CN107722971A - A kind of rear-earth-doped zinc citrate fluorescent material - Google Patents
A kind of rear-earth-doped zinc citrate fluorescent material Download PDFInfo
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- CN107722971A CN107722971A CN201711055807.5A CN201711055807A CN107722971A CN 107722971 A CN107722971 A CN 107722971A CN 201711055807 A CN201711055807 A CN 201711055807A CN 107722971 A CN107722971 A CN 107722971A
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- zinc citrate
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- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 title claims abstract description 63
- 239000011746 zinc citrate Substances 0.000 title claims abstract description 62
- 229940068475 zinc citrate Drugs 0.000 title claims abstract description 62
- 235000006076 zinc citrate Nutrition 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 37
- -1 rare-earth ion Chemical class 0.000 claims abstract description 34
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 230000005284 excitation Effects 0.000 claims description 11
- 229910052693 Europium Inorganic materials 0.000 abstract description 11
- 229910052771 Terbium Inorganic materials 0.000 abstract description 8
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- 239000007850 fluorescent dye Substances 0.000 abstract description 3
- 238000001215 fluorescent labelling Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 abstract 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000001509 sodium citrate Substances 0.000 description 18
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 244000248349 Citrus limon Species 0.000 description 8
- 235000005979 Citrus limon Nutrition 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000002242 deionisation method Methods 0.000 description 6
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 6
- 229910001940 europium oxide Inorganic materials 0.000 description 5
- 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 5
- 229910003451 terbium oxide Inorganic materials 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 4
- XYZSCUSDBHYQHL-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;terbium Chemical compound [Tb].OC(=O)CC(O)(C(O)=O)CC(O)=O XYZSCUSDBHYQHL-UHFFFAOYSA-N 0.000 description 3
- RUWKZSPFMDVLRC-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;zinc Chemical compound [Zn].OC(=O)CC(O)(C(O)=O)CC(O)=O RUWKZSPFMDVLRC-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- RLZDDMBZWWNZMX-UHFFFAOYSA-N europium;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Eu].OC(=O)CC(O)(C(O)=O)CC(O)=O RLZDDMBZWWNZMX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- OXAGUGIXGVHDGD-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate;dihydrate Chemical compound O.O.[Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OXAGUGIXGVHDGD-UHFFFAOYSA-H 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
-
- 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
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to luminous and fluorescence probe field, a kind of rear-earth-doped zinc citrate fluorescent material is more particularly related to.A kind of luminescent material provided by the invention, it is the rare-earth ion activated organic salt complex of zinc citrate, its chemical composition expression is C12H14O16Zn3‑x:xRe3+, wherein Re is Eu, Tb etc., and x substitutes the amount of zinc ion in zinc citrate matrix, 1%≤x≤9% for rare earth ion.The rear-earth-doped zinc citrate fluorescent material of the present invention is sheet, its length × a width of 1~10 × 0.5~5 μm.The luminescent powder is by the zinc ion in rare earth ion doped substitution zinc citrate and forms the centre of luminescence, has that synthetic product purity is high, product photism and the advantage such as have good stability.Rear-earth-doped zinc citrate fluorescent material provided by the present invention can be applied to the fields such as luminescent material, biological fluorescent labelling.
Description
Technical field
The present invention relates to a kind of novel rare-earth luminescent material, more particularly to a kind of rear-earth-doped zinc citrate fluorescent material.
Background technology
Rare earth ion has unique electron structure, can produce various spectral cterms and energy level, transmitting is ultraviolet, visible ray arrives
The electromagnetic radiation of the various wavelength of infrared light district.But directly using rare earth salts or oxide illumination effect can be made unstable, because
The f-f transition for the 4f interlayers being related to for rare earth is parity forbidden, caused ultraviolet region (200-400nm) in transition process
Extinction coefficient very little, it is weak to UV Absorption, cause rare earth luminescence less efficient, so in fluorescent material Rare Earth Ion
It is to be played a role in the form of adulterating or being coordinated mostly.
