CN106565966B - A kind of europium polymerization of olefin using catalyst polymer nanocomposite ball and the preparation method and application thereof - Google Patents
A kind of europium polymerization of olefin using catalyst polymer nanocomposite ball and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of europium polymerization of olefin using catalyst polymer nanocomposite ball and the preparation method and application thereof, which is made of following methods: by EuCl3·6H2O、H2BDC and polyvinylpyrrolidone are added to by N, the in the mixed solvent that dinethylformamide and dehydrated alcohol mix, and it stirs until being completely dissolved, then mixed solution is transferred in the reaction kettle with polytetrafluoroethylliner liner, it is placed in 150 DEG C of baking oven and stands 12 hours, then successively carry out cooling down, be centrifuged, washing and vacuum drying.Water body to be detected is added in the fluorescent material suspension made of the europium polymerization of olefin using catalyst polymer nanocomposite ball, and is stood after mixing, then is detected using Fluorescence Spectrometer, phosphate content in you can get it water body to be detected.Not only performance is stable by the present invention, is not easy photofading, good water solubility, can effectively detect the phosphate content in water-outlet body, and synthetic method is simple, low raw-material cost.
Description
Technical field
The present invention relates to water pollutant detection field more particularly to a kind of europium polymerization of olefin using catalyst polymer nanocomposite ball and its preparations
Method and application.
Background technique
Phosphorus is to constitute organism and participate in the essential element of metabolic processes, is produced in natural environment and people
It is widely distributed with having in life.With social economy's fast development, a large amount of industrial wastewater, sanitary sewage, fertilizer and pesticide etc.
Substance rich in P elements is discharged into natural environment, when these substances rich in P elements flow into rivers, lake, ocean etc.
When natural water, the phosphate content in water body is significantly increased, and these phosphate can be directly absorbed and utilized by aquatile, from
And will cause planktonic algae mass propagation, the dissolved oxygen in water is consumed, other aquatiles such as fishes and shrimps is caused not give birth to normally
It deposits, causes water eutrophication, this has not only broken up the ecological balance of aquatic system, and the society for also drastically influencing the mankind is raw
It is living, therefore phosphate content in water body detect and control very urgent.
Currently, the method that phosphate content in water body is tested and analyzed mainly have colorimetric method, fluorescence method, chromatography,
Electrochemical process, enzyme biologic sensor method etc.；Wherein, fluorescence method has easy to operate, high sensitivity, good selective, because
This is increasingly by the favor of scientific research personnel.In the prior art, fluorescent material used in fluorescence method is mainly quantum dot, gold
Belong to cluster, organic dyestuff and polymer etc., but these fluorescent materials at least exist that itself is toxic, unstable, be easy photofading,
It is one or more in the disadvantages of poorly water-soluble, cost of material are high, synthetic method is complicated, therefore which has limited the wide of fluorescence method
General application.
Summary of the invention
For above-mentioned shortcoming in the prior art, the present invention provides a kind of europium polymerization of olefin using catalyst polymer nanocomposite ball and its
Preparation method and application, not only performance is stable, is not easy photofading, good water solubility, and the phosphate that can effectively detect in water-outlet body contains
Amount, and synthetic method is simple, low raw-material cost.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of europium polymerization of olefin using catalyst polymer nanocomposite ball, is prepared: by EuCl using following methods3·6H2O、H2BDC and poly-
Vinylpyrrolidone is added to the in the mixed solvent mixed by n,N-Dimethylformamide and dehydrated alcohol, and stir until
It is completely dissolved, then mixed solution is transferred in the reaction kettle with polytetrafluoroethylliner liner, be placed in 150 DEG C of baking oven
12 hours are stood, so that reaction mixture be made in reaction kettle in an oven；The reaction mixture is successively carried out again cold
But, centrifugation, washing and vacuum drying, obtain europium polymerization of olefin using catalyst polymer nanocomposite ball；Wherein, EuCl3·6H2O、H2BDC, poly- second
The molar ratio of alkene pyrrolidone is 16:3:1.
Preferably, the partial size of the europium polymerization of olefin using catalyst polymer nanocomposite ball is 115~125nm.
Preferably, the volume ratio of the in the mixed solvent, n,N-Dimethylformamide and dehydrated alcohol is 5:3.
