CN108982453B - Fluorine ion fluorescence detection material and preparation method thereof - Google Patents
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Abstract
The invention discloses a fluorine ion fluorescence detection material and a preparation method thereof, wherein the preparation method comprises the following steps: preparing amino modified mesoporous silica, and then modifying NBD-Cl on the surface of the amino modified mesoporous silica to obtain the fluorine ion fluorescent detection material. NBD-Cl is used as a benzofurazan (NBD) derivative, has a conjugated electron donor (D) and an electron acceptor (A), is a typical fluorescent probe with an intramolecular charge transfer mechanism, can be subjected to a derivatization reaction with an active group amino group to be modified on the surface of amino modified mesoporous silicon oxide, and can also be used as a hydrogen bond type fluorine ion probe. The preparation method is simple, and the synthesized fluorine ion fluorescence detection material has good stability and dispersibility, can be repeatedly utilized, and can realize rapid qualitative and quantitative test of pollutants in the fields of environmental engineering, analysis and detection and the like.
Description
Technical Field
The invention relates to the field of fluorescence detection materials, in particular to a fluorine ion fluorescence detection material and a preparation method thereof.
Background
Although fluorine has a certain positive effect on human bodies, excessive fluorine can interfere the activity of enzymes, destroy the metabolic balance of calcium and phosphorus, and cause irreversible systemic chronic injury to teeth and bones. In recent years, the industry of China is rapidly developed, fluorine-removing enterprises are increasingly increased, the production scale is continuously enlarged, and the problem of fluorine environmental pollution is becoming serious. The development of sensitive fluorine ion detection materials is of great significance.
At present, most of fluorescent detection materials are designed and synthesized based on organic polymer materials, the preparation is complex, and the toxicity of a plurality of organic reagents is high.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a fluorine ion fluorescence detection material and a preparation method thereof, and aims to solve the problems of complicated preparation process and high toxicity of the conventional fluorine ion fluorescence detection material based on an organic polymer material.
The technical scheme of the invention is as follows:
a preparation method of a fluorine ion fluorescence detection material comprises the following steps: preparing amino modified mesoporous silica, and then modifying NBD-Cl on the surface of the amino modified mesoporous silica to obtain the fluorine ion fluorescent detection material.
The preparation method of the fluorine ion fluorescence detection material comprises the following steps:
dispersing a surfactant in a cosolvent, adding ammonia water, uniformly mixing, adding a mixture of ethyl orthosilicate and 3-aminopropyltriethoxysilane, stirring for reaction for 3-5 hours, and then carrying out separation treatment to obtain a white powdery solid;
and B, dispersing the white powdery solid into a mixed solvent of absolute ethyl alcohol and hydrochloric acid, stirring and reacting for 20-30h at the temperature of 60-90 ℃, and separating to obtain the amino modified mesoporous silica.
The preparation method of the fluorine ion fluorescence detection material comprises the step A, wherein the concentration of the surfactant is 4-6 g/L.
In the step A, the volume percentage of the mixture of the ethyl orthosilicate and the 3-aminopropyltriethoxysilane in the whole reaction system is 2-8%.
The preparation method of the fluorine ion fluorescence detection material comprises the following steps of A, wherein in the step A, the mass ratio of ethyl orthosilicate to 3-aminopropyltriethoxysilane is 1-5: 1.
in the step A, the cosolvent is a mixed solvent of deionized water, diethyl ether and ethanol.
The preparation method of the fluorine ion fluorescence detection material, wherein the step of modifying NBD-Cl on the surface of the amino modified mesoporous silica specifically comprises the following steps: dispersing the amino modified mesoporous silica in an organic solvent, adding NBD-Cl under the stirring condition, carrying out reflux reaction for 10-20h at the temperature of 60-90 ℃, and then carrying out separation treatment to obtain the fluorine ion fluorescence detection material.
The preparation method of the fluorine ion fluorescence detection material comprises the following steps: the reaction solution turned from an initial yellow-brown color to a greenish-black color.
