CN114408913A - Graphene oxide/carbon nitride three-dimensional composite material and preparation method and application thereof - Google Patents
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Abstract
The invention provides a graphene oxide/carbon nitride three-dimensional composite material as well as a preparation method and application thereof, belonging to the technical field of functional material preparation, wherein the graphene oxide/carbon nitride three-dimensional composite material is prepared according to the following steps: adding graphene oxide into distilled water, performing ultrasonic treatment until the graphene oxide is dissolved to obtain a graphene oxide solution, and then adding g-C into the graphene oxide solution3N4And obtaining a supernatant through ultrasonic self-assembly and standing, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material. The invention utilizes the graphene oxide/carbon nitrideThe fluorescence sensor constructed by the vitamin composite material can detect the antibiotic norfloxacin in different water samples.
Description
Technical Field
The invention relates to the technical field of functional material preparation, in particular to a graphene oxide/carbon nitride three-dimensional composite material and a preparation method and application thereof.
Background
Antibiotics refer to a class of secondary metabolites with anti-pathogen or other activities generated by microorganisms (including bacteria, fungi, actinomycetes) or higher animals and plants during life, and chemical substances capable of interfering with other life cell development functions. Antibiotics are widely used in various fields by virtue of their highly effective inhibitory and killing action on pathogenic microorganisms. In addition to human medicine, the need for antibiotics in livestock and aquaculture is enormous. The residual antibiotics in the environment become new micro-pollutants, promote the generation of pathogenic bacteria drug-resistant genes and endanger the balance of an ecological system and the health of a human body. Although the use of antibiotics has been controlled in many countries and regions in recent years, the management of environmental pollution caused by antibiotics remains a problem. Moreover, with the increasing use of antibiotic drugs, the hidden danger of burying is gradually exposed, and the pollution problem caused by antibiotics circulating into the natural environment has attracted high attention all over the world.
Norfloxacin, as a quinolone antibiotic, has strong antibacterial activity against gram-negative bacteria and mycoplasma, and is widely applied to industries such as medicine and animal husbandry. However, norfloxacin cannot be used excessively, causes certain toxic and side effects to human bodies, and usually shows side effect reactions of symptoms such as vomiting, inappetence, diarrhea and the like caused by the stimulation of gastrointestinal and digestive tract mucous membranes. Therefore, how to remove norfloxacin in water environment becomes a most concerned problem for researchers.
Disclosure of Invention
Aiming at the problems, the invention provides a graphene oxide/carbon nitride three-dimensional composite material and a preparation method and application thereof.
The first purpose of the invention is to provide a preparation method of a graphene oxide/carbon nitride three-dimensional composite material, which comprises the following steps: the preparation method comprises the following steps:
s1, calcining the nitrogen-containing organic matter under inert gas to obtain g-C3N4；
S2, adding graphene oxide into distilled water, performing ultrasonic treatment until the graphene oxide is dissolved to obtain a graphene oxide solution, and then adding g-C prepared from S1 into the graphene oxide solution3N4And obtaining a supernatant through ultrasonic self-assembly and standing, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material.
Preferably, the nitrogen-containing organic substance in S1 is urea or melamine.
Preferably, the calcination temperature in S1 is 500-600 ℃, and the calcination time is 1.8-2.5 h.
Preferably, the calcination temperature in S1 is 550 ℃ and the calcination time is 2 h.
Preferably, in S1, the inert gas is nitrogen or helium.
Preferably, in S2, the concentration of graphene oxide is 0.45-0.55mg/mL, g-C3N4And the mass ratio of the graphene oxide to the graphene oxide is 1:3-3: 1.
Preferably, in S2, the concentration of graphene oxide is 0.50mg/mL, g-C3N4And the mass ratio of the graphene oxide to the graphene oxide is 2: 1.
Preferably, in S2, the ultrasonic time of ultrasonic self-assembly is 3-4h, and the standing time is 24-30 h.
The second purpose of the invention is to provide the graphene oxide/carbon nitride three-dimensional composite material prepared by the preparation method.