A kind of preparation method of europium polymerization of olefin using catalyst polymer nanocomposite ball, comprising the following steps: by EuCl3·6H2O、H2BDC and
Polyvinylpyrrolidone is added to the in the mixed solvent mixed by n,N-Dimethylformamide and dehydrated alcohol, and stirs straight
To being completely dissolved, then mixed solution is transferred in the reaction kettle with polytetrafluoroethylliner liner, is placed in 150 DEG C of baking oven
It is middle to stand 12 hours, so that reaction mixture be made in reaction kettle in an oven；The reaction mixture is successively carried out again
Cooling, centrifugation, washing and vacuum drying, obtain europium polymerization of olefin using catalyst polymer nanocomposite ball；Wherein, EuCl3·6H2O、H2BDC, gather
The molar ratio of vinylpyrrolidone is 16:3:1.
Preferably, the partial size of the europium polymerization of olefin using catalyst polymer nanocomposite ball is 115~125nm.
Preferably, the volume ratio of the in the mixed solvent, n,N-Dimethylformamide and dehydrated alcohol is 5:3.
Preferably, described the reaction mixture successively carried out cool down, be centrifuged, washed and vacuum drying include: by
The reaction mixture is cooled to room temperature, and with the centrifugal treating of the revolving speed of 3000rpm progress 3~5 minutes, then removal centrifugation
Treated substrate, and the suspension after centrifugal treating is carried out with the revolving speed of 10000rpm at centrifugation again in 3~5 minutes
Reason, then the solid after centrifugal treating again is washed using n,N-Dimethylformamide and dehydrated alcohol, and carry out vacuum
Drying, obtains europium polymerization of olefin using catalyst polymer nanocomposite ball.
The detection method of phosphate content, water body to be detected is added in fluorescent material suspension in a kind of water body, and
40~50 minutes are stood after mixing, to obtain intermediate detection liquid；Again using Fluorescence Spectrometer to the intermediate detection liquid
Fluorescence emission spectrum detected to get phosphate content in water body to be detected out；Wherein, in the fluorescent material suspension
Using europium polymerization of olefin using catalyst polymer nanocomposite ball as described in the above technical scheme as fluorescent material.
Preferably, it using europium polymerization of olefin using catalyst polymer nanocomposite ball as described in the above technical scheme as fluorescent material, is dispersed in
Concentration is to form fluorescent material suspension in the Tris-HCl buffer of 25mmol/L；The pH value of the fluorescent material suspension is
7.5, the concentration of fluorescent material is 100ppm in the fluorescent material suspension.
Preferably, the fluorescent material is 2~100 μm of ol/L, inspection to the linear detection range of phosphate content in water body
Survey is limited to 0.83 μm of ol/L.
As seen from the above technical solution provided by the invention, europium polymerization of olefin using catalyst polymer nano provided in an embodiment of the present invention
Rice ball uses simple step solvent-thermal method and is prepared, and is produced in n,N-Dimethylformamide and dehydrated alcohol mixed solution
Under raw high temperature and high pressure environment, mutually it is coordinated using europium ion with terephthalic acid (TPA), and using polyvinylpyrrolidone as stabilizer
Pattern is adjusted, to be finally obtained partial size in 115~125nm, shaggy europium polymerization of olefin using catalyst polymer nanocomposite ball.The europium base
Coordination polymer nanosphere can be used as fluorescent material, and fluorescence is substantially interference-free in the range of pH value=5~9, right
Total-phosphorus detection is selectively excellent in water, and linear detection range is 2~100 μm of ol/L, up to 0.83 μm of ol/L, therefore detection limits
It can be applied to the phosphate content in detection water body.It can be seen that the embodiment of the present invention not only performance is stable, be not easy photofading,
Good water solubility can effectively detect the phosphate content in water-outlet body, and synthetic method is simple, low raw-material cost.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 a is the stereoscan photograph of europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1；
Fig. 1 b is the grain size distribution of europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1；
Fig. 1 c is the transmission electron microscope photo of europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1；
Fig. 1 d is the X ray diffracting spectrum of europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1；
Fig. 1 e is the energy spectrum diagram of europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1；
Fig. 2 is that fluorescence of the europium polymerization of olefin using catalyst polymer nanocomposite ball under condition of different pH obtained by the embodiment of the present invention 1 is strong
Degree variation schematic diagram；
Fig. 3 is that europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 exists in different ions and amino acid
Under the conditions of fluorescence intensity change schematic diagram；
Fig. 4 a is that there are items in various concentration phosphate for europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1
Fluorescent emission spectrogram under part；
Fig. 4 b is that there are items in various concentration phosphate for europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1
Fluorescence intensity ratio schematic diagram under part.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to protection scope of the present invention.
