CN106118632A - 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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- CN106118632A CN106118632A CN201610541058.6A CN201610541058A CN106118632A CN 106118632 A CN106118632 A CN 106118632A CN 201610541058 A CN201610541058 A CN 201610541058A CN 106118632 A CN106118632 A CN 106118632A
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- Prior art keywords
- calcium carbonate
- tta
- europium
- product
- europium complex
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- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 91
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000011575 calcium Substances 0.000 title claims abstract description 45
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 45
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 13
- 238000010668 complexation reaction Methods 0.000 title description 3
- 239000000843 powder Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 33
- 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 189
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 100
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 25
- PCJQOISZFZOTRH-UHFFFAOYSA-K trichloroeuropium;hydrate Chemical compound O.[Cl-].[Cl-].[Cl-].[Eu+3] PCJQOISZFZOTRH-UHFFFAOYSA-K 0.000 claims description 24
- 238000002329 infrared spectrum Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 carbonyldioxy europium Chemical compound 0.000 claims description 5
- 150000001298 alcohols Chemical group 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000012141 concentrate Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000001174 ascending effect Effects 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 14
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001669 calcium Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 130
- 239000000463 material Substances 0.000 description 33
- 239000002585 base 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
- 230000003595 spectral effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 239000012265 solid product Substances 0.000 description 10
- 238000002211 ultraviolet spectrum Methods 0.000 description 9
- 238000006862 quantum yield reaction Methods 0.000 description 8
- 150000002910 rare earth metals Chemical class 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 238000001228 spectrum Methods 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
- 230000008859 change Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000010438 heat treatment 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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 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
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method 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
- 241001494479 Pecora Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003556 assay Methods 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
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- 238000010586 diagram Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- 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 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
- 238000002156 mixing Methods 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
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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 invention provides a kind of calcium carbonate-base europium complex, this 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, considerably reduce the use of rare earth element, saved resource.Present invention also offers a kind of method preparing above-mentioned calcium carbonate-base europium complex, the method is simple to operate, it is possible to be effectively prevented from the loss of rare earth element, and the yield of calcium carbonate-base europium complex is high.
Description
Technical field
The present invention relates to fluorescent material field, particularly to a kind of calcium carbonate-base europium complex and preparation method thereof.
Background technology
Fluorescent material has important function in various fields, and the rare earth element of the main component as fluorescent material
It is extremely limited resource, therefore, how to improve the fluorescence intensity of fluorescent material, extend the fluorescence lifetime of fluorescent material, improve
The utilization of fluorescent material, the cost of reduction fluorescent material are then important topics.
China is the country that global rare earth resource is the abundantest, accounts for the 80% of world saving, has in terms of rare earth research
It the thickest advantage.And rare earth compounding is luminous as inorganic light-emitting, organic light emission, the cross discipline of bioluminescence research, again
There are highly important theoretical significance and actual application value.Because, the research of rare earth luminescent material 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, there is the most double part of two kinds of parts of use and prepare fluorescent material in prior art,
The fluorescent material fluorescence intensity obtained is big, but fluorescence is unstable, there is also two kinds of rare earth ions of use and prepares phosphor
Material, the fluorescent material fluorescence intensity obtained and fluorescence lifetime are the most more satisfactory, but relatively costly, therefore, when reality is applied
Have difficulties, it is difficult to large-scale promotion.
It would therefore be highly desirable to exploitation has excellent fluorescence property and lower-cost rare earth compounding fluorescent material and preparation thereof
Method.
Summary of the invention
In order to solve the problems referred to above, present inventor has performed and study with keen determination, found that: using calcium carbonate powder as base
Body, makes the absorption of TTA europium complex and/or is incorporated into calcium carbonate powder surface, forming calcium carbonate-base europium complex, prepared product
Fluorescence intensity is big, and fluorescence lifetime is long, and solves when organic fluorescence materials is extracted from solution and take considerable time and the energy
Problem, thus complete the present invention.
It is an object of the invention to provide following aspect:
First aspect, the present invention provides a kind of method preparing calcium carbonate-base europium complex, it is characterised in that the method bag
Include following steps:
(1) Europium chloride hydrate is mixed with calcium carbonate powder, add dispersant and disperse, obtain dispersion；And
TTA is dissolved in solvent, obtains TTA solution；
(2) dispersion step 1 obtained mixes with TTA solution, insulation reaction；
(3), after reaction terminates, solid content is separated.
Second aspect, the present invention also provides for the calcium carbonate-base europium complex prepared according to said method, wherein, Paris white
End and the weight that weight ratio is calcium carbonate of europium complex: the 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 present invention significantly reduces the rare earth compounding cost as luminescent material；
(2) making europium complex effectively settle in preparation system, europium complex can adsorb at calcium carbonate powder
Surface and be filtered out, make europium complex precipitate without the organic base that adds extra in system；
(3) raw material sources are extensive, it is easy to obtain, and the preparation method of calcium carbonate powder is easy, and yield is high；
(4) method preparing calcium carbonate-base europium complex is easy, uses conventional instrument and conventional equipment to be prepared；
(5) the calcium carbonate-base europium complex fluorescence intensity prepared is big, fluorescence lifetime is long, with calcium carbonate powder as matrix, and pole
The big cost reducing fluorescent material.
