CN110734759A - rare earth composite fluorescent materials using inorganic salt as matrix and preparation method thereof - Google Patents
rare earth composite fluorescent materials using inorganic salt as matrix and preparation method thereof Download PDFInfo
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- CN110734759A CN110734759A CN201810797694.4A CN201810797694A CN110734759A CN 110734759 A CN110734759 A CN 110734759A CN 201810797694 A CN201810797694 A CN 201810797694A CN 110734759 A CN110734759 A CN 110734759A
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- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 50
- 239000011159 matrix material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 title abstract description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 123
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 61
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 61
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 40
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 37
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- -1 europium ions Chemical class 0.000 claims abstract description 20
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims description 42
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- 238000010521 absorption reaction Methods 0.000 claims description 15
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 10
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- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
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- 239000012467 final product Substances 0.000 claims description 5
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 4
- 238000001429 visible spectrum Methods 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
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- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
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- AWDWVTKHJOZOBQ-UHFFFAOYSA-K europium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Eu+3] AWDWVTKHJOZOBQ-UHFFFAOYSA-K 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
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- 150000007942 carboxylates Chemical class 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 238000010168 coupling process Methods 0.000 description 1
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- 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
Abstract
The invention provides rare earth composite fluorescent materials with inorganic salt as a matrix and a preparation method thereof, europium ions are used as a luminous body, methylbenzotriazole (TTA) and triphenyl phosphorus oxide (TPPO) are used as organic ligands, inorganic salt sodium bicarbonate is used as a matrix, the europium complex composite fluorescent materials are prepared by reaction under set conditions, and the obtained composite fluorescent materials are characterized.
Description
Technical Field
The invention relates to the field of fluorescent materials, in particular to a rare earth europium complex composite fluorescent material taking inorganic carbonates as matrixes and a preparation method thereof.
Background
The rare earth elements (rare earth elements) are applied in fields, which are called gold industry, nowadays, the rare earth elements are applied in fields of electronic appliances, petrochemical industry, metallurgy, machinery, energy, light industry, environmental protection, agriculture and the like in fields, application of the rare earth elements can be used for producing fluorescent materials, rare earth metal hydride battery materials, electric light source materials, permanent magnetic materials, hydrogen storage materials, catalytic materials, precise ceramic materials, laser materials, superconducting materials, magnetostrictive materials, magnetic refrigeration materials, magneto-optical storage materials, optical fiber materials and the like.
The rare earth elements include 17 elements from the lanthanide series, having atomic numbers from 57 to 71, plus scandium and yttrium, which are members of the third subgroup of the periodic table. They are all very active metals, have very similar properties, have common valence +3, most of hydrated ions of the metals have colors, and are easy to form stable complex compounds.
The rare earth elements have 4f electron layers with unfilled electron orbitals, 5s and 5p electrons on the outer layers have -determined shielding effects on the 4f electrons, so that the rare earth elements are subjected to a small crystal field, and the J energy level is split due to the fact that the electrons on the 4f electron layers have large spin coupling constants, so that the rare earth complex has rich electron energy levels and has special luminescence performance.
Although rare earth luminescent materials have irreplaceable status in some fields, the cost of the luminescent materials is higher, the price is dozens of times of that of common metals, the light and heat stability is slightly poor, and the rare earth complex is difficult to recover after being used, so that the application of the rare earth complex in many aspects is greatly limited.
Therefore, there is a need to develop a rare earth complex composite fluorescent material with simple preparation method, long fluorescence lifetime, reduced cost and optimized fluorescence property, so as to expand the application range of rare earth luminescent materials.
Disclosure of Invention
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that rare earth composite fluorescent materials using inorganic salts as a matrix and a method for preparing the same, europium ions are used as a light-emitting body, methylbenzotriazole (TTA) and triphenylphosphonium oxide (TPPO) are used as organic ligands, sodium bicarbonate is used as a matrix, and a reaction is performed under a predetermined condition to prepare a europium complex composite fluorescent material, and the obtained composite fluorescent material is characterized.
The object of the present invention is to provide the following:
, the present invention provides kinds of composite RE fluorescent material with maximum absorption wavelength near 337 nm.