The third purpose of the invention is to provide an application of the graphene oxide/carbon nitride three-dimensional composite material in the preparation of a fluorescence sensor, specifically, the graphene oxide/carbon nitride three-dimensional composite material is prepared into the fluorescence sensor, and the norfloxacin antibiotic in the water body is detected by an aggregation-induced luminescence mechanism.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the ultrasonic self-assembly graphene oxide/carbon nitride three-dimensional composite material is utilized, GO is assembled with carbon nitride through pi-pi accumulation, the fluorescence sensor is constructed by utilizing the fluorescence resonance energy transfer principle, and the antibiotics norfloxacin, GO/g-C in different water samples can be detected through the aggregation-induced luminescence mechanism3N4The large specific surface area and the pi conjugated structure can fix norfloxacin on the surface of the sensor through pi-pi stacking effect. The sensor shows good selectivity, reproducibility and stability in detection of norfloxacin. The sensor preparation method is simple and cheap, and meanwhile, the detection speed is high, and the sample pretreatment is simple.
Drawings
FIG. 1 is GO/g-C prepared in example 13N4An infrared spectrum of (1);
FIG. 2 is GO/g-C prepared in example 13N4Transmission electron microscopy images of;
FIG. 3 is GO/g-C prepared in example 13N4XRD pattern of (a);
FIG. 4 is GO/g-C prepared in examples 1-53N4Ultraviolet spectrogram of (1);
FIG. 5 is a fluorescence spectrum, wherein FIG. 5a is a fluorescence spectrum of different sensor metal ions, and FIG. 5b is a partial enlarged view of FIG. 5 a;
FIG. 6 is a graph of fluorescence spectra of different sensing substances;
FIG. 7 shows norfloxacin plus GO/g-C prepared in example 13N4Reaction equilibrium time diagram of (a);
FIG. 8 shows different concentrations of norfloxacin versus GO/g-C prepared in example 13N4The effect of fluorescence intensity of (a);
FIG. 9 shows different concentrations of norfloxacin versus GO/g-C prepared in example 13N4A linear relationship of response intensity;
FIG. 10 is different pH vs. GO/g-C3N4And norfloxacin, wherein FIG. 10a is a graph of different pH vs. GO/g-C3N4And norfloxacin, fig. 10b is a partial magnified view of fig. 10 a;
FIG. 11 is different pH vs. GO/g-C3N4And histograms of norfloxacin effect;
FIG. 12 is a fluorescence analysis diagram of interfering ions;
FIG. 13 is a graph of different water sample pairs GO/g-C3N4Sensing the effects of norfloxacin;
FIG. 14 is a scheme for the preparation of GO/g-C3N4And a schematic diagram of the detection of the antibiotic norfloxacin in the water body.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified. In addition, GO represents graphene oxide, g-C3N4Denotes carbon nitride, GO/g-C3N4Represents a graphene oxide/carbon nitride three-dimensional composite material.
Example 1
S1, calcining the urea in a muffle furnace at 500 ℃ for 2h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: weighing 50mg of GO according to the mass ratio of 2:1, dissolving in 100mL of distilled water, carrying out ultrasonic treatment for 1h to completely dissolve, and weighing 100mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 2
S1, under the nitrogen atmosphere, placing ureaCalcining in a muffle furnace at 500 ℃ for 2h for thermal polycondensation to obtain g-C3N4；
S2, according to g-C3N4: weighing 50mg of GO according to the mass ratio of 3:1, dissolving in 100mL of distilled water, carrying out ultrasonic treatment for 1h to completely dissolve, and weighing 150mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 3
S1, calcining the urea in a muffle furnace at 500 ℃ for 2h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: the mass ratio of GO is 2: 3, weighing 50mg of GO to be dissolved in 100mL of distilled water, carrying out ultrasonic treatment for 1h to completely dissolve the GO, and weighing 33.3mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 4
S1, calcining the urea in a muffle furnace at 500 ℃ for 2h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: the mass ratio of GO is 1:3, weighing 50mg of GO to be dissolved in 100mL of distilled water, carrying out ultrasonic treatment for 1h to completely dissolve the GO, and weighing 16.7mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 5
S1, calcining the urea in a muffle furnace at 500 ℃ for 2h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: of GOThe mass ratio is 1: 1, weighing 50mg of GO to be dissolved in 100mL of distilled water, carrying out ultrasonic treatment for 1h to completely dissolve the GO, and weighing 50mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 6
