CN106432306B - The preparation method and application of a kind of Rare Earth Europium Complex and its fluorescent foam - Google Patents
The preparation method and application of a kind of Rare Earth Europium Complex and its fluorescent foam Download PDFInfo
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Abstract
The invention discloses the preparation methods and application of a kind of Rare Earth Europium Complex and its fluorescent foam.Wherein, the preparation method of Rare Earth Europium Complex is using Phen as raw material, by generating Phen-NO with concentrated acid solution reaction2, then react to obtain Phen-NH with hydrazine hydrate2, then with Eu (TTA)3·2H2O hybrid reaction, and then obtain Rare Earth Europium Complex Eu (TTA)3·Phen‑NH2.It is dissolved in DMSO solution, zwitterion is detected with the method that ion titrates, to H2PO4 ‑、CH3COO‑、F‑、Cu2+Play preferable recognition reaction.The preparation method of europium complex fluorescent foam is by Eu (TTA)3·Phen‑NH2PEG600 is introduced, in the system that open loop epoxy soybean oil polyalcohol and MDI foam jointly as light emitting molecule, prepares europium complex fluorescent foam.Fluorescent foam preparation method is simple, and the reaction time is short, and environmentally protective, to Cu2+Recognition reaction is good.For traditional product, large specific surface area due to more than the abscess, single recognition capability is strong, and the disadvantages of conventional fluorescent probe can be overcome to quench in aqueous solvent, has wide practical use in the fields such as medical treatment, agricultural, food.
Description
Technical field
The invention belongs to and rare earth high polymer composite luminescent material technical field, and in particular to a kind of Rare Earth Europium Complex and
The preparation method and application of its fluorescent foam.
Background technique
Rare earth is new function material that is a kind of while having the multifrequency natures such as light, magnetic, electricity and biology.Rare earth ion because
For its 4f electronic shell unique texture and possess unique luminosity, these unique luminosities are curing rare earth compound
Treatment, bio-imaging, optical fiber, lighting device etc. are widely used.Rare earth compounding is matched by ligand and rare earth ion
Position bonding obtains, and principle of luminosity, which is ligand, absorbs energy in ultra-violet (UV) band, then ligand in a manner of intramolecular charge-transfer transition,
Emission level by the energy transmission of its excitation state to rare earth ion leads to rare earth luminescence.
Although rare earth compounding has many advantages, such as that excitation purity is high, theoretical quantum efficiency is long up to 100% and luminescent lifetime,
But the fluorescent emission of rare earth compounding is easily quenched by hydrone.Therefore design synthesis can be done dilute for a long time in aqueous solution
Native complex is most important.
The Patent design has synthesized the novel europium complex containing amino, then by the method that is crosslinked by its at
Function is introduced into the polyurethane foam of environment-friendly type, effectively overcomes the europium complex deficiency that fluorescent emission is easily quenched in water.
Further, since the fluorescent foam contains the site that can be used as with zwitterion, therefore the foam can be in aqueous solution
Zwitterion is effectively identified.Currently, being rarely reported based on the rare-earth fluorescent foam based on polyurethane, such fluorescence
Foam has the advantages that illumination effect is good, environmentally friendly etc. multiple, it is often more important that the fluorescent foam probe is reusable, use cost
It is lower.
Summary of the invention
For the prior art, there are the above problems, and it is an object of the present invention to provide a kind of preparations of Rare Earth Europium Complex
Method and its application.
It is a further object to provide a kind of simple, strong operability, the high novel fluorescence foams of luminous efficiency
Preparation method and application.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of Rare Earth Europium Complex, the Rare Earth Europium Complex are Eu (TTA)3·Phen-NH2, including
Following steps:
1) dissolution of 1:1~10 in molar ratio of Phen and the concentrated sulfuric acid is placed in reflux unit.
