CN106118632B - A kind of calcium carbonate-base europium complex and preparation method thereof - Google Patents
A kind of calcium carbonate-base europium complex and preparation method thereof Download PDFInfo
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- CN106118632B CN106118632B CN201610541058.6A CN201610541058A CN106118632B CN 106118632 B CN106118632 B CN 106118632B CN 201610541058 A CN201610541058 A CN 201610541058A CN 106118632 B CN106118632 B CN 106118632B
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- calcium carbonate
- europium
- tta
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- europium complex
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- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 94
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011575 calcium Substances 0.000 title claims abstract description 48
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 48
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 12
- 238000010668 complexation reaction Methods 0.000 title description 3
- 239000000843 powder Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 201
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 105
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 63
- PCJQOISZFZOTRH-UHFFFAOYSA-K trichloroeuropium;hydrate Chemical compound O.[Cl-].[Cl-].[Cl-].[Eu+3] PCJQOISZFZOTRH-UHFFFAOYSA-K 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 230000003595 spectral effect Effects 0.000 claims description 15
- 238000004566 IR spectroscopy Methods 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 8
- 238000001228 spectrum Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- -1 carbonyldioxy europium Chemical compound 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000001174 ascending effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 14
- 150000000918 Europium Chemical class 0.000 abstract description 3
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 129
- 239000002585 base Substances 0.000 description 33
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 31
- 239000000463 material Substances 0.000 description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 15
- 239000003446 ligand Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000012265 solid product Substances 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 9
- 238000006862 quantum yield reaction Methods 0.000 description 9
- 238000002211 ultraviolet spectrum Methods 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001447 alkali salts Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- LTLZBUXMDBTFMC-UHFFFAOYSA-L calcium europium(3+) carbonate Chemical compound C([O-])([O-])=O.[Ca+2].[Eu+3] LTLZBUXMDBTFMC-UHFFFAOYSA-L 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001465805 Nymphalidae Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010397 one-hybrid screening Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention provides a kind of calcium carbonate-base europium complexes, the calcium carbonate-base europium complex is using solid carbonic acid calcium powder as matrix, TTA europium complex adsorbs and/or is incorporated into its surface, its fluorescence intensity is big, fluorescence lifetime is long, under conditions of identical luminous intensity and luminescent lifetime, the use of rare earth element is considerably reduced, resource has been saved.The present invention also provides a kind of methods for preparing above-mentioned calcium carbonate-base europium complex, and this method is easy to operate, can be effectively prevented from the loss of rare earth element, the high income of calcium carbonate-base europium complex.
Description
Technical field
The present invention relates to fluorescent material field, in particular to a kind of calcium carbonate-base europium complex and preparation method thereof.
Background technique
Fluorescent material plays a significant role in various fields, and the rare earth element of the main component as fluorescent material
It is extremely limited resource, therefore, how improves the fluorescence intensity of fluorescent material, extends the fluorescence lifetime of fluorescent material, improve
The utilization of fluorescent material, the cost for reducing fluorescent material are then an important topics.
China is the most abundant country of global rare earth resource, accounts for the 80% of world saving, is had in terms of rare earth research
Its only thick advantage.And the luminous cross discipline studied as inorganic light-emitting, organic light emission, bioluminescence of rare earth compounding, again
There are highly important theoretical significance and practical application value.Because the research of rare earth luminescent material is for China dilute
Soil resource advantage is converted into economic technique superiority and plays a very important role.
In terms of improving material fluorescence intensity, the prior art, which exists, prepares fluorescent material using the i.e. double ligands of two kinds of ligands,
Obtained fluorescent material fluorescence intensity is big, but fluorescence is unstable, and there is also use two kinds of rare earth ions to prepare phosphor
Material, obtained fluorescent material fluorescence intensity and fluorescence lifetime is all more satisfactory, but higher cost, therefore, in practical application
It has difficulties, it is difficult to large-scale promotion.
It would therefore be highly desirable to develop with excellent fluorescence property and lower-cost rare earth compounding fluorescent material and its preparation
Method.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that: using calcium carbonate powder as base
Body makes TTA europium complex adsorb and/or be incorporated into calcium carbonate powder surface, forms calcium carbonate-base europium complex, product obtained
Fluorescence intensity is big, and fluorescence lifetime is long, and solves and take considerable time when organic fluorescence materials are extracted from solution and the energy
The problem of, so as to complete the present invention.
The purpose of the present invention is to provide following aspect:
In a first aspect, the present invention provides a kind of method for preparing calcium carbonate-base europium complex, which is characterized in that this method packet
Include following steps:
(1) Europium chloride hydrate is mixed with calcium carbonate powder, dispersing agent is added and is dispersed, dispersion is obtained；And
TTA is dissolved in solvent, obtains TTA solution；
(2) dispersion that step 1 obtains is mixed with TTA solution, insulation reaction；
(3) after reaction, solid content is separated.
Second aspect, the present invention also provides the calcium carbonate-base europium complexes according to made from the above method, wherein Paris white
The weight ratio of end and europium complex is the weight of calcium carbonate: weight=2:(2~15 of europium complex), preferably 2:(2.8~
11.6)。
The calcium carbonate-base europium complex provided according to the present invention, has the advantages that
(1) method provided by the invention is used to significantly reduce rare earth compounding as the cost of luminescent material；
(2) settle europium complex effectively in preparation system, europium complex can be adsorbed on calcium carbonate powder
Surface and be filtered out come, precipitate europium complex without organic base is additionally added into system；
(3) raw material sources are extensive, are easily obtained, and the preparation method of calcium carbonate powder is easy, high income；
(4) method that calcium carbonate-base europium complex is made is easy, can be prepared using conventional instrument and conventional equipment；
(5) calcium carbonate-base europium complex fluorescence intensity made from is big, fluorescence lifetime is long, using calcium carbonate powder as matrix, pole
The big cost for reducing fluorescent material.