Organic carboxyl acid part is high in ultraviolet region absorption coefficient, if its triple excited level and rare earth ion excitation state energy
Level matches, then excited energy can be effectively transferred to the transmitting state of rare earth ion by radiationless transition, so as to be sensitized
Lighting for rare earth ion, compensate for the defects of absorption coefficient of the rare earth ion in Uv and visible light area is very low.In addition, with
Organic carboxyl acid is the luminous excitation height and rare earth organic carboxyl acid for having rare earth ion concurrently of the rare earth organic carboxyl acid complex of part
Excitation energy needed for complex is low, fluorescence efficiency is high, is soluble in the advantages of organic solvent, but rare earth organic carboxyl acid complex is being made
Synthesis technique is relative complex during standby, and prepared complex purity is generally relatively low, and product stability is poor, and decay of luminescence is bright
It is aobvious to cause service life short, in addition, rare earth ion is both as matrix compounds important component in organic carboxyl acid complex, again
As existing for the centre of luminescence, Product formation has used substantial amounts of rare earth oxide, have impact on answering for the luminescent rare earth complexes
With value.
Sheng-Gui Liu in 2005 etc. exist《Synthesis,structure and luminescent
properties of lanthanide(III)polymeric complexes constructed by citric acid》
Middle utilize reacts 96h under 170 DEG C of hydrothermal conditions of citric acid and europium oxide (or terbium oxide), has obtained the lemon with luminescent properties
Sour europium (or citric acid terbium) Rare Earth Carboxylates, it the shortcomings that be, substantial amounts of oxidation has been used in the synthesis of complex
Terbium and europium oxide, it have impact on the application value of citric acid europium (or citric acid terbium) Rare Earth Carboxylates fluorescent material.In addition,
The document reacts 96h under 170 DEG C of hydrothermal conditions, and illustrating that the complex structure is more complicated causes synthesis more difficult.Zinc citrate
Be it is a kind of using organic acid and inorganic cation with reference to and the organic carboxylate that is formed, while and organic and inorganic aspect property
Matter, the present invention are prepared for rare earth ion doped zinc citrate fluorescent material using hydro-thermal method method.It is open with Sheng-Gui Liu etc.
Document compare, the present invention utilize rare earth ion doped zinc citrate, rare earth ion enter zinc citrate lattice in, occupy zinc
The position of ion, form the centre of luminescence so that part citric acid zinc is changed into citric acid europium or citric acid terbium, both saves citric acid
The advantages such as zinc high stability, hypotoxicity and preferable biocompatibility, but due to zinc citrate structure is relatively simple and crystallinity compared with
Synthesis difficulty is significantly reduced by force, only 60 DEG C insulation 12h of reaction temperature can synthesize photism and the fluorescent material having good stability,
In addition, this scheme introduces rare earth ion by the way of doping, greatly reduces the dosage of rare earth ion, is obviously improved
The commercial value of rear-earth-doped zinc citrate fluorescent material.A kind of rare earth mixing with nano calcium citrate applied early stage compared to me
Fluorescent material and preparation method thereof, zinc citrate fluorescent material of the present invention has lower synthesis temperature, and shows more excellent
Different luminescent properties, illustrate that the property of rare earth ion and zinc ion is increasingly similar, needed for the substitution and lattice occupy-place of rare earth ion
Energy is smaller, and combined coefficient is high, prepares synthesizing citric acid zinc fluorescent material and is more prone to.
In summary, the preparation of zinc citrate fluorescent material not only remains the original advantage of zinc citrate, and because rare earth
The introducing of ion causes part citric acid zinc to be converted into rare earth compounding and have in fields such as biological fluorescent labeling, luminescent materials
Potential application value.In addition, a kind of rear-earth-doped zinc citrate fluorescent material provided by the invention, have synthetic product pure
The advantages such as degree height, product photism are with having good stability, preparation technology is simple, synthesis condition is gentle, cost is low, and overcome dilute
The problems such as native organic carboxyl acid complex technique is relative complex, purity is relatively low, product stability is poor, service life is short.
The content of the invention
It is an object of the invention to provide a kind of rear-earth-doped zinc citrate fluorescent material.The fluorescent material has been sufficiently reserved lemon
The basic performance of sour zinc, and impart the brand-new luminescent material application field of zinc citrate one.
A kind of rear-earth-doped zinc citrate fluorescent material, its content of the invention include：
The fluorescent material is the rare-earth ion activated organic salt complex of zinc citrate, and its chemical composition expression is
C12H14O16Zn3-x:xRe3+, wherein：Re3+For Eu3+、Tb3+Deng rare earth ion, x is that rare earth ion substitutes zinc in zinc citrate matrix
The amount of ion, 0.5%≤x≤20%, and it is further defined to 1%≤x≤9%.
