CN106565966A - Europium-based coordination polymer nanosphere and preparation method and application thereof - Google Patents
Europium-based coordination polymer nanosphere and preparation method and application thereof Download PDFInfo
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a europium-based coordination polymer nanosphere and a preparation method and application thereof. The preparation method of the europium-based coordination polymer nanosphere comprises the following steps of adding EuCl3.6H2O, H2BDC and polyvinylpyrrolidone to mixed solvent formed by mixing N, N-dimethylformamide and absolute ethyl alcohol, and conducting stirring till the materials are fully dissolved; then, transferring a mixed solution into a reaction still provided with a polytetrafluoroethylene inner container, and putting the reaction still in a drying oven at the temperature of 150 DEG C to leave the reaction still standing still for 12 hours; and then sequentially conducting cooling, centrifugalization, washing and vacuum drying, so that the europium-based coordination polymer nanospheres are obtained. A to-be-detected water body is added to fluorescent material suspension liquid prepared from the europium-based coordination polymer nanospheres; after being mixed uniformly, the materials are left standing still; and then a fluorescence spectrophotometer is adopted for detection, and the content of phosphate in the to-be-detected water body can be obtained. The europium-based coordination polymer nanosphere is stable in performance, not prone to photobleaching, good in water solubility, capable of effectively detecting the content of the phosphate in the water body, simple in synthesis method and low in raw material cost.
Description
Technical field
The present invention relates to water pollutant detection field, more particularly to a kind of europio coordination polymer nanosphere and its preparation
Method and application.
Background technology
Phosphorus is to constitute organism and participate in the requisite element of metabolic processes, is produced in natural environment and people
With have widely distributed in life.With social economy's fast development, substantial amounts of industrial wastewater, sanitary sewage, fertilizer and pesticide etc.
Material rich in P elements is discharged in natural environment, when these materials rich in P elements flow into rivers, lake, ocean etc.
During natural water, the phosphate content in water body is significantly increased, and these phosphate can directly be absorbed by aquatile, from
And planktonic algae amount reproduction can be caused, and the dissolved oxygen in water is consumed, cause other aquatiles such as fish and shrimp normally to give birth to
Deposit, cause body eutrophication, this has not only broken up the ecological balance of aquatic system, the society that also drastically influence the mankind is raw
It is living, therefore phosphate content in water body is detected and is controlled very urgent.
At present, the method for phosphate content in water body being tested and analyzed mainly have colorimetry, fluorescence method, chromatography,
Electrochemical process, enzyme biologic sensor method etc.；Wherein, fluorescence method has that simple to operate, sensitivity is high, good selective, because
This is increasingly favored by scientific research personnel.In the prior art, the fluorescent material that fluorescence method is used is mainly quantum dot, gold
Category cluster, organic dyestuff and polymer etc., but poisonous, unstable, the easy photofading of these fluorescent materials at least presence itself,
One or more in the shortcomings of poorly water-soluble, cost of material are high, synthetic method is complicated, therefore which has limited the wide of fluorescence method
General application.
The content of the invention
For above-mentioned weak point of the prior art, the invention provides a kind of europio coordination polymer nanosphere and its
Preparation method and application, not only stable performance, be difficult photofading, good water solubility, phosphate that can be in effective detection water-outlet body contains
Amount, and synthetic method is simple, low raw-material cost.
The purpose of the present invention is achieved through the following technical solutions：
A kind of europio coordination polymer nanosphere, is prepared from using following methods：By EuCl3·6H2O、H2BDC and poly-
Vinylpyrrolidone is added in the mixed solvent mixed by DMF and dehydrated alcohol, and stir until
It is completely dissolved, then mixed solution is transferred in the reactor with polytetrafluoroethylliner liner, in is placed in 150 DEG C of baking oven
12 hours are stood, so as to reactant mixture is obtained in reactor in an oven；The reactant mixture is carried out successively again cold
But, centrifugation, washing and vacuum drying, that is, be obtained europio coordination polymer nanosphere；Wherein, EuCl3·6H2O、H2BDC, poly- second
The mol ratio of alkene pyrrolidone is 16:3:1.
Preferably, the particle diameter of the europio coordination polymer nanosphere is 115～125nm.
Preferably, in described mixed solvent, DMF is 5 with the volume ratio of dehydrated alcohol:3.
