CN110655917A - Rare earth complex composite fluorescent material and preparation method thereof - Google Patents
Rare earth complex composite fluorescent material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 104
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 51
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 39
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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 24
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 europium ions Chemical class 0.000 claims abstract description 17
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- 239000003446 ligand Substances 0.000 claims description 54
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- 230000035484 reaction time Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
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- 238000001035 drying Methods 0.000 claims description 8
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- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 7
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- 238000002156 mixing Methods 0.000 claims description 6
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- 239000012467 final product Substances 0.000 claims description 4
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
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- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002835 absorbance Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
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- 229910052689 Holmium Inorganic materials 0.000 description 1
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- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000032912 absorption of UV light Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000012065 filter cake Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000001307 laser spectroscopy Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
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- 238000007430 reference method Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 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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- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 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
- 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
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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
- 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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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a rare earth complex composite fluorescent material and a preparation method thereof, europium ions are used as a luminous body, triphenyl phosphorus oxide (TPPO) and 2-thenoyltrifluoroacetone (TTA) are used as organic ligands, calcium carbonate is used as a matrix, the europium complex composite fluorescent material is prepared under set conditions, and the obtained composite fluorescent material is characterized.
Description
Technical Field
The invention relates to the field of fluorescent materials, in particular to a rare earth complex composite fluorescent material and a preparation method thereof.
Background
Rare earth elements are widely applied to the fields of nonferrous metallurgy, petrochemical industry, military field, glass ceramic industry, magnetic materials and various functional materials, light industry and textile industry, agricultural medicine and the like.
The rare earth elements refer to IIIB group in the periodic table, 21 # element scandium Sc, 39 # element yttrium Y and 57-71 lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, promethium Pm, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, and total 17 elements. Rare earth elements containing as a host component, activator, co-activator or dopant are a generic term for rare earth fluorescent materials.
The rare earth luminescent material is a rare earth functional material which utilizes the unique electronic layer structure of rare earth elements and adopts different excitation modes to make the rare earth luminescent material emit light, and is commonly called rare earth fluorescent powder.
Because the rare earth ions have abundant emission spectra and multiple energy levels, under the irradiation of ultraviolet light, several rare earth element ions can generate a luminous phenomenon in a visible light region or a near infrared spectrum region. The f-f transition spectrum is less affected by the external crystal field, so the spectrum has the characteristics of low spectral line intensity, long fluorescence service life, linear spectrum and the like, and the visible fluorescence of the spectrum is bright. The luminescence of rare earth ions has many excellent properties and many unique advantages, so the research on the luminescent properties of rare earth elements, the preparation of luminescent materials and the like has very important theoretical significance and great practical value.
The rare earth europium complex is a red fluorescent material, has the advantages of unique molecular structure, photoluminescence mechanism, strong fluorescence, good monochromaticity and the like, is applied to various fields of industry, agriculture, biology and the like, but has slightly poor light and heat stability, and in recent years, rare earth is gradually taken as strategic resource, so that more and more attention is paid, the price of the rare earth is continuously increased, and the rare earth complex is difficult to recover after being used, so that the application of the rare earth complex in various aspects is greatly limited.
Therefore, it is urgently needed to develop a rare earth complex composite fluorescent material which has long fluorescence lifetime and simple preparation method, reduces the cost and optimizes the performance of the complex, so as to expand the application range of the rare earth complex.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: a rare-earth complex composite fluorescent material and its preparation method, take europium ion as the illuminant, take triphenyl phosphorus oxide (TPPO) and 2-Thenoyl Trifluoroacetone (TTA) as organic ligand, and regard calcium carbonate as the basal body, react and prepare europium complex composite fluorescent material under the set condition, and characterize the composite fluorescent material obtained, the invention has not merely reduced the cost of the luminescent material, and the material prepared is good in thermostability, the fluorescence performance is good, thus has finished the invention.
The object of the present invention is to provide the following:
in a first aspect, the invention provides a rare earth complex composite fluorescent material, which comprises a rare earth complex and a matrix.
In a second aspect, the present invention also provides a method for preparing the rare earth complex composite fluorescent material according to the first aspect, which comprises the following steps:
step 1: mixing a matrix substance with a rare earth compound to obtain a mixed solution;
step 2: dissolving a ligand in a solvent to obtain a solution;
and step 3: adding the solution obtained in the step (2) into the mixed solution obtained in the step (1), and reacting under set conditions;
and 4, step 4: and carrying out post-treatment to obtain a final product.