Wherein the infrared visible spectrum characteristic peak of the composite fluorescent material is concentrated at 600cm-1～3750cm-1E.g. at 880cm-1、1439cm-1、3415cm-1A strong characteristic peak appears nearby.
The composite fluorescent material comprises a rare earth complex and a matrix, wherein the matrix comprises or more of sodium acetate, potassium acetate, sodium bicarbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate, and sodium bicarbonate is preferred.
The rare earth complex is a complex of europium or a complex of terbium, preferably a complex of europium, and more preferably an organic ligand complex of europium.
Wherein the organic ligand comprises methylbenzotriazole.
In a second aspect, the present invention also provides a method for preparing the rare earth composite fluorescent material of , comprising the steps of:
step 1: mixing a ligand and a rare earth compound to obtain a solution;
step 2: reacting the solution in the step 1 with a matrix substance under set conditions;
and step 3: and carrying out post-treatment to obtain a final product.
Drawings
FIG. 1 shows a UV-Vis spectrum of a sample;
FIG. 2 shows an infrared spectrum of a sample;
figure 3 shows an XRD analysis spectrum of the sample;
FIG. 4 shows a fluorescence emission spectrum of a sample;
FIG. 5 shows a fluorescence emission line graph of a sample;
FIG. 6 shows a fluorescence excitation spectrum of a sample;
FIG. 7 shows a plot of fluorescence excitation intensity for a sample;
fig. 8 shows a line graph of the mean fluorescence lifetime of the sample.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
According to th aspect of the present invention, rare earth complex composite fluorescent materials are provided, which have a maximum absorption wavelength of ultraviolet-visible spectrum around 337 nm.
The infrared visible spectrum characteristic peak of the composite fluorescent material is concentrated at 600cm-1～3750cm-1E.g. at 880cm-1、1439cm-1、3415cm-1A strong characteristic peak appears nearby.
The composite fluorescent material comprises a rare earth complex and a matrix, wherein the matrix comprises or more of sodium acetate, potassium acetate, sodium bicarbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate, and sodium bicarbonate is preferred.
The rare earth complex is a complex of europium or a complex of terbium, preferably a complex of europium, and more preferably the rare earth complex is an organic ligand complex of europium.
The organic ligand comprises methylbenzotriazole; also included are triphenyl phosphine oxide.
The methylbenzotriazole is abbreviated as TTA, is ligands of europium chloride, and interacts with the europium chloride to obtain the organic fluorescent material capable of emitting red light.
The interest of people in sensitized emission in the rare earth complexes starts in 1942, and Weissman finds that characteristic linear emission of Eu ions occurs after different β -diketone Eu complexes absorb ultraviolet light at that time, due to the appearance of laser spectrum after twenty years, a large amount of research on rare earth fluorescence phenomena is developed in different fields, and β -diketone ligands as ligands have the function of satisfying charge balance.
ligand also has carboxylic acids or carboxylates or other types.
The inventor finds that the performance of the rare earth composite fluorescent material prepared by adopting methylbenzotriazole as a th ligand and a second ligand of triphenyl phosphorus oxide, then adding a matrix of sodium bicarbonate and setting reaction conditions is better.
The inventors believe that the second ligand produces a synergistic effect during luminescence.
The rare earth organic complex is applied to various fields of industry, agriculture, biology and the like due to the advantages of strong fluorescence, good monochromaticity and the like, but the defects of poor light and thermal stability and high cost limit the practicability of the rare earth organic complex.
Therefore, the present inventors have attempted to add an inorganic salt sodium bicarbonate matrix as an inner core in order that a relatively stable environment may be provided to the rare earth complex to exhibit its light emitting characteristics, and it is expected that its light emitting performance may be improved and its light and thermal stability may be improved, and the cost of the rare earth composite fluorescent material may be greatly reduced.
The inventor researches the europium complex and basic carbonate composite luminescent material through a large amount of exploration experiments, and characterizes the structure and the performance of the europium complex and the basic carbonate composite luminescent material;
the inventor surprisingly finds that the fluorescent material compounded by europium complex of TTA (methyl benzotriazole) and TPPO (triphenyl phosphorus oxide) and sodium bicarbonate matrix not only improves the light stability of the europium complex, but also improves the fluorescent performance, including longer fluorescence life, high quantum yield and reduced cost of the fluorescent material.