Detailed description of the invention
Fig. 1 shows calcium carbonate powder used in the present invention, Europium chloride, ligand TTA and Examples 1 to 5 and the red of product is made
External spectrum；
Fig. 2 shows the purples that product is made in calcium carbonate powder, Europium chloride, ligand TTA and the Examples 1 to 5 used in the present invention
External spectrum；
Fig. 3 shows calcium carbonate powder used in the present invention and the XRD spectrum of product is made in Examples 1 to 5；
Fig. 4 a shows the thermogravimetric curve that product is made in Examples 1 to 5；
Fig. 4 b shows Examples 1 to 5 and product heat flow curve is made；
Fig. 5 shows the electron microscope that product is made in embodiment 3；
Fig. 6 shows the fluorescence excitation spectrum that product is made in Examples 1 to 5；
Fig. 7 shows the fluorescent excitation intensity figure that product is made in Examples 1 to 5；
Fig. 8 shows the fluorescence emission spectrum that product is made in Examples 1 to 5；
Fig. 9 shows the fluorescent emission intensity figure that product is made in Examples 1 to 5；
Figure 10 shows the mean fluorecence life diagram that product is made in Examples 1 to 5；
Figure 11 shows the quantum yield figure that product is made in Examples 1 to 5.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
The present invention described below.
According to a first aspect of the present invention, a kind of method for preparing calcium carbonate-base europium complex is provided comprising following steps:
Step 1, Europium chloride hydrate is mixed with calcium carbonate powder, dispersing agent is added and is dispersed, dispersion is obtained；
And TTA is dissolved in solvent, obtain TTA solution.
In the prior art, after preparing TTA europium complex, soluble organic base or inorganic is added usually into reaction system
Alkali, such as triethylamine, the pH of regulation system are precipitated out TTA europium complex obtained from system, then by filtering, washing
It the processing such as washs, dry and obtaining TTA europium complex.The above method is in processing, it is difficult to TTA europium complex in system be made completely to sink
Shallow lake comes out, moreover, the configuration of TTA europium complex may change during regulation system pH, leads to its fluorescence property
Decline, in addition, the loss of TTA europium complex will necessarily be generated during being filtered, washed, and rare earth element is rare money
Source should avoid this loss as possible.
Therefore, the present inventor looks for another way, and attempts to use the basic salt insoluble in preparation system as TTA europium complex
Carrier makes TTA europium complex adsorb and/or be incorporated into the surface of basic salt, obtains inorganic-organic hybrid fluorescent material.
The inventors discovered that calcium carbonate is a large amount of existing substances in nature, from a wealth of sources, cost is extremely low, compares
Whether commercially available or voluntarily prepare in the carbonate of the aobvious alkalinity such as sodium carbonate, potassium carbonate, cost advantage clearly, works as TTA
After europium complex absorption and/or conjugate calcium carbonate surface, obtained product is still present in system in solid form, it is only necessary to
Simply being filtered, washed can be obtained fluorescent material, and therefore, present invention trial uses calcium carbonate powder as solid base, simultaneously
As the matrix of organic fluorescence materials, it is used to prepare calcium carbonate-base europium complex.
In the present invention, the dispersing agent can be by Europium chloride hydrate dissolution, but cannot be by dissolution of calcium carbonate, preferably
For alcohols solvent, it is preferable to use one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol or a variety of, more preferably methanol or ethyl alcohol,
Particularly preferably methanol.
In the present invention, the solvent of selection is low boiling point solvent, i.e., boiling point is lower than 100 DEG C, to guarantee preparing carbon
System temperature is kept to be consistently lower than 100 DEG C during sour calcium base europium complex, to reduce the generation of side reaction.
In the present invention, Europium chloride hydrate is added to dispersing agent jointly with calcium carbonate powder and carries out pre-dispersed, Europium chloride
Hydrate can be dissolved in dispersing agent, and calcium carbonate powder then still exists in dispersing agent in solid form, therefore, chlorination
Some absorption is understood in europium and/or is incorporated into calcium carbonate powder surface.
In the present invention, it is preferred to be shaken after dispersing dispersing agent for Europium chloride hydrate and calcium carbonate powder using ultrasound
The method swung handles dispersion, and Europium chloride hydrate therein is made to disperse uniformly abundant with calcium carbonate powder, excellent
Selection of land, the time of ultrasonic vibration are 0.5~2 hour, preferably 1 hour.
In the present invention, the weight ratio of the Europium chloride hydrate and calcium carbonate powder is the weight of Europium chloride hydrate
Part: parts by weight=2:(10~70 of calcium carbonate powder), preferably 2:(12~60), such as 2:15,2:20,2:38,2:48 and 2:
57。
In the present invention, the TTA is methylbenzotriazole, is a kind of ligand of Europium chloride hydrate, with chlorination
Europium interacts to obtain the organic fluorescence materials that can issue feux rouges.
In the present invention, TTA is separately dissolved, TTA solution is made, wherein solvent used in dissolution TTA is preferably alcohols
Solvent, it is preferable to use one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol or a variety of, more preferably with dispersion Europium chloride hydrate with
The dispersing agent of calcium carbonate powder is identical.
In the present invention, the ratio between mole of Europium chloride hydrate and TTA is the parts by weight of Europium chloride hydrate: TTA's
Parts by weight=1:(2~5), preferably 1:3, wherein the mole of Europium chloride hydrate with the molar amount of wherein europium element,
The mole of TTA is with the molar amount of wherein methylbenzotriazole molecule.Europium chloride hydrate and TTA theoretically can be by
Cooperated according to the ratio of 1:3, therefore, inventors believe that they also can be according to approximate ratio on calcium carbonate powder surface
Cooperated.
In the present invention, the calcium carbonate powder can may be voluntarily to prepare for commercially available from.