A kind of preparation method of europio coordination polymer nanosphere, comprises the following steps：By EuCl3·6H2O、H2BDC and
Polyvinylpyrrolidone is added in the mixed solvent mixed by DMF and dehydrated alcohol, and stirs straight
To being completely dissolved, then mixed solution is transferred in the reactor with polytetrafluoroethylliner liner, is placed in 150 DEG C of baking oven
It is middle to stand 12 hours, so as to reactant mixture is obtained in reactor in an oven；The reactant mixture is carried out successively again
Cooling, centrifugation, washing and vacuum drying, that is, be obtained europio coordination polymer nanosphere；Wherein, EuCl3·6H2O、H2It is BDC, poly-
The mol ratio of vinylpyrrolidone is 16:3:1.
Preferably, the particle diameter of the europio coordination polymer nanosphere is 115～125nm.
Preferably, in described mixed solvent, DMF is 5 with the volume ratio of dehydrated alcohol:3.
Preferably, it is described the reactant mixture to be cooled down successively, is centrifuged, is washed and vacuum drying includes：Will
The reactant mixture is cooled to room temperature, and the centrifugal treating for carrying out 3～5 minutes with the rotating speed of 3000rpm, then removes centrifugation
Substrate after process, and the suspension after centrifugal treating is carried out at the recentrifuge of 3～5 minutes with the rotating speed of 10000rpm
Reason, then the solid after recentrifuge process is washed using DMF and dehydrated alcohol, and carry out vacuum
Drying, that is, be obtained europio coordination polymer nanosphere.
The detection method of phosphate content in a kind of water body, water body to be detected is added in fluorescent material suspension, and
40～50 minutes are stood after mix homogeneously, so as to obtain intermediate detection liquid；Again using fluorescence spectrophotometer to the intermediate detection liquid
Fluorescence emission spectrum detected, that is, draw phosphate content in water body to be detected；Wherein, in described fluorescent material suspension
The europio coordination polymer nanosphere described in above-mentioned technical proposal is employed as fluorescent material.
Preferably, the europio coordination polymer nanosphere described in above-mentioned technical proposal is dispersed in as fluorescent material
During concentration is for the Tris-HCl buffer of 25mmol/L, fluorescent material suspension is formed；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 to the linear detection range of phosphate content in water body, is examined
Survey is limited to 0.83 μm of ol/L.
As seen from the above technical solution provided by the invention, europio coordination polymer provided in an embodiment of the present invention is received
Rice ball employs simple step solvent-thermal method and is prepared from, and is produced with dehydrated alcohol mixed solution in DMF
Under raw high temperature and high pressure environment, mutually it is coordinated with p-phthalic acid using europium ion, and is come by stabilizer of polyvinylpyrrolidone
Pattern is adjusted, so as to be finally obtained particle diameter in 115～125nm, shaggy europio coordination polymer nanosphere.The europio
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 selectivity is excellent in water, linear detection range be 2～100 μm of ol/L, test limit up to 0.83 μm of ol/L, therefore
Can be applicable to detect the phosphate content in water body.As can be seen here, the embodiment of the present invention not only stable performance, be difficult photofading,
Good water solubility, the phosphate content in energy effective detection water-outlet body, and synthetic method are simple, low raw-material cost.
Description of the drawings
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below will be to use needed for embodiment description
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, can be obtaining other according to these accompanying drawings
Accompanying drawing.
Fig. 1 a are the stereoscan photograph of the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1；
Fig. 1 b are the grain size distribution of the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1；
Fig. 1 c are the transmission electron microscope photo of the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1；
Fig. 1 d are the X ray diffracting spectrum of the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1；
Fig. 1 e are the energy spectrum diagram of the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1；
Fluorescence of europio coordination polymer nanospheres of the Fig. 2 obtained by the embodiment of the present invention 1 under condition of different pH is strong
Degree change schematic diagram；
Fig. 3 is that the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 exists in different ions and aminoacid
Under the conditions of fluorescence intensity change schematic diagram；
Fig. 4 a are that the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 has bar in variable concentrations phosphate
Fluorescent emission spectrogram under part；
Fig. 4 b are that the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 has bar in variable concentrations phosphate
Fluorescence intensity ratio schematic diagram under part.
Specific embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground description, it is clear that described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based on this
Inventive embodiment, the every other enforcement that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
Europio coordination polymer nanosphere provided by the present invention and preparation method and application is retouched in detail below
State.