2) oil bath heating reflux unit is used, temperature is risen to 130~170 DEG C, concentrated acid solution is then added dropwise thereto, and
It is maintained at progress back flow reaction 3h at 130~170 DEG C, room temperature is cooled to and obtains reaction solution.The concentrated acid solution is the concentrated sulfuric acid
1:1~10 are mixed in molar ratio with concentrated nitric acid；The usage amount of the concentrated acid solution be step 1) in concentrated sulfuric acid usage amount 2~
8 times.
3) reaction solution for obtaining step 2) is cooled to room temperature, then pours into ice water, is 10%~50% with mass concentration
NaOH solution neutralization reaction liquid to neutral range, the light-yellow precipitate being precipitated filters the light-yellow precipitate, water
It washes, dry, obtain yellow solid；After ethyl alcohol recrystallization, filter, the Phen-NO of drying to obtain yellow powder2。
4) Phen-NO for obtaining step 3)21:5~15 mix in molar ratio with hydrazine hydrate, add dehydrated alcohol
Make Phen-NO2It is completely dissolved, forms mixed solution；After the mixed solution is reacted 2~10h at 30~100 DEG C, 10h is stood
Precipitating is generated, then will reheat the mixed solution to 30~100 DEG C；It when precipitating re-dissolves, filters while hot, by filter residue
Several times with dehydrated alcohol rinse, and by the rinse liquid that rinse generates it pours into filtrate.Filtrate is rotated with revolving instrument at 60 DEG C
Fall solvent, obtain brown solid, take out the brown solid and drying, then with dehydrated alcohol recrystallization purifying, it is filtering, dry
Afterwards, brown solid powder, i.e. Phen-NH are obtained2。
5) Phen-NH for obtaining step 4)2With Eu (TTA)3·2H2O is that 1:1~10 is mixed, then uses THF in molar ratio
It is dissolved into reaction solution；1~10h of reaction at 30~100 DEG C is placed it in again, is then cooled to room temperature, and is revolved then at 20~80 DEG C
Solvent is evaporated, after being dried, obtains red brown solid powder, i.e. Rare Earth Europium Complex Eu (TTA)3·Phen-NH2。
Wherein: the molar ratio 1:5 of Phen and the concentrated sulfuric acid in step 1).
The temperature of back flow reaction is 150 DEG C in step 2)；The concentrated acid solution being added dropwise in step 2) is the concentrated sulfuric acid and concentrated nitric acid
1:1 is mixed in molar ratio.
Phen-NO in step 4)21:8 is mixed in molar ratio with hydrazine hydrate；, mixed solution is anti-at 75 DEG C in step 4)
Answer 3h.
Phen-NH in step 5)2With Eu (TTA)3·2H2The molar ratio of O is 1:1；, reaction solution is at 70 DEG C in step 5)
Lower reaction 3h.
Above-mentioned europium complex and DMSO are mixed into detection reagent by application of the above-mentioned europium complex in ion detection,
Using DMSO solution to be detected as test agent to be checked, the fluorescent emission intensity value A1 of detection reagent is first measured, then by the detection
Reagent and test agent to be checked measure its fluorescent emission intensity value A2 after being mixed, if A2 is less than A1, determine substance to be detected
In contain F-、H2PO4 -、CH3COO-。
A kind of preparation method of europium complex fluorescent foam, the Rare Earth Europium Complex Eu that will be prepared according to the above method
(TTA)3·Phen-NH2The body that PEG600, open loop epoxy soybean oil polyalcohol and MDI foam jointly is introduced into as light emitting molecule
In system, europium complex fluorescent foam is prepared.
Specifically includes the following steps:
It (1) is in molar ratio that 1:1~10 mix, while 01~0.5mL February is added with poly- hexylene glycol by open loop polyalcohol
Dilaurylate stirs evenly, and forms mixture.
(2) by Eu (TTA)3·Phen-NH2It is dissolved in suitable THF, is configured to the solution of 0.5g~2g/L；Again should
Solution is added in the mixture of step (1), obtains mixed raw material.
(3) mixed raw material that step (2) obtains is mixed with MDI, and stirred evenly；Being subsequently poured into mold keeps it solid
Change, obtains europium complex fluorescent foam.