C12H14O16Zn3-x:x Eu 3+Fluorescent material is under 393nm excitation wavelengths, C12H14O16Zn3-x:xEu 3+Fluorescent material exists
There is emission peak in 601nm, 621nm, 705nm, and be respectively belonging to Eu3+'s5D0-7F1,5D0-7F2,5D0-7F4Transition, wherein
The most strong transmitting of display at 621nm；In the case where 621nm is excited, C12H14O16Zn3-x:xEu3+Zinc citrate fluorescent material in 361nm,
There is excitation peak in 380nm, 393nm, 415nm, 420nm, 536nm, and be respectively belonging to Eu3+'s7F0→5L8,7F0→5G3 5L7,7F0
→5L6,7F0→5D3,7F0→5D2,7F0→5D1Transition, the most strong excitation peak of display wherein at 393nm.
C12H14O16Zn3-x:x Eu 3+Zinc citrate fluorescent material shows strong red emission.
C12H14O16Zn3-x:xTb3+Fluorescent material is under 240nm excitation wavelengths, C12H14O16Zn3-x:xTb3+Fluorescent material exists
There is emission peak in 550nm, 591nm, 626nm, and be respectively belonging to Tb3+'s5D4-7F5,5D4-7F4,5D4-7F3Transition, wherein
The most strong transmitting of display at 550nm；In the case where 550nm is excited, C12H14O16Zn3-x:xTb3+Zinc citrate fluorescent material in 240nm,
277nm, stronger transmitting be present, and be respectively belonging to Tb3+'s7F6→7D,7F6→9D transition, wherein 300nm-400nm exist compared with
Weak excitation peak, belongs to Tb3+F-f transition.
Under 240nm excitation wavelengths, C12H14O16Zn3-x:xTb3+Fluorescent material has strong green emission.
The rear-earth-doped zinc citrate fluorescent material prepared be citrate dihydrate zinc, and its pattern is sheet, its length × a width of 1~
10 × 0.5~5 μm.
Beneficial effects of the present invention：
Rear-earth-doped zinc citrate fluorescent material obtained by the present invention is a kind of hair of rear-earth-doped organic-inorganic base status
Luminescent material, and the advantages of its preparation technology is simple, cost is low, stability is good, should in fields such as biological fluorescent labeling, luminescent materials
It is good with prospect.
Brief description of the drawings：
Fig. 1 is the XRD spectrum of europium ion-doped zinc citrate fluorescent material prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM photograph of europium ion-doped zinc citrate fluorescent material prepared by the embodiment of the present invention 1；
Fig. 3 is the fluorescence spectra of europium ion-doped zinc citrate fluorescent material prepared by the embodiment of the present invention 1；
Fig. 4 is the fluorescence spectra of terbium ion doping zinc citrate fluorescent material prepared by the embodiment of the present invention 4；
Embodiment：
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
(1) preparation of zinc nitrate solution：The zinc nitrate solid particle for weighing 4.462g is placed in beaker, add 10ml go from
Sub- water, being stirred under the conditions of 60 DEG C makes its dissolving, produces required zinc nitrate solution (solution 1)；
(2) preparation of sodium citrate solution：The sodium citrate for weighing 2.941g is placed in beaker, adds 10ml deionization
Water, being stirred under the conditions of 60 DEG C makes its dissolving, produces required sodium citrate solution (solution 2)；
(3) preparation of europium nitrate solution：0.1848g (doping concentration 7%) europium oxide is weighed in beaker, instills 1ml
Concentrated nitric acid, fully reaction, produce required europium nitrate solution (solution 3)；
(4) preparation of europium ion-doped zinc citrate fluorescent material：(solution 1) is mixed with (solution 3), in 60 DEG C of conditions
Lower reaction 10min, is then mixed with (solution 2), and keeping temperature is constant, reacts 10min, adds 8ml ethanol, zinc citrate analysis
Go out, configuration 5:2 water and alcohol mixeding liquid, the zinc citrate of precipitation is cleaned 3 times, sodium nitrate therein is removed, then to lemon
Sour zinc precursor carries out 120 DEG C of hydro-thermal reaction 24h, and the product 3000r/min centrifugations of gained, -30 DEG C are freeze-dried into what is obtained
White solid is europium ion-doped zinc citrate fluorescent material.Its XRD is as shown in figure 1, SEM is schemed as shown in Fig. 2 fluorescence spectrum
Figure is as shown in Figure 3.