Europium polymerization of olefin using catalyst polymer nanocomposite ball provided by the present invention and the preparation method and application thereof is retouched in detail below
It states.
A kind of europium polymerization of olefin using catalyst polymer nanocomposite ball, is prepared using simple step solvent-thermal method, specific preparation side
Method may comprise steps of: by EuCl3·6H2O (i.e. europium chloride crystal), H2BDC (i.e. terephthalic acid (TPA)) and polyethylene pyrrole
Pyrrolidone (i.e. PVP) is added to the mixing mixed by N,N-dimethylformamide (i.e. DMF) and dehydrated alcohol (i.e. EtOH)
It in solvent, and stirs until be completely dissolved, then mixed solution is transferred in the reaction kettle with polytetrafluoroethylliner liner, and
It is placed in 150 DEG C of baking oven and stands 12 hours, so that reaction mixture be made in reaction kettle in an oven；Again to the reaction
Mixture is successively carried out cooling down, is centrifuged, washing and vacuum drying, obtains europium polymerization of olefin using catalyst polymer nanocomposite ball；The europium polymerization of olefin using catalyst
Polymer nanocomposite ball is grayish powder.
Wherein, it in the preparation method of above-mentioned europium polymerization of olefin using catalyst polymer nanocomposite ball may include embodiment in detail below:
(1)EuCl3·6H2O、H2BDC, polyvinylpyrrolidone molar ratio be 16:3:1.
(2) volume ratio of the in the mixed solvent described in, n,N-Dimethylformamide and dehydrated alcohol is 5:3.
(3) the reaction mixture is successively carried out to cool down, is centrifuged, is washed described in and vacuum drying may include: by
The reaction mixture is cooled to room temperature, and with the centrifugal treating of the revolving speed of 3000rpm progress 3~5 minutes, then removal centrifugation
Treated substrate, and the suspension after centrifugal treating is carried out with the revolving speed of 10000rpm at centrifugation again in 3~5 minutes
Reason, then the solid after centrifugal treating again is repeatedly washed using n,N-Dimethylformamide and dehydrated alcohol, and carries out
Vacuum drying obtains europium polymerization of olefin using catalyst polymer nanocomposite ball.
Specifically, the preparation method of above-mentioned europium polymerization of olefin using catalyst polymer nanocomposite ball is a kind of simple step solvent-thermal method,
DMF is mutually coordinated using europium ion with terephthalic acid (TPA), and under high temperature and high pressure environment caused by EtOH mixed solution with PVP
Pattern is adjusted for stabilizer, to be finally obtained partial size in 115~125nm, shaggy europium polymerization of olefin using catalyst polymer nano
Rice ball.Through detecting, which has a good fluorescence property, and in the range of pH value=5~9
Fluorescence is substantially interference-free, selectively excellent to total-phosphorus detection in water, and linear detection range is 2~100 μm of ol/L, detection limit
Up to 0.83 μm of ol/L, therefore it can be applied to the phosphate content in detection water body.
Further, the method for being used to detect phosphate content in water body for above-mentioned europium polymerization of olefin using catalyst polymer nanocomposite ball can be with
It include: that it is slow to be dispersed in the Tris-HCl that concentration is 25mmol/L using above-mentioned europium polymerization of olefin using catalyst polymer nanocomposite ball as fluorescent material
(English name of Tris-HCl buffer is Tris (hydroxymethyl) aminomethane to fliud flushing, and Chinese nickname is three hydroxyls
Aminomethane, molecular formula C4H11NO3) in, form uniform suspension.Water body to be detected is added to described hang
In supernatant liquid, and 40~50 minutes are stood after mixing, to obtain intermediate detection liquid；Fluorescence light in the prior art is used again
Spectrometer detects the fluorescence emission spectrum of the intermediate detection liquid, phosphate content in you can get it water body to be detected.In reality
In the application of border, the pH value of the fluorescent material suspension can be 5~9, but preferably 7.5, and the fluorescent material suspends
The concentration of fluorescent material is preferably 100ppm in liquid, and the fluorescent material suspension can be improved to phosphate content in water body in this
Detection performance.