Accompanying drawing explanation
Fig. 1 illustrates that the calcium carbonate powder used by the present invention, Europium chloride, part TTA and embodiment 1～5 prepare the red of product
External spectrum；
Fig. 2 illustrates that the calcium carbonate powder used by the present invention, Europium chloride, part TTA and embodiment 1～5 prepare the purple of product
External spectrum；
Fig. 3 illustrates that the calcium carbonate powder used by the present invention and embodiment 1～5 prepare the XRD spectrum of product；
Fig. 4 a illustrates that embodiment 1～5 prepares the thermogravimetric curve of product；
Fig. 4 b illustrates that embodiment 1～5 prepares product heat flow curve；
Fig. 5 illustrates that embodiment 3 prepares the Electronic Speculum figure of product；
Fig. 6 illustrates that embodiment 1～5 prepares the fluorescence excitation spectrum of product；
Fig. 7 illustrates that embodiment 1～5 prepares the fluorescent excitation intensity figure of product；
Fig. 8 illustrates that embodiment 1～5 prepares the fluorescence emission spectrum of product；
Fig. 9 illustrates that embodiment 1～5 prepares the fluorescent emission intensity figure of product；
Figure 10 illustrates that embodiment 1～5 prepares the mean fluorecence life diagram of product；
Figure 11 illustrates that embodiment 1～5 prepares the quantum yield figure of product.
Detailed description of the invention
Below by the present invention is described in detail, the features and advantages of the invention will become more along with these explanations
For clear, clear and definite.
The present invention described below.
According to a first aspect of the present invention, it is provided that a kind of method preparing calcium carbonate-base europium complex, it comprises the following steps:
Step 1, mixes Europium chloride hydrate with calcium carbonate powder, adds dispersant and disperses, obtains dispersion；
And TTA is dissolved in solvent, obtain TTA solution.
In the prior art, after preparation TTA europium complex, in reaction system, generally add solubility organic base or inorganic
Alkali, such as triethylamine etc., the pH of regulation system, makes the TTA europium complex prepared be precipitated out from system, then by filtering, washing
Wash, be dried etc. processes and obtains TTA europium complex.Said method is when processing, it is difficult to make TTA europium complex in system sink completely
Form sediment out, and, during regulation system pH, the configuration of TTA europium complex is it may happen that change, causes its fluorescence property
Declining, additionally, will necessarily produce the loss of TTA europium complex during filtering, washing, and rare earth element is rare money
Source, it should avoid this loss as possible.
Therefore, the present inventor looks for another way, and attempts using the basic salt insoluble in preparation system as TTA europium complex
Carrier, makes the absorption of TTA europium complex and/or is incorporated into the surface of basic salt, obtaining inorganic-organic hybrid fluorescent material.
The inventors discovered that, calcium carbonate is a large amount of materials existed in nature, and its wide material sources, cost is extremely low, compares
In the carbonate of the aobvious alkalescence such as sodium carbonate, potassium carbonate, being whether purchased and prepare the most voluntarily, cost advantage clearly, works as TTA
After europium complex absorption and/or conjugate calcium carbonate surface, the product obtained is present in system the most in solid form, it is only necessary to
Simple filter, washing can obtain fluorescent material, therefore, the present invention attempt using calcium carbonate powder as solid base, simultaneously
As the matrix of organic fluorescence materials, it is used for preparing calcium carbonate-base europium complex.
In the present invention, described dispersant can by Europium chloride hydrate dissolution, but can not be by dissolution of calcium carbonate, preferably
For alcohols solvent, one or more in methanol, ethanol, normal propyl alcohol, isopropanol, more preferably methanol or ethanol are preferably used,
Particularly preferably methanol.
In the present invention, the solvent of selection is low boiling point solvent, i.e. boiling point is less than 100 DEG C, thus ensures preparing carbon
Keep system temperature to be consistently lower than 100 DEG C during acid calcio europium complex, thus decrease the generation of side reaction.
In the present invention, Europium chloride hydrate is added jointly with calcium carbonate powder dispersant and carries out pre-dispersed, Europium chloride
Hydrate can be dissolved in dispersant, and calcium carbonate powder then exists in dispersant the most in solid form, therefore, and chlorination
Europium is understood some absorption and/or is incorporated into calcium carbonate powder surface.
In the present invention, it is preferred to, after Europium chloride hydrate and calcium carbonate powder are scattered in dispersant, use ultrasonic shake
Dispersion is processed by the method swung so that it is in Europium chloride hydrate disperse the most abundant with calcium carbonate powder, excellent
Selection of land, the time of ultrasonic vibration is 0.5～2 hour, preferably 1 hour.
In the present invention, described Europium chloride hydrate and the weight that weight ratio is Europium chloride hydrate of calcium carbonate powder
Part: the weight portion=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, described TTA is TTA, is a kind of part of Europium chloride hydrate, itself and chlorination
Europium interacts and obtains sending the organic fluorescence materials of HONGGUANG.
In the present invention, TTA is dissolved separately, prepare TTA solution, wherein, dissolve the solvent used by TTA and be preferably alcohols
Solvent, is preferably used one or more in methanol, ethanol, normal propyl alcohol, isopropanol, more preferably with dispersion Europium chloride hydrate with
The dispersant of calcium carbonate powder is identical.
In the present invention, the weight portion that ratio is Europium chloride hydrate of Europium chloride hydrate and the mole of TTA: TTA's
Weight portion=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 TTA molecule.Europium chloride hydrate and TTA in theory can be by
Ratio according to 1:3 coordinates, and therefore, inventors believe that they also are able to the ratio according to approximation on calcium carbonate powder surface
Coordinate.
In the present invention, described calcium carbonate powder can be that be purchased can also be for prepare voluntarily.
Without being bound by any theory, inventors believe that, use nano-calcium carbonate calcium powder as basic salt obtain glimmering
Luminescent material also can have less granularity therewith, and meanwhile, the specific surface area of nanometer grade calcium carbonate is bigger, it is possible to adsorbs and/or combines
More TTA europium complex such that it is able to increase the fluorescence intensity of product, and the nano-calcium carbonate of even particle size distribution can obtain
Obtain the fluorescent material that stable performance is homogeneous.
Therefore, in the present invention, described calcium carbonate powder is preferably nano-calcium carbonate calcium powder, if particle diameter is 50nm～70nm
Nano-calcium carbonate calcium powder, more preferably particle size range is between 55nm～65nm, and particle diameter distribution width is the nanometer of 5～10nm
Calcium carbonate powder, such as the nano-calcium carbonate calcium powder that particle size range is 58nm～63nm.In the present invention, " particle diameter divides term used
Cloth width " refer in nano-calcium carbonate calcium powder, maximum particle diameter and the difference of minimum grain size.
