CN110964512A - 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. The invention aims to solve the problem of the existing Fe3+The fluorescent probe has the technical problems of high toxicity, low sensitivity and high detection limit. 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 can be used for detecting Fe3+The fluorescent probe of (2) can also be used as Fe3+The adsorbent of (1). Detection of Fe as Probe3+Detection limit of (2) is as low as 5.76X 10‑2Mu mol/L and good anti-interference performance; as adsorbent to adsorb Fe3+Has a capacity of more than 50mg/g, and can be used for Fe3+The field of detection and the field of 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
Metal cations widely exist in nature and play an important role in many fields such as life systems and environmental systems. Wherein the iron ion (Fe)3+) As one of the most basic trace elements in the living system, it plays an extremely important role in the intake and metabolism of oxygen. However, with the rapid development of the iron smelting industry, the iron ion content in the underground water is increased due to the infiltration and accumulation of iron ions and compounds thereof, and the iron ions are harmful to the health of human beings. Many proteins and enzymes have Fe in the catalytic site3+When free Fe3+When the concentration reaches 10M, the phenomenon of oxidative damage in cells can be promoted, and diseases such as liver and kidney damage, heart failure, Parkinson and the like are caused. The U.S. Environmental Protection Agency (EPA) specifies that iron content in drinking water can reach up to 5.4 μ M. Therefore, the detection of trace iron ions has more practical significance. At present, the detection of Fe is reported3+Fluorescent material probe detection modeIs single and has less research on the aspects of adsorption and desorption and the like. An article, namely a novel conjugated polymer fluorescent probe for detecting iron (III) ions, is reported in 2015, 34, 10, 1158-1162, namely an article, namely an analysis and test bulletin board, and has the defects of poor biocompatibility and high toxicity; an article, green and low-cost ball milling-hydrothermal method for preparing graphene quantum dots and application research thereof, on page 996-1004 of analytical chemistry, volume 7, volume 45, 2017, discloses a fluorescent probe, which is green and simple to synthesize, but low in sensitivity; an article, namely, a fluorescent probe based on gold nanocluster probe for detecting iron ions through fluorescence quenching is reported on pages 55-61 of the report on No. 1 of college chemistry of higher schools, 40 vol.2019, but the detection limit of the fluorescent probe is relatively large.
Disclosure of Invention
The invention aims to solve the problem of the existing Fe3+The fluorescent probe has the technical problems of high toxicity, low sensitivity and high detection limit, and the graphene oxide fluorescent material and the preparation method and the application thereof are provided.
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, removing unreacted glyoxal, 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 the coumarin derivative S into the S2 dispersion liquid under stirring, heating to boil under the protection of nitrogen, keeping reflux reaction for 24-36 h, cooling to room temperature, carrying out vacuum filtration, and using absolute ethyl alcohol and CH for filter cakes2Cl2Washing until no coumarin derivative S is detected by TLC, and drying in vacuum to obtain a graphene oxide fluorescent material which is marked as C-GO;
wherein the structural formula of the coumarin derivative S in the third step is as follows:
the application of the graphene oxide fluorescent material is to use the graphene oxide fluorescent material as Fe detection3+Or as Fe3+The adsorbent of (1).
Detection of Fe by using graphene oxide fluorescent material as fluorescent probe3+The method comprises the following steps:
preparing a graphene oxide fluorescent material into a dispersion liquid with the concentration of 30mg/L by using DMSO (dimethyl sulfoxide) to obtain a probe dispersion liquid;
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 fluorescence intensity A of the probe dispersion liquid by using a fluorescence spectrophotometer under the condition that the emission wavelength is 473nm1And the fluorescence intensity A of the sample dispersion2If A is2≤30％A1Then, 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 the graphene oxide fluorescent material into the 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. Since the graphene oxide fluorescent material has a large number of nitrogen-containing and oxygen-containing functional groups, electrons can be transferred 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+Detection limit of (2) is as low as 5.76X 10-2Mu mol/L, adding Fe3+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+A fluorescence spectrum of (a);
FIG. 5 shows the fluorescence intensity of the graphene oxide fluorescent material prepared in example 1 at 473nm in the range of 4-20. mu. mol/LFor Fe3+Linear regression plots of concentration;
FIG. 6 shows DMSO dispersion (30mg/L) of graphene oxide fluorescent material prepared in example 1 for different metal ions (Na) with concentration of 1.32mmol/L+,K+,Mg2+,Ca2+,Co2+,Zn2+,Ni2+,Cd2+,Cu2+,Fe3+,Cr3+,Pb2+, Hg2+And Ag+) Histogram of fluorescence response of;
FIG. 7 is a DMSO dispersion of the graphene oxide fluorescent material prepared in example 1, and Fe is added when the excitation wavelength is 393nm3+(1.32mmol/L) fluorescence intensity as a function of time.