A kind of europio coordination polymer nanosphere, is prepared from using simple step solvent-thermal method, its concrete preparation side
Method may comprise steps of：By EuCl3·6H2O (i.e. europium chloride crystal), H2BDC (i.e. p-phthalic acid) 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)
In solvent, and stir up to being completely dissolved, then mixed solution is transferred in the reactor with polytetrafluoroethylliner liner, and
It is placed in 150 DEG C of baking oven and stands 12 hours, so as to reactant mixture is obtained in reactor in an oven；Again to the reaction
Mixture is cooled down successively, is centrifuged, being washed and vacuum drying, that is, europio coordination polymer nanosphere is obtained；The europio coordination
Polymer nanocomposite ball is grayish powder.
Wherein, embodiment in detail below can be included in the preparation method of above-mentioned europio coordination polymer nanosphere：
(1)EuCl3·6H2O、H2BDC, the mol ratio of polyvinylpyrrolidone are 16:3:1.
(2) in the mixed solvent described in, DMF is 5 with the volume ratio of dehydrated alcohol:3.
(3) the reactant mixture is cooled down successively, is centrifuged, is washed described in and vacuum drying can include：Will
The reactant mixture is cooled to room temperature, and the centrifugal treating for carrying out 3～5 minutes with the rotating speed of 3000rpm, then removes centrifugation
Substrate after process, and the suspension after centrifugal treating is carried out at the recentrifuge of 3～5 minutes with the rotating speed of 10000rpm
Reason, then the solid after recentrifuge process is repeatedly washed using DMF and dehydrated alcohol, and carry out
Vacuum drying, that is, be obtained europio coordination polymer nanosphere.
Specifically, the preparation method of above-mentioned europio coordination polymer nanosphere is a kind of simple step solvent-thermal method,
Under high temperature and high pressure environment produced by DMF and EtOH mixed solutions, mutually it is coordinated with p-phthalic acid using europium ion, and with PVP
Pattern is adjusted for stabilizer, is received in 115～125nm, shaggy europio coordination polymer so as to be finally obtained particle diameter
Rice ball.After testing, the europio coordination polymer nanosphere has good fluorescence property, and in the range of pH value=5～9
Fluorescence is substantially interference-free, excellent to total-phosphorus detection selectivity in water, linear detection range be 2～100 μm of ol/L, test limit
Up to 0.83 μm of ol/L, therefore can be applicable to detect the phosphate content in water body.
Further, above-mentioned europio coordination polymer nanosphere is used to detect that the method for phosphate content in water body can be with
Including：Using above-mentioned europio coordination polymer nanosphere as fluorescent material, it is dispersed in the Tris-HCl that concentration is 25mmol/L and delays
(English name of Tris-HCl buffer is Tris (hydroxymethyl) aminomethane, and Chinese nickname is three hydroxyls to rush liquid
Aminomethane, its molecular formula is C4H11NO3) in, form uniform suspension.Water body to be detected is added to into described hanging
In supernatant liquid, and 40～50 minutes are stood after mix homogeneously, so as to obtain intermediate detection liquid；Fluorescence light of the prior art is adopted again
Spectrometer is detected to the fluorescence emission spectrum of the intermediate detection liquid, you can draw phosphate content in water body to be detected.In reality
In the application of border, the pH value of described 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 this can improve the fluorescent material suspension to phosphate content in water body
Detection performance.
As can be seen here, the embodiment of the present invention not only stable performance, be difficult photofading, good water solubility, can effective detection water outlet
Phosphate content in body, and synthetic method is simple, low raw-material cost.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with tool
Body embodiment is described in detail to europio coordination polymer nanosphere provided by the present invention and preparation method and application.
Embodiment 1
A kind of europio coordination polymer nanosphere, is prepared from 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 mixed solvent that mixes of volume ratio in, and stir until be completely dissolved, then mixed solution is transferred to poly- four
In the reactor of fluorothene inner bag, it is placed in standing 12 hours in 150 DEG C of baking oven, so as to be obtained in reactor in an oven
Reactant mixture.The reactant mixture is naturally cooled to into room temperature, and the centrifugation for carrying out 3～5 minutes with the rotating speed of 3000rpm
Process, then remove the substrate after centrifugal treating, and 3～5 are carried out with the rotating speed of 10000rpm to the suspension after centrifugal treating
The recentrifuge of minute is processed, then the solid after recentrifuge process is carried out using DMF and dehydrated alcohol
Repeatedly washing, and vacuum drying is carried out, so as to europio coordination polymer nanosphere is obtained.