Drawings
Figure 1 shows an XRD analysis spectrum of a sample;
FIG. 2 shows a UV-Vis spectrum of a sample;
FIG. 3 shows an infrared spectrum of a sample;
FIG. 4 shows fluorescence excitation spectra of a sample;
FIG. 5 shows a plot of fluorescence excitation intensity for a sample;
FIG. 6 shows a fluorescence emission spectrum of a sample;
FIG. 7 shows a fluorescence emission refractogram of a sample;
FIG. 8 shows a plot of the mean fluorescence lifetime of a sample;
fig. 9 shows a thermogravimetric measurement spectrum of a blank calcium carbonate;
figure 10 shows the thermogravimetric spectrum of the product of example 4.
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 a first aspect of the present invention, there is provided a rare earth complex composite fluorescent material comprising a rare earth complex and a matrix.
Wherein the rare earth complex is a complex of europium or a complex of terbium;
preferably, the rare earth complex is a complex of europium; the europium complex is a europium dual-ligand complex, the dual-ligand is a first ligand and a second ligand, the first ligand is beta-diketone (such as 2-thenoyl trifluoroacetone), and the second ligand is phenanthroline or triphenyl phosphorus oxide;
more preferably, the second ligand is triphenyl phosphine oxide (TPPO).
The luminescence of the rare earth organic fluorescent complex is a cross discipline of inorganic luminescence, organic luminescence and biological luminescence, and has important theoretical research significance and application research value. The interest in sensitized emission in rare earth complexes began in 1942, and Weissman discovered that characteristic linear emission of Eu ions occurs after absorption of uv light by different β -diketone Eu complexes. Since the advent of laser spectroscopy over the last two decades, a great deal of research on rare earth fluorescence phenomena has been conducted in different fields.
Beta-diketone has strong coordination ability and higher absorption coefficient to rare earth ions, and is an excellent ligand for researching transition of rare earth elements. The high-efficiency energy transfer from a ligand to a central ion (particularly europium ion, terbium ion and the like) exists in the rare earth beta-diketone complex, so that the complex has high luminous efficiency.
In order to expand the research range of rare earth organic complexes, materials with better luminescence performance are searched, and multi-ligand systems are researched, such as the introduction of second ligands (such as phosphine-oxygen bond-containing compounds, nitrogen-containing aromatic heterocyclic compounds and the like), wherein the second ligands generate synergistic effect in the luminescence process.
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 oxygen-containing inorganic compound 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.
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 (2-thenoyltrifluoroacetone) and TPPO (triphenyl phosphorus oxide) and calcium carbonate matrix not only improves the light and heat stability of the europium complex, but also improves the fluorescent property, and reduces the cost of the fluorescent material.
The substrate is an oxygen-containing inorganic compound which comprises one or more of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate.
Preferably, the matrix is calcium carbonate.
In the invention, the fluorescence emission intensity of the europium complex composite fluorescent material can reach 1050000CPS, and the average fluorescence lifetime is 0.56-0.60 ms.
According to a second aspect of the present invention, there is provided a method for preparing the above rare earth complex composite fluorescent material, comprising the steps of:
step 1: mixing a matrix substance with a rare earth compound to obtain a mixed solution;
step 2: dissolving a ligand in a solvent to obtain a solution;
and step 3: adding the solution obtained in the step (2) into the mixed solution obtained in the step (1), and reacting under set conditions;
and 4, step 4: and carrying out post-treatment to obtain a final product.
Step 1, mixing a matrix substance with a rare earth compound to obtain a mixed solution.
The matrix substance is an oxygen-containing inorganic compound and comprises one or more of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate; preferably, the matrix material is calcium carbonate; the rare earth compound is a europium compound, preferably europium chloride;
in a preferred embodiment, the base material is dried for 1-3 hours before mixing.
The inventor finds through experiments that water can affect the complexation of europium ions and ligands and finally affect the performance of the composite fluorescent material; since calcium carbonate readily absorbs water, calcium carbonate is dried to remove water.
In the invention, calcium carbonate 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 calcium carbonate, thereby obtaining the composite fluorescent material.
In the present invention, the calcium carbonate powder may be either commercially available or self-prepared.
