CN110643354B - Preparation method and application of tetraphenylethylene derivative/rare earth nanoparticle composite material for identifying variable-valence chromium ions - Google Patents
Preparation method and application of tetraphenylethylene derivative/rare earth nanoparticle composite material for identifying variable-valence chromium ions Download PDFInfo
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Abstract
The invention relates to the technical field of tetraphenyl ethylene derivative fluorescent probes, in particular to a preparation method and application of a tetraphenyl ethylene derivative/rare earth nanoparticle composite material for identifying variable valence chromium ions. The method comprises the following steps: 1) slowly dripping (4- (1,2, 2-triphenylvinyl) phenyl) boric acid dimethyl sulfoxide solution into polyvinyl alcohol dimethyl sulfoxide solution, and refluxing to obtain a tetraphenylethylene derivative modified polyvinyl alcohol ligand solution; 2) adding a dimethyl sulfoxide solution containing rare earth terbium (III) salt and rare earth europium (III) salt into the ligand solution obtained in the step 1), then adding a dimethyl sulfoxide solution of sodium fluoride, and then adding dimethyl sulfoxide to obtain a mixed reaction solution; 3) and (3) reacting the mixed reaction solution under a closed condition, separating a solid product in the reaction solution, and washing to obtain the catalyst. The tetraphenylethylene derivative/rare earth nanoparticle composite material provided by the invention can be used for simply, conveniently and efficiently identifying chromium ions with different valence states.
Description
Technical Field
The invention relates to the technical field of tetraphenyl ethylene derivative fluorescent probes, in particular to preparation and application of a tetraphenyl ethylene derivative/rare earth nanoparticle composite material capable of being used for identifying trivalent and hexavalent chromium ions.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
The tetraphenylethylene derivative has unique Aggregation Induced Emission (AIE) characteristics and has important application value in the aspects of fluorescent probes, photoelectric devices and the like. At present, aiming at the problem that the luminescent color of the material is single, rare earth nanoparticles with excellent optical properties are selected to be used as a carrier to fix one end of the tetraphenylethylene derivative so that the intramolecular rotation of the tetraphenylethylene derivative is limited, and the energy transfer effect between the tetraphenylethylene derivative and the rare earth nanoparticles is further utilized to change the luminescent property of the material, so that the method is a novel method for regulating and controlling the luminescent color of the tetraphenylethylene derivative modified composite material. Patent document 201810272607.3 discloses a method for preparing a tetraphenylethylene derivative-modified rare earth nanowire useful for organic carboxylic acid detection. The method comprises the steps of preparing a tetraphenylethylene derivative with one end connected with two carboxyl groups on a benzene ring through organic synthesis reaction, and then fixing the carboxyl groups of the tetraphenylethylene derivative on the surface of a nanowire through electrostatic action by modifying a rare earth nanowire coated with PSS, so that the rotation of the benzene ring molecule is limited to generate fluorescence.
Fluorescent probes based on tetraphenyl ethylene derivatives are widely applied to the field of metal ion identification, but the inventor researches and discovers that: the recognition of different valence states of the same metal element by such materials has been rarely studied. For metal chromium ions, trivalent chromium ions have small harm to human bodies and the environment, but hexavalent chromium ions have strong toxicity to human bodies and have lasting danger to the environment, the identification method is usually a dibenzoyl dihydrazide spectrophotometry, the operation is complicated, and therefore, the research on how to identify chromium ions with different valence states by using a novel fluorescent probe simply, conveniently and efficiently needs to be urgently carried out.
Disclosure of Invention
The technical problem to be solved/realized by the invention is that: the fluorescent probe can detect chromium ions with different valence states and has a simple preparation process. Therefore, the invention provides a preparation method of a tetraphenyl ethylene derivative/rare earth nanoparticle composite material for identifying variable-valence chromium ions.