Wherein: the molar ratio of open loop polyalcohol described in step (1) and poly- hexylene glycol is 1:1.
Application of the above-mentioned europium complex fluorescent foam in ion detection mixes above-mentioned europium complex fluorescent foam with water
It is combined into detection reagent, using aqueous solution to be detected as test agent to be checked, first measures the fluorescent emission intensity value A3 of detection reagent, then
Its fluorescent emission intensity value A4 is measured after the detection reagent and test agent to be checked are mixed, if A4 is less than A3, is determined
Contain Cu in substance to be detected2+。
Compared with prior art, the invention has the following beneficial effects:
1, the present invention is that prepared environment-friendly type fluorescent foam material can effectively overcome europium complex in aqueous solution
The deficiencies of transmitting is easily quenched, prepared fluorescence probe can be recycled in aqueous solution.
2, fluorescent foam of the invention is stronger to the selective recognition capability of zwitterion, can be effectively to Cu2+It carries out single
One identification.
3, fluorescent foam of the invention has stronger recognition reaction to zwitterion compared with gel-like large specific surface area.
4, preparation method provided by the invention is simple, and strong operability, the reaction time is short, and environmentally protective, is suitble to industry
Production, all has wide practical use in the fields such as medical treatment, agricultural, food.
Detailed description of the invention
Fig. 1 is Phen, Phen-NO2、Phen-NH2Infrared spectroscopy；
Fig. 2 is Phen-NH2、Eu(TTA)32H2O、Eu(TTA)3·Phen-NH2Infrared spectroscopy；
Fig. 3 is Phen-NH2、Eu(TTA)32H2O、Eu(TTA)3·Phen-NH2Fluorescence emission spectrum；
Fig. 4 is the emission spectrum of fluorescent foam；
Fig. 5 is fluorescent foam and Eu (TTA)3·Phen-NH2Thermal gravimetric analysis curve；
Fig. 6 is Eu (TTA)3·Phen-NH2Solution identifies fluorescence Spectra to the selection of anion；
Fig. 7-1 is Eu (TTA)3·Phen-NH2Solution is to CH3COO-Identification fluorescence Spectra；
Fig. 7-2 is Eu (TTA)3·Phen-NH2Solution is to F--Identification fluorescence Spectra；
Fig. 7-3 is Eu (TTA)3·Phen-NH2Solution is to H2PO4 -Identification fluorescence Spectra；
Fig. 8 is Eu (TTA)3·Phen-NH2Solution identifies fluorescence Spectra to the selection of cation；
Fig. 9 is Eu (TTA)3·Phen-NH2Solution is to Cu2+Identification fluorescence Spectra；
Figure 10 is Eu (TTA)3·Phen-NH2Solution identifies ultraviolet spectra to the selection of anion；
Figure 11 is Eu (TTA)3·Phen-NH2Fluorescent foam identifies fluorescence Spectra to the selection of cation；
Figure 12 is Eu (TTA)3·Phen-NH2Fluorescent foam is to Cu2+Identification fluorescence Spectra.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment 1
Rare Earth Europium Complex Eu (TTA) is prepared using following methods3·Phen-NH2, molecular formula is,
Synthetic route are as follows:
Specifically comprise the following steps:
1) 10.0g (55.5mmol) 1,10- Phen (Phen) is taken to be put into 250ml three-necked flask, then at three mouthfuls
The 15.0mL concentrated sulfuric acid is added in flask and is put into magnetite.
2) three-necked flask is installed on DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus with iron stand, is burnt at three mouthfuls
It installs reflux condensing tube on bottle additional, and blocks remaining two mouthfuls of three-necked flask with glass stopper.Setting oil bath temperature is 150 DEG C and stirs,
When temperature reaches set temperature, the concentrated sulfuric acid that addition is slowly dropped into that volume ratio is 1:1 in three-necked flask is mixed with concentrated nitric acid
Object 60ml (system temperature when mixture is added dropwise should be controlled at 170 DEG C or less).It is then refluxed for reaction 3h, is taken after reaction
Three-necked flask naturally cools to room temperature by it out.