S1, calcining urea in a muffle furnace at 600 ℃ for 1.8h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: weighing 50mg of GO according to the mass ratio of 2:1, dissolving in 100mL of distilled water, carrying out ultrasonic treatment for 1.5h to completely dissolve, and weighing 100mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 4 hours, standing for 30 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 7
S1, calcining the urea in a muffle furnace at 500 ℃ for 2.5h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: weighing 50mg of GO according to the mass ratio of 2:1, dissolving in 100mL of distilled water, carrying out ultrasonic treatment for 1h to completely dissolve, and weighing 100mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3.5 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 8
S1, calcining melamine in a muffle furnace at 550 ℃ for 2h for thermal polycondensation under the atmosphere of helium to obtain g-C3N4；
S2, according to g-C3N4: weighing 50mg of GO according to the mass ratio of 2:1, dissolving in 100mL of distilled water, carrying out ultrasonic treatment for 1h to completely dissolve, and weighing 100mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 9
S1, calcining the urea in a muffle furnace at 500 ℃ for 2h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: weighing 45mg of GO to be dissolved in 100mL of distilled water according to the mass ratio of 2:1, carrying out ultrasonic treatment for 1h to completely dissolve the GO, and weighing 90mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
Example 10
S1, calcining the urea in a muffle furnace at 500 ℃ for 2h for thermal polycondensation under the nitrogen atmosphere to obtain g-C3N4；
S2, according to g-C3N4: weighing 55mg of GO to dissolve in 100mL of distilled water according to the mass ratio of 2:1, carrying out ultrasonic treatment for 1h to completely dissolve the GO, and weighing 110mg of prepared g-C3N4Adding the solution into the solution, continuing to perform ultrasonic treatment for 3 hours, standing for 24 hours to obtain a supernatant, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material, namely GO/g-C3N4。
FIG. 1 shows a graphene oxide/carbon nitride three-dimensional composite material (i.e., GO/g-C) prepared in example 13N4) And GO, g-C3N4An infrared spectrum of (1). As can be seen from FIG. 1, g-C3N4In the infrared spectrum of (1), at 810cm-1、1200-1650cm-1And 3000-3300cm-1The characteristic peaks of (A) belong to the typical characteristic peak of the s-triazine ring system, the stretching mode of the carbon nitride heterocycle and the uncoagulated amine group respectively. Peak 3453cm-1Due to the presence of carboxyl groups, in 1620-1200cm-1The weak peak at (A) is divided into g-C3N4In (C ═And (3) an N heterocyclic ring. One infrared spectrum of GO is located at 3000-3450cm-1Absorption bands of the range, indicating elastic vibration in the presence of-OH; the other is at 1730cm-1The absorption on the left and right corresponds to the-COOH group. GO/g-C3N4In the infrared spectrum of 1835cm-1A small new peak is observed, which is a new group formed by the reaction of carbon nitride and graphene oxide.
FIG. 2 is GO/g-C prepared in example 13N4In the transmission electron micrograph of (1), GO/g-C can be observed from FIG. 23N4Belongs to a material with a nano-scale structure.
FIG. 3 is GO/g-C prepared in example 13N4And GO, g-C3N4As can be seen from fig. 3, the position of the crystal plane diffraction peak of GO is now around 10 degrees 2 θ, which is caused by the expansion of the interlayer distance after the graphite layer is oxidized. g-C3N4The position of the diffraction peak of the crystal face is about 27 degrees at present, and the prepared light yellow powdery solid is determined to be lamellar graphite phase carbon nitride.
FIG. 4 is the GO/g-C synthesized in examples 1-53N4Ultraviolet absorption spectrum of (2). Ultra-thin g-C3N4The absorption peak of ultraviolet visible light is 313 nm. As can be seen from fig. 4, the spectrum is clearly red-shifted. The absorption peak at about 338nm is largest and the ratio of the two compounds is different, which also affects the spectral shape. When the mass ratio of the graphite-phase carbon nitride to the graphene oxide is 2:1, the absorption peak at the wavelength of 338nm is maximum.
The following uses GO/g-C prepared in example 13N4The effect on norfloxacin was studied.