In the invention, the particle size of the calcium carbonate is 30-80 nm. Without being bound by any theory, the inventor believes that the fluorescent material obtained by using the nano-scale calcium carbonate powder as the basic salt has smaller particle size, and meanwhile, the nano-scale calcium carbonate 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 calcium carbonate with uniform particle size distribution can obtain the fluorescent material with stable and uniform performance.
In a preferred embodiment, the mass ratio of europium chloride to calcium carbonate is (0.02-1): 1, preferably (0.05-0.5): 1, such as 0.258: 1.
The inventor finds that the dosage of calcium carbonate influences the magnitude of the fluorescence intensity and the length of the fluorescence lifetime of the composite fluorescent material. Too much calcium carbonate can reduce the performance of the composite fluorescent material; the amount of calcium carbonate is too small to improve the thermal stability of the composite fluorescent material well, and therefore, the mass ratio of europium chloride to calcium carbonate is preferably (0.05-0.5): 1.
In the invention, a solvent is also added in the step 1, wherein the solvent is one or more of methanol, ethanol and isopropanol, ethanol is preferred, and absolute ethanol is more preferred.
The inventor finds that ethanol is used as a solvent, 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 a preferred embodiment, calcium carbonate, europium chloride and ethanol are mixed, and after the mixture is uniformly stirred, ultrasonic oscillation is performed for 30min, so that calcium carbonate particles are more uniformly dispersed, and the performance of the finally prepared composite fluorescent material is better.
And 2, dissolving the ligand in a solvent to obtain a solution.
The ligand is a dual ligand, the dual ligand is a first ligand and a second ligand, the first ligand is beta-diketone (such as 2-thenoyltrifluoroacetone), and the second ligand is phenanthroline and triphenyl phosphorus oxide; more preferably, the second ligand is triphenyl phosphorus oxide;
preferably, the first ligand is 2-thenoyltrifluoroacetone (TTA); the second ligand is triphenyl phosphorus oxide (TPPO), and the mass ratio of the second ligand to the second ligand is (0.5-3): 1, more preferably (1 to 2.5): 1, such as 1.2: 1.
The conversion between keto-enol forms in beta-diketone compounds endows the beta-diketone compounds with a plurality of unique coordination chemical properties, and the beta-diketone compounds are typical metal chelating agents, have larger light absorption coefficients and proper conjugated systems, 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. They react with europium ion Eu3+Form a stable six-membered ring that directly absorbs light energy and efficiently transfers energy.
Eu3+In addition to the organic anions which satisfy the charge balance as the first ligands, the multi-coordinated ions generally include second ligands which satisfy the multi-coordination requirement, and the second ligands are mostly neutral ligands.
The neutral ligand influences the photoluminescence efficiency and fluorescence intensity of the europium complex mainly by participating in energy transfer and influencing the lifetime of the first excited triplet state of the central ligand. The second ligand is introduced into the structure of the luminescent complex, so that the luminescent brightness of the material can be obviously improved.
In the invention, the performance of the finally obtained composite fluorescent material can be better by researching the TPPO as the second ligand.
In the invention, when TTA and TPPO are mixed, a solvent is added, wherein the solvent is one or more of methanol, ethanol and isopropanol, preferably ethanol, and more preferably absolute ethanol.
In the step 2, the volume ratio of the absolute ethyl alcohol to the sum of the mass of TTA and TPPO is 0.5g (5-15) mL. On the one hand, the amount of absolute ethyl alcohol is sufficient to dissolve TTA and TPPO completely, and on the other hand, the amount of absolute ethyl alcohol is sufficient to keep TTA and TPPO within a certain concentration so as to facilitate the subsequent reaction.
And 3, adding the solution in the step 2 into the mixed solution in the step 1, and reacting under set conditions.
In the step 3, the reaction temperature is 55-90 ℃, the reflux reaction is preferred, and the reaction time is 0.5-3.0 h.
In a preferred embodiment, the mixture of step 1 is stirred first, and then the mixture of step 2 is added dropwise.
The inventor finds that the performance of the final composite fluorescent material obtained by adopting the feeding mode is better. This is probably because the composite fluorescent material obtained by the feeding method is more uniform.
In step 3, the reaction time is preferably 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, more preferably 1.5h, 2.0h, 2.5h, and even more preferably 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 4, carrying out post-treatment to obtain a final product.
