CN111454717A - Graphene oxide fluorescent material and preparation method and application thereof - Google Patents
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Abstract
A graphene oxide fluorescent material and a preparation method and application thereof relate to a fluorescent material and preparation and application thereof. It aims to solve the problem of the existing Fe3+The fluorescent probe has poor identification selectivity and overlong response time, and can not realize the aim of Fe3+The technical problem of removal and enrichment. The structural formula of the graphene oxide fluorescent material is as follows:
the preparation method comprises the following steps: reacting graphene oxide with 3-aminopropyltriethoxysilane to obtain an intermediate product S1; the intermediate product S1 reacts with glyoxal to obtain an intermediate product S2; and reacting the intermediate product S2 with a coumarin derivative S to obtain the graphene oxide fluorescent material. The material is used for detecting Fe3+Fluorescent probe and Fe3+The adsorbent of (1). Detection of Fe as Probe3+Has a detection limit as low as 5.76 mu mol/L and good interference resistance, and can be used as adsorbent for Fe3+Has an adsorption capacity of more than 50mg/g, and can be used for Fe3+The field of detection and water treatment.
Description
Technical Field
The invention relates to a preparation method of a material fluorescent probe and application of fluorescent identification and adsorption.
Background
Fe3+Plays an important role in the fields of environment, biology and chemistry, so that the effective detection thereof is of great interest. Compared with other analysis and detection technologies, the fluorescence probe method has the advantages of high sensitivity, good selectivity, low cost, easy operation and the like, and is widely used for Fe3+Detection of (3). Inorganic chemistry communications published on page 14 of 2011 1656 and page 1658Anthracene-pyridine Fe3+Ionic fluorescent probes recognizing Fe3+While also identifying Zn2+And Cu2+The selectivity is not high, and the Journal of L discloses that a fluorescent probe containing Schiff base structure can detect Fe in a methanol/water (8:2, v/v, pH 7) system in 2015, 162, 14-24 pages3+The synthesis steps are complex and are not easy to separate; BODIPY dye pair Fe reported by chemical communications in 2012 at pages 4600 and 4602 of phase 383+The response time of recognition is 30min, the response time is long, and the sensitivity is not high. At present, the literature reports Fe3+Most of fluorescent probes only identify and prove the existence of ions in a homogeneous solution, cannot realize the removal and enrichment of the ions, and are not easy to recover and reuse, so that the practical application of the fluorescent probes is limited to a certain extent. Graphene Oxide (GO) has abundant oxygen-containing groups such as hydroxyl, carboxyl, epoxy and the like on the surface, so that GO is more easily functionalized through covalent bonds, coordination bonds, hydrogen bonds and electrostatic bonding. In addition, GO can also form complexes with heavy metal ions, thereby removing them. In recent years, the research of using organic small molecular probes to modify GO through covalent bonds to prepare material fluorescent probes for metal ion detection becomes an important research direction, and related fields have potential research spaces.
Disclosure of Invention
The invention aims to solve the problem of the existing Fe3+The fluorescent probe has poor identification selectivity and overlong response time, and can not realize the aim of Fe3+The technical problems of removal and enrichment, and provides a fluorescent probe material taking GO as a carrier, and a preparation method and application thereof.