The fluorine ion fluorescence detection material is prepared by the preparation method.
The fluorine ion fluorescence detection material is characterized in that the mesoporous silica is composed of spherical nanoparticles, and the spherical nanoparticles are provided with a plurality of radial pore channels.
Has the advantages that: the invention provides a preparation method of the fluorine ion fluorescence detection material, which is characterized in that NBD-Cl is modified on the surface of amino modified mesoporous silicon oxide to prepare the fluorine ion fluorescence detection material. The principle is as follows: NBD-Cl is used as a benzofurazan (NBD) derivative, has a conjugated electron donor (D) and an electron acceptor (A), is a typical fluorescent probe with an intramolecular charge transfer mechanism, can be subjected to a derivatization reaction with an active group amino group to be modified on the surface of amino modified mesoporous silicon oxide, and can also be used as a hydrogen bond type fluorine ion probe. The preparation method is simple, and the mesoporous silica particle matrix has the advantages of no toxicity, good biocompatibility, large specific surface area, stable chemical property, easy surface modification and the like, so that the fluorine ion fluorescence detection material has good stability and dispersibility, can be repeatedly utilized, and can realize rapid qualitative and quantitative test of pollutants in the fields of environmental engineering, analysis and detection and the like.
Drawings
FIG. 1 is an SEM image of amino-modified mesoporous silica of the present invention before loading NBD-Cl.
FIG. 2 is an SEM image of NBD-Cl supported amino-modified mesoporous silica of the present invention.
FIG. 3 is a UV-Vis chart of NBD-Cl, TBAF (tetrabutylammonium fluoride) and NBD-Cl before and after loading of NBD-Cl on the amino-modified mesoporous silica of the present invention.
FIG. 4 is an infrared spectrum of NBD-Cl and before and after loading of NBD-Cl on the amino-modified mesoporous silica of the present invention.
FIG. 5 is a TG curve before and after loading NBD-Cl on the amino-modified mesoporous silica of the present invention.
FIG. 6 is a fluorescence spectrum of the fluorine ion fluorescence detection material of amino-modified mesoporous silica according to the present invention, as the concentration of fluorine ions changes.
FIG. 7 is a graph showing the variation trend of the maximum fluorescence intensity value (470 nm) corresponding to different fluorine ion concentrations for the fluorine ion fluorescence detection material of amino-modified mesoporous silica according to the present invention.
FIG. 8 is a histogram of the maximum fluorescence intensity of the fluorescence detection material for fluorine ions of amino-modified mesoporous silica according to the present invention when detecting fluorine ions at different water contents.
FIG. 9 is a fluorescence spectrum diagram of the selective response of the fluorine ion fluorescence detection material of amino-modified mesoporous silica to fluorine ions in an ethanol solution.
FIG. 10 is a histogram of the maximum fluorescence intensity of the selective response of the fluorine ion fluorescence detection material of amino-modified mesoporous silica according to the present invention to fluorine ions in an ethanol solution.
FIG. 11 is a fluorescence spectrum of the amino-modified mesoporous silica fluorine ion fluorescence detection material of the present invention in the presence of different interfering anions after addition of fluorine ions.
FIG. 12 is a histogram of the presence of different interfering anions after the fluorine ions are added to the fluorine ion fluorescence detection material of amino-modified mesoporous silica of the present invention.
Detailed Description
The invention provides a fluorine ion fluorescence detection material and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a fluorine ion fluorescence detection material, which comprises the following steps: preparing amino modified mesoporous silica, and then modifying NBD-Cl on the surface of the amino modified mesoporous silica to obtain the fluorine ion fluorescent detection material.