Specifically, pattern and performance detection are carried out to europio coordination polymer nanosphere obtained in the embodiment of the present invention 1：
(1) to microscopic appearance, particle diameter distribution, the X-ray of europio coordination polymer nanosphere obtained in the embodiment of the present invention 1
Diffracting spectrum, particle diameter distribution are observed and detect, so as to obtain the grain shown in stereoscan photograph as shown in Figure 1a, Fig. 1 b
The X ray diffracting spectrum shown in transmission electron microscope photo, Fig. 1 d and the energy spectrum diagram shown in Fig. 1 e shown in footpath scattergram, Fig. 1 c.By
Fig. 1 a, Fig. 1 b, Fig. 1 c, Fig. 1 d and Fig. 1 e can be seen that：Europio coordination polymer nanosphere particle diameter obtained in the embodiment of the present invention 1
Mainly between 115～125nm, rough surface.
(2) using the europio coordination polymer nanosphere 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.Take the fluorescent material that 7 parts of fluorescent material concentration are 400ppm
Suspension, and adopt HCl solution of the concentration for the NaOH solution of 0.1mol/L with concentration for 0.1mol/L to adjust this 7 parts of phosphors
The pH value of pulp suspension, it is the suspension of 100ppm to be then diluted to fluorescent material concentration, and hangs final this 7 parts of fluorescent materials
The pH value of supernatant liquid is respectively 4,5,6,7,8,9,10；Surveyed with fluorescence spectrophotometer again this 7 parts of fluorescent material suspensions are existed respectively
Fluorescence emission spectrum under 260nm exciting lights is detected, and records fluorescence intensity of the launch wavelength at 615nm, so as to obtain
Fluorescence of the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 as described in Figure 2 under different pH condition is strong
Degree change schematic diagram.As seen from Figure 2：When the pH value of the fluorescent material suspension is in less than 5 and more than 9, fluorescence is strong
Degree is changed greatly, and the europio coordination polymer nanosphere obtained by this explanation 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
Europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 is relatively specific in the water environment of neutrality, can be used for general
The fluorescence analysiss of natural water.
(3) using the europio coordination polymer nanosphere 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.It is 50mmol/L that the pH value for taking 13 parts of 2mL is 7.5, concentration
Fluorescent material concentration described in 1mL is added in Tris-HCl buffer, and every portion of Tris-HCl buffer for the outstanding of 400ppm
Supernatant liquid, is then respectively adding the Na that 0.2mL deionized waters, 0.2mL concentration are 4mmol/L3PO4(Pi) solution, 0.2mL concentration are
NaAc, 0.2mL concentration of 20mmol/L is that NaCl, 0.2mL concentration of 20mmol/L is for NaI, 0.2mL concentration of 20mmol/L
The NaNO of 20mmol/L2, 0.2mL concentration for 20mmol/L NaNO3, 0.2mL concentration for 20mmol/L CaCl2, 0.2mL it is dense
Spend the MgCl for 20mmol/L2, 0.2mL concentration for 20mmol/L BaCl2, 0.2mL concentration for 20mmol/L CdCl2、
Arginine (Arg), this 13 kinds detection liquid of glutamic acid (Glu) that 0.2mL concentration is 20mmol/L of 0.2mL concentration for 20mmol/L
In one kind, and in every portion of Tris-HCl buffer add detection liquid it is different, add water and be settled to 4mL, mix homogeneously,
40 minutes are stood, so as to obtain 13 parts of differences suspension to be detected；Survey to be detected to this 13 parts outstanding respectively with fluorescence spectrophotometer again
Fluorescence emission spectrum of the supernatant liquid under 260nm exciting lights is detected, and records fluorescence intensity of the launch wavelength at 615nm, from
And the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 as described in Figure 3 is obtained in different ions and aminoacid
Fluorescence intensity change schematic diagram under existence condition.As seen from Figure 3：Europio polycomplexation obtained by the embodiment of the present invention 1
In the Tris-HCl buffer of pH=7.5, fluorescence intensity can be substantially reduced compound nanosphere by phosphate, and receive other ions
Less with amino acids, the europio coordination polymer nanosphere obtained by this explanation embodiment of the present invention 1 can be sudden using fluorescence
Go out effect to detect phosphate, and have good selectivity to phosphate.