The structural formula of the graphene oxide fluorescent material is as follows:
the preparation method of the graphene oxide fluorescent material comprises the following steps:
firstly, adding Graphene Oxide (GO) into toluene, and ultrasonically dispersing for 1-2 hours to obtain a graphene oxide dispersion liquid; dropwise adding 3-aminopropyltriethoxysilane into the graphene oxide dispersion liquid under the stirring condition, reacting for 2-3 hours at the temperature of 30-50 ℃, continuously heating to boil and keeping reflux reaction for 2-3 hours to obtain black mixed liquid; cooling to room temperature, filtering, repeatedly washing with toluene, and vacuum drying to obtain an intermediate product S1;
ultrasonically dispersing the intermediate product S1 in deionized water, then adding a glyoxal water solution, stirring for 2-3 h at room temperature, carrying out vacuum filtration, washing a filter cake with the deionized water and absolute ethyl alcohol, and carrying out vacuum drying to obtain an intermediate product S2;
thirdly, ultrasonically dispersing the intermediate product S2 in toluene to obtain S2 dispersion liquid; dropwise adding a toluene solution of coumarin derivative S into S2 dispersion liquid under stirring, heating to boil under the protection of nitrogen, keeping reflux reaction for 24-36 h, cooling to room temperature, performing vacuum filtration, and filtering a filter cake with anhydrous ethanol and CH2Cl2Washing until no S is detected by T L C, and performing vacuum drying to obtain a graphene oxide fluorescent material which is marked as C-GO;
wherein the structural formula of the coumarin derivative S in the step III is as follows:
the application of the graphene oxide fluorescent material is to use the graphene oxide fluorescent material as Fe detection3+The fluorescent probe of (1), which can also be used as Fe3+The adsorbent of (1).
Detection of Fe by using graphene oxide fluorescent material as fluorescent probe3+The method comprises the following steps:
firstly, preparing a dispersion solution with the concentration of 30 mg/L from a graphene oxide fluorescent material by using DMSO (dimethyl sulfoxide) to obtain a probe dispersion solution;
secondly, adding a sample to be detected into the probe dispersion liquid, and uniformly mixing to obtain a sample dispersion liquid;
thirdly, respectively testing the probe dispersion liquid and the sample dispersion liquid by using a fluorescence spectrophotometerThe fluorescence spectra of (1) and the fluorescence intensities at the emission wavelength of 473nm are respectively denoted as I0And IFIf I isF≤0.14I0Then, it is determined that the sample to be measured contains Fe3+。
Adsorbing Fe by using graphene oxide fluorescent material as adsorbent3+The method comprises the following steps:
adding graphene oxide fluorescent material to a solution containing Fe3+Dissolving the graphene oxide fluorescent material in the solution, standing for 24-48 h at room temperature, and centrifuging the graphene oxide fluorescent material to obtain Fe3+Adsorption of (3).
The graphene oxide fluorescent material is obtained by modifying graphene oxide with coumarin derivatives, and the preparation process diagram is shown in fig. 1. Because the graphene oxide fluorescent material has a large amount of nitrogen-containing and oxygen-containing functional groups, electrons can be converted from the graphene oxide fluorescent material to Fe3+Transfer, plus Fe3+So that the graphene oxide fluorescent material is aligned with Fe3+Specific selective recognition is generated, and is not influenced by Na in the system+,K+,Mg2+,Ca2+,Co2+,Zn2+,Ni2+,Cd2+,Cu2+,Cr3+, Pb2 +,Hg2+And Ag+Has good interference resistance and is used for Fe3+Has a detection limit as low as 5.76. mu. mol/L, and Fe is added3+The post-fluorescence intensity is quenched to the lowest within 1min, and the reaction is fast. Can be used as a probe for rapid fluorescence detection.
Meanwhile, the graphene oxide fluorescent material has a large number of oxygen-containing and nitrogen-containing functional groups, so that free Fe in a solution can be adsorbed through electrostatic adsorption3+Can be used as Fe3+The adsorbent is used, the adsorption capacity is more than 50mg/g, and the removal rate is more than 92%. After the adsorbed graphene oxide fluorescent material is regenerated, the graphene oxide fluorescent material still has good adsorption capacity and can be repeatedly used.
The graphene oxide fluorescent material can be used for Fe3+The field of detection and the field of water treatment.