In the invention, the fluorescence emission intensity of the europium complex composite fluorescent material can reach 1050000CPS, the average fluorescence lifetime can reach 1.35ms, and the quantum yield reaches 20.90%.
According to a second aspect of the present invention, there are provided methods for preparing the above rare earth complex composite fluorescent material, comprising the steps of:
step 1: mixing a ligand and a rare earth compound to obtain a solution;
step 2: reacting the solution in the step 1 with a matrix substance under set conditions;
and step 3: and carrying out post-treatment to obtain a final product.
the ligand is a dual ligand, the dual ligand is an th ligand and a second ligand, the th ligand is methylbenzotriazole, and the second ligand is triphenyl phosphorus oxide;
preferably, the th ligand is tolyltriazole (TTA), and the second ligand is triphenylphosphine oxide (TPPO) in a molar ratio of (0.5-3.5): 1, more preferably (1-3.0): 1, such as 1.5: 1.
In the invention, the molar ratio of TTA to the rare earth compound is (1-6): 1, preferably (2-5): 1, such as 3: 1.
The inventors found that the amount of TTA used as the th ligand is not too low, not too high, and too low, which results in failure to achieve optimum coordination and too high, but rather in deterioration of coordination performance, and therefore, it is preferable that the molar ratio of TTA to the rare earth compound is (2-5): 1, and more preferably 3: 1.
The methylbenzotriazole TTA has a large light absorption coefficient and a proper conjugated system, and can effectively sensitize rare earth ions to emit light after being coordinated with the rare earth ions. The substituent group in the rare earth complex has a great influence on the luminous efficiency.
Eu3+In addition to the th ligand, is a polydentate ion, which is a polydentate ion, and the second ligand is usually a neutral ligand.
The neutral ligand influences the photoluminescence efficiency and fluorescence intensity of the europium complex mainly by participating in energy transfer and influencing the life of th excited triplet state of the central ligand, and the introduction of the second ligand into the structure of the luminescent complex can obviously improve the luminescent brightness of the material.
In the invention, the performance of the finally obtained composite fluorescent material can be better by researching the TPPO as the second ligand.
The rare earth compound is europium oxide or europium chloride, preferably europium chloride. The europium chloride used in the present invention is europium chloride hexahydrate.
In the present invention, when the TTA and TPPO ligands are mixed with the rare earth compound, a solvent is added, wherein the solvent is or more of methanol, ethanol, isopropanol and n-butanol, preferably ethanol, and more preferably absolute ethanol.
In the step 1, the amount of the absolute ethyl alcohol is 0.5g (5-40) mL, wherein the amount of the absolute ethyl alcohol is , the amount of the absolute ethyl alcohol is required to be enough to completely dissolve the TTA, the TPPO and the rare earth compound, and the amount of the absolute ethyl alcohol is required to be , so that the TTA, the TPPO and the rare earth compound are in constant concentration, and the subsequent reaction is facilitated.
In preferred embodiments, the dual ligand and the rare earth compound are added to the solvent separately and are shaken with ultrasound for 30min to dissolve the dual ligand and the rare earth compound completely.
The inventor believes that the rare earth compound and the double ligands are dissolved more completely and mixed with the double ligands more uniformly by utilizing the mechanical effect, the thermal effect and the cavitation of the ultrasound.
Step 2: reacting the solution in the step 1 with a matrix substance under set conditions;
in step 2, pretreating the matrix substance;
the pretreatment comprises mixing a matrix substance with a dispersing agent and optionally carrying out ultrasonic oscillation, wherein the dispersing agent is or more of methanol, ethanol, isopropanol and n-butanol, and preferably the same solvent used in the step 1;
in preferred embodiments, the pretreatment comprises drying the matrix material for 1-3 hours before mixing.
The inventor finds that water can affect the complexation of europium ions and ligands and finally affect the performance of the composite fluorescent material.