The preparation mechanism of the invention is as follows: NBD-Cl is used as a benzofurazan (NBD) derivative, has a conjugated electron donor (D) and an electron acceptor (A), is a typical fluorescent probe with an intramolecular charge transfer mechanism, can be subjected to a derivatization reaction with an active group amino group to be modified on the surface of amino modified mesoporous silicon oxide, and can also be used as a hydrogen bond type fluorine ion probe. The preparation method is simple, and the mesoporous silica particle matrix has the advantages of no toxicity, good biocompatibility, large specific surface area, stable chemical property, easy surface modification and the like, so that the fluorine ion fluorescence detection material has good stability and dispersibility, can be repeatedly utilized, and can realize rapid qualitative and quantitative test of pollutants in the fields of environmental engineering, analysis and detection and the like
The preparation of the amino modified mesoporous silica is mature, and the invention provides a better embodiment of the preparation method of the amino modified mesoporous silica, which comprises the following steps:
a, dispersing a surfactant (such as Cetyl Trimethyl Ammonium Bromide (CTAB)) in a cosolvent, preferably, the concentration of the surfactant is 4-6 g/L, and a nano mesoporous structure with uniform pore diameter can be obtained; the cosolvent can be a mixed solvent of deionized water, diethyl ether and ethanol, and has good solubility on CTAB. Preferably, the cosolvent comprises the following components in percentage by volume: 65-80% of deionized water, 12-18% of diethyl ether and 3-8% of ethanol, and the surfactant has a better dispersing effect under the cosolvent.
Then adding ammonia water, wherein the concentration of the ammonia water can be 0.5-2% (v/v), uniformly mixing, adding a mixture of Tetraethoxysilane (TEOS) and 3-Aminopropyltriethoxysilane (APTES), wherein the volume percentage of the mixture in the whole reaction system is preferably 2-8%, and further preferably, the mass ratio of tetraethoxysilane to 3-aminopropyltriethoxysilane is 1-5: 1. under the above conditions, spherical nanoparticles having mesopores on the surface can be obtained. Stirring for reaction for 3-5h, separating, such as centrifuging, purifying, and oven drying at 60 deg.C to obtain white powdery solid;
and B, dispersing the white powdery solid into a mixed solvent of absolute ethyl alcohol and hydrochloric acid (the concentration is 2-3 mol/L), stirring and reacting for 20-30h at the temperature of 60-90 ℃, and separating to obtain the amino modified mesoporous silicon oxide.
The invention further provides a method for modifying NBD-Cl on the surface of the amino modified mesoporous silica, which comprises the following steps: dispersing the amino modified mesoporous silica in an organic solvent (such as absolute ethyl alcohol), adding NBD-Cl under the condition of stirring, and carrying out reflux reaction for 10-20h at the temperature of 60-90 ℃. Preferably, the determination of the end point of the reaction can be made with reference to: the reaction solution turned from an initial yellow-brown color to a greenish-black color. And then carrying out separation treatment, for example, carrying out centrifugal cleaning on the precipitate for 5 to 6 times by adopting absolute ethyl alcohol, and drying at 60 ℃ to obtain a dark green powdery substance, namely the fluorine ion fluorescence detection material.
The preparation process shows that the separation and purification process of the invention adopts simple washing and centrifugal separation, and the separation reagents are common nontoxic solvents, thus overcoming the problems of complicated purification work and high toxicity of a plurality of organic reagents in the traditional design and synthesis based on organic high molecular materials.
The invention also provides a fluorine ion fluorescence detection material prepared by the preparation method. Preferably, the synthetic material has such a structure that: the mesoporous silica is composed of spherical nanoparticles, the spherical nanoparticles are provided with a plurality of radial pore channels, the structure has a larger specific surface area, and the NBD-Cl content and the load efficiency can be improved.
The present invention will be described in detail below with reference to examples.