The post-treatment comprises cooling to room temperature after the reaction is finished, filtering, drying,
preferably, the drying temperature is 45-110 ℃.
In the present invention, the filtration method is not particularly limited, and any conventional filtration method may be used, and suction filtration is employed in the present invention.
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 70-95 ℃.
According to the method disclosed by the invention, the prepared calcium carbonate-based europium complex composite fluorescent material has high fluorescence intensity which can reach 1050000CPS, long fluorescence life which can reach 0.59ms, and high quantum yield which can reach 25.09%.
The inventor believes that, without being bound by any theory, the fluorescence intensity of the calcium carbonate-based europium complex composite fluorescent material prepared according to the invention is remarkably increased, and the fluorescence lifetime is remarkably prolonged, because the europium complex is subjected to steric hindrance brought by calcium carbonate powder on the surface of calcium carbonate powder, the structure of the europium complex is changed, such as bond angle, bond length and the like, and simultaneously, the coordination number of the complex and europium can be distinguished, 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 europium complex composite fluorescent material prepared by the invention, two characteristic vibration absorption peaks of calcium carbonate located at 872 cm-1 and 714cm-1 can be displayed in the material, which indicates that the calcium carbonate exists in the material. Characteristic absorption peaks of the ligand appear at 1616 and 1637cm-1, which indicates that the europium complex and calcium carbonate form a europium complex/calcium carbonate composite fluorescent material.
According to the rare earth complex 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 prepared by the method has uniform particle size and can be controlled within a proper particle size range;
(3) the composite fluorescent material has high fluorescence excitation intensity, high fluorescence emission intensity, high quantum yield and long fluorescence life;
(4) the composite fluorescent material has low cost and good thermal stability, and is expected to become a good luminous body in a high-temperature resistant device.
Examples
Example 1
Weighing 1g of dried calcium carbonate and 0.258g of europium chloride, adding the calcium carbonate and the europium chloride into a reaction bottle, adding 20mL of absolute ethyl alcohol serving as a solvent, uniformly stirring, and performing ultrasonic oscillation for 30 min;
0.2781g of TPPO and 0.3334g of TTA are respectively weighed and added into a beaker, 10mL of absolute ethyl alcohol is added, stirred and dissolved, and then the mixture is transferred into an addition funnel;
placing the reaction bottle in a heating sleeve, starting stirring, connecting a reflux device, then dropwise adding the two ligand solutions in a feeding funnel, heating to reflux reaction after 10min of dropwise addition is finished, and reacting for 0.5 h;
after the reaction is finished, cooling to room temperature, filtering, and drying the obtained filter cake in an oven at the temperature of 90 ℃ for 2 hours to obtain a product; denoted as E1.
Example 2
This example was the same as example 1 except for the reaction time, which was 1 hour. The product obtained is designated as E2.
Example 3
This example was the same as example 1 except for the reaction time, which was 1.5 hours. The product obtained is designated as E3.
Example 4
This example was the same as example 1 except for the reaction time, which was 2.0 h. The product obtained is designated as E4.
Example 5
This example was the same as example 1 except for the reaction time, which was 2.5 hours. The product obtained is designated as E5.
Example 6
This example was the same as example 1 except for the reaction time, which was 3.0 h. The product obtained is designated as E6.
Examples of the experiments
XRD analysis of sample of Experimental example 1
The XRD patterns of the composite products prepared in examples 1-6 were measured and compared with a standard diffraction pattern card, and the results are shown in FIG. 1. XRD measurements were performed using 8 degrees per minute scans.
As can be seen from FIG. 1, the peaks of the europium-doped composite fluorescent material prepared from 1g of calcium carbonate with different reaction times can be seen and the peak shapes are quite distinct. As can be seen from FIG. 1, the peaks in this figure are similar to the calcium carbonate peaks, indicating that the product contains calcium carbonate. The peak value changes along with the change of the reaction time, the peak value generally increases along with the increase of the time from 0.5h to 2.0h, and the peak value is reduced along with the increase of the time from 2h to 3 h. The positions of the peaks in the general view of FIG. 1 are not changed basically, but some miscellaneous peaks appear at 0.5h and 1.0h, which may be the reason of incomplete reaction.