Without being bound by any theory, inventors believe that, nano-calcium carbonate calcium powder is used to obtain as basic salt glimmering
Luminescent material can also have smaller granularity therewith, meanwhile, the specific surface area of nanometer grade calcium carbonate is bigger, can adsorb and/or combine
More TTA europium complexes, so as to increase the fluorescence intensity of product, and the uniform nanometer calcium carbonate of particle diameter distribution can obtain
Obtain the fluorescent material of performance stable uniform.
Therefore, in the present invention, the calcium carbonate powder is preferably nano-calcium carbonate calcium powder, if partial size is 50nm~70nm
Nano-calcium carbonate calcium powder, more preferably particle size range between 55nm~65nm, particle diameter distribution width be 5~10nm nanometer
Calcium carbonate powder, such as the nano-calcium carbonate calcium powder that particle size range is 58nm~63nm.In the present invention, term " partial size point used
Cloth width " refers in nano-calcium carbonate calcium powder, the difference of maximum particle diameter and minimum grain size.
In a kind of preferred embodiment of the present invention, the calcium carbonate powder is prepared by the following:
(1.1) sodium carbonate and calcium chloride are weighed, is completely dissolved in water respectively；
(1.2) sodium carbonate liquor made from step 1.1 is poured into three-necked flask, under stirring conditions to three-necked flask
The prepared calcium chloride solution of interior addition step 1.1, until calcium chloride solution is all added drop-wise in sodium carbonate liquor, after reaction
Separate the solid generated, it is preferable that dry obtained solid, as calcium carbonate powder.
(1.3) it takes calcium carbonate powder made from step 1.2 to be ground with planetary ball mill, obtains calcium carbonate superfine powder powder
End, wherein the revolving speed of grinder is 480r/min, is ground 8 hours, and the nanometer calcium carbonate that particle size range is 58nm~63nm is obtained
Powder.
In the present invention, the Europium chloride hydrate, can be by commercially available, can also voluntarily prepare.
In a kind of preferred embodiment of the present invention, Europium chloride hydrate can be prepared according to following methods:
Europium oxide is placed in water and is heated up, is added under conditions of heat preservation and stirring into the water for be dispersed with europium oxide dense
Hydrochloric acid, until reaction system clear, stops heating, evaporative crystallization after filtering and impurity removing, up to six chloride hydrate europiums after drying.
When the present invention prepares six chloride hydrate europiums, the temperature for controlling reaction system from the beginning to the end is no more than 90 DEG C.
Step 2, the dispersion that step 1 obtains is mixed with TTA solution, insulation reaction.
In the present invention, mix Europium chloride hydrate with calcium carbonate powder, and common distribution, thus effectively
Avoid Europium chloride hydrate with TTA the local concentration when mixing it is excessive and cause side reaction.
In the present invention, the hybrid mode of the dispersion and TTA solution that obtain to step 1 is not specially limited, can be with
It using any one hybrid mode in the prior art, such as mixed once, is added portionwise or is added dropwise, the present invention is preferably in stirring
Under the conditions of TTA solution is added drop-wise in the system that step 1 obtains, thus make TTA europium complex generate while be adsorbed
And/or conjugate calcium carbonate surface, calcium carbonate europium complex is formed immediately, makes europium complex in calcium carbonate europium complex obtained
More uniformly spread, so that europium complex is more adsorbed and/or be incorporated into calcium carbonate surface, improve europium complex
Service efficiency.
In the present invention, it is preferred to before TTA solution is added, the temperature that system is made of ascending step 1 first.
The inventors discovered that the temperature of system made from step 1 is increased, the cooperation speed of TTA and europium can be significantly improved
Degree, and the fluorescence intensity of calcium carbonate europium complex obtained and fluorescence lifetime are significantly enhanced, and therefore, the present invention is preferably first
The temperature of system made from step 1 is increased, is more preferably increased to the boiling point of dispersing agent, that is, reflux temperature.
In the present invention, after TTA solution being added in system made from step 1, insulation reaction under conditions of reflux, instead
Preferably 0.5~2 hour, preferably 1 hour between seasonable.
The inventors discovered that the TTA europium complex in mixed system is gradually adsorbed and/or is combined under heat-retaining condition
In the surface of calcium carbonate powder, calcium carbonate-base fluorescent material is formed.
After insulation reaction 0.5 hour, the structure and performance of obtained calcium carbonate-base fluorescent material tend towards stability, with solvent
When washing to it, some can be washed down for the TTA europium complex of surface attachment, and also some can not be by
Washing is got off, when insulation reaction carry out it is 2 small when after, the structure and performance of calcium carbonate-base fluorescent material obtained basically reach surely
Fixed, when being washed with solvent to it, the TTA europium complex of surface attachment will not be washed down, that is, form stable carbon
Sour calcium base fluorescent material.
It is not bound by any theory, inventors believe that, calcium carbonate powder is on the one hand as the base for adsorbing TTA europium complex
Body, on the other hand it is also used as between basic salt and TTA europium complex there are certain specific cooperations, causes TTA europium complex
It is firmly bonded to calcium carbonate powder surface, but this cooperation need further to study.
According to the method for the present invention, the fluorescence intensity of calcium carbonate-base fluorescent material obtained is big, can reach
1100000CPS, fluorescence lifetime is long, can reach 0.00053s.
Without being bound by any theory, the present inventor is also believed that calcium carbonate-base fluorescent material obtained according to the present invention
Fluorescence intensity significantly increases, and fluorescence lifetime significantly extends, and is on calcium carbonate powder surface due to TTA europium complex by calcium carbonate
Powder bring steric hindrance, and so that the structure of TTA europium complex is changed, such as bond angle, bond distance change, while
There is a possibility that the ligancy of TTA and Europium chloride changes, so that the fluorescence intensity of TTA europium complex and fluorescence lifetime be made to obtain
It significantly increases and extends.
Step 3, after reaction, solid content is separated.