Example 1
(1) Preparation of amino modified mesoporous silica
Ultrasonically dispersing 1 g of hexadecyl trimethyl ammonium bromide (CTAB) into 140 mL of deionized water, sequentially adding 30 mL of diethyl ether, 10 mL of absolute ethyl alcohol and 1.6 mL of ammonia water, and mechanically stirring at room temperature for 40 min; then, 5 mL of tetraethyl orthosilicate (TEOS) and 0.4 mL of 3-Aminopropyltriethoxysilane (APTES) are slowly added into the solution by an injector, when the solution slowly becomes turbid from clarification, mechanical stirring is continuously carried out for 4 hours at room temperature to obtain milky turbid liquid, centrifugal separation and purification are carried out, the precipitate is centrifugally cleaned by absolute ethyl alcohol and deionized water for 4 times, and drying is carried out at 60 ℃ to obtain white powdery solid. Dispersing the obtained white powdery solid into a mixed solvent of 240 mL of absolute ethyl alcohol and 30 mL of hydrochloric acid (2 mol/L), performing ultrasonic dispersion, magnetically stirring at 70 ℃, performing reflux reaction for 24 hours, and removing the template. Cooling to room temperature, performing centrifugal separation, centrifugally cleaning the precipitate for 4 times by using absolute ethyl alcohol and deionized water, and drying at 60 ℃ to obtain white powdery amino modified mesoporous silica.
(2) Preparation of mesoporous silica-loaded fluorine ion fluorescent probe detection material
0.3 g of amino modified mesoporous silica is taken to be put into a single-neck flask, 100 mL of absolute ethyl alcohol is added, after ultrasonic dispersion and dissolution, 0.5 g of NBD-Cl is added under magnetic stirring, and the solution is changed from milky white to yellow white. The reaction solution is changed from initial yellow brown to final dark green by magnetic stirring and refluxing for 15 h at 70 ℃. After the reaction is finished, cooling the reaction system to room temperature, performing centrifugal separation, centrifugally cleaning the precipitate for 6 times by using absolute ethyl alcohol, and drying at 60 ℃ to obtain a dark green powdery material, namely the fluorine ion fluorescence detection material.
Testing and characterization
(1) Morphology change of mesoporous silica before and after loading NBD-Cl
As can be seen from fig. 1 and 2, the prepared mesoporous silica has a spherical shape, has radial pores and a dense wrinkle structure on the surface, and has a particle size of about several hundred nanometers; compared with the situation before and after the loading of the NBD-Cl, the basic morphology particle size of the mesoporous silica particle is not obviously changed and is still regular fold spherical particles, which shows that the loading of the NBD-Cl by using the mesoporous silica as a carrier is feasible and does not damage the morphology structure of the carrier.
(2) Ultraviolet spectrum change before and after TBAF (tetrabutylammonium fluoride), NBD-Cl and mesoporous silica-supported NBD-Cl
As shown in FIG. 3, TBAF only has an absorption peak in the range of 200 nm-250 nm, NBD-Cl only has an absorption peak in the range of 200 nm-400 nm, no NBD-Cl-loaded mesoporous silica has an absorption peak in the range of 200 nm-800 nm, NBD-Cl-loaded mesoporous silica has an absorption peak in the range of 460 nm-540 nm, and the maximum absorption peak is around 470 nm. Analysis of the above four curves in the figure shows that the absorption peak in curve 4 is due to loading of NBD-Cl onto the surface of mesoporous silica, and is not the absorption peak of pure NBD-Cl or mesoporous silica itself, which indicates that the mesoporous silica is successfully loaded with NBD-Cl.
(3) Infrared spectrum change before and after loading of mesoporous silica with NBD-Cl
As can be seen from FIG. 4, the mesoporous silica material before loading is 1055 cm-1The antisymmetric stretching vibration absorption peak of Si-O-Si appears, 769 cm-1And 464 cm-1The absorption peaks of the symmetric stretching vibration and the bending vibration of Si-O-Si are respectively positioned; 3200 cm-1And 3552 cm-1The strong absorption peak in between is the stretching vibration of the amino group and is related to the water in the sample, 1550 cm-1And 1662 cm-1The peak is the bending vibration absorption peak of amino and water, 2935 cm-1The peak is the stretching vibration absorption peak of methylene in an APTES chain, and is 620 cm-1And (3) plane swinging vibration of methylene. Compared with the spectrogram before loading, the methylene stretching vibration absorption peak in the spectrogram after loading is shifted to 2941 cm-1Here, the bending vibration absorption peak of the amino group was shifted to 1407c cm-1And the three absorption peak patterns of the Si-O-Si are changed, which is caused by the reaction of NBD-Cl and amino, and indicates that the NBD-Cl is successfully loaded on the mesoporous silicon oxide.