(4) using the europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 as fluorescent material, deionization is disperseed
In water, the suspension that fluorescent material concentration is 400ppm is obtained.It is 50mmol/L that the pH value for taking 10 parts of 2mL is 7.5, concentration
Fluorescent material concentration described in 1mL is added in Tris-HCl buffer, and every portion of Tris-HCl buffer for the glimmering of 400ppm
Finish pulp suspension, is then respectively adding the Na of variable concentrations3PO4Solution, 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, mix homogeneously stands 40 minutes, to be checked so as to obtain 10 parts of differences
Survey suspension；Surveyed respectively to this fluorescence emission spectrum of 10 parts of suspensions to be detected under 260nm exciting lights with fluorescence spectrophotometer again
Detected, and recorded fluorescence intensity of the launch wavelength at 615nm, so as to obtain the embodiment of the present invention 1 as described in fig. 4 a
Fluorescent emission spectrogram of the obtained europio coordination polymer nanosphere under variable concentrations phosphate existence condition and as schemed
The europio coordination polymer nanosphere obtained by the embodiment of the present invention 1 described in 4b is under variable concentrations phosphate existence condition
Fluorescence intensity ratio schematic diagram.Can be seen that by Fig. 4 a and Fig. 4 b：With the increase of phosphate concn, using the embodiment of the present invention
Fluorescent material suspension made by europio coordination polymer nanosphere in 1, its fluorescence intensity is sequentially reduced, and makes fluorescence intensity
Curve of the ratio to phosphate concn, it is found that linear fit very well, calculates institute in the concentration ranges of 2～100 μm of ol/L
Linear regression coeffficient is obtained up to 0.9973, fluorescent quenching constant is 2.79 × 104L/mol, detection is limited to 0.83 μm of ol/L；Therefore
Europio coordination polymer nanosphere in the embodiment of the present invention 1 can detect water body phosphate in the range of 2～100 μM.
As fully visible, the embodiment of the present invention not only stable performance, be difficult photofading, good water solubility, can effective detection water outlet
Phosphate content in body, and synthetic method is simple, low raw-material cost.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
All should be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of europio coordination polymer nanosphere, it is characterised in that be prepared from using following methods：
By EuCl3·6H2O、H2BDC and polyvinylpyrrolidone are added to and are mixed with dehydrated alcohol by N,N-dimethylformamide
Mixed solvent in, and stir until be completely dissolved, then mixed solution is transferred to polytetrafluoroethylliner liner
In reactor, it is placed in standing 12 hours in 150 DEG C of baking oven, so as to reactant mixture is obtained in reactor in an oven；
Again the reactant mixture cooled down successively, is centrifuged, being washed and vacuum drying, that is, europio coordination polymer nanometer is obtained
Ball；
Wherein, EuCl3·6H2O、H2BDC, the mol ratio of polyvinylpyrrolidone are 16:3:1.
2. europio coordination polymer nanosphere according to claim 1, it is characterised in that the europio coordination polymer nanometer
The particle diameter of ball is 115～125nm.
3. europio coordination polymer nanosphere according to claim 1 and 2, it is characterised in that in described mixed solvent,
N,N-dimethylformamide is 5 with the volume ratio of dehydrated alcohol:3.
4. a kind of preparation method of europio coordination polymer nanosphere, it is characterised in that comprise the following steps：
By EuCl3·6H2O、H2BDC and polyvinylpyrrolidone are added to and are mixed with dehydrated alcohol by N,N-dimethylformamide
Mixed solvent in, and stir until be completely dissolved, then mixed solution is transferred to polytetrafluoroethylliner liner
In reactor, it is placed in standing 12 hours in 150 DEG C of baking oven, so as to reactant mixture is obtained in reactor in an oven；
Again the reactant mixture cooled down successively, is centrifuged, being washed and vacuum drying, that is, europio coordination polymer nanometer is obtained
Ball；
Wherein, EuCl3·6H2O、H2BDC, the mol ratio of polyvinylpyrrolidone are 16:3:1.
5. the preparation method of europio coordination polymer nanosphere according to claim 4, it is characterised in that europio coordination
The particle diameter of polymer nanocomposite ball is 115～125nm.
6. the preparation method of the europio coordination polymer nanosphere according to claim 4 or 5, it is characterised in that described
In mixed solvent, DMF is 5 with the volume ratio of dehydrated alcohol:3.
7. the preparation method of the europio coordination polymer nanosphere according to claim 4 or 5, it is characterised in that described
The reactant mixture is cooled down successively, is centrifuged, is washed and vacuum drying is included：
The reactant mixture is cooled to into room temperature, and the centrifugal treating for carrying out 3～5 minutes with the rotating speed of 3000rpm, then go
Except the substrate after centrifugal treating, and to the suspension after centrifugal treating with the rotating speed of 10000rpm carry out 3～5 minutes again from
Heart process, then the solid after recentrifuge process is washed using DMF and dehydrated alcohol, and carry out
Vacuum drying, that is, be obtained europio coordination polymer nanosphere.