After the completion of reaction, TTA europium complex almost entirely adsorbs and/or is incorporated into calcium carbonate powder surface, obtains
Calcium carbonate-base europium complex be present in system in solid form, calcium carbonate-base europium can be obtained match by simply separating
Close object.
The present invention is not specially limited isolated mode, can be using any one side being separated by solid-liquid separation in the prior art
Method, such as natural filtration, be filtered under diminished pressure.
Preferably, isolated product is washed, it is preferable to use solvent used in preparation process is washed
It washs.
It is highly preferred that products therefrom is dried, the present invention is not specially limited drying mode used, can adopt
It is dried under reduced pressure with any one drying mode in the prior art, such as normal temperature and pressure drying, room temperature.
The infrared spectroscopy characteristic peak of carbonyldioxy europium complex obtained concentrates on 600cm-1~3700cm-1, such as 1400cm-1
And 3440cm-1Nearby there are strong absworption peak, 875cm-1、1130cm-1And 1630cm-1Nearby there is time strong peak.
With the increase of europium complex weight ratio in product, characteristic peak position does not have significant change there is no bright, leads yet
Concentrate on 600cm-1~3700cm-1, but 1130cm-1The intensity at neighbouring peak gradually increases, the carbonylic stretching vibration of TTA by
Positioned at 1401cm-1And 1614cm-1Two vibration peak compositions, the two peaks belong to carbonyl antisymmetric stretching vibration peak.
The ultraviolet characteristic absorption peak that product is made is weaker, near a length of 341nm of maximum absorption wave.
It is made in product, the weight ratio of calcium carbonate powder and europium complex is the weight of calcium carbonate: the weight of europium complex
=2:(2~15), preferably 2:(2.8~11.6).
According to the second aspect of the invention, the calcium carbonate-base europium complex according to made from the above method is provided, with carbonic acid
Calcium powder is matrix, calcium carbonate surface absorption and/be incorporated into TTA europium complex, wherein calcium carbonate powder and TTA europium cooperate
The weight ratio of object is the weight of calcium carbonate: weight=2:(2~15 of TTA europium complex), preferably 2:(2.8~11.6).
The infrared spectroscopy characteristic peak of the calcium carbonate-base europium complex concentrates on 600cm-1~3700cm-1, such as 1400cm-1
And 3440cm-1Nearby there are strong absworption peak, 875cm-1、1130cm-1And 1630cm-1Nearby there is time strong peak.
The ultraviolet characteristic absorption peak of its europium complex of the calcium carbonate is weaker, near a length of 341nm of maximum absorption wave.
The calcium carbonate-base europium complex provided according to the present invention, has the advantages that
(1) method provided by the invention is used to significantly reduce rare earth compounding as the cost of luminescent material；
(2) settle europium complex effectively in preparation system, europium complex can be adsorbed on calcium carbonate powder
Surface and be filtered out come, precipitate europium complex without organic base is additionally added into system；
(3) raw material sources are extensive, are easily obtained, and the preparation method of calcium carbonate powder is easy, high income；
(4) method that calcium carbonate-base europium complex is made is easy, can be prepared using conventional instrument and conventional equipment；
(5) calcium carbonate-base europium complex fluorescence intensity made from is big, fluorescence lifetime is long, using calcium carbonate powder as matrix, pole
The big cost for reducing fluorescent material.
Embodiment
(1) preparation of calcium carbonate powder
A. natrium carbonicum calcinatum 5.3269g, anhydrous calcium chloride 5.5136g are weighed respectively, in two clean beakers, are distinguished
The distilled water for measuring 100ml pours into load weighted drug, then be individually placed in ultrasonic vibration cleaning machine concussion be dissolved to all at
For colourless solution, the sodium carbonate liquor prepared is poured into three-necked flask, is put into after medium size magneton and is fixed on heating with iron stand
In set, configured calcium chloride solution is added dropwise into flask with dropping liquid machine after opening stirring, until calcium chloride solution is all added drop-wise to
In calcium carbonate soln, a large amount of white precipitates are generated, white precipitate is filtered, as calcium carbonate, obtained calcium carbonate is put into baking
It is dried in case；
B. by dried CaCO3It is divided into quarter, is placed in four grinding pots, and is added respectively in each grinding pot
Enter 50 small-sized grinding beads, 16 medium size grinding beads, 16 large size grinding beads cover ground cover with spoon after mixing evenly, will
Four grinding pots are symmetrically placed on grinder, and are fixed with spanner, are then shut off grinder caping, are powered on, with maximum
Revolving speed 480r/min after grinding 8h, obtains the calcium carbonate powder that partial size is 58~63nm.
The infrared spectroscopy of product is as shown in figure 1 1413cm in wave number shown in curve 6-1There is the peak of maximum intensity in place,
Wave number is 873cm-1、1106cm-1、2358cm-1And 1209cm-1There is absorption peak in place, in 3465cm-1Place occurs wide and strong
Peak.
(2) preparation of Europium chloride
A. 4.5740g Eu is dissolved with 100mL distilled water in 250mL beaker2O3, it is put into magneton and heating stirring, heating
To 90 DEG C or so, the drop hydrogen peroxide of dense HCL and 4 of a dropper is added, and constantly heats, alternate dropwise addition concentrated hydrochloric acid and peroxidating
Hydrogen, until solution eventually becomes clear state, stopping heating；
B. solvent in the colourless solution that evaporation step a is obtained, cooling and standings after epitaxial to appear filter, and evaporation occurs white
The paste of color is put into paper bag after water base is evaporated and saves product, it is to be dried two days later by product taking-up be put into plastics from
It is saved in heart pipe.
The infrared spectroscopy of product is as shown in figure 1 1400cm in wave number shown in curve 7-1And 1631cm-1There is intensity in place
Maximum peak is 678cm in wave number-1、2362cm-1There is absorption peak in place, in 3070cm-1、3309cm-1And 3538cm-1Locate
Existing wide and strong peak.