Experimental example 2 ultraviolet-visible Spectroscopy analysis of sample
The composite products obtained in examples 1-6 were subjected to UV analysis, and the liquid-phase UV spectrum was measured with a TU-1901 dual-beam UV-visible spectrophotometer, and the UV absorption spectrum was measured in the range of 200-600nm, the results are shown in FIG. 2.
As can be seen from FIG. 2, when the prepared complex was qualitatively analyzed, the first peak, which is the absorption peak of calcium carbonate, appeared at 284nm, and the second peak, which is the absorption peak of the ligand forming a complex with europium, appeared at 348 nm. As can be seen from fig. 2, the maximum absorption wavelength changes with the change in the reaction time, and the absorption peak also changes to a certain extent. Since the reaction time is varied, it can be seen from fig. 2 that the peaks of the resulting products are different with time, i.e., their luminescence intensities are also varied, i.e., the variation of the reaction time has an influence on the fluorescence intensity thereof.
EXAMPLE 3 Infrared spectroscopic analysis of sample
The infrared spectrum of the composite product prepared in the test examples 1-6 is shown in FIG. 3. Mixing the rare earth europium complex composite fluorescent material prepared for infrared spectrum and potassium bromide in a ratio of 1:100, grinding, drying, tabletting on a tabletting machine, and performing Fourier transform infrared spectrum (Nicolet iS50) at 4000cm-1-400cm-1The range was measured.
As can be seen from fig. 3, after the complex is formed, C ═ O of TTA coordinates with Eu, and two characteristic vibration absorption peaks of calcium carbonate at 872 and 714cm "1 can be shown in the material, indicating that calcium carbonate is present in the material. Characteristic absorption peaks of the ligand appear at 1616 and 1637cm-1, which indicates that the europium complex and calcium carbonate form a europium complex/calcium carbonate composite fluorescent material. From this, it can be concluded that the presence of less ligand alone, as the reaction proceeds, indicates that the complex formed initially becomes easier to cover the surface of calcium carbonate, as the reaction time increases, so that its absorption peak appears clearly, but that, as the reaction time increases, a larger amount of calcium carbonate is more reacted, so that its absorption peak is difficult to show.
Experimental example 4Fluorescence excitation spectrum of the product
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.
FIG. 4 shows fluorescence excitation spectra of the products of examples 1 to 6;
FIG. 5 shows a plot of fluorescence excitation intensity for the products of examples 1-6;
as can be seen from FIGS. 4 and 5, λ was measured at 2h for the luminescent materialemThe 380nm luminous effect is best, the luminous intensity is gradually increased from 0.5h to 2h, and then gradually reduced after 2h, and it is known that the reaction is most complete about 2h, the reaction before 2h is not complete, the luminous intensity does not reach the peak, and the reaction after 2h is excessive, and the luminous intensity is reduced.
Experimental example 5 fluorescence emission spectrum of sample
Fig. 6 shows fluorescence emission spectra of the products (complex fluorescent materials) of examples 1 to 6, where λ em ═ 620nm is the excitation detection wavelength;
FIG. 7 shows fluorescence emission refractograms of the products of examples 1-6 (composite fluorescent materials); λ em-620 nm is the excitation detection wavelength;
from fig. 6 and 7, it can be seen that the emission intensity changes with time from 0.5h to 2h, which increases with time, and from 2h to 3h, which decreases with time, and that the emission intensity is strongest at 2.0h and the surface time affects the emission intensity, and from fig. 6 and 7, it can be seen that λ at 2.0hexThe fluorescence intensity is strongest at 620 nm. In conclusion, it can be seen that the change in reaction time has an effect on the fluorescence emission effect of the composite material.
Experimental example 6 fluorescence lifetime map of sample
The fluorescence life test uses an LED excitation light source with 370nm to collect 50000 photons, and a three-order life fitting method is adopted for a fluorescence life curve.
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
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.
The fluorescence quantum yield was determined by the reference method. Under the same excitation condition, the integral 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 are respectively measured.
The quantum yields of the products of examples 1-6 are shown in table 2.
TABLE 2 Quantum yields of the products of examples 1-6
As can be seen from Table 4, the quantum yield reaches the highest value at 2.5h, and the absorbance reaches 3.8% at 2.5h, which indicates that the change of the reaction time has a greater effect on the quantum yield, and the quantum yield gradually increases from 0.5h to 2.5h, and decreases with the further increase of the reaction time.