Preparing 100mL of magnesium sulfate heptahydrate, anhydrous calcium chloride, potassium iodide, sodium chloride, lithium chloride, ferric chloride hexahydrate, nickel sulfate hexahydrate, barium chloride, copper nitrate, zinc sulfate, lead nitrate, cobalt nitrate, silver nitrate and cadmium nitrate with the concentration of 0.001mol/L, taking a quartz cuvette, rinsing the cuvette with distilled water, and adding 2.5mL of distilled water and 60 mu L of GO/g-C3N4Supernatant, and measuring the fluorescence intensity when the system is balanced.Then, 10. mu.L of each of the prepared metal ion solutions was added to the quartz cuvette, and measurement was performed in order to measure the fluorescence spectra of each of the metal ion solutions, as shown in FIG. 5. In FIG. 5, the curves in the direction of the arrows represent Na respectively2+、Cr2+、Li+、K+、Ni+、Cd2+、Co2+、Ca2+、Pb2+、GO/g-C3N4、Fe3+、Mg2+、Ag+Fluorescence spectrum of (2). As can be seen from FIG. 5, these inorganic metal ions appear at a wavelength of 415nm to 440 nm. As can be seen from the observation of FIG. 5, the fluorescence intensity after addition of these inorganic metal ions was less pronounced than before, indicating that GO/g-C3N4No response is generated to these inorganic metal ions,
separately, 25mL of each of norfloxacin and ciprofloxacin hydrochloride was prepared at 0.001mol/L for use. Fluorescence intensity was measured in the same manner using norfloxacin and ciprofloxacin hydrochloride solutions prepared at the same concentration of 0.001mol/L, as shown in FIG. 6. Appears at a wavelength of 420-440nm and has a fluorescence intensity far from GO/g-C3N4. I.e. determining GO/g-C3N4The sensing substance of (2) is norfloxacin.
Taking a quartz cuvette, adding 60 mu L of GO/g-C into the cuvette3N4After the supernatant was allowed to stand for 1min, 10. mu.L of a 0.001mol/L norfloxacin solution was added thereto and the fluorescence intensity was immediately measured. The fluorescence intensity was measured at 2min intervals, as shown in FIG. 7, and careful observation and analysis of the experimental data revealed that the difference in GO/g-C3N4The fluorescence intensity after mixing with norfloxacin for 9min tends to reach equilibrium stably.
Taking a quartz cuvette, adding 60 mu L of GO/g-C into the cuvette3N4The supernatant was added with 10. mu.L of norfloxacin solutions of different concentrations and immediately examined for fluorescence intensity. As shown in fig. 8. Wherein the norfloxacin concentration in FIG. 8 is 0mol/L and 1.4X 10, respectively, from bottom to top, as indicated by the arrows-4mol/L、1.6×10-4mol/L、1.8×10- 4mol/L、2.0×10-4mol/L、2.2×10-4mol/L、2.4×10-4mol/L、2.6×10-4mol/L、2.8×10-4mol/L、3.0×10-4mol/L、3.2×10-4mol/L. As can be seen from FIG. 8, the concentration of norfloxacin solution was 1.4X 10- 4mol/L to 3.2X 10-4At the time between mol/L, the fluorescence intensity of the mixed solution is enhanced along with the increase of the concentration of the added norfloxacin solution.
As shown in FIG. 9, the concentration of norfloxacin solution was 1.4X 10-4mol/L to 3.2X 10-4Between mol/L range, GO/g-C3N4The fluorescence intensity (I) of (A) is linearly related to the concentration (C) of the added norfloxacin solution. The linear relation is as follows: i is 4.84 multiplied by 107C-594.7，R2＝0.9957。
Respectively adding 2.5mL of acid-base solution with pH of 4-12 and 60 mu L of GO/g-C into a quartz cuvette3N4The fluorescence property detection was performed on the solution and 10. mu.L of the sensor substance solution as shown in FIGS. 10 to 11, in which pH was 6, 5, 4, 9, 7, 10, 8, 11, and 12 in the order of arrow in FIG. 10. The acid and alkali solutions used are hydrochloric acid solution and sodium hydroxide solution respectively, and as can be seen from fig. 10-11, GO/g-C at pH 63N4The best fluorescence properties are found, GO/g-C at pH 123N4The lowest fluorescence property. GO/g-C at pH between 7 and 113N4All the fluorescence properties are not very different, so that GO/g-C is used3N4The optimum pH should be maintained between 7 and 11.
To GO/g-C3N4Adding Na into the mixed solution of norfloxacin+、Ni2+、Ma2+、Fe3+、Cr2+、Cd2+、Co2+、Pb2+Measuring the fluorescence intensity of the inorganic metal ion solution, wherein the concentration of norfloxacin and metal ions is 1 x 10- 3mol/L As shown in FIG. 12, the fluorescence intensity was measured and the change in fluorescence intensity before and after the measurement was compared to determine which ions had an influence or interference on the fluorescence intensity. Most of the inorganic metal ions are for the GO/g-C constructed3N4For a sensing system for sensing and detecting norfloxacin, the influence strength of interference is almost lower. The interference effect of sodium ions on the sensing system is the largest relative to other inorganic metal ions, and exceeds the interference of other inorganic metal ions on the constructed sensing system.