In the invention, sodium bicarbonate is used as a matrix and is used as alkali and an inner core, so that the europium complex is adsorbed and/or bonded on the surface of the sodium bicarbonate, thereby obtaining the composite fluorescent material.
In the present invention, the sodium bicarbonate powder may be either commercially available or self-prepared. In the invention, the particle size of the sodium bicarbonate is 20-100 nm.
Without being bound by any theory, the inventor believes that the fluorescent material obtained by using the nano-scale sodium bicarbonate powder as the basic salt has smaller particle size, and meanwhile, the nano-scale sodium bicarbonate has larger specific surface area and can adsorb and/or combine more rare earth complexes, so that the fluorescence intensity of the product can be increased, and the nano-scale sodium bicarbonate with uniform particle size distribution can obtain the fluorescent material with stable performance of .
In the invention, the pretreatment also comprises the step of adding dried sodium bicarbonate into a dispersing agent for ultrasonic oscillation, wherein the dispersing agent is or more of methanol, ethanol, isopropanol and n-butanol, ethanol is preferred, and absolute ethanol is more preferred.
The inventor finds that ethanol is used as a dispersing agent, so that the solubility is better, and the favorable temperature can be easily controlled when the composite fluorescent material is prepared.
In the present invention, the amount of ethanol used is not particularly limited, and it is sufficient to dissolve all the raw materials.
In preferred embodiments, sodium bicarbonate and ethanol are mixed, and after being uniformly stirred, ultrasonic oscillation is performed for 30min, so that sodium bicarbonate particles are more uniformly dispersed, and the performance of the finally prepared composite fluorescent material is better.
In the invention, the dosage ratio of the sodium bicarbonate to the ethanol is 1 g: (5-20) mL.
In step 2 of the invention, the set conditions comprise that the reaction temperature is 50-110 ℃ and the reaction time is 0.5-5.5 h.
In preferred embodiments, the mass ratio of sodium bicarbonate to europium chloride hexahydrate is (5-100): 1, preferably (6-85): 1.
The inventor finds that the amount of sodium bicarbonate influences the magnitude of the fluorescence intensity and the length of the fluorescence lifetime of the composite fluorescent material. Too much sodium bicarbonate can degrade the performance of the composite fluorescent material; the mass ratio of the sodium bicarbonate to the europium chloride is preferably (6-85): 1 because the amount of the sodium bicarbonate is too small and the thermal stability of the composite fluorescent material cannot be improved well.
The europium chloride used in the present invention is europium chloride hexahydrate.
In preferred embodiments, the pretreated matrix material is added dropwise to the mixture of step 1.
The inventor finds that a matrix substance sodium bicarbonate is added into the mixed solution obtained in the step 3 in a dropwise manner, so that the sodium bicarbonate, the rare earth compound and the ligand thereof are uniformly mixed, and the finally obtained rare earth europium complex composite fluorescent material with the sodium bicarbonate as the matrix has better fluorescence performance.
In the step 2, the reaction temperature is 50-110 ℃, reflux reaction is preferred, and the reaction time is 0.5-5.5 h, preferably 2-4 h, such as 2.0 h.
The inventors have found that the length of the reaction time affects the properties of the final composite fluorescent material. In the present invention, the reaction time is more preferably 2.0 hours. The obtained composite fluorescent material has good fluorescence performance and long fluorescence life.
And 3, carrying out post-treatment to obtain a final product.
And the post-treatment comprises cooling and filtering after the reaction is finished, and drying the obtained filter cake. Preferably, the drying temperature is 60-120 ℃.
In the present invention, the filtration method is not particularly limited, and any conventional filtration method may be used, and in the present invention, filtration is performed while the solution is hot by suction filtration under reduced pressure.
The inventor finds that after the reaction is finished, the temperature is reduced to 45-55 ℃ for filtration, namely hot filtration is adopted, so that the performance of the finally obtained rare earth composite fluorescent material is the best, probably because impurities can be left in the filtrate by the hot filtration, the quality of the obtained final product is better, and the performance is better.
In the invention, the drying mode is not particularly limited, infrared rays, an oven and a vacuum drying oven can be adopted, the oven is adopted in the invention, and the drying temperature is more preferably 60-120 ℃, such as 80 ℃.