One of the present invention preferred embodiment in, described calcium carbonate powder is prepared by the following:
(1.1) weighing sodium carbonate and calcium chloride, is completely dissolved in water respectively；
(1.2) sodium carbonate liquor that step 1.1 prepares is poured in there-necked flask, to there-necked flask under conditions of stirring
The calcium chloride solution that interior addition step 1.1 prepares, is all added drop-wise in sodium carbonate liquor to calcium chloride solution, after reaction terminates
Separate the solid generated, it is preferable that dried by the solid obtained, be calcium carbonate powder.
(1.3) the calcium carbonate powder planetary ball mill taking step 1.2 prepared is ground, it is thus achieved that calcium carbonate superfine powder powder
End, wherein, the rotating speed of grinder is 480r/min, grinds 8 hours, it is thus achieved that particle size range is the nano-calcium carbonate of 58nm～63nm
Powder.
In the present invention, described Europium chloride hydrate, can be by commercially available, it is also possible to prepare voluntarily.
One of the present invention preferred embodiment in, Europium chloride hydrate can be prepared according to following methods:
Europium oxide it is placed in water and heats up, adding dense under conditions of insulation and stirring in the water be dispersed with europium oxide
Hydrochloric acid, until reaction system clear, stops heating, evaporative crystallization after filtering and impurity removing, the most i.e. obtains six chloride hydrate europiums.
When the present invention prepares six chloride hydrate europiums, control the temperature of reaction system from the beginning to the end less than 90 DEG C.
Step 2, dispersion step 1 obtained mixes with TTA solution, insulation reaction.
In the present invention, Europium chloride hydrate is first made to mix with calcium carbonate powder, and common distribution, thus effectively
Avoid that Europium chloride hydrate is excessive with TTA local concentration when mixing and the side reaction that causes.
In the present invention, the dispersion obtaining step 1 is not specially limited with the hybrid mode of TTA solution, permissible
Using any one hybrid mode in prior art, such as mixed once, be dividedly in some parts or dropping etc., the present invention is preferably in stirring
Under the conditions of TTA solution is added drop-wise in the system that step 1 obtains so that TTA europium complex generate while the most adsorbed
And/or conjugate calcium carbonate surface, form calcium carbonate europium complex immediately, make europium complex in the calcium carbonate europium complex prepared
More uniformly spread, also enable europium complex more adsorb and/or be incorporated into calcium carbonate surface, improve europium complex
Service efficiency.
In the present invention, it is preferred to, before adding TTA solution, first ascending step 1 prepares the temperature of system.
The inventors discovered that, the temperature of system step 1 prepared raises, it is possible to significantly improve TTA and europium coordinates speed
Spending, and the fluorescence intensity of the calcium carbonate europium complex prepared and fluorescence lifetime are significantly enhanced, therefore, the present invention is first
The temperature of system step 1 prepared raises, and is more preferably increased to the boiling point of dispersant, i.e. reflux temperature.
In the present invention, after TTA solution is added in the system that step 1 prepares, insulation reaction under conditions of backflow, instead
Between Ying Shi be preferably 0.5～2 hour, preferably 1 hour.
The inventors discovered that, under heat-retaining condition, the TTA europium complex in mixed system little by little adsorbs and/or combines
In the surface of calcium carbonate powder, form calcium carbonate-base fluorescent material.
After insulation reaction 0.5 hour, structure and the performance of the calcium carbonate-base fluorescent material obtained tend towards stability, with solvent
When it is washed, the TTA europium complex of surface attachment some can be washed down, also some can not be by
Washing is got off, and after insulation reaction is carried out 2 hours, structure and the performance of the calcium carbonate-base fluorescent material prepared basically reach surely
Fixed, when washing it with solvent, the TTA europium complex of surface attachment will not be washed down, i.e. defines stable carbon
Acid calcio fluorescent material.
Being not bound by any theory, inventors believe that, calcium carbonate powder is on the one hand as the base of absorption TTA europium complex
Body, on the other hand it also serves as there is some between basic salt with TTA europium complex and specifically coordinates, and causes TTA europium complex
It is firmly bonded to calcium carbonate powder surface, but this cooperation need to study further.
The method according to the invention, the fluorescence intensity of prepared calcium carbonate-base fluorescent material is big, it is possible to reach
1100000CPS, fluorescence lifetime is long, it is possible to reach 0.00053s.
Without being bound by any theory, the present inventor is it is also believed that the calcium carbonate-base fluorescent material for preparing according to the present invention
Fluorescence intensity significantly increases, and fluorescence lifetime significantly extends, be due to TTA europium complex on calcium carbonate powder surface by calcium carbonate
It is sterically hindered that powder brings, and makes the structure of TTA europium complex change, as bond angle, bond distance etc. change, the most also
There is a possibility that TTA changes with the ligancy of Europium chloride, so that the fluorescence intensity of TTA europium complex and fluorescence lifetime obtain
It is obviously enhanced and extends.
Step 3, after reaction terminates, separates solid content.
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 solid form in system, i.e. can get calcium carbonate-base europium by simple separation and join
Compound.
The mode separated is not specially limited by the present invention, can use the side of any one solid-liquid separation in prior art
Method, such as natural filtration, filtration under diminished pressure etc..
Preferably, the product of isolated is washed, solvent preparation process used in is preferably used and washes
Wash.
It is highly preferred that be dried products therefrom, drying mode used is not specially limited by the present invention, can adopt
With any one drying mode in prior art, as normal temperature and pressure be dried, room temperature drying under reduced pressure etc..
The infrared spectrum characteristic peak of the carbonyldioxy europium complex prepared concentrates on 600cm-1～3700cm-1, such as 1400cm-1
And 3440cm-1Near there is strong absworption peak, 875cm-1、1130cm-1And 1630cm-1The strong peak of neighbouring existence time.
