at room temperature for 30min, and fluorescence was measured using a fluorescence spectrometer.
Example 3
1mL of ethylenediamine-functionalized carbon quantum dot dispersion (0.3 g/L) was injected into a 10mL sample bottle, 8mL of PBS buffer (0.01M, pH = 7.4) was added, 1mL of catechol solutions with different concentrations was injected, the mixture was shaken uniformly and then allowed to stand at room temperature for 30min, and fluorescence was measured using a fluorescence spectrometer.
Example 4
1mL of ethylenediamine-functionalized carbon quantum dot dispersion (0.4 g/L) was injected into a 10mL sample bottle, 8mL of PBS buffer (0.01M, pH = 7.4) was added, 1mL of catechol solutions with different concentrations was injected, the mixture was shaken uniformly and then allowed to stand at room temperature for 30min, and fluorescence was measured using a fluorescence spectrometer.
Example 5
Injecting 1mL of ethylenediamine functionalized carbon quantum dot dispersion (0.5 g/L) into a 10mL sample bottle, adding 8mL of PBS buffer (0.01M, pH = 7.4), injecting 1mL of catechol solutions with different concentrations, shaking uniformly, standing at room temperature for 30min, and performing fluorescence test by using a fluorescence spectrometer.
FIG. 2 shows fluorescence emission spectrum curves and quenching rates (F) of ethylenediamine-functionalized carbon quantum dots with different concentrations of catechol 0 Linear relationship between-F)/F and catechol concentration (F) 0 And F respectively refer to the fluorescence intensity of the ethylenediamine-functionalized carbon quantum dot when no catechol was added and the fluorescence intensity of the ethylenediamine-functionalized carbon quantum dot after catechol was added). When the concentration of catechol is in the range of 2-40 μ M, the linear regression equation is Y =0.0494+0.00855X, and the correlation coefficient R thereof 2 At 0.995, the detection limit was 0.65. Mu.M (0.07 mg/L).
Comparative example 1
Injecting 1mL of ethylenediamine functionalized carbon quantum dots into a 10mL sample bottle, adding 8mL of PBS buffer solution (0.01M, pH = 7.4), respectively injecting 1mL of 100 μ M catechol, resorcinol and hydroquinone solution, standing at room temperature for 30min after uniform oscillation, performing spectrum test by using a fluorescence spectrometer at the excitation wavelengths of 310nm, 370nm and 460nm, and respectively calculating the quenching rates of the catechol, the resorcinol and the hydroquinone on the ethylenediamine functionalized carbon quantum dots at different excitation wavelengths.
FIG. 3 shows the quenching rates of catechol, resorcinol, and hydroquinone for ethylene diamine functionalized carbon quantum dots at excitation wavelengths corresponding to a core state (310 nm), a rim state (370 nm), and a surface state (460 nm). It can be seen that the fluorescence emission of the carbon core state and the surface state exhibit a consistent fluorescence response behavior, and the edge state emission exhibits an "inert" character.
Comparative example 2
1mL of ethylenediamine was added to a 10mL sample bottle, 8mL of PBS buffer (0.01M, pH = 7.4) was added, 1mL of catechol solution with a concentration of 50. Mu.M was added, and 1mL of resorcinol, hydroquinone, phenol, acetic acid, benzoic acid, p-aminophenol, oxytetracycline, tryptophan, lysine, tyrosine, or 10. Mu.M Ba was added thereto, respectively 2+ 、Ca 2+ 、C 2 O 7 2- 、Cu 2+ 、Fe 2+ 、Fe 3+ 、K + 、Mg 2+ 、NH 4 + 、SiO 3 2- 、Zn 2+ 、Cl - 、Na + 、SO 4 2- 、NO 3- ,、Co 2+ 、Cr 3+ 、Al 3+ And (3) carrying out anion and cation oscillation, standing at room temperature for 30min, and carrying out fluorescence test at an excitation wavelength of 310nm by using a fluorescence spectrometer.
FIG. 4 shows the effect of different organic substances and anions and catechol on the fluorescence quenching rate of ethylenediamine-functionalized carbon quantum dots. After the interferent and catechol are added into the ethylenediamine functional carbon quantum dot detection system at the same time, the fluorescence quenching rate of the quantum dot is basically consistent with the quenching rate of the catechol existing alone, which shows that the ethylenediamine functional carbon quantum dot system has good selective detection capability and anti-interference performance on the catechol.
Comparative example 3
Collecting tap water and effluent of a sewage treatment plant, filtering the effluent through a 0.22 mu M filter membrane to remove impurities, adding pyrocatechol (6 mu M,10 mu M and 25 mu M) with three different concentrations into each type of water body, injecting 1mL of ethylenediamine functionalized carbon quantum dots into a 10mL sample bottle, adding 8mL of PBS buffer solution (0.01M, pH = 7.4), respectively injecting 1mL of water sample, standing the solution for 30min at room temperature after uniform oscillation, and performing spectrum test by using a fluorescence spectrometer at an excitation wavelength of 310 nm.