In order to realize the purpose, the invention discloses the following technical scheme:
the preparation method of the tetraphenyl ethylene derivative/rare earth nano particle composite material for identifying variable valence chromium ions comprises the following steps:
(1) slowly dripping a (4- (1,2, 2-triphenylvinyl) phenyl) boric acid dimethyl sulfoxide solution into a polyvinyl alcohol dimethyl sulfoxide solution, and refluxing to obtain a polyvinyl alcohol ligand solution modified with a tetraphenylethylene derivative;
(2) adding a dimethyl sulfoxide solution containing a rare earth terbium (III) salt and a rare earth europium (III) salt into the ligand solution obtained in the step (1), then adding a dimethyl sulfoxide solution of sodium fluoride, and then adding dimethyl sulfoxide to obtain a mixed reaction solution;
(3) and (3) reacting the mixed reaction solution under a closed condition, separating a solid product in the reaction solution, and washing to obtain the tetraphenylethylene derivative-rare earth nanoparticle composite material.
One of the characteristics of the composite material prepared by the invention is as follows: the B-OH functional group of the tetraphenylethylene derivative and the-OH functional group of the polyvinyl alcohol are bonded together by a covalent bond through a condensation dehydration reaction, and are further used as a coating ligand to synthesize the rare earth europium (III) and terbium (III) ion codoped nano particle, because one end of the ligand is fixed on the surface of the rare earth nano particle, the intramolecular rotation of a benzene ring is limited, aggregation induced luminescence is generated, and because an energy transfer process exists between the tetraphenylethylene derivative and the terbium (III) ion, the terbium (III) ion further transfers energy with the europium (III) ion; and the luminous color of the system can be regulated and controlled by adjusting the ratio of the three components.
The basic principle of identifying the variable valence chromium ions by the composite material prepared by the invention is as follows: the oxidant of dichromate containing hexavalent chromium ions can destroy a C-B bond between a benzene ring and a boron atom in the tetraphenylethylene derivative to convert the tetraphenylethylene derivative into a C-OH bond, so that the tetraphenylethylene derivative fixed on polyvinyl alcohol is separated from the surface of the nano-particles, the rotation of the benzene ring molecule is not limited any more, the fluorescence intensity is obviously reduced, a compound of trivalent chromium ions is added under the system, the chromium (III) salt is not a strong oxidant, the structure of the composite nano-particles is kept unchanged, and the emission spectrum is basically unchanged, so that the identification/detection of trivalent and hexavalent chromium ions is realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) the light-emitting color of the tetraphenyl ethylene derivative/rare earth nanoparticle composite material provided by the invention can be regulated, and chromium ions with different valence states can be simply, conveniently and efficiently identified. The method not only utilizes the property of aggregation-induced luminescence of the tetraphenylethylene derivative, but also utilizes the energy transfer effect between the derivative and rare earth ions. The combination of the tetraphenylethylene derivative and the rare earth nano material not only solves the problem that the luminescence of the tetraphenylethylene derivative is mostly limited to blue light, but also solves the problem that the luminescence intensity is low when rare earth ions exist alone under the condition of lacking a sensitizer.
(2) In the aspect of response to chromium ions, different valence states of the chromium ions cannot be identified by an element analysis method such as an inductively coupled plasma emission spectrum, and the hexavalent chromium ions can be identified by a diphenylcarbazide spectrophotometry method but the operation is complicated.
(3) The preparation method is simple, short in reaction time, mild in reaction condition, high in detection efficiency, strong in practicability and easy to popularize.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows the fluorescence spectra and 1931CIE chromaticity diagram (excitation wavelength: 365nm) of the tetraphenylethylene derivative/rare earth nanoparticle composites of examples 1-4 of the present invention, in which the molar ratios of terbium ion (III) and europium ion (III) are different.
FIG. 2 is a fluorescence spectrum (excitation wavelength 365nm) of a tetraphenylethylene derivative/rare earth nanoparticle composite material obtained after dropwise adding chromium trichloride (0.001moL/L) in example 1 of the present invention.
FIG. 3 is a fluorescence spectrum (excitation wavelength: 365nm) of a tetraphenylethylene derivative/rare earth nanoparticle composite material after potassium dichromate (0.001moL/L) was added dropwise in example 1 of the present invention.