Along with the increase of europium complex weight ratio in product, characteristic peak position does not has and bright does not has significant change, leads yet
600cm to be concentrated on-1～3700cm-1, but 1130cm-1Near the intensity at peak gradually strengthen, the carbonylic stretching vibration of TTA by
It is positioned at 1401cm-1And 1614cm-1Two vibration peak compositions, the two peak belongs to carbonyl antisymmetric stretching vibration peak.
The ultraviolet characteristic absorption peak preparing product is more weak, near a length of 341nm of maximum absorption wave.
Prepare in product, calcium carbonate powder and the weight that weight ratio is calcium carbonate of europium complex: the weight of europium complex
=2:(2～15), preferably 2:(2.8～11.6).
According to the second aspect of the invention, it is provided that the calcium carbonate-base europium complex prepared according to said method, it is with carbonic acid
Calcium powder is matrix, calcium carbonate surface absorption and/be incorporated into TTA europium complex, wherein, calcium carbonate powder coordinates with TTA europium
The weight ratio of thing is the weight of calcium carbonate: the weight=2:(2～15 of TTA europium complex), preferably 2:(2.8～11.6).
The infrared spectrum characteristic peak of described calcium carbonate-base europium complex concentrates on 600cm-1～3700cm-1, such as 1400cm-1
And 3440cm-1Near there is strong absworption peak, 875cm-1、1130cm-1And 1630cm-1The strong peak of neighbouring existence time.
Its europium complex ultraviolet characteristic absorption peak of described calcium carbonate is more weak, 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 present invention significantly reduces the rare earth compounding cost as luminescent material；
(2) making europium complex effectively settle in preparation system, europium complex can adsorb at calcium carbonate powder
Surface and be filtered out, make europium complex precipitate without the organic base that adds extra in system；
(3) raw material sources are extensive, it is easy to obtain, and the preparation method of calcium carbonate powder is easy, and yield is high；
(4) method preparing calcium carbonate-base europium complex is easy, uses conventional instrument and conventional equipment to be prepared；
(5) the calcium carbonate-base europium complex fluorescence intensity prepared is big, fluorescence lifetime is long, with calcium carbonate powder as matrix, and pole
The big cost reducing fluorescent material.
Embodiment
(1) preparation of calcium carbonate powder
Weigh natrium carbonicum calcinatum 5.3269g, anhydrous calcium chloride 5.5136g the most respectively, in two clean beakers, respectively
The distilled water measuring 100ml is poured in load weighted medicine, then be individually placed in ultrasonic vibration cleaning machine concussion be dissolved to all become
For colourless solution, the sodium carbonate liquor prepared is poured in there-necked flask, after putting into medium size magneton, be fixed on heating with iron stand
In set, in flask, drip, with dropping liquid machine, the calcium chloride solution configured after opening stirring, be all added drop-wise to calcium chloride solution
In calcium carbonate soln, produce a large amount of white precipitate, by white precipitate sucking filtration, be calcium carbonate, the calcium carbonate obtained is put into baking
Case is dried；
B. by dried CaCO3It is divided into quarter, is positioned in four grinding pots, and each grinding pot adds respectively
Enter 50 small-sized grinding bead, 16 medium size grinding bead, 16 large size grinding bead, stir ground cover on bonnet with spoon, will
Four grinding pots are symmetrically placed on grinder, and fix with spanner, are then shut off grinder caping, switch on power, by maximum
Rotating speed 480r/min, after grinding 8h, obtains the calcium carbonate powder that particle diameter is 58～63nm.
The infrared spectrum of product is as shown in curve 6 in Fig. 1, and it is 1413cm in wave number-1There is the peak of maximum intensity in place,
Wave number is 873cm-1、1106cm-1、2358cm-1And 1209cm-1There is absworption peak in place, at 3465cm-1Place occurs wide and strong
Peak.
(2) preparation of Europium chloride
A. in 250mL beaker, 4.5740g Eu is dissolved with 100mL distilled water2O3, put into magneton heated and stirred, heating
To about 90 DEG C, add the dense HCL of a dropper and 4 hydrogen peroxide, and constantly heat, alternate dropwise addition concentrated hydrochloric acid and peroxidating
Hydrogen, until solution eventually becomes clear state, stops heating；
B. solvent in the colourless solution that evaporation step a obtains, after epitaxial to appear, cooling stands, sucking filtration, evaporation, occurs white
The pastel of color, puts in paper bag preservation product after water base is evaporated, to be dried two days later product is taken out put into plastics from
Heart pipe preserves.
The infrared spectrum of product is as shown in curve 7 in Fig. 1, and it is 1400cm in wave number-1And 1631cm-1There is intensity in place
Maximum peak, is 678cm in wave number-1、2362cm-1There is absworption peak in place, at 3070cm-1、3309cm-1And 3538cm-1Place goes out
Existing wide and strong peak.
Embodiment 1
(1) CaCO prepared in 0.2g () is weighed with analytical balance3It is positioned in the beaker of 250mL, adds in beaker
Enter 0.15g Europium chloride, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour；0.13gTTA is positioned over
In 250ml beaker, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour；
(2) Europium chloride step 1 obtained is poured in clean there-necked flask and in oil bath pan with the mixed liquor of calcium carbonate,
Back flow reaction 1 hour, after dropwise dripping the reaction of TTA methanol solution during this period 1 hour, will react sufficient system in system
Use buchner funnel sucking filtration, obtain solid product, solid product is placed in 80 DEG C of baking ovens and is dried.
(3) take out product, product is scraped from filter paper, put in plastic centrifuge tube and preserve.
The infrared spectrum of product is as shown in curve 1 in Fig. 1, and it is 1434cm in wave number-1There is the peak of maximum intensity in place,
Wave number is 875cm-1、1132cm-1And 1650cm-1There is absworption peak in place, at 3444cm-1There is wide and stronger peak in place.