Embodiment 1
(1) CaCO obtained in 0.2g (one) is weighed with assay balance3It is placed in the beaker of 250mL, adds into beaker
Enter 0.15g Europium chloride, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour；0.13gTTA is placed in
In 250ml beaker, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour；
(2) mixed liquor of Europium chloride and calcium carbonate that step 1 obtains is poured into clean three-necked flask and in oil bath pan,
Back flow reaction 1 hour, after the reaction of TTA methanol solution being added dropwise dropwise into system during this period 1 hour, sufficient system will be reacted
It is filtered with Buchner funnel, obtains solid product, solid product is placed in 80 DEG C of baking ovens dry.
(3) product is taken out, product is scraped from filter paper, is put into plastic centrifuge tube and saves.
The infrared spectroscopy of product is as shown in figure 1 1434cm in wave number shown in curve 1-1There is the peak of maximum intensity in place,
Wave number is 875cm-1、1132cm-1And 1650cm-1There is absorption peak in place, in 3444cm-1There is wide and stronger peak in place.
The fluorescence lifetime for testing product, is fitted, obtaining three fluorescence lifetimes is respectively T1=4.90754*10 with three-level- 4Sec, T2=1.06566*10-3Sec, T3=1.466523*10-4Sec, mean fluorecence service life are 4.773869*10-4sec。
Embodiment 2
(1) CaCO obtained in 0.2g (one) is weighed with assay balance3It is placed in the beaker of 250mL, adds into beaker
Enter 0.20g Europium chloride, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour；0.21gTTA is placed in
In 250ml beaker, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour,
(2) mixed liquor of Europium chloride and calcium carbonate that step 1 obtains is poured into clean three-necked flask and in oil bath pan,
Back flow reaction 1 hour, after the reaction of TTA methanol solution being added dropwise dropwise into system during this period 1 hour, sufficient system will be reacted
It is filtered with Buchner funnel, obtains solid product, solid product is placed in 80 DEG C of baking ovens dry.
(3) product is taken out, product is scraped from filter paper, is put into plastic centrifuge tube and saves.
The infrared spectroscopy of product is as shown in figure 1 1417cm in wave number shown in curve 2-1There is the peak of maximum intensity in place,
Wave number is 875cm-1、1116cm-1、619cm-1And 1650cm-1There is absorption peak in place, in 3325cm-1Place occurs wide and weaker
Peak.
The fluorescence lifetime for testing product, is fitted, obtaining three fluorescence lifetimes is respectively T1=5.242796*10 with three-level- 4Sec, T2=9.268121*10-4Sec, T3=2.04035*10-4Sec, mean fluorecence service life are 5.28146*10-4sec。
Embodiment 3
(1) CaCO obtained in 0.20g (one) is weighed with assay balance3It is placed in the beaker of 250mL, adds into beaker
Enter 0.38g Europium chloride, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour；0.39gTTA is placed in
In 250ml beaker, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour；
(2) mixed liquor of Europium chloride and calcium carbonate that step 1 obtains is poured into clean three-necked flask and in oil bath pan,
Back flow reaction 1 hour, after the reaction of TTA methanol solution being added dropwise dropwise into system during this period 1 hour, sufficient system will be reacted
It is filtered with Buchner funnel, obtains solid product, solid product is placed in 80 DEG C of baking ovens dry.
(3) product is taken out, product is scraped from filter paper, is put into plastic centrifuge tube and saves.
The infrared spectroscopy of product is as shown in figure 1 1430cm in wave number shown in curve 3-1There is the peak of maximum intensity in place,
Wave number is 1130cm-1、875cm-1、619cm-1And 1635cm-1There is absorption peak in place, in 3451cm-1There is wide and weak peak in place.
The fluorescence lifetime for testing product, is fitted, obtaining three fluorescence lifetimes is respectively T1=1.465659*10 with three-level- 4Sec, T2=4.592247*10-4Sec, T3=9.305643*10-4Sec, mean fluorecence service life are 4.495344*10-4sec。
Embodiment 4
(1) CaCO obtained in 0.2g (one) is weighed with assay balance3It is placed in the beaker of 250mL, adds into beaker
Enter 0.48g Europium chloride, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour；0.50gTTA is placed in
In 250ml beaker, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour,
(2) mixed liquor of Europium chloride and calcium carbonate that step 1 obtains is poured into clean three-necked flask and in oil bath pan,
Back flow reaction 1 hour, after the reaction of TTA methanol solution being added dropwise dropwise into system during this period 1 hour, sufficient system will be reacted
It is filtered with Buchner funnel, obtains solid product, solid product is placed in 80 DEG C of baking ovens dry.
(3) product is taken out, product is scraped from filter paper, is put into plastic centrifuge tube and saves.
The infrared spectroscopy of product is as shown in figure 1 1457cm in wave number shown in curve 4-1And 1130cm-1There is intensity in place
Maximum peak is 875cm in wave number-1、619cm-1And 1650cm-1There is absorption peak in place, in 3442cm-1Place occurs wide and strong
Peak.
The fluorescence lifetime for testing product, is fitted, obtaining three fluorescence lifetimes is respectively T1=1.606353 × 10 with three-level- 4Sec, T2=5.348394 × 10-4Sec, T3=1.093081 × 10-3Sec, mean fluorecence service life are 5.226885 × 10- 4sec。
Embodiment 5
(1) CaCO obtained in 0.57g (one) is weighed with assay balance3It is placed in the beaker of 250mL, adds into beaker
Enter 0.57g Europium chloride, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour；0.59gTTA is placed in
In 250ml beaker, methanol 30mL is added, is then placed in ultrasonic disperse machine and disperses 1 hour,
(2) mixed liquor of Europium chloride and calcium carbonate that step 1 obtains is poured into clean three-necked flask and in oil bath pan,
Back flow reaction 1 hour, after the reaction of TTA methanol solution being added dropwise dropwise into system during this period 1 hour, sufficient system will be reacted
It is filtered with Buchner funnel, obtains solid product, solid product is placed in 80 DEG C of baking ovens dry.