FIG. 4 is a preparation method and an ion recognition mechanism of a tetraphenylethylene derivative/rare earth nanoparticle composite material in an embodiment of the invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms also are intended to include the plural forms as well, unless the context clearly indicates otherwise, and it should be further understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
As mentioned above, hexavalent chromium ions are extremely toxic to human body and have a long-lasting risk to the environment, and the existing identification method is generally a dibenzoyl dihydrazide spectrophotometry, but the operation of the method is complicated. Therefore, the invention provides a preparation method of the tetraphenyl ethylene derivative/rare earth nanoparticle composite material for identifying variable valence chromium ions.
In some embodiments of the method, in step (1), the mass ratio of the (4- (1,2, 2-triphenylvinyl) phenyl), the polyvinyl alcohol and the dimethyl sulfoxide is 1.0: (2.70-6.76): 297.7.
in some examples of the method, in the step (1), the polyvinyl alcohol is any one selected from the group consisting of PVA-117 (viscosity: 25 to 31 mPas), PVA-124 (viscosity: 54 to 66 mPas), PVA-217 (viscosity: 20.5 to 24.5 mPas) and PVA-224 (viscosity: 40 to 48 mPas) available from Colorado, Japan.
In some embodiments of the method, in step (1), the refluxing conditions are: refluxing for 1-5 hours at 50-80 ℃.
In some embodiments of the method, in step (2), the rare earth europium salt is any one or more of europium (III) chloride, europium (III) nitrate, and europium (III) acetate.
In some embodiments of the method, in step (2), the rare earth terbium salt is any one or more of terbium (iii) chloride, terbium (iii) nitrate and terbium (iii) acetate.
In some embodiments of the method, in step (2), the addition molar ratios of the tetraphenylethylene derivative, the rare earth terbium salt, the rare earth europium salt, the sodium fluoride and the dimethyl sulfoxide in the ligand solution are, in order: (1.47X 10) -3 -4.92×10 -3 ):1.0：(5.9×10 -4 -1.0×10 -3 ):3.2：704.0。
In some embodiments of the method, in the step (3), the reaction temperature is 50 to 80 ℃ and the reaction time is 5 to 10 hours.
In some embodiments, the method and/or the tetraphenyl ethylene derivative/rare earth nanoparticle composite material prepared by the method, which can identify valence-variable chromium ions, are used in the environmental field, such as detection of chromium ions in sewage and the like.
The invention will now be further described with reference to specific embodiments.
Example 1
A preparation method of tetraphenyl ethylene derivative/rare earth nano particle composite material for identifying variable valence chromium ions comprises the following steps:
1. and (2) synthesis of a tetraphenylethylene derivative modified polyvinyl alcohol ligand:
(1) 0.037g of (4- (1,2, 2-triphenylvinyl) phenyl) boric acid is dissolved in 2.0mL of dimethyl sulfoxide, 0.1g of polyvinyl alcohol PVA-124 is dissolved in 8.0mL of dimethyl sulfoxide solution, and then the solution containing the tetraphenylethylene derivative is slowly dripped into the solution containing the polyvinyl alcohol;
(2) refluxing at 50 deg.C for 5 hr to obtain modified tetraphenylethylene derivative polyvinyl alcohol ligand solution;
2. and (2) synthesizing the tetraphenylethylene derivative modified rare earth nanoparticles:
(1) adding 1.0mL of terbium (III) chloride dimethyl sulfoxide solution with the concentration of 0.1mol/L and 0.059mL of europium (III) chloride dimethyl sulfoxide solution with the concentration of 1.0 mu mol/L into 0.05mL of the ligand solution respectively;
(2) then dropwise adding 1.0mL of dimethyl sulfoxide solution of sodium fluoride with the concentration of 0.32 mol/L;
(3) then adding 2.90mL of dimethyl sulfoxide;
(4) uniformly stirring the solution and transferring the solution into a reaction kettle with the volume of 15mL and the lining of polytetrafluoroethylene;
(5) then placing the reaction kettle into an oven with the temperature of 80 ℃, and keeping for 5 hours under a static condition;
(6) and (3) centrifugally separating out a solid product, and washing the solid product with deionized water and dimethyl sulfoxide three times respectively to obtain the tetraphenylethylene derivative modified rare earth nanoparticles.