Table 1 shows the evaluation of the detection effect of the ethylenediamine functionalized carbon quantum dot on catechol in the actual water body using the standard addition recovery method. The pyrocatechol recovery was measured to range from 93.36% to 127.54% with a Relative Standard Deviation (RSD) ranging from 2.44% to 8.39%. The system is suitable for measuring catechol in natural water sample and has good repeatability.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (14)
1. A preparation method of ethylenediamine functionalized carbon quantum dots is characterized by comprising the following steps: the method comprises the following steps:
(1) Dissolving citric acid and urea in ethylene glycol, stirring, heating, filtering, dialyzing with deionized water as dialysis external liquid, and freeze-drying the dialyzate to obtain carbon quantum dot powder;
(2) Adding the carbon quantum dot powder obtained in the step (1) into a 2- (N-morpholine) ethanesulfonic acid buffer solution, and introducing nitrogen after ultrasonic dispersion;
(3) Adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and hydroxysuccinimide into the solution obtained in the step (2) at the environmental condition of 0 ℃, continuously introducing nitrogen, and stirring;
(4) Adding tert-butoxycarbonylethylenediamine into the solution of the step (3) at 0 ℃ under the nitrogen atmosphere, adding a sodium hydroxide solution, adjusting the pH value, and stirring;
(5) Adding a certain amount of hydrochloric acid into the solution obtained in the step (4), and continuously stirring;
(6) Adding sodium bicarbonate powder into the solution obtained in the step (5), adjusting the pH of the solution, and dialyzing by taking deionized water as dialysis external liquid;
(7) And (5) freeze-drying the dialysate obtained in the step (6) to obtain ethylenediamine functionalized carbon quantum dot powder.
2. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the citric acid to the urea to the glycol is 1: (1 to 3): (40 to 80); the heating temperature is 120 to 240 ℃, and the heating time is 2 to 24 hours; the diameter of a filter membrane used for filtering is 0.1 to 0.5 mu m, and the quantity of dialysis external liquid deionized water used for dialysis is 800 to 1500mL; the dialysis time is 2 to 72 hours; the time for replacing the dialysis external liquid is 2 to 4 times every 24 hours, and the time for freeze drying is 12 to 48 hours.
3. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 2, wherein the method comprises the following steps: in the step (1), the molar ratio of the citric acid to the urea to the glycol is 1: (1.5 to 2.5): (50 to 60); the heating time is 8 to 16 hours; the dialysis time is 12 to 48 hours.
4. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 1, wherein the method comprises the following steps: in the step (2), the volume ratio of the mass of the carbon quantum dot powder to the volume of the 2- (N-morpholine) ethanesulfonic acid buffer solution is 1mg: (0.5 to 2.0) mL.
5. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 4, wherein the method comprises the following steps: the pH value of the ethanesulfonic acid buffer solution is 6, the ultrasonic time is 5 to 60min, and the nitrogen gas is introduced for 10 to 60min.
6. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 1, wherein the method comprises the following steps: in the step (3), the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the hydroxysuccinimide to the carbon quantum dot powder used in the step (2) is (2 to 5): (0.2 to 10): 1, stirring for 2 to 24 hours.
7. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 6, wherein the method comprises the following steps: in the step (3), the stirring time is 8 to 16 hours.
8. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 1, wherein the method comprises the following steps: in the step (4), the mass ratio of the volume of the added tert-butoxycarbonyl ethylenediamine to the mass of the carbon quantum dots in the step (2) is (5 to 10) mu L:1mg, wherein the adding amount of the sodium hydroxide solution depends on the pH of the solution, the sodium hydroxide solution is stopped to be added when the pH of the solution is 7.2 to 7.8, and the stirring time is 2 to 48 hours.
9. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 1, wherein the method comprises the following steps: in the step (5), the mass ratio of the volume of the added 1M hydrochloric acid to the carbon quantum dots in the step (2) is (0.2 to 1) mL:1mg, and the stirring time is 1 to 6 hours.
10. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 1, wherein the method comprises the following steps: and (6) adding sodium bicarbonate powder, adjusting the pH to 6, wherein the deionized water used for the external dialysis liquid is 800-1600 mL, and the dialysis time is 2-72 h.
11. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 10, wherein the method comprises the following steps: in the step (6), the dialysis time is 12 to 48 hours.
12. The method for preparing the ethylenediamine functionalized carbon quantum dot according to claim 1, wherein the method comprises the following steps: the freeze drying time in the step (7) is 12 to 48 hours.
13. The application of the ethylenediamine functionalized carbon quantum dot prepared by the preparation method of any one of claims 1 to 8 in catechol detection in water environment.
14. Use according to claim 13, characterized in that: with 310nm as an excitation wavelength, testing the fluorescence emission of the sample by using a fluorescence spectrometer; during detection, the concentration of the ethylenediamine functionalized carbon quantum dots is 0.01-0.05g/L.
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