Drawings
FIG. 1 is a diagram of a synthetic reaction process of a graphene oxide fluorescent material according to the present invention;
fig. 2 is an SEM image of the graphene oxide fluorescent material prepared in example 1;
FIG. 3 is a FT-IR chart of the graphene oxide fluorescent material prepared in example 1;
FIG. 4 shows that different concentrations of Fe were added to the DMSO dispersion of the graphene oxide fluorescent material prepared in example 13+The insert graph shows the fluorescence intensity of the graphene oxide fluorescent material at 473nm and Fe3+Concentration dependence graph, excitation wavelength 393 nm;
FIG. 5 shows the fluorescence intensity at 473nm in the range of 0-20 μmol/L of the graphene oxide fluorescent material prepared in example 1 vs. Fe3+Linear regression plots of concentration;
FIG. 6 shows the graphene oxide fluorescent material (30 mg/L) prepared in example 1 and its reaction with different metal ions (1.32 mmol/L, Na)+,K+,Mg2+,Ca2+,Co2+,Zn2+,Ni2+,Cd2+,Cu2+,Fe3+,Cr3+,Pb2+,Hg2+，Ag+) Fluorescence response profiles in coexistence;
FIG. 7 shows a DMSO dispersion of graphene oxide fluorescent material prepared in example 1, with Fe added3+The change of fluorescence intensity with time after (1.32 mmol/L).
Detailed Description
The first embodiment is as follows: the structural formula of the graphene oxide fluorescent material of the embodiment is as follows:
the second embodiment is as follows: the preparation method of the graphene oxide fluorescent material according to the first embodiment comprises the following steps:
firstly, adding Graphene Oxide (GO) into toluene, and performing ultrasonic dispersion for 1-2 hours to obtain a GO dispersion liquid; dropwise adding 3-aminopropyltriethoxysilane into the GO dispersion liquid under the stirring condition, reacting for 2-3 hours at the temperature of 30-50 ℃, continuously heating to boil and keeping reflux reaction for 2-3 hours to obtain black mixed liquid; cooling to room temperature, filtering, repeatedly washing with toluene, and vacuum drying to obtain an intermediate product S1;
ultrasonically dispersing the intermediate product S1 in deionized water, then adding a glyoxal water solution, stirring for 2-3 h at room temperature, carrying out vacuum filtration, washing a filter cake with the deionized water and absolute ethyl alcohol, and carrying out vacuum drying to obtain an intermediate product S2;
thirdly, ultrasonically dispersing the intermediate product S2 in toluene to obtain S2 dispersion liquid; dropwise adding a toluene solution of coumarin derivative S into S2 dispersion liquid under stirring, heating to boil under the protection of nitrogen, keeping reflux reaction for 24-36 h, cooling to room temperature, performing vacuum filtration, and filtering a filter cake with anhydrous ethanol and CH2Cl2Washing until no S is detected by T L C, and performing vacuum drying to obtain a graphene oxide fluorescent material which is marked as C-GO;
wherein the structural formula of the coumarin derivative S in the step III is as follows:
the third concrete implementation mode: the difference between the embodiment and the second embodiment is that the mass ratio of GO to 3-aminopropyltriethoxysilane in the first step is 1: (6-7). The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first embodiment in that the vacuum drying in the first step is drying for 24-36 h under a vacuum condition of 60 ℃. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between the second embodiment and the fourth embodiment is that the mass percentage concentration of the glyoxal water solution in the second step is 1% -2%. The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the difference between the present embodiment and one of the second to fifth embodiments is that the mass ratio of the intermediate product S1 in the second step to glyoxal in the aqueous glyoxal solution is 1: (2-4). The rest is the same as one of the second to fifth embodiments.
The seventh embodiment: the difference between the second embodiment and the sixth embodiment is that the vacuum drying in the second step is drying for 24-36 h under a vacuum condition of 60 ℃. The rest is the same as one of the second to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and the second to seventh embodiments is that the vacuum drying in the third step is drying for 24 to 36 hours under a vacuum condition of 60 ℃. The rest is the same as one of the second to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and one of the second to seventh embodiments is that the mass ratio of the intermediate product S2 to the coumarin derivative S in step three is 1: (1-2). The rest is the same as one of the second to seventh embodiments.
The detailed implementation mode is ten: the application of the graphene oxide fluorescent material according to the first embodiment is characterized in that the graphene oxide fluorescent material is used for detecting Fe3+The fluorescent probe of (1), which can also be used as Fe3+The adsorbent of (1).