3) liquid in three-necked flask is added in the deionized water of ice again.Then in the NaOH solution for being 30% with concentration
It is 6.0 or so with pH value is titrated to.Light-yellow precipitate is precipitated at this time, then by filtering, washing, being dried to obtain yellow solid.
With ethyl alcohol recrystallization yellow solid, 2.2g yellow powder is obtained after filtration drying, this powder is that 5- nitro -1,10- is adjacent
Phenanthroline (Phen-NO2), yield 24%.
4) 0.64g (6.0mmol) 10% palladium/carbon is weighed as catalyst, 4.85g 80% (mass fraction) hydrazine hydrate
It is added in 250mL three-necked flask with 20.0mL dehydrated alcohol, three-necked flask is installed to DF-101S heat collecting type constant temperature with iron stand
It heats on magnetic stirring apparatus, installs reflux condensing tube additional on three-necked flask, and block remaining two mouthfuls of three-necked flask with glass stopper.If
It sets oil bath temperature to be 72 DEG C and stir, weighs 2.03g (9mmol) 5- nitro -1,10- Phen at this time and be packed into three-necked flask
In, 40mL dehydrated alcohol is then added and make its sufficiently dissolve (total additional amount of dehydrated alcohol to be completely dissolved nitro -1 5-,
Subject to 10- Phen).When oil bath temperature reaches set temperature, the solution dissolved is poured into three-necked flask rapidly.Instead
After answering 10h, then about 10h is stood, then oil bath pan is warming up to 60 DEG C again, after the precipitating in reaction system re-dissolves,
It removes three-necked flask at once and pours out solution and filter while hot, filter residue is with dehydrated alcohol rinse 5 times or so.Filtrate is taken to use revolving instrument
Solvent is rotated, brown solid is obtained, the drying 12 hours of 60 DEG C of vacuum drying oven is used after taking out brown solid, finally with anhydrous
Ethyl alcohol recrystallization purified product, filtering, 60 DEG C are dried in vacuo 12 hours, obtain 1.28g brown solid powder, this powder is
5- amino -1,10- Phen (Phen-NH2), yield 72.9%.
B in Fig. 1 is the infrared spectrogram of 5- nitro -1,10- Phen, we will become apparent from B figure in 1286cm-1Place
There is absorption peak, this is-NO2Stretching vibration characteristic peak, 1618cm in the figure-1、1501cm-1、1444cm-1Absorption peak at three
For the stretching vibration characteristic peak of C=C, and the bending vibration characteristic peak of c h bond appears in 902cm-1, 828cm-1, 729cm-1Three
Place.C (infrared spectrogram of 1,10- Phen) in comparison diagram 1, it was demonstrated that nitro -1 5- has been synthesized by 1,10- Phen,
10- Phen.A is the infrared spectrogram of 5- amino -1,10- Phen in Fig. 1, we will become apparent from from figure
3326cm-1And 3207cm-1There is absorption peak at place, this is the stretching vibration characteristic peak of N-H, and in 1642cm-1And 1587cm-1Locate
The characteristic peak of C=N double bond, 1249cm are showed-1The absorption peak at place is the characteristic peak of C-N, and the B in comparison diagram 1, to demonstrate
5- amino -1,10- Phen has been synthesized by 5- nitro -1,10- Phen.
5) 0.391g (0.002mol) 5- amino -1,10- Phen and 1.695g (0.002mol) Eu are weighed
(TTA)3·2H2O, by the two with pouring into beaker, and with 50mL tetrahydrofuran (THF) dissolution (to guarantee dissolution sufficiently, can be with
Made it dissolve sufficiently with supersonic wave cleaning machine ultrasonic half an hour), it is subsequently poured into single-necked flask, flask is installed to iron stand
On DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus, reflux condensing tube is installed additional on three-necked flask, setting oil bath temperature is 70
DEG C, use moderate-speed mixer.It after reacting 3h, takes out flask and is cooled to room temperature, then fall solvent, setting rotation using revolving instrument vacuum distillation
Steaming temperature is 50 DEG C.After solvent is gradually rotated, red brown solid is precipitated gradually.Then 60 DEG C of vacuum oven are used
It is 12 hours dry, 1.873g red brown solid powder is obtained, this solid powder, that is, Eu (TTA)3·Phen-NH2, yield 92.7%.