In the invention, the drying time is 1-6 h, preferably 2-5 h, such as 2 h.
According to the method, the prepared sodium bicarbonate-based europium complex composite fluorescent material has high fluorescence intensity which can reach 1050000CPS, long fluorescence life, average fluorescence life of 1.35ms and quantum yield of 20.90%.
The inventor believes that, without being bound by any theory, the fluorescence intensity and the fluorescence lifetime of the sodium bicarbonate-based europium complex composite fluorescent material prepared according to the invention are remarkably increased, and the fluorescence lifetime is remarkably prolonged because the europium complex is subjected to steric hindrance brought by the sodium bicarbonate powder on the surface of the sodium bicarbonate powder, so that the structure of the europium complex is changed, such as the bond angle, the bond length and the like, and the coordination number of the complex and europium is possibly changed, so that the fluorescence intensity and the fluorescence lifetime of the europium complex composite fluorescent material are remarkably enhanced and prolonged.
In the infrared spectrogram of the rare earth europium complex composite fluorescent material prepared by the invention and taking sodium bicarbonate as a matrix, the characteristic peak of the infrared visible spectrum is concentrated at 600cm-1～3750cm-1E.g. at 880cm-1、1439cm-1、3415cm-1A strong characteristic peak appears nearby. And sodium bicarbonate is at 880cm-1Can be shown in the material, indicating that sodium bicarbonate is present in the material.
According to the organic-inorganic hybrid rare earth composite fluorescent material and the preparation method thereof provided by the invention, the following beneficial effects are achieved:
(1) the preparation method of the composite fluorescent material is simple and easy to implement;
(2) the composite fluorescent material has high fluorescence excitation intensity, high fluorescence emission intensity, high quantum yield and long fluorescence life;
(3) the solvent used in the method for preparing the composite fluorescent material is more environment-friendly, and the obtained rare earth composite fluorescent material is easy to recover and has higher social benefit;
(4) the sodium bicarbonate raw material of the invention is , is easy to obtain, has low cost and low cost of the composite fluorescent material, and is expected to expand the application range of the rare earth luminescent material.
Examples
Example 1
0.2781g of TPPO (1mmol), 0.3339g of TTA (1.5mmol) and 0.1294g of europium chloride hexahydrate are weighed respectively and added into a reaction bottle, then 20mL of absolute ethyl alcohol is added, stirring is carried out, and ultrasonic oscillation is carried out for 30min, so as to obtain a solution;
weighing dried 1.0000g of sodium bicarbonate into a 50ml beaker, adding 10ml of absolute ethyl alcohol, putting into an ultrasonic cleaning machine, sealing the opening of the beaker with preservative paper, and carrying out ultrasonic oscillation for 30 min; dropwise adding the pretreated sodium bicarbonate solution into the reaction bottle, starting stirring, after dropwise adding for 10min, heating to reflux reaction, and reacting for 2 h;
after the reaction is finished, cooling to 50 ℃, filtering, putting the obtained filter cake into an oven for drying at the temperature of 80 ℃ for 2 hours to obtain a product; denoted as C1.
Example 2
This example was the same as example 1 except that the amount of sodium bicarbonate was 2 g; the product obtained is designated C2.
Example 3
This example was the same as example 1 except that the amount of sodium bicarbonate was 3 g; the product obtained is designated C3.
Example 4
This example was the same as example 1 except that the amount of sodium bicarbonate was 4 g; the product obtained is designated C4.
Example 5
This example was the same as example 1 except that the amount of sodium bicarbonate was 5 g; the product obtained is designated C5.
Example 6
This example was the same as example 1 except that the amount of sodium bicarbonate was 6 g; the product obtained is designated C6.
Examples of the experiments
Experimental example 1 ultraviolet-visible Spectroscopy analysis of sample
The ultraviolet-visible spectrum of the composite product prepared in the test examples 1-6 is shown in fig. 1. Ultraviolet analysis the liquid phase ultraviolet spectrum was measured with a TU-1901 dual-beam ultraviolet visible spectrophotometer, and the ultraviolet absorption spectrum was measured at 200-600 nm.