(4) Thermal stability of mesoporous silica before and after loading of NBD-Cl
A certain amount of samples before and after loading NBD-Cl are respectively taken, and the temperature is raised from room temperature to 700 ℃ at the temperature raising rate of 10 ℃/min under the protection of nitrogen for thermogravimetric analysis, as shown in figure 5. As can be seen from the TG curve in the figure, the sample before loading has the weight loss of 35.7 percent and the sample after loading has the weight loss of 34 percent in the range of 25-700 ℃. The weight loss of the sample at the temperature of less than 100 ℃ is caused by the moisture in the sample, the weight loss of the sample before loading is 8.6%, and the weight loss of the sample after loading is 3.3%, which indicates that the water content of the sample before loading is much more than that of the sample after loading, probably because the surface of the sample before loading is provided with a large amount of hydroxyl and amino, part of water molecules form hydrogen bonds with the hydroxyl and amino, and the surface of the sample after loading is reduced in amino due to the reaction of part of amino and NBD-Cl, so the water content is less, and the successful loading of NBD-Cl can be indicated to a certain extent. In the range of 100-700 ℃, the sample before loading loses 26.9 percent of weight, and only has a step at 550 ℃, which is caused by the thermal decomposition of APTES connected with the surface of the mesoporous silica; compared with the curve before loading, the sample after loading has weight loss of 30.7 percent, the weight loss is more than that of the sample before loading, and the sample after loading has two steps which are respectively at the temperature of 250-350 ℃ and the temperature of 500-600 ℃, the former step is caused by thermal decomposition of NBD-Cl, and the latter step is caused by thermal decomposition of APTES. The thermal decomposition temperature of NBD-Cl is higher than that of pure NBD-Cl, and the decomposition temperature of APTES of the loaded sample changes due to the reaction of NBD-Cl and amino groups in APTES, which can further indicate that NBD-Cl is successfully loaded on the surface of the mesoporous silica.
(5) Fluorescence detection of fluorine ion fluorescence detection material based on mesoporous silica on fluorine ions with different concentrations
The prepared fluorescence detection sample solution 40. mu.L of 0.1 g/L is measured by a pipette and put into 17 numbered centrifuge tubes, and TBAF solution (25 mM) 0. mu.L, 10. mu.L, 15. mu.L, 20. mu.L, 30. mu.L, 40. mu.L, 55. mu.L, 75. mu.L, 100. mu.L, 150. mu.L, 300. mu.L, 400. mu.L, 450. mu.L, 480. mu.L, 500. mu.L, 600. mu.L and 650. mu.L are added into centrifuge tubes from No. 1 to No. 17, and the volume is adjusted to 4 mL by absolute ethyl alcohol.
The sensitivity of the prepared fluorescent detection material to the detection of fluorine ions was studied by fluorescence titration, and the experimental results are shown in fig. 6. When the fluorine ion concentration is increased to 3.125 mM, the fluorescence intensity reaches the maximum value 447, the enhancement effect can reach about 6 times of the fluorescence intensity of the material, the fluorine ion concentration is continuously increased, and the fluorescence intensity is hardly changed. As can be seen from FIG. 7, when the fluorine ion concentration is in the range of 0.0625-0.125 mM, there is a certain linear relationship between the fluorescence intensity and the fluorine ion concentration, and it can be seen that the response range of the material to fluorine ions is 0.0625-3.125 mM, the limit of the material to fluorine ion detection is 4.39 μ M as can be found by the formula 3 σ/s, where σ is the standard deviation of the blank sample and s is the slope of the curve of the inset in FIG. 7.