Example 2 is to example 4
The preparation method of use is same as Example 1, the difference is that hen-NH in step 4)2With Eu (TTA)3·2H2O's
It is molar ratio, the usage amount of THF, reaction temperature and reaction time, specific such as table 1:
Table 1
| THF dosage | Reaction temperature | Reaction time | Phen-NH2With Eu (TTA)3·2H2The molar ratio of O | |
| Embodiment 2 | 45 | 60 | 2 | 1:1 |
| Embodiment 3 | 55 | 75 | 3 | 1:2 |
| Embodiment 4 | 65 | 85 | 4 | 1:3 |
In Fig. 2, A and C are in 3328cm-1And 3218cm-1There is absorption peak at place, this is apparent N-H stretching vibration peak, says
Bright there are same amino in Fig. 2A and 4C, and A and C are in 1662cm-1There is absorption peak at place, this is that the stretching vibration of C=N double bond is special
Peak is levied, these all illustrate to contain Phen-NH in C2Characteristic peak.Because of itself water containing coordination in B,
3412cm-1Locate the characteristic absorption peak of hydroxyl, and in C, without identical broad peak, in 1609cm-1There is C=O identical with B in place
The stretching vibration peak of key, this is the carbonyl peak of TTA.It is 575cm in wavelength-1There is Eu in place, B and C3+Characteristic peak, these
It all demonstrates achievement and has synthesized complex Eu (TTA)3·Phen-NH2, but obvious discovery, complex Eu (TTA)3·Phen-
NH2In 575cm-1The absorption peak at place is compared with Eu (TTA)32H2O weakens, this may be due to as Eu (TTA)32H2O and Phen-NH2Match
Behind position, to Eu3+Absorption peak weakened.
In Fig. 3, it is respectively from left to right5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4Transition emission peak.?
Emission peak at 616nm is most strong, and corresponding transition emission peak is hypersensitive transition emission peak, belongs to magnetic dipole transition, herein
In transition process, europium complex issues feux rouges.It can clearly find, monomer 5- amino -1,10- Phen is in wavelength
It is not no emission peak at 616nm.When it and europium complex Eu (TTA)32H2After O cooperatively forms new ligand, hence it is evident that in 616nm
There is the characteristic emission peak of rare earth ion europium in place.It can be seen from the figure that working as Eu (TTA)32H2O and monomer Phen-NH2It is formed
After complex, emissive porwer decreases at 616nm.
As shown in Fig. 6,7-1,7-2,7-3, when respectively to europium complex Eu (TTA)3·Phen-NH2Solution titrates 8 equivalents
Different anions DMSO solution when, F-、H2PO4 -、CH3COO-Fluorescence intensity at 616nm sharply declines, and titrates it
Variation after him be it is negligible, this illustrates europium complex Eu (TTA)3·Phen-NH2Solution is can be to F-、H2PO4 -、
CH3COO-It is identified.
As shown in Fig. 8,11, when respectively to europium complex Eu (TTA)3·Phen-NH2Solution titrate 8 equivalents difference sun from
When the ethanol solution of daughter ion, Cu2+Fluorescence intensity at 616nm sharply declines, this illustrates Eu (TTA)3·Phen-
NH2Solution can be to Cu2+It is identified.
Thus, it is possible to europium complex is proved in ion detection, the F that can preferably identify-、H2PO4 -、CH3COO-And Cu2+,
All have wide application prospects in the fields such as medical treatment, agricultural, food.
Embodiment 5
Europium complex fluorescent foam (the polyurethane fluorescent foam for being doped with europium complex) is prepared using following methods, can be adopted
The Rare Earth Europium Complex Eu (TTA) prepared with embodiment 1-43·Phen-NH2As light emitting molecule.