Embodiment 2
(1) preparation of zinc nitrate solution：The zinc nitrate solid particle for weighing 4.462g is placed in beaker, add 10ml go from
Sub- water, being stirred under the conditions of 60 DEG C makes its dissolving, produces required zinc nitrate solution (solution 1)；
(2) preparation of sodium citrate solution：The sodium citrate for weighing 2.941g is placed in beaker, adds 10ml deionization
Water, being stirred under the conditions of 60 DEG C makes its dissolving, produces required sodium citrate solution (solution 2)；
(3) preparation of europium nitrate solution：0.0132g (doping concentration 0.5%) europium oxide is weighed in beaker, is instilled
1ml concentrated nitric acid, fully reaction, produce required europium nitrate solution (solution 3)；
(4) preparation of europium ion-doped zinc citrate fluorescent material：(solution 1) is mixed with (solution 3), in 60 DEG C of conditions
Lower reaction 10min, is then mixed with (solution 2), and keeping temperature is constant, reacts 10min, adds 8ml ethanol, zinc citrate analysis
Go out, configuration 5:2 water and alcohol mixeding liquid, the zinc citrate of precipitation is cleaned 3 times, sodium nitrate therein is removed, then to lemon
Sour zinc precursor carries out 120 DEG C of hydro-thermal reaction 24h, and the product 3000r/min centrifugations of gained, -30 DEG C are freeze-dried into what is obtained
White solid is europium ion-doped zinc citrate fluorescent material.
Embodiment 3
(1) preparation of zinc nitrate solution：The zinc nitrate solid particle for weighing 4.462g is placed in beaker, add 10ml go from
Sub- water, being stirred under the conditions of 60 DEG C makes its dissolving, produces required zinc nitrate solution (solution 1)；
(2) preparation of sodium citrate solution：The sodium citrate for weighing 2.941g is placed in beaker, adds 10ml deionization
Water, being stirred under the conditions of 60 DEG C makes its dissolving, produces required sodium citrate solution (solution 2)；
(3) preparation of europium nitrate solution：0.4752g (doping concentration 18%) europium oxide is weighed in beaker, instills 1ml
Concentrated nitric acid, fully reaction, produce required europium nitrate solution (solution 3)；
(4) preparation of europium ion-doped zinc citrate fluorescent material：(solution 1) is mixed with (solution 3), in 60 DEG C of conditions
Lower reaction 10min, is then mixed with (solution 2), and keeping temperature is constant, reacts 10min, adds 8ml ethanol, zinc citrate analysis
Go out, configuration 5:2 water and alcohol mixeding liquid, the zinc citrate of precipitation is cleaned 3 times, sodium nitrate therein is removed, then to lemon
Sour zinc precursor carries out 120 DEG C of hydro-thermal reaction 24h, and the product 3000r/min centrifugations of gained, -30 DEG C are freeze-dried into what is obtained
White solid is europium ion-doped zinc citrate fluorescent material.
Embodiment 4
(1) preparation of zinc nitrate solution：The zinc nitrate solid particle for weighing 4.462g is placed in beaker, add 10ml go from
Sub- water, being stirred under the conditions of 30 DEG C makes its dissolving, produces required zinc nitrate solution (solution 1)；
(2) preparation of sodium citrate solution：The sodium citrate for weighing 2.941g is placed in beaker, adds 10ml deionization
Water, being stirred under the conditions of 30 DEG C makes its dissolving, produces required sodium citrate solution (solution 2)；
(3) preparation of terbium nitrate solution：The terbium oxide of 0.0280 (doping concentration 1%) is weighed in beaker, instills 1ml's
Concentrated nitric acid, fully reaction, produce required terbium nitrate solution (solution 3)；
(4) preparation of the zinc citrate fluorescent material of terbium ion doping：(solution 1) is mixed with (solution 3), in 60 DEG C of conditions
Lower reaction 10min, is then mixed with (solution 2), and keeping temperature is constant, reacts 10min, adds 8ml ethanol, zinc citrate analysis
Go out, configuration 5:2 water and alcohol mixeding liquid, the zinc citrate of precipitation is cleaned 3 times, sodium nitrate therein is removed, then to lemon
Sour zinc precursor carries out 120 DEG C of hydro-thermal reaction 24h, and the product 3000r/min centrifugations of gained, -30 DEG C are freeze-dried into what is obtained
White solid is the zinc citrate fluorescent material of terbium ion doping, and its fluorescence spectra is as shown in Figure 4.