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 ultrasonically dispersing for 0.5-2 h 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, removing unreacted glyoxal, 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; under stirring, the mixture is mixedDropwise adding the coumarin derivative S into the S2 dispersion liquid, heating to boil under the protection of nitrogen, keeping reflux reaction for 24-36 h, cooling to room temperature, carrying out vacuum filtration, and using absolute ethyl alcohol and CH to prepare a filter cake2Cl2Washing until no coumarin derivative S is detected by TLC, and drying in vacuum to obtain a graphene oxide fluorescent material which is marked as C-GO;
wherein the structural formula of the coumarin derivative S in the third step is as follows:
the third concrete implementation mode: the difference between the present embodiment and the second embodiment is that the mass ratio of the graphene oxide to the 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 36-48 h under the 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 other 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 36-48 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 36 to 48 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 molar ratio of the intermediate product S2 to the coumarin derivative S in step three is 1: (2-4). 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+Or 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:
preparing a graphene oxide fluorescent material into a dispersion liquid with the concentration of 30mg/L by using DMSO (dimethyl sulfoxide) to obtain a probe dispersion liquid;
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 fluorescence intensity A of the probe dispersion liquid by using a fluorescence spectrophotometer under the condition that the emission wavelength is 473nm1And the fluorescence intensity A of the sample dispersion2If A is2≤30％A1Then, 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+The method comprises the following steps:
adding the graphene oxide fluorescent material into the 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 50mL of toluene, and ultrasonic dispersion is carried out for 1h to obtain a graphene oxide dispersion liquid; then, 0.62g (0.66mL) of 3-aminopropyltriethoxysilane is added into the GO dispersion liquid dropwise under continuous stirring, the mixture reacts for 3 hours at the temperature of 30 ℃, then the mixture is heated to boiling and kept under reflux for reaction for 3 hours to obtain a black mixed liquid, the black mixed liquid is cooled to room temperature, filtered, washed for 3 times by 50mL of toluene, and placed in a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 36 hours to obtain an intermediate product S1; intermediate S1 was a dark brown solid;
ultrasonically dispersing 50mg of the intermediate product S1 in 20mL of deionized water, then adding 10mL of 1 mass percent aqueous solution of glyoxal, stirring for 2 hours at room temperature, carrying out vacuum filtration, washing a filter cake with deionized water and absolute ethyl alcohol, removing unreacted glyoxal, and placing the filter cake in a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 36 hours to obtain an intermediate product S2; intermediate S2 was a dark brown solid;
thirdly, ultrasonically dispersing 50mg of the intermediate product S2 in 20mL of toluene to obtain S2 dispersion liquid; dissolving 50mg of coumarin derivative S in 30mL of toluene to obtain a coumarin derivative S solution; dropwise adding 50mg of coumarine derivative S solution into the S2 dispersion liquid under stirring, heating to boil under the protection of nitrogen, keeping reflux reaction for 24h, cooling to room temperature, vacuum filtering, and adding anhydrous ethanol and CH into filter cake2Cl2Washing until no coumarin derivative S is detected by TLC, and putting the coumarin derivative S in a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 36 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 third step is as follows:
the scanning electron microscope photo of the graphene oxide fluorescent material obtained in the embodiment is shown in fig. 2, and it can be seen from fig. 2 that Graphene Oxide (GO) is dispersed more uniformly, connected tightly and has more lamellar structures after being functionally modified by a coupling agent.
An FT-IR diagram of the graphene oxide fluorescent material obtained in the embodiment is shown in FIG. 3, and it can be seen from FIG. 3 that coumarin derivatives S and Graphene Oxide (GO) are successfully connected through a coupling agent, and C-GO contains functional groups such as-OH, -CONH, -Si-O-C, and the like.
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 solution: and (2) taking DMSO as a solvent, and preparing the graphene oxide fluorescent material into a main body solution with the concentration of 30mg/L 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 solute to prepare metal ion solution with the concentration of 0.10mol/L for standby.