(1) 2.69g (0.0025mol) open loop epoxy soybean oil polyalcohol is weighed, 1.50g (0.0025mol) polyethylene glycol,
0.1mL dibutyl tin dilaurate, stirs evenly, and forms mixture.
(2) Eu (TTA) of 0.028g is weighed3·Phen-NH2, and dissolved with a small amount of tetrahydrofuran solution, Eu is made
(TTA)3·Phen-NH2The europium complex solution that content is 0.5%, is then added in plastic cup together with mixture, and stirring is equal
It is even.
(3) 1.35g (0.005mol) MDI (methyl diphenylene diisocyanate) is then added and stirs three minutes left sides rapidly
The right side, mixture temperature is significantly raised in plastic cup at this time, and viscosity becomes larger.Finally mixing liquid is poured into mold, and at 60 DEG C
Baking oven in solidify half an hour.
Doping europium complex Eu (TTA) is prepared by above-mentioned identical experimental method3·Phen-NH2Content is 0.5%,
1%, 1.5%, 3%, 5% fluorescent foam, from Fig. 4, we it can clearly be seen that this five fluorescent foams in λem=616nm
The fluorescence intensity at place enhances with the increase of europium complex doping.
If Fig. 5 is the TGA curve of europium complex and its fluorescent foam, from the figure we can see that the heat of europium complex point
Solution is divided into three sections, and first segment is about to 236 DEG C, this stage may be the volatilization that water and remaining difficulty wave solvent, and second stage is about
Terminate to 310 DEG C, from the point of view of percent weight loss, this section accounts for whole 15%, from the point of view of the mass fraction of complex, this section
It is possible for Phen-NH2Decomposition, the third section stage to 394 DEG C or so terminate probably be TTA decomposition, be finally europium
The thermal decomposition of compound, the quality of remnants about 40% are the oxide of europium.Because being that europium complex is doped to polyurethane foam
In foam matrix, and measure seldom, therefore several foams start to thermally decompose at 158 DEG C or so.Foam after doping, relatively undopes
Foam slightly there are a little decomposition to change at 310 DEG C, and increasing with doping quality, variation is more obvious, and this phenomenon should
It is related to europium complex.From this, the fluorescent foam at 150 DEG C or less be it is more stable, can satisfy in certain temperature
Under the conditions of use.
Embodiment 6 is to embodiment 8
The method for preparing europium complex fluorescent foam is same as Example 5, the difference is that PEG and open loop are more in step (1)
THF and Rare Earth Europium Complex Eu (TTA) in the molar ratio of first alcohol, step (2)3·Phen-NH2Molar ratio, it is specific such as table 2:
Table 2
| PEG and open loop polyol mole ratio | THF and Rare Earth Europium Complex molar ratio | |
| Embodiment 6 | 1:2 | 0.1:1 |
| Embodiment 7 | 1:3 | 0.3:1 |
| Embodiment 8 | 1:4 | 0.7:1 |
As shown in Figure 10, after being respectively dropped into the different anions solution of 8 equivalents, the H at 345nm is found2PO4Extinction
Degree variation is obvious, and the change of other ions variation is less, therefore passes through Eu (TTA)3·Phen-NH2The ultraviolet spectra of solution, can
To H2PO4 -It is identified.
As shown in Figure 11,12, after instilling the aqueous solution of different ions of 8 equivalents, Cu2+Fluorescence intensity occur it is larger under
Drop, and the variation of other ions is subtle, it is therefore believed that Eu (TTA)3·Phen-NH2Fluorescent foam is to Cu2+Have preferable
Recognition reaction.
Thus, it is possible to prove that europium complex fluorescent foam prepared by the present invention in ion detection, can identify well
Cu2+, all have wide application prospects in the fields such as medical treatment, agricultural, food.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the art, other can also be made not on the basis of the above description
With the variation and variation of form.Here all embodiments can not be exhaustive.It is all to belong to technical solution of the present invention
Changes and variations that derived from are still in the scope of protection of the present invention.