Embodiment 5
(1) preparation of zinc nitrate solution：The zinc nitrate solid particle for weighing 4.462g is placed in beaker, add 10ml go from
Sub- water, being stirred under the conditions of 30 DEG C makes its dissolving, produces required zinc nitrate solution (solution 1)；
(2) preparation of sodium citrate solution：The sodium citrate for weighing 2.941g is placed in beaker, adds 10ml deionization
Water, being stirred under the conditions of 30 DEG C makes its dissolving, produces required sodium citrate solution (solution 2)；
(3) preparation of terbium nitrate solution：The terbium oxide of 0.2520 (doping concentration 9%) is weighed in beaker, instills 1ml's
Concentrated nitric acid, fully reaction, produce required terbium nitrate solution (solution 3)；
(4) preparation of the zinc citrate fluorescent material of terbium ion doping：(solution 1) is mixed with (solution 3), in 60 DEG C of conditions
Lower reaction 10min, is then mixed with (solution 2), and keeping temperature is constant, reacts 10min, adds 8ml ethanol, zinc citrate analysis
Go out, configuration 5:2 water and alcohol mixeding liquid, the zinc citrate of precipitation is cleaned 3 times, sodium nitrate therein is removed, then to lemon
Sour zinc precursor carries out 120 DEG C of hydro-thermal reaction 24h, and the product 3000r/min centrifugations of gained, -30 DEG C are freeze-dried into what is obtained
White solid is the zinc citrate fluorescent material of terbium ion doping.
Embodiment 6
(1) preparation of zinc nitrate solution：The zinc nitrate solid particle for weighing 4.462g is placed in beaker, add 10ml go from
Sub- water, being stirred under the conditions of 30 DEG C makes its dissolving, produces required zinc nitrate solution (solution 1)；
(2) preparation of sodium citrate solution：The sodium citrate for weighing 2.941g is placed in beaker, adds 10ml deionization
Water, being stirred under the conditions of 30 DEG C makes its dissolving, produces required sodium citrate solution (solution 2)；
(3) preparation of terbium nitrate solution：The terbium oxide of 0.56 (doping concentration 20%) is weighed in beaker, instills 1ml's
Concentrated nitric acid, fully reaction, produce required terbium nitrate solution (solution 3)；
(4) preparation of the zinc citrate fluorescent material of terbium ion doping：(solution 1) is mixed with (solution 3), in 60 DEG C of conditions
Lower reaction 10min, is then mixed with (solution 2), and keeping temperature is constant, reacts 10min, adds 8ml ethanol, zinc citrate analysis
Go out, configuration 5:2 water and alcohol mixeding liquid, the zinc citrate of precipitation is cleaned 3 times, sodium nitrate therein is removed, then to lemon
Sour zinc precursor carries out 120 DEG C of hydro-thermal reaction 24h, and the product 3000r/min centrifugations of gained, -30 DEG C are freeze-dried into what is obtained
White solid is the zinc citrate fluorescent material of terbium ion doping.
Claims (6)
1. claim 1：The fluorescent material is the rare-earth ion activated organic salt complex of zinc citrate, and its chemical composition represents
Formula is C12H14O16Zn3-x: xRe3+。
2. claim 2：The chemical constitution formula of zinc citrate fluorescent material according to claim 1, wherein Re3+For Eu3+、
Tb3+Deng rare earth ion.
3. claim 3：The chemical constitution formula of zinc citrate fluorescent material according to claim 1, x substitute for rare earth ion
The amount of zinc ion, 0.5%≤x≤20% in zinc citrate matrix, and it is further defined to 1%≤x≤9%.
4. claim 4：C12H14O16Zn3-x: xEu 3+Fluorescent material under 393nm excitation wavelengths, main emission peak in 621nm,
C12H14O16Zn3-x: xEu3+Zinc citrate fluorescent material shows strong red emission.
5. claim 5：C12H14O16Zn3-x: xTb3+Fluorescent material under 240nm excitation wavelengths, main emission peak in 550nm,
C12H14O16Zn3-x: xTb3+Fluorescent material shows strong green emission.
6. claim 6：The rear-earth-doped zinc citrate fluorescent material that 1-5 any one obtains, its pattern are sheet, its length × wide
For 1~10 × 0.5~5 μm.
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