The fluorescence lifetime of test product, with three grades of matchings, obtains three fluorescence lifetimes and is respectively T1=4.90754*10- 4Sec, T2=1.06566*10-3Sec, T3=1.466523*10-4Sec, the mean fluorecence life-span is 4.773869*10-4sec。
Embodiment 2
(1) CaCO prepared in 0.2g () is weighed with analytical balance3It is positioned in the beaker of 250mL, adds in beaker
Enter 0.20g Europium chloride, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour；0.21gTTA is positioned over
In 250ml beaker, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour,
(2) Europium chloride step 1 obtained is poured in clean there-necked flask and in oil bath pan with the mixed liquor of calcium carbonate,
Back flow reaction 1 hour, after dropwise dripping the reaction of TTA methanol solution during this period 1 hour, will react sufficient system in system
Use buchner funnel sucking filtration, obtain solid product, solid product is placed in 80 DEG C of baking ovens and is dried.
(3) take out product, product is scraped from filter paper, put in plastic centrifuge tube and preserve.
The infrared spectrum of product is as shown in curve 2 in Fig. 1, and it is 1417cm in wave number-1There is the peak of maximum intensity in place,
Wave number is 875cm-1、1116cm-1、619cm-1And 1650cm-1There is absworption peak in place, at 3325cm-1Place occurs wide and more weak
Peak.
The fluorescence lifetime of test product, with three grades of matchings, obtains three fluorescence lifetimes and is respectively T1=5.242796*10- 4Sec, T2=9.268121*10-4Sec, T3=2.04035*10-4Sec, the mean fluorecence life-span is 5.28146*10-4sec。
Embodiment 3
(1) CaCO prepared in 0.20g () is weighed with analytical balance3It is positioned in the beaker of 250mL, adds in beaker
Enter 0.38g Europium chloride, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour；0.39gTTA is positioned over
In 250ml beaker, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour；
(2) Europium chloride step 1 obtained is poured in clean there-necked flask and in oil bath pan with the mixed liquor of calcium carbonate,
Back flow reaction 1 hour, after dropwise dripping the reaction of TTA methanol solution during this period 1 hour, will react sufficient system in system
Use buchner funnel sucking filtration, obtain solid product, solid product is placed in 80 DEG C of baking ovens and is dried.
(3) take out product, product is scraped from filter paper, put in plastic centrifuge tube and preserve.
The infrared spectrum of product is as shown in curve 3 in Fig. 1, and it is 1430cm in wave number-1There is the peak of maximum intensity in place,
Wave number is 1130cm-1、875cm-1、619cm-1And 1635cm-1There is absworption peak in place, at 3451cm-1There is wide and weak peak in place.
The fluorescence lifetime of test product, with three grades of matchings, obtains three fluorescence lifetimes and is respectively T1=1.465659*10- 4Sec, T2=4.592247*10-4Sec, T3=9.305643*10-4Sec, the mean fluorecence life-span is 4.495344*10-4sec。
Embodiment 4
(1) CaCO prepared in 0.2g () is weighed with analytical balance3It is positioned in the beaker of 250mL, adds in beaker
Enter 0.48g Europium chloride, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour；0.50gTTA is positioned over
In 250ml beaker, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour,
(2) Europium chloride step 1 obtained is poured in clean there-necked flask and in oil bath pan with the mixed liquor of calcium carbonate,
Back flow reaction 1 hour, after dropwise dripping the reaction of TTA methanol solution during this period 1 hour, will react sufficient system in system
Use buchner funnel sucking filtration, obtain solid product, solid product is placed in 80 DEG C of baking ovens and is dried.
(3) take out product, product is scraped from filter paper, put in plastic centrifuge tube and preserve.
The infrared spectrum of product is as shown in curve 4 in Fig. 1, and it is 1457cm in wave number-1And 1130cm-1There is intensity in place
Maximum peak, is 875cm in wave number-1、619cm-1And 1650cm-1There is absworption peak in place, at 3442cm-1Place occurs wide and strong
Peak.
The fluorescence lifetime of test product, with three grades of matchings, obtains three fluorescence lifetimes and is respectively T1=1.606353 × 10- 4Sec, T2=5.348394 × 10-4Sec, T3=1.093081 × 10-3Sec, the mean fluorecence life-span is 5.226885 × 10- 4sec。
Embodiment 5
(1) CaCO prepared in 0.57g () is weighed with analytical balance3It is positioned in the beaker of 250mL, adds in beaker
Enter 0.57g Europium chloride, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour；0.59gTTA is positioned over
In 250ml beaker, add methanol 30mL, be then placed in ultrasonic disperse machine dispersion 1 hour,
(2) Europium chloride step 1 obtained is poured in clean there-necked flask and in oil bath pan with the mixed liquor of calcium carbonate,
Back flow reaction 1 hour, after dropwise dripping the reaction of TTA methanol solution during this period 1 hour, will react sufficient system in system
Use buchner funnel sucking filtration, obtain solid product, solid product is placed in 80 DEG C of baking ovens and is dried.
(3) take out product, product is scraped from filter paper, put in plastic centrifuge tube and preserve.
The infrared spectrum of product is as shown in curve 5 in Fig. 1, and it is 1434cm in wave number-1There is the peak of maximum intensity in place,
Wave number is 1132cm-1、875cm-1And 1650cm-1There is absworption peak in place, at 3442cm-1There is wide and weak peak in place.
The fluorescence lifetime of test product, with three grades of matchings, obtains three fluorescence lifetimes and is respectively T1=1.620232 × 10- 4Sec, T2=4.061475 × 10-4Sec, T3=7.889101 × 10-3Sec, the mean fluorecence life-span is 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 matrix used for sodium carbonate solid, prepares product
Fluorescence lifetime is 0.4ms, and fluorescence intensity is 1,300,000 CPS.