The concrete implementation mode eleven: detection of Fe by using graphene oxide fluorescent material as fluorescent probe3+The method comprises the following steps:
firstly, preparing a dispersion solution with the concentration of 30 mg/L from a graphene oxide fluorescent material by using DMSO (dimethyl sulfoxide) to obtain a probe dispersion solution;
secondly, adding a sample to be detected into the probe dispersion liquid, and uniformly mixing to obtain a sample dispersion liquid;
respectively testing the fluorescence spectra of the probe dispersion liquid and the sample dispersion liquid by using a fluorescence spectrophotometer, and respectively recording the fluorescence intensity at the position of 473nm of emission wavelength as I0And IFIf I isF≤0.14I0Then, it is determined that the sample to be measured contains Fe3+。
The specific implementation mode twelve: adsorbing Fe by using graphene oxide fluorescent material as adsorbent3+In the method of (a) to (b),the method comprises the following steps:
adding graphene oxide fluorescent material to a solution containing Fe3+Dissolving the graphene oxide fluorescent material in the solution, standing for 24-48 h at room temperature, and centrifuging the graphene oxide fluorescent material to obtain Fe3+Adsorption of (3).
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the graphene oxide fluorescent material of the embodiment is carried out according to the following steps:
firstly, 100mg of Graphene Oxide (GO) is placed in 50m L toluene, ultrasonic dispersion is carried out for 1h, graphene oxide dispersion liquid is obtained, then 0.62g (0.66m L) of 3-aminopropyltriethoxysilane is added into the GO dispersion liquid drop by drop under continuous stirring, reaction is carried out for 3h at the temperature of 30 ℃, then the temperature is raised to boiling and reflux reaction is kept for 3h, black mixed liquid is obtained, after cooling to the room temperature, filtration is carried out, 50m L toluene is used for washing for 3 times, and vacuum drying is carried out in a vacuum drying oven at the temperature of 60 ℃ for 24h, so that dark brown solid is obtained, namely an intermediate S1;
ultrasonically dispersing 50mg of the intermediate product S1 in 20m of L deionized water, then adding 1% glyoxal aqueous solution with the mass percentage concentration of 10m of L, stirring for 2 hours at room temperature, carrying out vacuum filtration, washing a filter cake with deionized water and absolute ethyl alcohol, and putting the filter cake in a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 24 hours to obtain a dark brown solid, namely the intermediate S2;
thirdly, ultrasonically dispersing 50mg of intermediate product S2 in 20m L toluene to obtain S2 dispersion liquid, dissolving 50mg of coumarin derivative S in 30m L toluene to obtain coumarin derivative S solution, dropwise adding 50mg of coumarin derivative S solution into the S2 dispersion liquid under stirring, heating to boil under the protection of nitrogen, keeping reflux reaction for 24 hours, cooling to room temperature, carrying out vacuum filtration, and using anhydrous ethanol and CH to prepare filter cakes2Cl2Washing until no S is detected by T L C, and vacuum-drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain 48mg of graphene oxide fluorescent material which is marked as C-GO;
wherein the structural formula of the coumarin derivative S in the step III is as follows:
the scanning electron microscope photo of the graphene oxide fluorescent material obtained in the embodiment is shown in fig. 2, and as can be seen from fig. 2, after the Graphene Oxide (GO) is functionally modified by the coupling agent, the graphene oxide fluorescent material is dispersed uniformly, is connected tightly, and has a plurality of lamellar structures.
The FT-IR diagram of the graphene oxide fluorescent material obtained in this example is shown in fig. 3, and as can be seen from fig. 3, C-GO contains characteristic peaks of groups such as-OH, -C ═ N, -Si-O-C, and the like, which indicates that the coumarin derivative S and graphene oxide are successfully connected through the coupling agent.
From the above data, the structure of the graphene oxide fluorescent material prepared in this embodiment can be obtained as follows:
the graphene oxide fluorescent material prepared in the embodiment is subjected to a spectrum performance test, and the steps are as follows:
preparing a main body solution, namely preparing the graphene oxide fluorescent material into the main body solution with the concentration of 30 mg/L by taking DMSO as a solvent for later use.