Mixing GO/g-C3N4As a fluorescence sensor for detecting antibiotic norfloxacin in different water samples, FIG. 13 shows that GO/g-C is added in sequence to distilled water, Qin pool water and Suiyang lake water3N4、GO/g-C3N4Fluorescence intensity profile for ganofloxacin. The volume of water was 2.5mL and the concentration of norfloxacin solution was 2.8X 10-4mol/L, the results are shown in Table 1, and GO/g-C is obtained by calculation3N4The recovery rate of the Ganorfloxacin in different water samples is not more than 20 percent. From this, it can be derived that GO, g-C3N4Constructed optical sensor GO/g-C3N4The antibiotic norfloxacin can be detected in different water samples.
TABLE 1GO/g-C3N4Sensing the effect of fluorescence intensity of norfloxacin
| Water sample | GO/g-C3N4 | Norfloxacin hydrochloride | Recovery volume | Recovery rate | |
| Distilled water | | 10μL | 10μL | 100％ | |
| Water in Qin pool | 60μL | 10μL | 11μL | 110％ | |
| Saline lake water | 60μL | 10μL | 9.8μL | 98％ |
FIG. 14 is a scheme of the present invention for preparing GO/g-C3N4And a schematic diagram of detection of antibiotic norfloxacin in water, as shown in fig. 14, GO/g-C was prepared from graphene oxide and carbon nitride by means of ultrasonic self-assembly3N4The method comprises the steps of constructing a fluorescence sensor by utilizing a fluorescence resonance energy transfer principle, and detecting the antibiotic norfloxacin in the water body by utilizing Aggregation-induced emission (AIE).
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The preparation method of the graphene oxide/carbon nitride three-dimensional composite material is characterized by comprising the following steps:
s1, calcining the nitrogen-containing organic matter under inert gas to obtain g-C3N4；
S2, adding graphene oxide into distilled water, performing ultrasonic treatment until the graphene oxide is dissolved to obtain a graphene oxide solution, and then adding g-C prepared from S1 into the graphene oxide solution3N4And obtaining a supernatant through ultrasonic self-assembly and standing, wherein the supernatant is the prepared graphene oxide/carbon nitride three-dimensional composite material.
2. The method for preparing the graphene oxide/carbon nitride three-dimensional composite material according to claim 1, wherein the nitrogen-containing organic substance in the S1 is urea or melamine.
3. The method for preparing the graphene oxide/carbon nitride three-dimensional composite material as claimed in claim 2, wherein the calcination temperature in S1 is 500-600 ℃, and the calcination time is 1.8-2.5 h.
4. The method for preparing the graphene oxide/carbon nitride three-dimensional composite material according to claim 3, wherein the calcination temperature in S1 is 550 ℃ and the calcination time is 2 h.
5. The method for preparing the graphene oxide/carbon nitride three-dimensional composite material according to claim 4, wherein in S1, the inert gas is nitrogen or helium.
6. The method for preparing the graphene oxide/carbon nitride three-dimensional composite material according to claim 1, wherein in S2, the concentration of the graphene oxide is 0.45-0.55mg/mL, g-C3N4And the mass ratio of the graphene oxide to the graphene oxide is 1:3-3: 1.
7. The method for preparing the graphene oxide/carbon nitride three-dimensional composite material according to claim 6, wherein in S2, the concentration of the graphene oxide is 0.50mg/mL, g-C3N4And the mass ratio of the graphene oxide to the graphene oxide is 2: 1.
8. The method for preparing the graphene oxide/carbon nitride three-dimensional composite material according to claim 7, wherein in S2, the ultrasonic time of ultrasonic self-assembly is 3-4h, and the standing time is 24-30 h.
9. A graphene oxide/carbon nitride three-dimensional composite material prepared by the preparation method of any one of claims 1 to 8.
10. The application of the graphene oxide/carbon nitride three-dimensional composite material in preparing a fluorescence sensor according to claim 9, wherein the graphene oxide/carbon nitride three-dimensional composite material is prepared into the fluorescence sensor, and the norfloxacin antibiotic in the water body is detected by a aggregation-induced emission mechanism.
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