(3) product is taken out, product is scraped from filter paper, is put into plastic centrifuge tube and saves.
The infrared spectroscopy of product is as shown in figure 1 1434cm in wave number shown in curve 5-1There is the peak of maximum intensity in place,
Wave number is 1132cm-1、875cm-1And 1650cm-1There is absorption peak in place, in 3442cm-1There is wide and weak peak in place.
The fluorescence lifetime for testing product, is fitted, obtaining three fluorescence lifetimes is respectively T1=1.620232 × 10 with three-level- 4Sec, T2=4.061475 × 10-4Sec, T3=7.889101 × 10-3Sec, mean fluorecence service life are 3.547393 × 10- 4sec。
Comparative example
Comparative example 1 uses sodium carbonate as matrix
This comparative example method therefor is similar to Example 3, and difference is that matrix used is sodium carbonate solid, and product is made
Fluorescence lifetime is 0.4ms, and fluorescence intensity is 1,300,000 CPS.
Experimental example
The infrared spectrum analysis of 1 product of experimental example
The infrared light of product is made in calcium carbonate powder, Europium chloride, ligand TTA and Examples 1 to 5 used in the test present invention
Spectrum, as a result as shown in Figure 1, wherein
Curve 1 indicates that the infrared spectrum curve of product is made in embodiment 1,
Curve 2 indicates that the infrared spectrum curve of product is made in embodiment 2,
Curve 3 indicates that the infrared spectrum curve of product is made in embodiment 3,
Curve 4 indicates that the infrared spectrum curve of product is made in embodiment 4,
Curve 5 indicates that the infrared spectrum curve of product is made in embodiment 5,
Curve 6 indicates the infrared spectrum curve of calcium carbonate powder,
Curve 7 indicates the infrared spectrum curve of Europium chloride,
The infrared spectrum curve of the expression of curve 8 ligand TTA.
As shown in Figure 1, the infrared spectroscopy characteristic peak that product is made in Examples 1 to 5 concentrates on 600cm-1~3700cm-1, with
The increase of europium complex weight ratio in product, characteristic peak position there is no significant change there is no bright, be 600cm in wave number-1
~3700cm-1, eight characteristic peaks are mainly concentrated in range, wherein in 1130cm-1The intensity at neighbouring peak gradually increases,
The carbonylic stretching vibration of TTA is by being located at 1401cm-1And 1614cm-1Two vibration peak compositions, the two peaks belong to carbonyl antisymmetry
Stretching vibration peak.
TTA and Eu3+Condensation product carbonyl vibration frequency obvious blue shift compared with TTA, and product is in 1430cm-1, 2350cm-1, 3400cm-1The characteristic peak that left and right occurs is the public characteristic peak of calcium carbonate, TTA and Europium chloride, in 875cm-1What left and right occurred
Characteristic peak is calcium carbonate and the public characteristic peak of TTA, and product is in 2050cm-1The characteristic peak that left and right occurs is the distinctive spy of product
Peak is levied, shows that C=O key original after carbonyl and europium are coordinated is weakened by the resonant structure of C-O-Eu and C=O-Eu, so that bonding force is normal
Number, which weakens, causes carbonyl to be displaced to low frequency, and infrared spectroscopy is shown, the infrared spectroscopy that product is made in Examples 1 to 5 is similar, only peak position
Micro-displacement occurs, shows that they have similar structure.
The ultraviolet spectral analysis of 2 product of experimental example
The ultraviolet light of product is made in calcium carbonate powder, Europium chloride, ligand TTA and Examples 1 to 5 used in the test present invention
Spectrum, as a result as shown in Figure 2, wherein
Curve 1 indicates embodiment1The ultraviolet spectra curve of product is made,
Curve 2 indicates that the ultraviolet spectra curve of product is made in embodiment 2,
Curve 3 indicates that the ultraviolet spectra curve of product is made in embodiment 3,
Curve 4 indicates that the ultraviolet spectra curve of product is made in embodiment 4,
Curve 5 indicates that the ultraviolet spectra curve of product is made in embodiment 5,
Curve 6 indicates the ultraviolet spectra curve of calcium carbonate powder,
Curve 7 indicates the ultraviolet spectra curve of Europium chloride,
The ultraviolet spectra curve of the expression of curve 8 ligand TTA.
As shown in Figure 2, the ultraviolet spectra maximum absorption wavelength that product is made in Examples 1 to 5 is held essentially constant, and is followed successively by
340nm, 341nm, 341nm, 341nm and 341nm.
The uv absorption spectra of each calcium carbonate-base europium complex is similar, and peak shape change is little, this shows that rare earth is organic and matches
It is only related with organic ligand to close object absorbing wavelength, and in 250nm to the small chopped cooked entrails of sheep peak occurred between 300nm, not by any theory
Constraint lead to a small amount of small peak occurred inventors believe that may be to be mixed into a small amount of impurity after product standing time is long.
And calcium carbonate powder made from method (one) does not have ultraviolet absorption peak；Europium chloride made from method (two) is in wavelength
There are a strong absworption peaks at 297nm；Ligand TTA used in embodiment is that there are a strongest suctions at 297nm in wavelength
Peak is received, is that there are one strong absworption peaks at 341nm in wavelength.
Product is made in the UV lamp in Examples 1 to 5, the fluorescence with pale pink.
The XRD of 3 sample of experimental example composes measurement
Test the present invention used in calcium carbonate powder and Examples 1 to 5 be made product XRD spectrum, as a result as shown in figure 3,
Wherein,
Curve 1 indicates that the XRD curve of product is made in embodiment 1,
Curve 2 indicates that the XRD curve of product is made in embodiment 2,
Curve 3 indicates that the XRD curve of product is made in embodiment 3,
Curve 4 indicates that the XRD curve of product is made in embodiment 4,
Curve 5 indicates that the XRD curve of product is made in embodiment 5,
The XRD curve of the expression calcium carbonate powder of curve 6.