It can be seen that not only performance is stable, is not easy photofading, good water solubility for the embodiment of the present invention, water outlet can be effectively detected
Phosphate content in body, and synthetic method is simple, low raw-material cost.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
Europium polymerization of olefin using catalyst polymer nanocomposite ball provided by the present invention and the preparation method and application thereof is described in detail in body embodiment.
Embodiment 1
A kind of europium polymerization of olefin using catalyst polymer nanocomposite ball, is prepared using following methods: by the EuCl of 0.2345g3·6H2O、
The H of 0.0192g2The polyvinylpyrrolidone of BDC and 1.6g is added to by N,N-dimethylformamide and dehydrated alcohol according to 5:3
The in the mixed solvent that mixes of volume ratio, and stir until be completely dissolved, then mixed solution be transferred to poly- four
It in the reaction kettle of vinyl fluoride liner, is placed in 150 DEG C of baking oven and stands 12 hours, to be made in reaction kettle in an oven
Reaction mixture.By the reaction mixture cooled to room temperature, and with the centrifugation of the revolving speed of 3000rpm progress 3~5 minutes
Then processing removes the substrate after centrifugal treating, and carries out 3~5 to the suspension after centrifugal treating with the revolving speed of 10000rpm
The centrifugal treating again of minute, then the solid after centrifugal treating again is carried out using n,N-Dimethylformamide and dehydrated alcohol
Repeatedly washing, and vacuum drying is carried out, to obtain europium polymerization of olefin using catalyst polymer nanocomposite ball.
Specifically, pattern and performance detection are carried out to europium polymerization of olefin using catalyst polymer nanocomposite ball made from the embodiment of the present invention 1:
(1) to the microscopic appearance of europium polymerization of olefin using catalyst polymer nanocomposite ball, particle diameter distribution, X-ray made from the embodiment of the present invention 1
Diffracting spectrum, particle diameter distribution are observed and detect, to obtain grain shown in stereoscan photograph as shown in Figure 1a, Fig. 1 b
Transmission electron microscope photo shown in diameter distribution map, Fig. 1 c, energy spectrum diagram shown in X ray diffracting spectrum and Fig. 1 e shown in Fig. 1 d.By
Fig. 1 a, Fig. 1 b, Fig. 1 c, Fig. 1 d and Fig. 1 e are it can be seen that europium polymerization of olefin using catalyst polymer nanocomposite spherolite diameter made from the embodiment of the present invention 1
Mainly between 115~125nm, rough surface.
(2) using europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 as fluorescent material, be dispersed in from
In sub- water, the suspension that fluorescent material concentration is 400ppm is obtained.Taking 7 parts of fluorescent material concentration is the fluorescent material of 400ppm
Suspension, and the HCl solution for using concentration to be 0.1mol/L for the NaOH solution of 0.1mol/L and concentration adjusts this 7 parts of phosphors
Then the pH value of pulp suspension is diluted to fluorescent material concentration and is the suspension of 100ppm, and keep this final 7 parts of fluorescent materials outstanding
The pH value of supernatant liquid is respectively 4,5,6,7,8,9,10；Existed respectively to this 7 parts of fluorescent material suspension with Fluorescence Spectrometer survey again
Fluorescence emission spectrum under 260nm exciting light is detected, and records fluorescence intensity of the launch wavelength at 615nm, to obtain
The fluorescence of europium polymerization of olefin using catalyst polymer nanocomposite ball under different ph values obtained by the embodiment of the present invention 1 as described in Figure 2 is strong
Degree variation schematic diagram.As seen from Figure 2: when the pH value of the fluorescent material suspension is in 5 or less and 9 or more, fluorescence is strong
Degree changes greatly, this illustrates that europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 is not suitable for peracid or crosses alkali
Water environment in；And when the pH value of the fluorescent material suspension is between 5 to 9, fluorescence intensity change very little, this explanation
Europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 is relatively specific in neutral water environment, can be used for general
The fluorescence analysis of natural water.