As can be seen from fig. 1, as the mass of sodium bicarbonate increases, the maximum absorption wavelength is substantially unchanged, but the peak changes. As can be seen from the figure, 290nm is the characteristic absorption peak of sodium bicarbonate, 337nm is the maximum absorption peak of the complex, the height of the peak is only related to the amount of the sample added during the measurement, and the occurrence of the impurity peak near 200-300nm is probably due to the impurity mixing caused by the long standing time of the sample.
Experimental example 2 Infrared Spectroscopy of samples
Test examples 1-6, the IR spectra of the composite products prepared in examples 1-6 were measured by mixing and grinding the prepared rare earth europium complex composite fluorescent material and potassium bromide at a ratio of 1:100, drying, tabletting on a tabletting machine, and measuring the thickness of the tablets at 4000cm using Fourier transform IR Spectroscopy (Nicolet iS50)-1-400cm-1The range was measured. The results are shown in FIG. 2.
As can be seen from FIG. 2, the characteristic absorption peak of the ligand mainly existed at 1439cm-1And 3414cm-1With the addition of sodium bicarbonate, the peak shape changes and blue shift and red shift occur, indicating that Eu, a rare earth element3+The degree of coordination reaction that occurs varies. At 1439cm-1The strong absorption peak is near, which is the characteristic absorption peak of the ligand, at 880cm-1The strong broad peak of (a) belongs to the characteristic absorption peak of sodium bicarbonate, indicating that the europium complex has formed a complex with sodium bicarbonate. 1400cm with increasing sodium bicarbonate-1-1600cm-1Becomes stronger and stronger, 880cm-1The peaks at (a) also become stronger. It can be concluded that as the reaction proceeds, less ligand is present alone, indicating that the ligand is involved in the reaction and the reaction is more complete, whereas sodium bicarbonate is not involved. Is located at 3100-3500 cm-1An wide absorption peak appears at the position, which is a water molecule absorption vibration absorption peak, and shows that the complex contains crystal water.
XRD analysis of sample of Experimental example 3
XRD analysis was performed on the product samples of examples 1 to 6, and the results are shown in FIG. 3. In fig. 3, the blank refers to pure sodium bicarbonate.
It can be seen from fig. 3 that the complex has a sharp peak at 30 °, and the peak shape becomes more and more distinct with the increase of the mass of sodium bicarbonate, from which it can be seen that the X-ray diffraction peak of europium complex and sodium bicarbonate is substantially , which indicates that the main component of the complex is , the increase of the mass of sodium bicarbonate does not affect the whole structure, and it can be speculated that sodium bicarbonate exists as a "carrier" of the composite material and does not participate in the complexation reaction, and the change of the peak shape indicates that europium complex is attached to the surface of sodium bicarbonate, which can have a definite effect on the surface structure.
Experimental example 4 fluorescence emission spectrum of sample
FIG. 4 shows fluorescence emission spectra, λ, of the products (complex fluorescent materials) of examples 1 to 6ex374nm is the emission detection wavelength;
FIG. 5 shows fluorescence emission line graphs of the products (composite fluorescent materials) of examples 1 to 6; lambda [ alpha ]ex374nm is the emission detection wavelength;
the white powder of the europium complex shows red fluorescence under the irradiation of a 360nm ultraviolet lamp, the fixed excitation wavelength is 374nm, the emission spectrum of the europium complex is measured under the condition that the slit of incident light and emergent light is 1nm, and the strongest peak is positioned at 614 nm. And exciting the europium complex at the optimal excitation wavelength of 374nm to obtain the emission spectrum of the complex.
As can be seen from FIGS. 4 and 5, the maximum absorption peak of the ligand at the excitation wavelength of 374nm is at the wavelength of 614 nm. As can be seen from the figure, the ligand prepared from 1g of sodium bicarbonate has the strongest fluorescence, the fluorescence intensity basically shows a decreasing trend along with the increase of the amount of sodium bicarbonate, and the fluorescence intensity of 5g of samples is greater than that of 4g of samples, which is probably an accidental error in the experiment and basically meets the theoretical requirement. Since sodium bicarbonate merely acts as a "support" and does not participate in the reaction, the amounts of europium chloride hexahydrate and organic ligand participating in the complexing reaction are not changed, and the surface area increases with the increase in the amount of the "support", so that the fluorescence intensity tends to decrease.