3. The regulation and control of the luminescence property of the tetraphenylethylene derivative modified rare earth nanoparticles are as follows:
(1) dispersing the tetraphenylethylene derivative modified rare earth nanoparticles obtained in the step (6) in 1.0mL of dimethyl sulfoxide, and taking 0.5mL of dimethyl sulfoxide solution; the emission spectrum is detected under the excitation wavelength of 365nm, as shown in the line A of figure 1, a series of emission peaks which are assigned to tetraphenylethylene derivatives (about 460 nm) and rare earth ions are obtained, and due to the existence of an efficient energy transfer process among the tetraphenylethylene derivatives, terbium (III) ions and europium (III) ions, the intensity of the emission peaks of the rare earth ions is enhanced, and the 1931CIE color coordinate is (0.1854, 0.2176).
4. Identification of chromium ions with different valence states:
(1) taking 0.5mL of the tetraphenylethylene-modified rare earth nanoparticles obtained in the step 3, dispersing into 2.0mL of dimethyl sulfoxide, and detecting the emission spectrum of the tetraphenylethylene-modified rare earth nanoparticles under the excitation wavelength of 365 nm;
(2) chromium (III) trichloride and sodium dichromate compound solutions with the concentration of 0.001mol/L are respectively prepared (the volume ratio of dimethyl sulfoxide to water is 5000/1), and then the two solutions are respectively dropwise added into the nanoparticle solution, wherein the dropwise adding amount is 0mL, 0.01mL, 0.05mL, 0.1mL, 0.2mL and 0.5mL, as shown in figures 2 and 3, the addition of chromium (III) nitrate does not cause obvious change of an emission spectrum, the luminescent color is kept, and the addition of sodium dichromate causes obvious reduction of the fluorescence intensity at 460 nm. The reason is that the oxidant, bichromate containing hexavalent chromium ions, can destroy the C-B bond between benzene ring and boron atom in the tetraphenylethylene derivative to convert the tetraphenylethylene derivative into a C-OH bond, so that the tetraphenylethylene derivative fixed on polyvinyl alcohol is separated from the surface of the nano particles, the rotation of benzene ring molecules is not limited any more, the fluorescence intensity is obviously reduced, while the trivalent chromium ion compound is added under the system, the chromium (III) salt is not a strong oxidant, the structure of the composite nano particles is kept unchanged, and the emission spectrum is basically unchanged, so that the identification/detection of trivalent and hexavalent chromium ions is realized, and the reaction mechanism is shown in figure 4.
Example 2
A preparation method of tetraphenyl ethylene derivative/rare earth nano particle composite material for identifying variable valence chromium ions comprises the following steps:
1. and (2) synthesis of a tetraphenylethylene derivative modified polyvinyl alcohol ligand:
(1) 0.037g of (4- (1,2, 2-triphenylvinyl) phenyl) boric acid is dissolved in 2.0mL of dimethyl sulfoxide, 0.15g of polyvinyl alcohol PVA-224 is dissolved in 8.0mL of dimethyl sulfoxide solution, and then the solution containing the tetraphenylethylene derivative is slowly dripped into the solution containing the polyvinyl alcohol;
(2) refluxing for 1 hour at 80 ℃ to obtain a polyvinyl alcohol ligand solution of the tetraphenylethylene derivative modified by hydroxyl;
2. and (2) synthesizing the tetraphenylethylene derivative modified rare earth nanoparticles:
(1) adding 1.0mL of terbium (III) chloride dimethyl sulfoxide solution with the concentration of 0.1mol/L and 0.1mL of europium (III) chloride dimethyl sulfoxide solution with the concentration of 1.0 mu mol/L into 0.05mL of the solution respectively;
(2) then dropwise adding 1.0mL of dimethyl sulfoxide solution of sodium fluoride with the concentration of 0.32 mol/L;
(3) then 2.85mL of dimethyl sulfoxide is added;
(4) uniformly stirring the solution and transferring the solution into a reaction kettle with the volume of 15mL and the lining of polytetrafluoroethylene;
(5) then placing the reaction kettle into a drying oven at 50 ℃, and keeping for 10 hours under a static condition;
(6) and (3) centrifugally separating out a solid product, and washing the solid product with deionized water and dimethyl sulfoxide for three times respectively to obtain the tetraphenylethylene derivative modified rare earth nanoparticles.