Claims (6)
1. a kind of application of europium complex in ion detection, which is characterized in that the ion is F-、H2PO4 -Or CH3COO-；Institute
The Rare Earth Europium Complex stated is Eu (TTA)3·Phen-NH2, the preparation method of the Rare Earth Europium Complex the following steps are included:
1) dissolution of 1:1~10 in molar ratio of Phen and the concentrated sulfuric acid is placed in reflux unit；The Phen is 1,10- neighbour's Féraud
Quinoline；
2) oil bath heating reflux unit is used, temperature is risen to 130~170 DEG C, concentrated acid solution is then added dropwise thereto, and keep
Back flow reaction 3h is carried out at 130~170 DEG C, is cooled to room temperature and is obtained reaction solution；The concentrated acid solution is the concentrated sulfuric acid and dense
1:1~10 are mixed nitric acid in molar ratio；The usage amount of the concentrated acid solution is 2 ~ 8 times of concentrated sulfuric acid usage amount in step 1)；
3) reaction solution for obtaining step 2 is cooled to room temperature, then pours into ice water, the NaOH for being 10%~50% with mass concentration
To neutral range, the light-yellow precipitate being precipitated filters the light-yellow precipitate, is washed, is done solution neutralization reaction liquid
It is dry, obtain yellow solid；After ethyl alcohol recrystallization, filter, the Phen-NO of drying to obtain yellow powder2；
4) Phen-NO for obtaining step 3)21:5~15 mix in molar ratio with hydrazine hydrate, and adding dehydrated alcohol makes
Phen-NO2It is completely dissolved, forms mixed solution；After the mixed solution is reacted 2~10h at 30~100 DEG C, it is raw to stand 10h
At precipitating, the mixed solution then will be reheated to 30~100 DEG C；It when precipitating re-dissolves, filters while hot, filter residue is used
Dehydrated alcohol rinse several times, and the rinse liquid that rinse generates is poured into filtrate；Filtrate is rotated with revolving instrument at 60 DEG C
Solvent obtains brown solid, takes out the brown solid and drying, then with dehydrated alcohol recrystallization purifying, filtering, dry
Afterwards, brown solid powder, i.e. Phen-NH are obtained2；
5) Phen-NH for obtaining step 4)2With Eu (TTA)3·2H2O is that 1:1~10 is mixed, then is dissolved with THF in molar ratio
At reaction solution；1~10h of reaction at 30~100 DEG C is placed it in again, is then cooled to room temperature, is rotated then at 20~80 DEG C
Solvent obtains red brown solid powder, i.e. Rare Earth Europium Complex Eu (TTA) after being dried3·Phen-NH2。
2. application of the europium complex in ion detection according to claim 1, which is characterized in that in step 1) Phen with it is dense
The molar ratio 1:5 of sulfuric acid.
3. application of the europium complex in ion detection according to claim 1, which is characterized in that back flow reaction in step 2
Temperature be 150 DEG C；The concentrated acid solution being added dropwise in step 2 is that 1:1 is mixed in molar ratio for the concentrated sulfuric acid and concentrated nitric acid.
4. application of the europium complex in ion detection according to claim 1, which is characterized in that Phen-NO in step 4)2
1:8 is mixed in molar ratio with hydrazine hydrate, and mixed solution reacts 3h at 75 DEG C in step 4).
5. application of the europium complex in ion detection according to claim 1, which is characterized in that Phen-NH in step 5)2
With Eu (TTA)3·2H2The molar ratio of O is 1:1；Reaction solution reacts 3h at 70 DEG C in step 5).
6. a kind of europium complex fluorescent foam is in Cu2+Application in detection, which is characterized in that the europium complex fluorescent foam
Preparation method uses following methods: Rare Earth Europium Complex Eu (TTA) prepared by claim 13·Phen-NH2Divide as shining
Son is introduced into the system that PEG600, open loop epoxy soybean oil polyalcohol and MDI foam jointly, prepares europium complex fluorescence bubble
Foam.
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