Experimental example 5 fluorescence excitation Spectroscopy of sample
The fluorescence spectrum adopts FM4 NIR TCSPC fluorescence spectrometer, and a 400nm light reduction sheet is used for eliminating the influence caused by the light source of the instrument. The entrance and emission slits of the fluorescence spectrometer are both 1nm and are used to reduce the light source intensity by using a 10-fold dimmer. The excitation spectrum of the complex is measured byAt λemAnd 614nm is the excitation detection wavelength.
FIG. 6 shows fluorescence excitation spectra of the products of examples 1 to 6;
FIG. 7 shows a plot of fluorescence excitation intensity for the products of examples 1-6;
as can be seen from fig. 6, the excitation spectra of the 6 products did not differ much by varying the amount of sodium bicarbonate used. With the increase of the amount of sodium bicarbonate, the peak position of the excitation spectrum of the obtained product shows a gradual blue shift trend, and gradually moves from 371nm to 374 nm. This result indicates that, as the amount of sodium bicarbonate is increased, the decrease in the density of europium complex on the surface of the support may be responsible for the shift and change in the peak shape of the fluorescence excitation spectrum. FIG. 7 is a line graph showing the maximum fluorescence excitation intensity formed on the surface of sodium bicarbonate with different amounts, and it is understood that the trend of the fluorescence intensity increases first with the increase of the amount of sodium bicarbonate, and the maximum excitation intensity is maximum when the amount of sodium bicarbonate is 5g, and the excitation wavelength is 374 nm.
Experimental example 6 analysis of fluorescence lifetime of sample
The fluorescence lifetime test uses an LED excitation light source to collect 10000 photons, and the fluorescence lifetime analysis adopts a three-level fitting method, and the results are shown in Table 1 and FIG. 8.
Table 1 shows the average fluorescence lifetimes of the composite phosphors of examples 1-6;
FIG. 8 shows a line graph of the average fluorescence lifetime of the composite fluorescent materials of examples 1 to 6;
TABLE 1 mean fluorescence lifetimes of the products of examples 1-6
| Numbering | Mean fluorescence lifetime/ms | CHISQ |
| C1 | 0.5845976 | 1.135194 |
| C2 | 0.6932945 | 1.07905 |
| C3 | 0.7383188 | 1.060861 |
| C4 | 0.8243821 | 1.062464 |
| C5 | 0.7243856 | 1.02627 |
| C6 | 1.347979 | 1.140132 |
As can be seen from Table 1 and FIG. 8, the fluorescence excitation lifetime increased with the increase in the mass of sodium bicarbonate before 4g, dips after 5g, and then the fluorescence lifetime increased again, so it is known that the fluorescence lifetime was the greatest when complexes were synthesized with 6g of sodium bicarbonate.
Experimental example 7 fluorescence quantum yield analysis of sample
The fluorescence quantum yield (Yf) is the ratio of the number of photons of the emitted fluorescence to the number of photons of the absorbed excitation light after absorption by the fluorescent substance. The larger the value of YF, the more fluorescent the compound, while the fluorescence quantum yield of non-fluorescent material is equal to or very close to zero.
And under the same excitation condition, respectively measuring the integrated fluorescence intensity of two samples of the fluorescence pattern to be measured and the reference fluorescence standard substance with known quantum yield and the absorbance of incident light with the same excitation wavelength of .
The quantum yields of the products of examples 1-6 are shown in table 2. The excitation wavelength of this test was determined by using λ ex 373nm as the excitation detection wavelength and λ ex 614nm as the emission detection wavelength.