Experimental example
The infrared spectrum analysis of experimental example 1 product
Test calcium carbonate powder, Europium chloride, part TTA and embodiment 1～5 used by the present invention prepares the infrared light of product
Spectrum, result as it is shown in figure 1, wherein,
Curve 1 represents that embodiment 1 prepares the infrared spectrum curve of product,
Curve 2 represents that embodiment 2 prepares the infrared spectrum curve of product,
Curve 3 represents that embodiment 3 prepares the infrared spectrum curve of product,
Curve 4 represents that embodiment 4 prepares the infrared spectrum curve of product,
Curve 5 represents that embodiment 5 prepares the infrared spectrum curve of product,
Curve 6 represents the infrared spectrum curve of calcium carbonate powder,
Curve 7 represents the infrared spectrum curve of Europium chloride,
Curve 8 represents the infrared spectrum curve of part TTA.
As shown in Figure 1, embodiment 1～5 prepares the infrared spectrum characteristic peak of product and concentrates on 600cm-1～3700cm-1, with
The increase of europium complex weight ratio in product, characteristic peak position does not has and bright does not has significant change, is 600cm in wave number-1
～3700cm-1Eight characteristic peaks mainly it are concentrated with, wherein, at 1130cm in the range of,-1The intensity at neighbouring peak gradually strengthens,
The carbonylic stretching vibration of TTA is by being positioned at 1401cm-1And 1614cm-1Two vibration peak compositions, the two peak belongs to carbonyl antisymmetry
Stretching vibration peak.
TTA and Eu3+Condensation substance carbonyl frequency of vibration obvious blue shift compared with TTA, and product is at 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, at 875cm-1Left and right occurs
Characteristic peak is the public characteristic peak of calcium carbonate and TTA, and product is at 2050cm-1The characteristic peak that left and right occurs is the distinctive spy of product
Levy peak, show carbonyl and europium be coordinated after original C=O key weakened by the resonant structure of C-O-Eu and C=O-Eu, thus bonding force is normal
Counting to weaken causes carbonyl to show to low frequency displacement, infrared spectrum, and the infrared spectrum that embodiment 1～5 prepares product is similar, only peak position
There is micro-displacement, show that they have similar structure.
The ultraviolet spectral analysis of experimental example 2 product
Test calcium carbonate powder, Europium chloride, part TTA and embodiment 1～5 used by the present invention prepares the ultraviolet light of product
Spectrum, result as in figure 2 it is shown, wherein,
Curve 1 represents embodiment1Prepare the ultraviolet spectra curve of product,
Curve 2 represents that embodiment 2 prepares the ultraviolet spectra curve of product,
Curve 3 represents that embodiment 3 prepares the ultraviolet spectra curve of product,
Curve 4 represents that embodiment 4 prepares the ultraviolet spectra curve of product,
Curve 5 represents that embodiment 5 prepares the ultraviolet spectra curve of product,
Curve 6 represents the ultraviolet spectra curve of calcium carbonate powder,
Curve 7 represents the ultraviolet spectra curve of Europium chloride,
Curve 8 represents the ultraviolet spectra curve of part TTA.
As shown in Figure 2, embodiment 1～5 prepares the ultraviolet spectra maximum absorption wavelength of product and 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 to, and peak shape change is little, and this shows that rare earth is organic and joins
Compound absorbing wavelength is only relevant with organic ligand, and the little chopped cooked entrails of sheep peak occurred between 250nm to 300nm, not by any theory
Constraint, inventors believe that and be mixed into a small amount of impurity after being probably product length standing time, cause occurring in that a small amount of small peak.
And the calcium carbonate powder that method () prepares does not has ultraviolet absorption peak；The Europium chloride that method (two) prepares at wavelength is
A strong absworption peak is there is at 297nm；The part TTA used in embodiment is one suction the strongest of existence at 297nm at wavelength
Receive peak, be at 341nm, to there is one strong absworption peak at wavelength.
Embodiment 1～5 prepares product under uviol lamp, has the fluorescence of pale pink.
The XRD spectrum of experimental example 3 sample measures
Test calcium carbonate powder used by the present invention and embodiment 1～5 prepare the XRD spectrum of product, result as it is shown on figure 3,
Wherein,
Curve 1 represents that embodiment 1 prepares the XRD curve of product,
Curve 2 represents that embodiment 2 prepares the XRD curve of product,
Curve 3 represents that embodiment 3 prepares the XRD curve of product,
Curve 4 represents that embodiment 4 prepares the XRD curve of product,
Curve 5 represents that embodiment 5 prepares the XRD curve of product,
Curve 6 represents the XRD curve of calcium carbonate powder.
From the figure 3, it may be seen that it is similar that embodiment 1～5 prepares peak type in the XRD spectra of product, itself and system in method ()
The XRD spectra of calcium carbonate powder the most similar, this shows that calcium carbonate serves as " carrier " in the product, and this is with ultraviolet above with red
The conclusion obtained outward is identical.
The thermogravimetric analysis of experimental example 4 product
Testing example 1～5 prepares the thermogravimetric curve of product, and result as shown in figures 4 a and 4b, can by Fig. 4 a and Fig. 4 b
Knowing, embodiment 1～5 prepares the better heat stability of product, and the product that embodiment 1,2 and 5 prepares is opened when temperature about 300 DEG C
Beginning to decompose, the product that embodiment 3 and 4 prepares starts when temperature is more than 600 DEG C to decompose.
The electronic microscope photos of experimental example 5 product
Testing example 3 prepares the Electronic Speculum of product, as it is shown in figure 5, as shown in Figure 5, calcium carbonate-base europium complex is result
By many little particle aggregations, the oarse-grained particle diameter assembled can reach 500nm.