8. in a kind of water body phosphate content detection method, it is characterised in that water body to be detected is added to into fluorescent material and is hanged
In supernatant liquid, and 40～50 minutes are stood after mix homogeneously, so as to obtain intermediate detection liquid；Again using fluorescence spectrophotometer in described
Between detect liquid fluorescence emission spectrum detected, that is, draw phosphate content in water body to be detected；
Wherein, the europio polycomplexation any one of the claims 1 to 3 is employed in described fluorescent material suspension
Compound nanosphere is used as fluorescent material.
9. in water body according to claim 8 phosphate content detection method, it is characterised in that by the claims
Europio coordination polymer nanosphere any one of 1 to 3 is dispersed in concentration for 25mmol/L's as fluorescent material
In Tris-HCl buffer, fluorescent material suspension is formed；The pH value of the fluorescent material suspension is 7.5, and the fluorescent material hangs
The concentration of fluorescent material is 100ppm in supernatant liquid.
10. in water body according to claim 8 phosphate content detection method, it is characterised in that the fluorescent material
It is 2～100 μm of ol/L to the linear detection range of phosphate content in water body, detection is limited to 0.83 μm of ol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610979515.XA CN106565966B (en) | 2016-11-08 | 2016-11-08 | A kind of europium polymerization of olefin using catalyst polymer nanocomposite ball and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610979515.XA CN106565966B (en) | 2016-11-08 | 2016-11-08 | A kind of europium polymerization of olefin using catalyst polymer nanocomposite ball and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106565966A true CN106565966A (en) | 2017-04-19 |
| CN106565966B CN106565966B (en) | 2019-04-09 |
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| CN107677716A (en) * | 2017-09-26 | 2018-02-09 | 山东理工大学 | A kind of preparation method and application of the immunosensor based on AuPdCu/N GQDs@PS |
| CN110305334A (en) * | 2019-08-08 | 2019-10-08 | 东北大学 | Organic unlimited coordination polymer material of wet sensitive three-dimensional structure nano flower-like metal and its preparation method and application |
| CN112646191A (en) * | 2019-10-12 | 2021-04-13 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN114015068A (en) * | 2021-11-23 | 2022-02-08 | 中国医学科学院生物医学工程研究所 | Flower-shaped MOF material based on coordination of baicalein and copper ions and preparation method and application thereof |
| CN115197439A (en) * | 2022-08-12 | 2022-10-18 | 复旦大学 | Plant interface super-assembly SAFs fluorescent material and preparation method thereof |
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| CN105837830A (en) * | 2016-04-19 | 2016-08-10 | 大连理工大学 | Preparation method and application of europium coordination polymer for visible detection on p-nitrophenol and iron ion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107677716A (en) * | 2017-09-26 | 2018-02-09 | 山东理工大学 | A kind of preparation method and application of the immunosensor based on AuPdCu/N GQDs@PS |
| CN110305334A (en) * | 2019-08-08 | 2019-10-08 | 东北大学 | Organic unlimited coordination polymer material of wet sensitive three-dimensional structure nano flower-like metal and its preparation method and application |
| CN112646191A (en) * | 2019-10-12 | 2021-04-13 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN112646191B (en) * | 2019-10-12 | 2022-03-22 | 中国科学院福建物质结构研究所 | Rare earth-organic framework nano fluorescent probe and preparation method and application thereof |
| CN114015068A (en) * | 2021-11-23 | 2022-02-08 | 中国医学科学院生物医学工程研究所 | Flower-shaped MOF material based on coordination of baicalein and copper ions and preparation method and application thereof |
| CN114015068B (en) * | 2021-11-23 | 2023-02-10 | 中国医学科学院生物医学工程研究所 | Flower-shaped MOF material based on coordination of baicalein and copper ions and preparation method and application thereof |
| CN115197439A (en) * | 2022-08-12 | 2022-10-18 | 复旦大学 | Plant interface super-assembly SAFs fluorescent material and preparation method thereof |
| CN115197439B (en) * | 2022-08-12 | 2023-06-20 | 复旦大学 | Plant interface super-assembled SAFs fluorescent material and preparation method thereof |
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