(3) using europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 as fluorescent material, be dispersed in from
In sub- water, the suspension that fluorescent material concentration is 400ppm is obtained.The pH value for taking 13 parts of 2mL is 7.5, concentration is 50mmol/L's
Tris-HCl buffer, and it is the outstanding of 400ppm that fluorescent material concentration described in 1mL is added in every portion of Tris-HCl buffer
Supernatant liquid is then respectively adding 0.2mL deionized water, the Na that 0.2mL concentration is 4mmol/L3PO4(Pi) solution, 0.2mL concentration are
NaI, 0.2mL concentration that NaCl, 0.2mL concentration that NaAc, 0.2mL concentration of 20mmol/L is 20mmol/L are 20mmol/L is
The NaNO of 20mmol/L2, 0.2mL concentration be 20mmol/L NaNO3, 0.2mL concentration be 20mmol/L CaCl2, 0.2mL it is dense
Degree is the MgCl of 20mmol/L2, 0.2mL concentration be 20mmol/L BaCl2, 0.2mL concentration be 20mmol/L CdCl2、
Arginine (Arg) that 0.2mL concentration is 20mmol/L, this 13 kinds detection liquid of glutamic acid (Glu) that 0.2mL concentration is 20mmol/L
One of, and the detection liquid being added in every portion of Tris-HCl buffer is different, adds water and is settled to 4mL, is uniformly mixed,
40 minutes are stood, to obtain 13 parts of difference suspension to be detected；It is surveyed again with Fluorescence Spectrometer to be detected outstanding to this 13 parts respectively
Fluorescence emission spectrum of the supernatant liquid under 260nm exciting light is detected, and records fluorescence intensity of the launch wavelength at 615nm, from
And europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 as described in Figure 3 is obtained in different ions and amino acid
Fluorescence intensity change schematic diagram under existence condition.As seen from Figure 3: europium polymerization of olefin using catalyst obtained by the embodiment of the present invention 1 is poly-
Object nanosphere is closed in the Tris-HCl buffer of pH=7.5, fluorescence intensity can be substantially reduced by phosphate, and by other ions
Smaller with amino acids, this illustrates that europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 can be sudden using fluorescence
Effect go out to detect phosphate, and have good selectivity to phosphate.
(4) using europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 as fluorescent material, disperse deionization
In water, the suspension that fluorescent material concentration is 400ppm is obtained.The pH value for taking 10 parts of 2mL is 7.5, concentration is 50mmol/L's
Tris-HCl buffer, and it is the glimmering of 400ppm that fluorescent material concentration described in 1mL is added in every portion of Tris-HCl buffer
Finish pulp suspension is then respectively adding the Na of various concentration3PO4Solution adds deionized water and is settled to 4mL, and make this 10
The final phosphate concn of part suspension is respectively 0,1 μm of ol/L, 2 μm of ol/L, 5 μm of ol/L, 10 μm of ol/L, 20 μm of ol/L, 50 μ
Mol/L, 100 μm of ol/L, 200 μm of ol/L and 500 μm of ol/L are uniformly mixed, and 40 minutes are stood, so that it is to be checked to obtain 10 parts of differences
Survey suspension；It is surveyed again with Fluorescence Spectrometer respectively to this fluorescence emission spectrum of 10 parts of suspension to be detected under 260nm exciting light
It is detected, and records fluorescence intensity of the launch wavelength at 615nm, to obtain the embodiment of the present invention 1 as described in fig. 4 a
Fluorescent emission spectrogram and such as figure of the obtained europium polymerization of olefin using catalyst polymer nanocomposite ball under various concentration phosphate existence condition
Europium polymerization of olefin using catalyst polymer nanocomposite ball obtained by the embodiment of the present invention 1 described in 4b is under various concentration phosphate existence condition
Fluorescence intensity ratio schematic diagram.By Fig. 4 a and Fig. 4 b it can be seen that with phosphate concn increase, using the embodiment of the present invention
Fluorescent material suspension made of europium polymerization of olefin using catalyst polymer nanocomposite ball in 1, fluorescence intensity are sequentially reduced, and make fluorescence intensity
Curve of the ratio to phosphate concn, it is found that linear fit is fine in the concentration ranges of 2~100 μm of ol/L, calculates institute
Linear regression coeffficient is obtained up to 0.9973, fluorescent quenching constant is 2.79 × 104L/mol, detection are limited to 0.83 μm of ol/L；Therefore
Europium polymerization of olefin using catalyst polymer nanocomposite ball in the embodiment of the present invention 1 can detect water body phosphate within the scope of 2~100 μM.