The elementary analysis of experimental example 6 product
Testing example 3 prepares the elementary analysis of product, and result is as shown in table 1 below,
The elementary analysis result of table 1 product
| Element | Percetage by weight % | Atomic percentage % |
| Oxygen | 89.56 | 91.51 |
| Fluorine | 9.69 | 8.34 |
| Sulfur | 0.17 | 0.09 |
| Europium | 0.57 | 0.06 |
As shown in Table 1, there is fluorine and element sulphur in the product, i.e. product exists part TTA, thus shows that product is
Europium complex is composited with calcium carbonate powder.
The fluorescence excitation spectrum of experimental example 7 product
Testing example 1～5 prepares the fluorescent exciting spectral curve of product, result as shown in Figure 6, wherein,
Curve 1 represents that embodiment 1 prepares the fluorescent exciting spectral curve of product,
Curve 2 represents that embodiment 2 prepares the fluorescent exciting spectral curve of product,
Curve 3 represents that embodiment 3 prepares the fluorescent exciting spectral curve of product,
Curve 4 represents that embodiment 4 prepares the fluorescent exciting spectral curve of product,
Curve 5 represents that embodiment 5 prepares the fluorescent exciting spectral curve of product.
It will be appreciated from fig. 6 that along with the minimizing of europium complex weight ratio in product, the fluorescent exciting spectral peak type of product broadens,
And, a kind of product has two to excite peak position, and one of them is the absworption peak of part, it can be seen that, different weight proportions
Part the excitating performance of calcium carbonate-base europium complex is had certain impact.
The excitation intensity of above-mentioned five kinds of products is depicted as curve, result as it is shown in fig. 7, as shown in Figure 7, when Europium chloride
When quality is 0.38g, fluorescence intensity is the strongest, along with Europium chloride and the increasing of part quality before the quality of Europium chloride is 0.38g
Add what its emissive porwer was to increase, and after this along with Europium chloride and the increase of part quality, emissive porwer tapers into, this
Being likely to be experiment and add the calcium carbonate of equal in quality, and only working as Europium chloride, TTA, during mol ratio 1:3:0.4 of calcium carbonate
Effect is best.
The fluorescence emission spectrum of experimental example 8 product
Testing example 1～5 prepares the fluorescence emission spectral curve of product, result as shown in Figure 8, wherein,
Curve 1 represents that embodiment 1 prepares the fluorescence emission spectral curve of product,
Curve 2 represents that embodiment 2 prepares the fluorescence emission spectral curve of product,
Curve 3 represents that embodiment 3 prepares the fluorescence emission spectral curve of product,
Curve 4 represents that embodiment 4 prepares the fluorescence emission spectral curve of product,
Curve 5 represents that embodiment 5 prepares the fluorescence emission spectral curve of product.
As shown in Figure 8, the product that embodiment 1～4 prepares has four to launch wavelength, respectively 580nm, 593nm,
612nm, 652nm, wherein, the transmitting spectral peak at 612nm is the strongest, and product is at λexAfter=354nm excites, Eu occurs3+?
Transmitting spectral peak at 580nm, 593nm, 612nm and 652nm, is respectively belonging to5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4
Energy level transition.Wherein coordination compound Eu3+Ion is at 612nm5D0→7F2Transition is launched the strongest, occurs that strong sharp line is launched,
Therefore there is preferable monochromaticity.
The emissive porwer of above-mentioned five kinds of products is depicted as curve, and result as it is shown in figure 9, as shown in Figure 9, make by embodiment 3
The fluorescent emission intensity of product is the strongest, when the weight ratio of Europium chloride and calcium carbonate is less than 38:2, the fluorescent emission of product with
The proportioning Europium chloride weight in calcium carbonate-base europium complex increases and increases, when the weight ratio of Europium chloride with calcium carbonate is more than
During 38:2, the fluorescent emission of product increases along with the proportioning of Europium chloride weight in calcium carbonate-base europium complex and reduces, i.e. when
During mol ratio 1:3:0.4 of Europium chloride, TTA and calcium carbonate, effect is best.
The fluorescence lifetime analysis of embodiment 9 product
The mean fluorecence life-span that embodiment 1～5 prepares product is depicted as curve, and result as shown in Figure 10, can by Figure 10
Knowing, the fluorescence lifetime that embodiment 1～5 prepares product has bigger fluctuation, along with the increase of europium complex content, product in product
The big minor swing of fluorescence lifetime.
The quantum yield analysis of embodiment 10 product
Testing example 1～5 prepares the quantum yield of product, and the quantum yield recorded is depicted as curve, and result is such as
Shown in Figure 11, as shown in Figure 11, the quantum yield that embodiment 1～5 prepares product is respectively 0.22, and 0.18,0.43,0.69,
0.18, what quantum yield was maximum is the prepared product of embodiment 4, and overall quantum yield is the highest, is not restrainted by any theory
Tiing up, inventors believe that and cause the reason that product overall quantum productivity is the highest to have following 2 points, one is product middle rare earth europium ion
The most fully mated with part TTA, two is that wavelength selection is improper when product carrying out quantum yield and characterizing.
The granularmetric analysis of experimental example 11 product
Calcium carbonate powder that respectively assay method () prepares and embodiment 1～5 prepare the particle diameter of product, result such as following table
Shown in 2,
Table 2 calcium carbonate powder and embodiment 1～5 prepare the particle diameter of product
| Sample | Particle diameter (nm) |
| Method (one) prepares calcium carbonate powder | 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 particle diameter ratio that embodiment 1～5 prepares product is more uniform, and particle size range is narrow, but each is implemented
The particle diameter difference that example prepares between product is bigger.
Above in association with detailed description of the invention and exemplary example, the present invention is described in detail, but these explanations are also
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 carry out technical solution of the present invention and embodiment thereof multiple equivalencing, modify or improve, these each fall within the present invention
In the range of.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. the method preparing calcium carbonate-base europium complex, it is characterised in that the method comprises the following steps:
(1) Europium chloride hydrate is mixed with calcium carbonate powder, add dispersant and disperse, obtain dispersion；And by TTA
It is dissolved in solvent, obtains TTA solution；
(2) dispersion step 1 obtained mixes with TTA solution, insulation reaction；
(3), after reaction terminates, solid content is separated.