Preparing a metal ion stock solution: deionized water is used as a solvent, and Fe is used as a solvent3+、Na+、K+、Mg2+、Ca2+、 Co2+、Zn2+、Ni2+、Cd2+、Cu2+、Cr3+、Pb2+、Hg2+And Ag+The nitrate is used as a solute to prepare a metal ion solution with the concentration of 0.10 mol/L for standby.
Detection of the graphene oxide fluorescent material prepared in this example on Fe3+The identification sensitivity is determined by adding Fe with a concentration of 0-1800 μmol/L to DMSO dispersion of C-GC (30 mg/L)3+FIG. 4 shows the change of fluorescence spectrum measured by fluorescence spectrophotometer, with the fluorescence intensity being dependent on Fe3+The change in concentration is shown in the inset in FIG. 4, where it can be seen that with Fe3+The quantity is continuously increased, the fluorescence quenching degree at 473nm is also continuously enhanced, when Fe3+When the concentration increased to 1.32 mmol/L, the fluorescence quenched to a minimum, after which Fe3+The increase of the concentration does not substantially cause the change of the fluorescence spectrum of the system, which indicates that Fe3+The concentration had reached saturation, at which time the fluorescence intensity of the system was quenched by 86%. Fluorescence intensity F as ordinate and Fe3+The concentration of (a) is plotted on the abscissa, and as shown in FIG. 5, when the concentration is in the range of 0-20. mu. mol/L, the fluorescence intensity of C-GO is related to Fe3+The concentration of the compound shows a good linear relation (R)20.9939) and a linear fitting equation of-3.5779X +735.4319 with a detection limit of 5.76 μmol/L.
The graphene oxide fluorescent material prepared by the embodiment is used for preparing Fe3+The method for testing the anti-interference capability during detection comprises the following steps:
to a DMSO dispersion of C-GC (30 mg/L), Na was added in a concentration of 1.32 mmol/L+、K+、 Mg2+、Ca2 +、Co2+、Zn2+、Ni2+、Cd2+、Cu2+、Cr3+、Pb2+、Hg2+And Ag+While adding 1.32 mmol/L Fe3+And then mixing uniformly. The fluorescence emission spectrum was measured at an excitation wavelength of 393nm, and the results are shown in FIG. 6,
the bars represent the change in fluorescence of C-GO (30 mg/L) in the presence of metal ions (1.32 mmol/L) alone,
bars represent Fe3+Fluorescence change after addition to a system in which C-GO and these metal ions coexist; as can be seen from FIG. 6, Fe3+In the presence of other metal ions (Na)+、K+、Mg2 +、Ca2+、Co2+、Zn2+、Ni2+、 Cd2+、Cu2+、Cr3+、Pb2+、Hg2+And Ag+) The quenching efficiency of the generated fluorescence is combined with Fe under the condition of coexistence3+The graphene oxide fluorescent material prepared by the embodiment is basically the same when existing alone, so that the fact that the graphene oxide fluorescent material prepared by the embodiment is used for detecting Fe can be proved3+The anti-interference performance is good.
The graphene oxide fluorescent material prepared in the embodiment is used for detecting Fe3+The response time of (2) was measured by adding Fe at a concentration of 1.32 mmol/L to a DMSO dispersion of C-GC (30 mg/L)3+The fluorescence intensity at different times was measured, and the change curve of the fluorescence intensity (473 nm) with time at an excitation wavelength of 393nm is shown in FIG. 7, which indicates that Fe3+The addition of (A) can quench the fluorescence intensity of the system to the minimum value within 1min and tend to be stable, so that the material realizes the effect of Fe-based fluorescence intensity control3+Rapid selective detection of ions.