Thermogravimetric analysis of sample of Experimental example 8
The thermogravimetric measurement is that the balance displacement caused by the weight change of a sample is converted into electromagnetic quantity, and the tiny electric quantity is amplified by an amplifier and then sent to a recorder for recording.
Fig. 9 shows a thermogravimetric measurement spectrum of a blank calcium carbonate;
figure 10 shows the thermogravimetric spectrum of the product of example 4.
As can be seen from fig. 9, two peaks, one large peak and one small peak, appear in the graph, the mass percentage is basically unchanged when the temperature rises from the beginning, and the mass percentage is reduced to 98.9% when the temperature rises, wherein the reduction is that the moisture in the air begins to volatilize to reduce the mass of the calcium carbonate, and then the temperature continues to rise and the mass continues to decrease, which is that the calcium carbonate is decomposed at a certain high temperature, the calcium carbonate is decomposed into calcium oxide and carbon dioxide, the carbon dioxide is volatilized as gas, and the relative molecular mass of the calcium oxide is smaller than that of the calcium carbonate, so the mass percentage is reduced again. FIG. 10 is a thermogravimetric spectrum of a europium complex composite fluorescent material prepared in example 4, showing three peaks, the first peak being the volatilization of water in the air, the second peak being the volatilization of water in TTA and TPPO components in the ligand, and the third peak being the decomposition of calcium carbonate. Therefore, the composite fluorescent luminescent material has better thermal stability.
From the above, the invention not only prepares the expected europium complex composite fluorescent material, but also has the advantages of good product performance, high fluorescence quantum efficiency and good fluorescence performance through characterization. The invention uses cheap calcium carbonate, TTA and TPPO to synthesize the rare earth composite material, not only reduces the cost of the luminescent material, but also has good thermal stability of the prepared material, and can possibly become a good luminescent body in a high-temperature resistant device.
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. The rare earth complex composite fluorescent material is characterized by comprising a rare earth complex and a matrix.
2. The composite fluorescent material according to claim 1, wherein the rare earth complex is a complex of europium or a complex of terbium.
3. The composite fluorescent material of claim 2, wherein the rare earth complex is a complex of europium;
preferably, the europium complex is a europium dual-ligand complex, the dual-ligand is a first ligand and a second ligand, the first ligand is a beta-diketone (such as 2-thenoyl trifluoroacetone), and the second ligand is phenanthroline or triphenyl phosphorus oxide; more preferably, the second ligand is triphenyl phosphorus oxide.
4. The composite fluorescent material of claim 1,
the matrix is an oxygen-containing inorganic compound, and comprises one or more of sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate, and calcium carbonate is preferred.
5. A method for preparing a rare earth complex composite fluorescent material, preferably a composite fluorescent material according to one of claims 1 to 4, characterized in that the method comprises the following steps:
step 1: mixing a matrix substance with a rare earth compound to obtain a mixed solution;
step 2: dissolving a ligand in a solvent to obtain a solution;
and step 3: adding the solution obtained in the step (2) into the mixed solution obtained in the step (1), and reacting under set conditions;
and 4, step 4: and carrying out post-treatment to obtain a final product.
6. The production method according to claim 5,
in the step 1, the matrix substance is an oxygen-containing inorganic compound, and the rare earth compound is a europium compound, preferably europium chloride;
preferably, a solvent is also added in the step 1, wherein the solvent is one or more of methanol, ethanol and isopropanol, and ethanol is more preferred.
7. The production method according to claim 5,
in the step 2, the ligand is a dual ligand, the dual ligand is 2-thenoyltrifluoroacetone and triphenyl phosphorus oxide, and the mass ratio of the dual ligand is (0.5-3): 1,
preferably, the solvent is one or more of methanol, ethanol, isopropanol, more preferably the same solvent as used in step 1.
8. The production method according to claim 5,
in the step 3, the reaction temperature is 55-90 ℃, and the reaction time is 0.5-3.0 h.
9. The production method according to claim 5,
in step 4, the post-treatment comprises cooling to room temperature after the reaction is finished, filtering, drying,
preferably, the drying temperature is 45-110 ℃.
10. The rare earth complex composite fluorescent material according to any one of claims 1 to 4, which is produced or prepared according to the method of any one of claims 5 to 9.
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