Method the most according to claim 1, it is characterised in that in step 1,
Described dispersant is alcohols solvent, one or more in methanol, ethanol, normal propyl alcohol, isopropanol is preferably used, more preferably
For methanol or ethanol, particularly preferably methanol；And/or
Dissolve solvent used by TTA and be preferably alcohols solvent, be preferably used the one in methanol, ethanol, normal propyl alcohol, isopropanol or
Multiple, more preferably identical with the dispersant of calcium carbonate powder with dispersion Europium chloride hydrate.
Method the most according to claim 1 and 2, it is characterised in that in step 1, described Europium chloride hydrate and calcium carbonate
The weight ratio of powder is the weight portion of Europium chloride hydrate: the weight portion=2:(10～70 of calcium carbonate powder), preferably 2:(12
～60), such as 2:15,2:20,2:38,2:48 and 2:57.
4., according to the method one of claims 1 to 3 Suo Shu, it is characterised in that in step 1, Europium chloride hydrate rubs with TTA's
The mole that ratio is Europium chloride hydrate of your amount: the mole=1:(2～5 of TTA), preferably 1:3, wherein, Europium chloride water
The mole of compound with the molar amount of wherein europium element, the mole of TTA with wherein TTA molecule mole
Gauge.
5., according to the method one of Claims 1 to 4 Suo Shu, it is characterised in that in step 1, described calcium carbonate powder is preferably
Nano-calcium carbonate calcium powder, as the nano-calcium carbonate calcium powder that particle diameter is 50nm～70nm, more preferably particle size range at 55nm～
Between 65nm, particle diameter distribution width is the nano-calcium carbonate calcium powder of 5～10nm, such as the nano-sized carbon that particle size range is 58nm～63nm
Acid calcium powder.
6. according to the method one of Claims 1 to 5 Suo Shu, it is characterised in that in step 2, before adding TTA solution, first
First ascending step 1 prepares the temperature of system, it is preferable that the temperature of system is increased to the boiling point of dispersant；And/or
After being added in the system that step 1 prepares by TTA solution, insulation reaction under conditions of backflow, the response time is preferably 0.5
～2 hours, preferably 1 hour.
7. according to the method one of claim 1～6 Suo Shu, it is characterised in that in step 3, the carbonyldioxy europium complex prepared
Infrared spectrum characteristic peak concentrate on 600cm-1～3700cm-1, such as 1400cm-1And 3440cm-1Near there is strong absworption peak,
875cm-1、1130cm-1And 1630cm-1The strong peak of neighbouring existence time.
8. the calcium carbonate-base europium complex prepared according to the method one of claim 1～7 Suo Shu, it is characterised in that its
With calcium carbonate powder as matrix, calcium carbonate surface absorption and/be incorporated into TTA europium complex.
Calcium carbonate-base europium complex the most according to claim 8, it is characterised in that calcium carbonate powder and TTA europium complex
The weight that weight ratio is calcium carbonate: the weight=2:(2～15 of TTA europium complex), preferably 2:(2.8～11.6).
Calcium carbonate-base europium complex the most according to claim 8 or claim 9, it is characterised in that its infrared spectrum characteristic peak is concentrated
At 600cm-1～3700cm-1, such as 1400cm-1And 3440cm-1Near there is strong absworption peak, 875cm-1、1130cm-1With
1630cm-1The strong peak of neighbouring existence time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN110655916A (en) * | 2018-06-29 | 2020-01-07 | 阜阳师范学院 | Rare earth composite fluorescent material with carbonate as matrix and preparation method thereof |
| CN110655917A (en) * | 2018-06-29 | 2020-01-07 | 阜阳师范学院 | Rare earth complex composite fluorescent material and preparation method thereof |
| CN110734759A (en) * | 2018-07-19 | 2020-01-31 | 阜阳师范学院 | rare earth composite fluorescent materials using inorganic salt as matrix and preparation method thereof |
| CN110734760A (en) * | 2018-07-19 | 2020-01-31 | 阜阳师范学院 | rare earth europium composite fluorescent material using sodium acetate as matrix and preparation method thereof |
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| CN115197693A (en) * | 2021-04-09 | 2022-10-18 | 中国科学院理化技术研究所 | NIR-II region luminous core-shell structure nano particle and preparation method and application thereof |
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| CN110655915A (en) * | 2018-06-29 | 2020-01-07 | 阜阳师范学院 | Organic-inorganic hybrid rare earth composite fluorescent material and preparation method thereof |
| CN110655916A (en) * | 2018-06-29 | 2020-01-07 | 阜阳师范学院 | Rare earth composite fluorescent material with carbonate as matrix and preparation method thereof |
| CN110655917A (en) * | 2018-06-29 | 2020-01-07 | 阜阳师范学院 | Rare earth complex composite fluorescent material and preparation method thereof |
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| CN110734760A (en) * | 2018-07-19 | 2020-01-31 | 阜阳师范学院 | rare earth europium composite fluorescent material using sodium acetate as matrix and preparation method thereof |
| CN112250710A (en) * | 2019-07-22 | 2021-01-22 | 阜阳师范大学 | Application of saving type rare earth europium complex/sodium acetate composite fluorescent powder in water-based ink |
| CN112341492A (en) * | 2019-08-08 | 2021-02-09 | 阜阳师范大学 | Calcium carbonate/europium complex composite fluorescent material and preparation method thereof |
| CN115197693A (en) * | 2021-04-09 | 2022-10-18 | 中国科学院理化技术研究所 | NIR-II region luminous core-shell structure nano particle and preparation method and application thereof |
| CN115197693B (en) * | 2021-04-09 | 2024-05-07 | 中国科学院理化技术研究所 | NIR-II region luminescent core-shell structure nanoparticle and preparation method and application thereof |
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