3. The regulation and control of the luminescence property of the tetraphenylethylene derivative modified rare earth nanoparticles are as follows:
(1) dispersing the tetraphenylethylene derivative modified rare earth nanoparticles obtained in the step (6) in 1.0mL of dimethyl sulfoxide, and taking 0.5mL of dimethyl sulfoxide solution; the emission spectrum is detected under the excitation wavelength of 365nm, as shown by a line B in figure 1, a series of emission peaks which are assigned to tetraphenylethylene derivatives (about 460 nm) and rare earth ions are obtained, and due to the existence of an efficient energy transfer process among the tetraphenylethylene derivatives, terbium (III) ions and europium (III) ions, the intensity of the emission peaks of the rare earth ions is enhanced, and the 1931CIE color coordinates are (0.2305, 0.2464).
4. Identification of chromium ions in different valence states:
(1) taking 0.5mL of the tetraphenylethylene-modified rare earth nanoparticles obtained in the step 3, dispersing into 2.0mL of dimethyl sulfoxide, and detecting the emission spectrum of the tetraphenylethylene-modified rare earth nanoparticles under the excitation wavelength of 365 nm;
(2) chromium trichloride and sodium dichromate compound solutions with the concentration of 0.001mol/L are respectively prepared (the volume ratio of dimethyl sulfoxide to water is 5000/1), then the two solutions are respectively dripped into a nanoparticle solution, the dripping amount is 0.01mL, 0.05mL, 0.1mL, 0.2mL and 0.5mL, the obvious change of an emission spectrum is not caused by the addition of the chromium trichloride, the luminescent color is kept, and the fluorescence intensity at 460nm is obviously reduced by the addition of the sodium dichromate.
Example 3
A preparation method of tetraphenyl ethylene derivative/rare earth nano particle composite material for identifying variable valence chromium ions comprises the following steps:
1. and (2) synthesis of a tetraphenylethylene derivative modified polyvinyl alcohol ligand:
(1) 0.037g of (4- (1,2, 2-triphenylvinyl) phenyl) boric acid was dissolved in 2.0mL of dimethyl sulfoxide, 0.2g of polyvinyl alcohol PVA-117 was dissolved in 8.0mL of the dimethyl sulfoxide solution, and then a solution containing a tetraphenylethylene derivative was slowly dropped into the solution containing polyvinyl alcohol;
(2) refluxing for 3 hours at 70 ℃ to obtain a polyvinyl alcohol ligand solution of the tetraphenylethylene derivative modified by hydroxyl;
2. and (2) synthesizing the tetraphenylethylene derivative modified rare earth nanoparticles:
(1) adding 1.0mL of terbium (III) nitrate dimethyl sulfoxide solution with the concentration of 0.1mol/L and 0.059mL of europium (III) nitrate dimethyl sulfoxide solution with the concentration of 1.0 mu mol/L into 0.02mL of the solution respectively;
(2) then dropwise adding 1.0mL of dimethyl sulfoxide solution of sodium fluoride with the concentration of 0.32 mol/L;
(3) then 2.92mL of dimethyl sulfoxide is added;
(4) uniformly stirring the solution and transferring the solution into a reaction kettle with the volume of 15mL and the lining of polytetrafluoroethylene;
(5) then, the reaction kettle is placed into a 75 ℃ oven and kept for 5 hours under a static condition;
(6) and (3) centrifugally separating out a solid product, and washing the solid product with deionized water and dimethyl sulfoxide for three times respectively to obtain the tetraphenylethylene derivative modified rare earth nanoparticles.