(6) The fluorescent material can detect fluorine ions under different water contents
40. mu.L of a fluorescence detection sample solution (0.1 g/L) and 500. mu.L of a TBAF solution (25 mM) were added to 16 numbered centrifuge tubes, and 0. mu.L, 10. mu.L, 20. mu.L, 30. mu.L, 40. mu.L, 60. mu.L, 80. mu.L, 100. mu.L, 200. mu.L, 300. mu.L, 400. mu.L, 600. mu.L, 1000. mu.L, 2000. mu.L, 3000. mu.L and 3500. mu.L of deionized water were added to test tubes No. 1 to 16, respectively, and the volume was adjusted to 4 mL with absolute ethanol.
The influence of water on the detection performance of the material was investigated by fluorescence titration, and the results are shown in fig. 8 and 9. When the water content is less than 1%, the fluorine ions do not greatly influence the fluorescence enhancement performance of the material, the fluorescence intensity changes little, when the water content is more than 1%, the fluorescence intensity gradually weakens along with the increase of the water content, and when the water content exceeds 75%, the fluorescence intensity is almost the same as the fluorescence intensity of the material without the fluorine ions. From the above analysis, the performance of the material for detecting fluorine ions is greatly influenced by water, and the detection of the fluorine ions should be carried out in an environment with the water content of less than 1% or a pure organic solvent.
(7) Selective test of fluorine ion fluorescence detection material based on mesoporous silica
40 mul of the prepared sample 5 solution (0.1 g/L) was added to 10 numbered centrifuge tubes, 40 mul of deionized water was added to centrifuge tube 1, 500 mul of TBAF solution (25 mM) and 40 mul of deionized water were added to centrifuge tube 2, 40 mul of aqueous sodium fluoride solution, 40 mul of aqueous sodium chloride solution, 40 mul of aqueous sodium bromide solution, 40 mul of aqueous sodium iodide solution, 40 mul of aqueous sodium dihydrogen phosphate solution, 40 mul of aqueous disodium hydrogen phosphate solution, 40 mul of aqueous sodium carbonate solution, 40 mul of aqueous anhydrous sodium acetate solution, and the volume was adjusted to 4 mL with anhydrous ethanol.
The results of the selectivity test of the material on various anions are shown in fig. 10, when organic fluoride ions are added, the fluorescence of the material is enhanced most, when inorganic fluoride salt is added, the fluorescence of the material is also enhanced to a greater extent, and other anions Cl are added-、Br-、I-、H2PO4-、HPO4 2-、CO3 2-、CH3COO-The change in fluorescence intensity was slight. It can be seen from fig. 10 that the fluorescence intensity of the solution with the added fluoride ion is changed greatly, and the fluorescence intensity of the solution with the added organic fluoride ion is changed greatly more than that of the solution with the added inorganic fluoride ion, which should be the reason that the solubility of the inorganic salt NaF in the ethanol solution is lower than that of the organic fluoride TBAF. As can be seen from the above analysis, the material has good selectivity for detecting fluorine ions.
(8) Anti-interference test of fluorine ion fluorescence detection material based on mesoporous silica
To 10 numbered centrifuge tubes, 40. mu.L of a test sample solution (25 mM) was added, 40. mu.L of deionized water was added to centrifuge tube No. 1, and then 40. mu.L of an aqueous sodium chloride solution, 40. mu.L of an aqueous sodium bromide solution, 40. mu.L of an aqueous sodium iodide solution, 40. mu.L of an aqueous sodium dihydrogen phosphate solution, 40. mu.L of an aqueous disodium hydrogen phosphate solution, 40. mu.L of an aqueous sodium carbonate solution, 40. mu.L of an aqueous anhydrous sodium acetate solution, 40. mu.L of an aqueous sodium fluoride solution were added, and a volume of 4 mL was made up with anhydrous ethanol. Then 500. mu.L of TBAF solution (25 mM) was added to each of No. 2 to No. 10 centrifuge tubes, and the fluorescence intensity of the solution in each centrifuge tube was measured with a fluorescence spectrophotometer to obtain a fluorescence spectrum.