To sum up, not only performance is stable, is not easy photofading, good water solubility for the embodiment of the present invention, can effectively detect water outlet
Phosphate content in body, and synthetic method is simple, low raw-material cost.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (10)
1. a kind of europium polymerization of olefin using catalyst polymer nanocomposite ball, which is characterized in that be prepared using following methods:
By EuCl3·6H2O、H2BDC and polyvinylpyrrolidone, which are added to, to be mixed by N,N-dimethylformamide with dehydrated alcohol
Made of in the mixed solvent, and stir until be completely dissolved, then mixed solution be transferred to polytetrafluoroethylliner liner
It in reaction kettle, is placed in 150 DEG C of baking oven and stands 12 hours, so that reaction mixture be made in reaction kettle in an oven；
The reaction mixture successively carried out again cooling down, be centrifuged, washed and vacuum drying, obtaining europium polymerization of olefin using catalyst polymer nanocomposite
Ball；
Wherein, EuCl3·6H2O、H2BDC, polyvinylpyrrolidone molar ratio be 16:3:1.
2. europium polymerization of olefin using catalyst polymer nanocomposite ball according to claim 1, which is characterized in that the europium polymerization of olefin using catalyst polymer nanocomposite
The partial size of ball is 115~125nm.
3. europium polymerization of olefin using catalyst polymer nanocomposite ball according to claim 1 or 2, which is characterized in that the in the mixed solvent,
The volume ratio of N,N-dimethylformamide and dehydrated alcohol is 5:3.
4. a kind of preparation method of europium polymerization of olefin using catalyst polymer nanocomposite ball, which comprises the following steps:
By EuCl3·6H2O、H2BDC and polyvinylpyrrolidone, which are added to, to be mixed by N,N-dimethylformamide with dehydrated alcohol
Made of in the mixed solvent, and stir until be completely dissolved, then mixed solution be transferred to polytetrafluoroethylliner liner
It in reaction kettle, is placed in 150 DEG C of baking oven and stands 12 hours, so that reaction mixture be made in reaction kettle in an oven；
The reaction mixture successively carried out again cooling down, be centrifuged, washed and vacuum drying, obtaining europium polymerization of olefin using catalyst polymer nanocomposite
Ball；
Wherein, EuCl3·6H2O、H2BDC, polyvinylpyrrolidone molar ratio be 16:3:1.
5. the preparation method of europium polymerization of olefin using catalyst polymer nanocomposite ball according to claim 4, which is characterized in that the europium polymerization of olefin using catalyst
The partial size of polymer nanocomposite ball is 115~125nm.
6. the preparation method of europium polymerization of olefin using catalyst polymer nanocomposite ball according to claim 4 or 5, which is characterized in that described
The volume ratio of in the mixed solvent, n,N-Dimethylformamide and dehydrated alcohol is 5:3.
7. the preparation method of europium polymerization of olefin using catalyst polymer nanocomposite ball according to claim 4 or 5, which is characterized in that described
The reaction mixture successively carried out cool down, be centrifuged, washed and vacuum drying includes:
The reaction mixture is cooled to room temperature, and with the centrifugal treating of the revolving speed of 3000rpm progress 3~5 minutes, is then gone
Except the substrate after centrifugal treating, and to the suspension after centrifugal treating with the revolving speed of 10000rpm carry out 3~5 minutes again from
Heart processing, then the solid after centrifugal treating again is washed using n,N-Dimethylformamide and dehydrated alcohol, and carries out
Vacuum drying obtains europium polymerization of olefin using catalyst polymer nanocomposite ball.
8. the detection method of phosphate content in a kind of water body, which is characterized in that water body to be detected is added to fluorescent material and is hanged
In supernatant liquid, and 40~50 minutes are stood after mixing, to obtain intermediate detection liquid；Again using Fluorescence Spectrometer in described
Between detect liquid fluorescence emission spectrum detected to get phosphate content in water body to be detected out；
Wherein, it is poly- that europium polymerization of olefin using catalyst described in any one of the claims 1 to 3 is used in the fluorescent material suspension
Object nanosphere is closed as fluorescent material.
9. the detection method of phosphate content in water body according to claim 8, which is characterized in that by the claims
For europium polymerization of olefin using catalyst polymer nanocomposite ball described in any one of 1 to 3 as fluorescent material, being dispersed in concentration is 25mmol/L's
In Tris-HCl buffer, fluorescent material suspension is formed；The pH value of the fluorescent material suspension is 7.5, and the fluorescent material is outstanding
The concentration of fluorescent material is 100ppm in supernatant liquid.
10. the detection method of phosphate content in water body according to claim 8, which is characterized in that the fluorescent material
Linear detection range to phosphate content in water body is 2~100 μm of ol/L, and detection is limited to 0.83 μm of ol/L.
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