3. The regulation and control of the luminescence property of the tetraphenylethylene derivative modified rare earth nanoparticles are as follows:
(1) dispersing the tetraphenylethylene derivative modified rare earth nanoparticles obtained in the step (6) in 0.5mL of dimethyl sulfoxide, and taking 2.0mL of dimethyl sulfoxide solution; detecting the emission spectrum under the excitation wavelength of 365nm, and obtaining a series of emission peaks which are assigned as tetraphenylethylene derivatives (about 460 nm) and rare earth ions as shown by a line C in figure 1, wherein the emission peaks of the rare earth ions are enhanced due to the efficient energy transfer process among the tetraphenylethylene derivatives, terbium (III) ions and europium (III) ions, and the 1931CIE color coordinates are (0.2738, 0.2870);
4. identification of chromium ions in different valence states:
(1) taking 0.5mL of the tetraphenylethylene-modified rare earth nanoparticles obtained in the step 3, dispersing into 2.0mL of dimethyl sulfoxide, and detecting the emission spectrum of the tetraphenylethylene-modified rare earth nanoparticles under the excitation wavelength of 365 nm;
(2) chromium trichloride and potassium dichromate compound solutions with the concentration of 0.001mol/L are respectively prepared (the volume ratio of dimethyl sulfoxide to water is 5000/1), then the two solutions are respectively dripped into the nanoparticle solution, the dripping amount is 0.01mL, 0.05mL, 0.1mL, 0.2mL and 0.5mL, the addition of the chromium trichloride does not cause obvious change of an emission spectrum, the luminescent color is kept, and the addition of the potassium dichromate obviously reduces the fluorescence intensity at 460 nm.
Example 4
A preparation method of tetraphenyl ethylene derivative/rare earth nano particle composite material for identifying variable valence chromium ions comprises the following steps:
1. and (2) synthesis of a tetraphenylethylene derivative modified polyvinyl alcohol ligand:
(1) 0.037g of (4- (1,2, 2-triphenylvinyl) phenyl) boric acid was dissolved in 2.0mL of dimethyl sulfoxide, 0.25g of polyvinyl alcohol PVA-217 was dissolved in 8.0mL of the dimethyl sulfoxide solution, and then a solution containing a tetraphenylethylene derivative was slowly dropped into the solution containing polyvinyl alcohol;
(2) refluxing for 3 hours at 70 ℃ to obtain a polyvinyl alcohol ligand solution of the tetraphenylethylene derivative modified by hydroxyl;
2. and (2) synthesizing the tetraphenylethylene derivative modified rare earth nanoparticles:
(1) adding 1.0mL of terbium (III) nitrate dimethyl sulfoxide solution with the concentration of 0.1mol/L and 0.059mL of europium (III) nitrate dimethyl sulfoxide solution with the concentration of 1 mu mol/L into 0.015mL of the solution respectively;
(2) then dropwise adding 1.0mL of dimethyl sulfoxide solution of sodium fluoride with the concentration of 0.32 mol/L;
(3) then 2.93mL of dimethyl sulfoxide is added;
(4) uniformly stirring the solution and transferring the solution into a reaction kettle with the volume of 15mL and the lining of polytetrafluoroethylene;
(5) then putting the reaction kettle into a 75 ℃ oven, and keeping for 6 hours under a static condition;
(6) and (3) centrifugally separating out a solid product, and washing the solid product with deionized water and dimethyl sulfoxide for three times respectively to obtain the tetraphenylethylene derivative modified rare earth nanoparticles.