From the figure 3, it may be seen that Examples 1 to 5 be made product XRD spectra in peak type be it is similar, with method (one) in system
Calcium carbonate powder XRD spectra it is also similar, this shows that calcium carbonate serves as " carrier " in the product, this with it is ultraviolet and red above
The conclusion obtained outside is identical.
The thermogravimetric analysis of 4 product of experimental example
The thermogravimetric curve of the obtained product of testing example 1~5 as a result as shown in figures 4 a and 4b can by Fig. 4 a and Fig. 4 b
Know, the better heat stability of product is made in Examples 1 to 5, and product made from embodiment 1,2 and 5 is opened when temperature is about 300 DEG C
Begin to decompose, product made from embodiment 3 and 4 starts to decompose when temperature is 600 DEG C or more.
The electron microscope analysis of 5 product of experimental example
The Electronic Speculum of product is made in testing example 3, as a result as shown in figure 5, as shown in Figure 5, calcium carbonate-base europium complex is
As made of the aggregation of many little particles, the partial size of bulky grain made of aggregation can achieve 500nm.
The elemental analysis of 6 product of experimental example
The elemental analysis of product is made in testing example 3, as a result as shown in table 1 below,
The elemental analysis result of 1 product of table
| Element | Weight percent % | Atomic percentage % |
| Oxygen | 89.56 | 91.51 |
| Fluorine | 9.69 | 8.34 |
| Sulphur | 0.17 | 0.09 |
| Europium | 0.57 | 0.06 |
As shown in Table 1, there is fluorine and element sulphur in the product, that is, there are ligand TTA in product, to show that product is
What europium complex and calcium carbonate powder were combined.
The fluorescence excitation spectrum of 7 product of experimental example
The fluorescent exciting spectral curve of the obtained product of testing example 1~5, as a result as shown in Figure 6, wherein
Curve 1 indicates that the fluorescent exciting spectral curve of product is made in embodiment 1,
Curve 2 indicates that the fluorescent exciting spectral curve of product is made in embodiment 2,
Curve 3 indicates that the fluorescent exciting spectral curve of product is made in embodiment 3,
Curve 4 indicates that the fluorescent exciting spectral curve of product is made in embodiment 4,
Curve 5 indicates that the fluorescent exciting spectral curve of product is made in embodiment 5.
It will be appreciated from fig. 6 that the fluorescence excitation spectrum peak type of product broadens with the reduction of europium complex weight ratio in product,
Moreover, a kind of product is all there are two peak position is excited, one of them is the absorption peak of ligand, it can be seen that, different weight proportions
Ligand have certain influence to the excitating performance of calcium carbonate-base europium complex.
The excitation intensity of above-mentioned five kinds of products is depicted as curve, as a result as shown in fig. 7, as shown in Figure 7, when Europium chloride
When quality is 0.38g, fluorescence intensity is most strong, with Europium chloride and with the increasing of weight before the quality of Europium chloride is 0.38g
It is increased for adding its emissive porwer, and after this with Europium chloride and with the increase of weight, emissive porwer gradually becomes smaller, this
Being likely to be experiment joined the calcium carbonate of phase homogenous quantities, and only work as Europium chloride, when TTA, the molar ratio 1:3:0.4 of calcium carbonate
Effect is best.
The fluorescence emission spectrum of 8 product of experimental example
The fluorescence emission spectral curve of the obtained product of testing example 1~5, as a result as shown in Figure 8, wherein
Curve 1 indicates that the fluorescence emission spectral curve of product is made in embodiment 1,
Curve 2 indicates that the fluorescence emission spectral curve of product is made in embodiment 2,
Curve 3 indicates that the fluorescence emission spectral curve of product is made in embodiment 3,
Curve 4 indicates that the fluorescence emission spectral curve of product is made in embodiment 4,
Curve 5 indicates that the fluorescence emission spectral curve of product is made in embodiment 5.
As shown in Figure 8, product made from Examples 1 to 4 is all there are four launch wavelength, respectively 580nm, 593nm,
612nm, 652nm, wherein the transmitting spectral peak at 612nm is most strong, and product is in λexAfter=354nm excitation, there is Eu3+?
Transmitting spectral peak at 580nm, 593nm, 612nm and 652nm, is respectively belonging to5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4
Energy level transition.Wherein complex Eu3+Ion is at 612nm5D0→7F2Transition transmitting is most strong, strong sharp line transmitting occurs,
Therefore there is preferable monochromaticjty.
The emissive porwer of above-mentioned five kinds of products is depicted as curve, as a result as shown in figure 9, as shown in Figure 9, embodiment 3 is made
Product fluorescent emission intensity it is most strong, when the weight ratio of Europium chloride and calcium carbonate is less than 38:2, the fluorescent emission of product with
Europium chloride weight in calcium carbonate-base europium complex proportion increase and increase, when the weight ratio of Europium chloride and calcium carbonate is greater than
When 38:2, the fluorescent emission of product is reduced as the proportion of Europium chloride weight in calcium carbonate-base europium complex increases, that is, when
Effect is best when the molar ratio 1:3:0.4 of Europium chloride, TTA and calcium carbonate.
The fluorescence lifetime analysis of 9 product of embodiment
The mean fluorecence service life that product is made in Examples 1 to 5 is depicted as curve, the results are shown in Figure 10, can by Figure 10
Know, the fluorescence lifetime that product is made in Examples 1 to 5 has biggish fluctuation, with the increase of europium complex content in product, product
The big minor swing of fluorescence lifetime.