The results of the interference selectivity experiments are shown in fig. 11 and 12. As can be seen from the figure, under the condition of the existence of different interfering ions, the fluorescence intensity is greatly enhanced as long as the fluoride ions exist, and the fluorescence intensity of each solution is not greatly different, which shows that the fluorescence enhancement is mainly caused by the fluoride ions and is not greatly influenced by other anions, and further shows that the material has single selectivity on the detection of the fluoride ions and anti-interference performance on other anions.
In summary, the invention provides a fluorine ion fluorescence detection material and a preparation method thereof, wherein NBD-Cl is modified on the surface of amino modified mesoporous silica to prepare the fluorine ion fluorescence detection material. The preparation method is simple, and the mesoporous silica particle matrix has the advantages of no toxicity, good biocompatibility, large specific surface area, stable chemical property, easy surface modification and the like, so that the fluorine ion fluorescence detection material has good stability and dispersibility, can be repeatedly utilized, and can realize rapid qualitative and quantitative test of pollutants in the fields of environmental engineering, analysis and detection and the like. The separation and purification process of the invention adopts simple washing and centrifugal separation, and overcomes the problems of more complex purification work and more toxicity of a plurality of organic reagents in the traditional design and synthesis based on organic high polymer materials.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a fluorine ion fluorescence detection material is characterized by comprising the following steps: preparing amino modified mesoporous silica, and then modifying NBD-Cl on the surface of the amino modified mesoporous silica to obtain a fluorine ion fluorescent detection material;
the preparation method of the amino modified mesoporous silica comprises the following steps:
dispersing a surfactant in a cosolvent, adding ammonia water, uniformly mixing, adding a mixture of ethyl orthosilicate and 3-aminopropyltriethoxysilane, stirring for reaction for 3-5 hours, and then carrying out separation treatment to obtain a white powdery solid;
b, dispersing the white powdery solid into a mixed solvent of absolute ethyl alcohol and hydrochloric acid, stirring and reacting for 20-30h at the temperature of 60-90 ℃, and separating to obtain amino modified mesoporous silica; the mesoporous silica is composed of spherical nano particles, and the spherical nano particles are provided with a plurality of radial pore channels;
the step of modifying NBD-Cl on the surface of the amino modified mesoporous silica specifically comprises the following steps: dispersing the amino modified mesoporous silica in an organic solvent, adding NBD-Cl under the stirring condition, carrying out reflux reaction for 10-20h at the temperature of 60-90 ℃, and then carrying out separation treatment to obtain the fluorine ion fluorescence detection material.
2. The method for preparing the fluoride ion fluorescence detection material according to claim 1, wherein in the step A, the concentration of the surfactant is 4-6 g/L.
3. The method for preparing a fluorescent detection material for fluorine ions according to claim 1, wherein in the step a, the mixture of tetraethoxysilane and 3-aminopropyltriethoxysilane accounts for 2-8% by volume of the whole reaction system.
4. The method for preparing a fluorescent detection material for fluorine ions according to claim 1, wherein in the step a, the ratio of the amounts of the substance of tetraethoxysilane and 3-aminopropyltriethoxysilane is 1-5: 1.
5. the method for preparing the fluoride ion fluorescence detection material of claim 1, wherein in the step A, the cosolvent is a mixed solvent of deionized water, diethyl ether and ethanol.
6. The method for preparing a fluorine ion fluorescence detection material according to claim 1, wherein the conditions for terminating the reflux reaction are as follows: the reaction solution turned from an initial yellow-brown color to a greenish-black color.
7. A fluorine ion fluorescence detection material, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. The fluoride ion fluorescence detection material of claim 7, wherein the mesoporous silica is composed of spherical nanoparticles having a plurality of radial pores.
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