3. The regulation and control of the luminescence property of the tetraphenylethylene derivative modified rare earth nanoparticles are as follows:
(1) dispersing the tetraphenylethylene derivative modified rare earth nanoparticles obtained in the step (6) in 0.5mL of dimethyl sulfoxide, and taking 2.0mL of dimethyl sulfoxide solution; detecting the emission spectrum under the excitation wavelength of 365nm, and obtaining a series of emission peaks which are attributed to tetraphenylethylene derivatives (about 460 nm) and rare earth ions as shown by a line D in figure 1, wherein the emission peak intensity of the rare earth ions is enhanced due to the efficient energy transfer process among the tetraphenylethylene derivatives, terbium (III) ions and europium (III) ions, and the 1931CIE color coordinate is (0.3291, 0.3475);
4. identification of chromium ions with different valence states:
(1) taking 0.5mL of the tetraphenylethylene-modified rare earth nanoparticles obtained in the step 3, dispersing into 2.0mL of dimethyl sulfoxide, and detecting the emission spectrum of the tetraphenylethylene-modified rare earth nanoparticles under the excitation wavelength of 365 nm;
(2) chromium trichloride and potassium dichromate compound solutions with the concentration of 0.001mol/L are respectively prepared (the volume ratio of dimethyl sulfoxide to water is 5000/1), then the two solutions are respectively dripped into the nanoparticle solution, the dripping amount is 0.01mL, 0.05mL, 0.1mL, 0.2mL and 0.5mL, the addition of the chromium trichloride does not cause obvious change of an emission spectrum, the luminescent color is kept, and the addition of the potassium dichromate obviously reduces the fluorescence intensity at 460 nm.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the tetraphenyl ethylene derivative/rare earth nano particle composite material for identifying variable valence chromium ions is characterized by comprising the following steps:
(1) slowly dripping a (4- (1,2, 2-triphenylvinyl) phenyl) boric acid dimethyl sulfoxide solution into a polyvinyl alcohol dimethyl sulfoxide solution, and refluxing to obtain a polyvinyl alcohol ligand solution modified with a tetraphenylethylene derivative;
(2) adding a dimethyl sulfoxide solution containing rare earth terbium (III) salt and rare earth europium (III) salt into the ligand solution obtained in the step (1), then adding a dimethyl sulfoxide solution of sodium fluoride, and then adding dimethyl sulfoxide to obtain a mixed reaction solution;
(3) and (3) reacting the mixed reaction solution under a closed condition, separating a solid product in the reaction solution, and washing to obtain the catalyst.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the (4- (1,2, 2-triphenylvinyl) phenyl) boric acid to the polyvinyl alcohol to the dimethyl sulfoxide is 1.0: (2.70-6.76): 297.7.
3. the method according to claim 1, wherein in the step (1), the polyvinyl alcohol is any one selected from the group consisting of PVA-117, PVA-124, PVA-217 and PVA-224 manufactured by Coly, Japan.
4. The method according to claim 3, wherein the PVA-117 has a viscosity of 25 to 31mPa s; the viscosity of the PVA-124 is 54-66 mPa & s; the viscosity of the PVA-217 is 20.5-24.5 mPa & s; the viscosity of the PVA-224 is 40-48 mPas.
5. The method according to claim 1, wherein in the step (1), the reflux conditions are: refluxing for 1-5 hours at 50-80 ℃.
6. The production method according to claim 1, wherein in step (2), the addition molar ratios of the tetraphenylethylene derivative, the rare earth terbium salt, the rare earth europium salt, the sodium fluoride, and the dimethyl sulfoxide in the ligand solution are, in order: (1.47X 10) -3 -4.92×10 -3 ):1.0：(5.9×10 -4 -1.0×10 -3 ):3.2：704.0。
7. The method according to claim 1, wherein in the step (3), the reaction temperature is 50 to 80 ℃ and the reaction time is 5 to 10 hours.
8. The production method according to any one of claims 1 to 7, wherein in step (2), the rare earth europium salt is any one or more of europium (III) chloride, europium (III) nitrate, and europium (III) acetate.
9. The method according to any one of claims 1 to 7, wherein in step (2), the rare earth terbium salt is any one or more of terbium (III) chloride, terbium (III) nitrate and terbium (III) acetate.
10. The preparation method of any one of claims 1 to 9 and/or the application of the tetraphenyl ethylene derivative/rare earth nanoparticle composite material for identifying valence-variable chromium ions prepared by the method in the environmental field.
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| CN108424349A (en) * | 2018-03-29 | 2018-08-21 | 山东大学 | A kind of preparation method of the rare earth nano line for the tetraphenyl ethylene Derivatives Modified can be used for organic carboxyl acid detection |
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| CN107602417A (en) * | 2017-09-06 | 2018-01-19 | 华南理工大学 | It is a kind of based on aggregation-induced emission mechanism can quick detection zinc ion fluorescence probe and preparation method and application |
| CN108424349A (en) * | 2018-03-29 | 2018-08-21 | 山东大学 | A kind of preparation method of the rare earth nano line for the tetraphenyl ethylene Derivatives Modified can be used for organic carboxyl acid detection |
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