TABLE 2 Quantum yield tables for product samples of examples 1-6
| Numbering | Abs | Quantum yield% |
| C1 | 0.029 | 20.90 |
| C2 | 0.008 | 12.49 |
| C3 | 0.056 | 20.06 |
| C4 | 0.040 | 7.94 |
| C5 | 0.039 | 0.52 |
| C6 | 0.040 | 0.37 |
As can be seen from table 2, the quantum yield of the composite fluorescent material is greater at the amount of sodium bicarbonate of 1g, and the quantum yield of the product tends to decrease gradually as the amount of sodium bicarbonate increases. While the sudden rise in quantum yield for the 3g sample may be due to slight variations in sample preparation and measurement leading to occasional errors.
According to the invention, the rare earth europium composite fluorescent material with sodium bicarbonate as the matrix is prepared, and the product has excellent performance, higher fluorescence quantum efficiency and good fluorescence performance through characterization. The invention uses cheap sodium bicarbonate, TTA and TPPO to synthesize the rare earth composite material, reduces the cost of the luminescent material, has long service life of the prepared material, high quantum yield and good fluorescence performance, and widens the application and research range of the rare earth europium complex.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1, rare earth composite fluorescent materials, which are characterized in that the maximum absorption wavelength of the ultraviolet-visible spectrum of the composite fluorescent material is near 337 nm.
2. The rare earth composite fluorescent material according to claim 1, wherein the infrared-visible spectrum characteristic peak of the composite fluorescent material is concentrated at 600cm-1～3750cm-1E.g. at 880cm-1、1439cm-1、3415cm-1A strong characteristic peak appears nearby.
3. The rare earth composite fluorescent material according to claim 1 or 2, wherein the composite fluorescent material comprises a rare earth complex and a matrix, and the matrix comprises or more of sodium acetate, potassium acetate, sodium bicarbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate, and is preferably sodium bicarbonate.
4. The rare earth composite fluorescent material according to claim 3,
the rare earth complex is a complex of europium or a complex of terbium, preferably a complex of europium, and more preferably the rare earth complex is an organic ligand complex of europium.
5. The rare earth composite fluorescent material according to claim 4,
the organic ligand comprises methylbenzotriazole.
6, A method for preparing rare earth composite fluorescent material, preferably A rare earth composite fluorescent material according to claims 1 to 5, characterized in that the method comprises the following steps:
step 1: mixing a ligand and a rare earth compound to obtain a solution;
step 2: reacting the solution in the step 1 with a matrix substance under set conditions;
and step 3: and carrying out post-treatment to obtain a final product.
7. The production method according to claim 6,
in the step 1, the ligand comprises methylbenzotriazole and triphenyl phosphorus oxide, and the molar ratio of the methylbenzotriazole to the triphenyl phosphorus oxide is (0.5-3.5): 1;
the rare earth compound is europium trichloride;
mixing with solvent comprising kinds of methanol, ethanol, isopropanol, and n-butanol.
8. The production method according to claim 6,
in step 2, pretreating the matrix substance;
the pretreatment comprises mixing a matrix substance with a dispersing agent and optionally carrying out ultrasonic oscillation, wherein the dispersing agent is or more of methanol, ethanol, isopropanol and n-butanol, and preferably the same solvent used in the step 1;
the set conditions comprise that the reaction temperature is 50-110 ℃ and the reaction time is 0.5-5.5 h.
9. the method according to any one of claims 6 to 8, wherein,
and in the step 3, after the reaction is finished, cooling, filtering and drying the obtained filter cake.
10. the rare earth composite fluorescent material according to claims 1 to 5, characterized in that, it is prepared or prepared according to the method of of claims 6 to 9.
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| CN106118632A (en) * | 2016-07-11 | 2016-11-16 | 阜阳师范学院 | A kind of calcium carbonate-base europium complex and preparation method thereof |
| CN106118633A (en) * | 2016-07-11 | 2016-11-16 | 阜阳师范学院 | A kind of acetic acid sodio rare-earth luminescent material and preparation method thereof |
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| CN106118632A (en) * | 2016-07-11 | 2016-11-16 | 阜阳师范学院 | A kind of calcium carbonate-base europium complex and preparation method thereof |
| CN106118633A (en) * | 2016-07-11 | 2016-11-16 | 阜阳师范学院 | A kind of acetic acid sodio rare-earth luminescent material and preparation method thereof |
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