The graphene oxide fluorescent material prepared in the embodiment is used as an adsorbent to adsorb Fe3+The specific method comprises the following steps:
preparing ferric nitrate crystal into 10 mg/L aqueous solution, weighing 20m L, adding 3mg graphene oxide fluorescent material C-GO, performing ultrasonic treatment to fully dissolve, standing at room temperature for 24h, centrifuging at 10000r/min for 10min, filtering supernatant with 0.22 μm microporous filter membrane to obtain balance system 1, and centrifuging to obtain solid phase substance with Fe adsorbed3+The graphene oxide fluorescent material is regenerated, and the specific method comprises the following steps: to absorb Fe3+Adding 20m of EDTA disodium solution with L concentration of 12 mg/L into the graphene oxide fluorescent material, performing ultrasonic treatment for 0.5h, filtering and washing, and putting a filter cake into a vacuum drying oven at 60 ℃ for vacuum drying for 36 hours to obtain the reversibly regenerated graphene oxide fluorescent material.
For further investigation of reversible regeneration of graphene oxide fluorescent material, Fe recognition is carried out3+The adsorption capacity of the regenerated graphene oxide fluorescent material is evaluated by the same method, namely 20m L Fe3+Adding 3mg of reversibly regenerated graphene oxide fluorescent material C-GO into the aqueous solution, and performing ultrasonic fillingRespectively dissolving; standing at room temperature for 24h, centrifuging at 10000r/min for 10min, collecting supernatant, and filtering with 0.22 μm microporous membrane to obtain balance system 2;
respectively testing Fe in solution without adding C-GO by using atomic absorption spectrometer3+Has a mass concentration of B1And then Fe in equilibrium system 1 was measured3+Has a mass concentration of B2And calculating to obtain Fe3+The removal rate of (D) was 96.1%, and the adsorption capacity was 64.07 mg/g.
The regenerated graphene oxide fluorescent material is evaluated by the same method, and Fe in the equilibrium system 2 is measured3+At a concentration of B3. The calculated removal rate is 92.8 percent, the adsorption capacity is 61.87mg/g, which shows that the graphene oxide fluorescent material C-GO can reversibly regenerate Fe3+Still has the desorption ability, and the reuse efficiency is high.
Example 2: the preparation method of the graphene oxide fluorescent material of the embodiment is carried out according to the following steps:
firstly, 100mg of Graphene Oxide (GO) is placed in 50m L toluene, ultrasonic dispersion is carried out for 1h, graphene oxide dispersion liquid is obtained, then 0.62g (0.66m L) of 3-aminopropyltriethoxysilane is added into the GO dispersion liquid drop by drop under continuous stirring, reaction is carried out for 2h under the condition of 50 ℃, then the temperature is raised to boiling and reflux reaction is kept for 3h, black mixed liquid is obtained, after cooling to room temperature, filtration is carried out, 50m L toluene is used for washing for 3 times, and vacuum drying is carried out for 36h in a vacuum drying oven with the temperature of 60 ℃, so that dark brown solid is obtained, namely an intermediate S1;
ultrasonically dispersing 50mg of intermediate product S1 in 20m of L deionized water, then adding 8m of aqueous solution of L mass percent of 1.5% of glyoxal, stirring for 2.5h at room temperature, carrying out vacuum filtration, washing a filter cake with deionized water and absolute ethyl alcohol, and putting the filter cake in a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 36h to obtain a dark brown solid, namely the intermediate S2;
thirdly, ultrasonically dispersing 50mg of the intermediate product S2 in 20m L toluene to obtain S2 dispersion liquid, dissolving 50mg of coumarin derivative S in 20m L toluene to obtain coumarin derivative S solution, and dropwise adding the coumarin derivative S solution into 20m L toluene under stirringAdding into S2 dispersion, heating to boil under nitrogen protection, reflux reacting for 24 hr, cooling to room temperature, vacuum filtering, filtering with anhydrous ethanol and CH2Cl2Washing until no coumarin derivative S is detected by T L C, and vacuum-drying in a vacuum drying oven at 60 ℃ for 36 hours to obtain 45mg of graphene oxide fluorescent material, which is marked as C-GO, wherein the structural formula of the coumarin derivative S in the step three is as follows:
the structure of the graphene oxide fluorescent material prepared in this embodiment is as follows:
Claims (9)
1. a graphene oxide fluorescent material is characterized in that the structural formula of the material is as follows:
2. the method for preparing the graphene oxide fluorescent material of claim 1, which is characterized by comprising the following steps:
firstly, adding graphene oxide into toluene, and ultrasonically dispersing for 1-2 hours to obtain a graphene oxide dispersion liquid; dropwise adding 3-aminopropyltriethoxysilane into the graphene oxide dispersion liquid under the stirring condition, reacting for 2-3 hours at the temperature of 30-50 ℃, continuously heating to boil and keeping reflux reaction for 2-3 hours to obtain black mixed liquid; cooling to room temperature, filtering, repeatedly washing with toluene, and vacuum drying to obtain an intermediate product S1;
ultrasonically dispersing the intermediate product S1 in deionized water, then adding a glyoxal water solution, stirring for 2-3 h at room temperature, carrying out vacuum filtration, washing a filter cake with the deionized water and absolute ethyl alcohol, and carrying out vacuum drying to obtain an intermediate product S2;
thirdly, ultrasonically dispersing the intermediate product S2 in toluene to obtain S2 dispersion liquid; dropwise adding a toluene solution of coumarin derivative S into S2 dispersion liquid under stirring, heating to boil under the protection of nitrogen, keeping reflux reaction for 24-36 h, cooling to room temperature, performing vacuum filtration, and filtering a filter cake with anhydrous ethanol and CH2Cl2Washing until no S is detected by T L C, and performing vacuum drying to obtain a graphene oxide fluorescent material which is marked as C-GO;
wherein the structural formula of the coumarin derivative S in the step III is as follows:
3. the method for preparing a graphene oxide fluorescent material according to claim 2, wherein the mass ratio of the graphene oxide to the 3-aminopropyltriethoxysilane in the step one is 1: (6-7).
4. The method for preparing a graphene oxide fluorescent material according to claim 2 or 3, wherein the mass percentage concentration of the glyoxal water solution in the second step is 1% -2%.
5. The method for preparing a graphene oxide fluorescent material according to claim 2 or 3, wherein the mass ratio of the intermediate product S1 in the step two to glyoxal in a glyoxal aqueous solution is 1: (2-4).
6. The method for preparing a graphene oxide fluorescent material according to claim 2 or 3, wherein the mass ratio of the intermediate product S2 to the coumarin derivative S in the step three is 1: (1-2).
7. The use of the graphene oxide fluorescent material as claimed in claim 1, wherein the graphene oxide fluorescent material is used for detectionFe3+Or using a graphene oxide fluorescent material as Fe3+The adsorbent of (1).
8. The use of the graphene oxide fluorescent material according to claim 7, wherein the graphene oxide fluorescent material is used as a fluorescent probe to detect Fe3+The method comprises the following steps:
firstly, preparing a dispersion solution with the concentration of 30 mg/L from a graphene oxide fluorescent material by using DMSO (dimethyl sulfoxide) to obtain a probe dispersion solution;
secondly, adding a sample to be detected into the probe dispersion liquid, and uniformly mixing to obtain a sample dispersion liquid;
respectively testing the fluorescence spectra of the probe dispersion liquid and the sample dispersion liquid by using a fluorescence spectrophotometer, and respectively recording the fluorescence intensity at the position of 473nm of emission wavelength as I0And IFIf I isF≤0.14I0Then, it is determined that the sample to be measured contains Fe3+。
9. The use of the graphene oxide fluorescent material according to claim 7, wherein the graphene oxide fluorescent material is used as an adsorbent to adsorb Fe3+The method comprises the following steps:
adding graphene oxide fluorescent material to a solution containing Fe3+Dissolving the graphene oxide fluorescent material in the solution, standing for 24-48 h at room temperature, and centrifuging the graphene oxide fluorescent material to obtain Fe3+Adsorption of (3).
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