Detection of the graphene oxide fluorescent material prepared in this example on Fe3+The sensitivity of selectivity is specifically as follows: in a DMSO system, respectively adding 0-1800 mu mol/L Fe into a probe solution with the concentration of 30mg/L3+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 amount of the compound is increased, the fluorescence quenching degree of the system at 473nm is also increased, and when the Fe is used3+When the concentration increased to 1.32mmol/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%. Using fluorescence intensity F as vertical scaleWith Fe3+The concentration of (a) is plotted as a horizontal line, as shown in FIG. 5, when the concentration is in the range of 4-20. mu. mol/L, the fluorescence intensity of C-GO and Fe3+The concentration of the compound shows a good linear relation (R)20.9938) with a linear fitting equation of-3.5779X +735.4319 with a detection limit of 5.76 × 10-2μmol/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: na was added to the probe solutions at a concentration of 30mg/L in an amount of 1.32mmol/L, respectively+、K+、Mg2+、 Ca2+、Co2+、Zn2+、Ni2+、Cd2+、Cu2+、Cr3+、Pb2+、Hg2+And Ag+While adding 1.32mmol/L Fe3+And then mixing uniformly. The fluorescence emission spectrum was measured at an excitation wavelength of 473nm, and the results are shown in FIG. 6,
the bars represent the change in fluorescence of C-GO (30mg/L) in the presence of metal ions (1.32mmol/L) alone,
bars represent Fe3+The fluorescence changes after being added into a system with the coexistence of C-GO and the metal ions; 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 same condition exists when the graphene oxide fluorescent material exists independently, 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 test method of (2) is as follows: preparing by taking DMSO as a solventPreferably, the probe solution with the concentration of 30mg/L is added with Fe with the concentration of 0.10mol/L3+The fluorescence intensity at different times was measured, and the change with time of the fluorescence intensity (473 nm) 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 probe realizes the aim of detecting Fe3+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 Fe with the concentration of 10mg/L3+Measuring 20mL of aqueous solution, adding 3mg of graphene oxide fluorescent material C-GO, and carrying out ultrasonic treatment to fully dissolve the graphene oxide fluorescent material C-GO; 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 1; the solid phase substance obtained by centrifugation is adsorbed with Fe3+The graphene oxide fluorescent material is regenerated, and the specific method comprises the following steps: to absorb Fe3+Adding 20mL of EDTA disodium solution with the concentration of 12mg/L into the graphene oxide fluorescent material, carrying out ultrasonic treatment for 0.5h, filtering and washing, and putting a filter cake into a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 36h 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 removal capacity of the graphene oxide fluorescent material is evaluated by the same method after regeneration. To 20mL of Fe3+Adding 3mg of reversibly regenerated graphene oxide fluorescent material C-GO into the aqueous solution, and performing ultrasonic treatment to fully dissolve the graphene oxide fluorescent material C-GO; 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+Has a removal rate of 96% and an adsorption capacity of 64mg/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%, the adsorption capacity is 61mg/g, and the results show 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 50mL of toluene, and ultrasonic dispersion is carried out for 1h to obtain a graphene oxide dispersion liquid; then, 0.62g (0.66mL) of 3-aminopropyltriethoxysilane is added dropwise into the GO dispersion liquid under continuous stirring, the mixture reacts for 2 hours at 50 ℃, then the mixture is heated to boiling and kept under reflux for reaction for 3 hours to obtain a black mixed liquid, the black mixed liquid is cooled to room temperature, filtered, washed for 3 times by 50mL of toluene and placed in a vacuum drying oven at 60 ℃ for vacuum drying for 36 hours to obtain an intermediate product S1; intermediate S1 was a dark brown solid;
ultrasonically dispersing 50mg of the intermediate product S1 in 20mL of deionized water, then adding 8mL of glyoxal aqueous solution with the mass percentage concentration of 1.5%, stirring for 2.5h at room temperature, carrying out vacuum filtration, washing a filter cake with the deionized water and absolute ethyl alcohol, removing unreacted glyoxal, and carrying out vacuum drying for 36h in a vacuum drying oven at the temperature of 60 ℃ to obtain an intermediate product S2; intermediate S2 was a dark brown solid;
thirdly, ultrasonically dispersing 50mg of the intermediate product S2 in 20mL of toluene to obtain S2 dispersion liquid; dissolving 50mg of coumarin derivative S in 20mL of toluene to obtain a coumarin derivative S solution; dropwise adding coumarin derivative S solution into S2 dispersion under stirring, heating to boil under the protection of nitrogen gas, maintaining reflux reaction for 24h, cooling to room temperature, vacuum filtering, filtering filter cake with anhydrous ethanol and CH2Cl2Washing until no coumarin derivative S is detected by TLC, and putting the coumarin derivative S in a vacuum drying oven at the temperature of 60 ℃ for vacuum drying for 36 hours to obtain 45mg of graphene oxide fluorescent material which is marked as C-GO; wherein the coumarin derivative described in step threeThe structural formula of substance S 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 (added into toluene for ultrasonic dispersion for 0.5-2 h to obtain graphene oxide dispersion liquid, then dropwise adding 3-aminopropyltriethoxysilane into the graphene oxide dispersion liquid under the stirring condition, reacting for 2-3 h at the temperature of 30-50 ℃, continuously heating to boil and keeping reflux reaction for 2-3 h to obtain black mixed liquid, cooling to room temperature, filtering, repeatedly washing with toluene, and drying in vacuum 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, removing unreacted glyoxal, 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 the coumarin derivative S into the S2 dispersion liquid under stirring, heating to boil under the protection of nitrogen, keeping reflux reaction for 24-36 h, cooling to room temperature, carrying out vacuum filtration, and using absolute ethyl alcohol and CH for filter cakes2Cl2Washing until no coumarin derivative S is detected by TLC, and drying in vacuum to obtain a graphene oxide fluorescent material;
wherein the structural formula of the coumarin derivative S in the third step 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 molar ratio of the intermediate product S2 to the coumarin derivative S in the step three is 1: (2-4).
7. The use of the graphene oxide fluorescent material as claimed in claim 1, wherein the graphene oxide fluorescent material is used for detecting Fe3+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 liquid with the concentration of 30mg/L from a graphene oxide fluorescent material by using DMSO (dimethyl sulfoxide) to obtain a probe dispersion liquid;
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 fluorescence intensity A of the probe dispersion liquid by using a fluorescence spectrophotometer under the condition that the emission wavelength is 473nm1And the fluorescence intensity A of the sample dispersion2If A is2≤30％A1Then, 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 the graphene oxide fluorescent material into the 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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