The quantum yield of 10 product of embodiment is analyzed
The quantum yield of the obtained product of testing example 1~5, and the quantum yield measured is depicted as curve, as a result such as
Shown in Figure 11, as shown in Figure 11, the quantum yield that product is made in Examples 1 to 5 is respectively 0.22,0.18,0.43,0.69,
0.18, maximum quantum yield is product made from embodiment 4, and overall quantum yield is not high, not by any theoretical beam
It ties up, inventors believe that the reason for causing product overall quantum yield not high has following two points, first is that rare-earth europium ion in product
It is not fully mated with ligand TTA, second is that wavelength selection is improper when carrying out quantum yield characterization to product.
The granularmetric analysis of 11 product of experimental example
The partial size of product is made in calcium carbonate powder made from measuring method (one) and Examples 1 to 5 respectively, as a result such as following table
Shown in 2,
The partial size of product is made in 2 calcium carbonate powder of table and Examples 1 to 5
| Sample | Partial size (nm) |
| Calcium carbonate powder is made in method (one) | 58~63 |
| Embodiment 1 | 321~354 |
| Embodiment 2 | 123~133 |
| Embodiment 3 | 259~283 |
| Embodiment 4 | 173~189 |
| Embodiment 5 | 356~384 |
As shown in Table 2, the partial size of the obtained product of Examples 1 to 5 is relatively uniform, and particle size range is narrow, but each implementation
Partial size difference between the obtained product of example is larger.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (18)
1. a kind of method for preparing calcium carbonate-base europium complex, which is characterized in that method includes the following steps:
(1) Europium chloride hydrate is mixed with calcium carbonate powder, dispersing agent is added and is dispersed, dispersion is obtained；And by TTA
It is dissolved in solvent, obtains TTA solution；Dissolve the dispersion of solvent used in TTA and dispersion Europium chloride hydrate and calcium carbonate powder
Agent is identical；
(2) dispersion that step (1) obtains is mixed with TTA solution, insulation reaction；
(3) after reaction, solid content is separated；
In step (1), the calcium carbonate powder is the nano-calcium carbonate calcium powder that partial size is 50nm~70nm.
2. the method according to claim 1, wherein in step (1), the dispersing agent is methanol, ethyl alcohol, just
One of propyl alcohol, isopropanol are a variety of.
3. according to the method described in claim 2, it is characterized in that, the dispersing agent is methanol or ethyl alcohol in step (1).
4. the method according to claim 1, wherein in step (1), the Europium chloride hydrate and Paris white
The weight ratio at end is the parts by weight of Europium chloride hydrate: parts by weight=2:(10~70 of calcium carbonate powder).
5. according to the method described in claim 4, it is characterized in that, in step (1), the Europium chloride hydrate and Paris white
The weight ratio at end is the parts by weight of Europium chloride hydrate: parts by weight=2:(12~60 of calcium carbonate powder).
6. according to the method described in claim 5, it is characterized in that, in step (1), the mole of Europium chloride hydrate and TTA
The ratio between be Europium chloride hydrate mole: mole=1:(2~5 of TTA), wherein the mole of Europium chloride hydrate with
The wherein molar amount of europium element, the mole of TTA is with the molar amount of wherein methylbenzotriazole molecule.
7. according to the method described in claim 6, it is characterized in that, in step (1), the mole of Europium chloride hydrate and TTA
The ratio between be Europium chloride hydrate mole: mole=1:3 of TTA, wherein the mole of Europium chloride hydrate is with wherein europium
The molar amount of element, the mole of TTA is with the molar amount of wherein methylbenzotriazole molecule.
8. the method according to the description of claim 7 is characterized in that the calcium carbonate powder is nanometer calcium carbonate in step (1)
Powder, for particle size range between 55nm~65nm, particle diameter distribution width is the nano-calcium carbonate calcium powder of 5~10nm.
9. according to the method described in claim 8, it is characterized in that, the calcium carbonate powder is that particle size range is in step (1)
The nano-calcium carbonate calcium powder of 58nm~63nm.
10. method described according to claim 1 or 5 or 9, which is characterized in that in step (2), before TTA solution is added,
The temperature of system, is increased to the boiling point of dispersing agent by the temperature of the obtained system of ascending step (1) first；And/or
After TTA solution is added made from step (1) in system, insulation reaction under conditions of reflux, the reaction time is 0.5~
2 hours.
11. according to the method described in claim 10, it is characterized in that, step (1) being added in TTA solution and is made in step (2)
System in after, insulation reaction under conditions of reflux, react 1 hour.
12. according to the method for claim 11, which is characterized in that in step (3), carbonyldioxy europium complex obtained it is red
External spectrum characteristic peak concentrates on 600cm-1~3700cm-1, 875cm-1、1130cm-1And 1630cm-1Nearby there is time strong peak.
13. according to the method for claim 12, which is characterized in that in step 3, carbonyldioxy europium complex obtained it is infrared
In spectral signature peak, 1400cm-1And 3440cm-1Nearby there are strong absworption peaks.
14. it is a kind of according to claim 1~one of 13 described in calcium carbonate-base europium complex made from method, which is characterized in that
Its using calcium carbonate powder as matrix, calcium carbonate surface absorption and/be incorporated into TTA europium complex.
15. calcium carbonate-base europium complex according to claim 14, which is characterized in that calcium carbonate powder and TTA europium cooperate
The weight ratio of object is the weight of calcium carbonate: weight=2:(2~15 of TTA europium complex).
16. calcium carbonate-base europium complex according to claim 15, which is characterized in that calcium carbonate powder and TTA europium cooperate
The weight ratio of object is the weight of calcium carbonate: weight=2:(2.8~11.6 of TTA europium complex).
17. calcium carbonate-base europium complex described in 4 or 16 according to claim 1, which is characterized in that its infrared spectroscopy characteristic peak collection
In in 600cm-1~3700cm-1, 875cm-1、1130cm-1And 1630cm-1Nearby there is time strong peak.
18. calcium carbonate-base europium complex according to claim 17, which is characterized in that its infrared spectroscopy characteristic peak exists
1400cm-1And 3440cm-1Nearby there are strong absworption peaks.
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