CN109734120B - Flower-like microsphere structure potassium yttrium tungstate material and preparation method thereof - Google Patents
Flower-like microsphere structure potassium yttrium tungstate material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to a potassium yttrium tungstate material with a flower-like microsphere structure and a preparation method thereof. According to the invention, the flower-like microsphere structure potassium yttrium tungstate is prepared by using a hydrothermal method to assist a surfactant, and the surfactant is added to change the interfacial tension, so that the nanosheets are self-assembled into the flower-like microsphere structure. The prepared potassium yttrium tungstate with the flower-like microsphere structure has larger specific surface area, and the surface activity, the surface adsorption capacity, the catalytic capacity, the luminous intensity and the like are enhanced, so that the photoelectric function of the material can be effectively improved; the preparation method has the advantages of simple process, low cost, good repeatability, convenient post-treatment, no need of high-temperature sintering, energy conservation and environmental protection. Can be widely applied to the fields of high-definition display equipment, photocatalysis, agricultural sunlight conversion, photoelectric devices, biological fluorescent markers and the like as a luminescent material.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a potassium yttrium tungstate material with a flower-like microsphere structure and a preparation method thereof.
Background
Rare earth doped alkaline earth complex tungstate crystal (AB (WO)4)2(A is alkaline earth metal, B = Re = Y, Gd, La, Lu, Yb, etc.) is an excellent laser matrix material, has high nonlinear refractive index, good mechanical and physicochemical properties, disordered crystal structure, unfixed positions of rare earth ions and alkaline earth metal ions, wider absorption peak of the rare earth ions, higher material conversion efficiency and laser output energy than those of the common tungstate crystal material, and [ WO ] in the crystal4]2-The strong covalent bond effect of the group W-O weakens the quenching effect of the fluorescence concentration, increases the doping concentration of the active ions, is an optical material with great prospect, and has potential application in the wide fields of remote sensing, medical treatment, scientific research, communication and the like.
The invention discloses a near-spherical potassium yttrium tungstate particle and a preparation method thereof in the patent of the invention with the Chinese patent application number of 201310245935.1, namely the name of the near-spherical potassium yttrium tungstate particle, wherein the near-spherical potassium yttrium tungstate particle has a plurality of defects in practical application, and the near-spherical potassium yttrium tungstate particle has the defects of smooth surface and no special appearance of pore diameter, so that the near-spherical potassium yttrium tungstate particle is not ideal enough in improving the optical, electric, magnetic and catalytic properties of potassium yttrium tungstate, and the like, and the near-spherical potassium yttrium tungstate particle needs to be sintered at high temperature in the preparation process, so that the energy consumption is high, and the preparation cost is high.
Disclosure of Invention
In view of the above, the invention provides a potassium yttrium tungstate material with a flower-like microsphere structure and a preparation method thereof. The preparation method adopts a hydrothermal method to assist the surfactant to prepare the potassium yttrium tungstate with the flower-like microsphere structure, the preparation method is simple, the prepared material has a high specific surface area, and the surface activity, the surface adsorption capacity, the catalytic capacity and the luminous intensity of the material are also greatly improved.
In order to achieve the purpose, the preparation method of the potassium yttrium tungstate with the flower-like microsphere structure comprises the following steps:
(1) dropwise adding an yttrium ion solution into a tungstate ion solution to form a mixed solution, dropwise adding an europium ion solution into the mixed solution, adjusting the pH value to 7.5-8, uniformly stirring, adding a certain amount of surfactant, and performing ultrasonic stirring to obtain a precursor solution; the molar ratio of tungstate ions, yttrium ions and europium ions in the precursor solution is 2:1: 1;
(2) putting the precursor solution prepared in the step (1) into an autoclave, carrying out hydrothermal sealing and heat preservation on the precursor solution to obtain white precipitate, wherein the hydrothermal temperature is 100-135 ℃, the heat preservation time is 15-19 h, and naturally cooling the autoclave to room temperature after the reaction is finished;
(3) and (3) cleaning, centrifuging, drying and grinding the white precipitate obtained in the step (2) to obtain the flower-like microsphere structure potassium yttrium tungstate. As a further improvement of the invention, the molar ratio of the surfactant to tungstate ions in step (1) is 1.4: 1.
As a further improvement of the invention, the surfactant in step (1) is cetyltrimethylammonium bromide (CTAB) or Sodium Dodecylbenzenesulfonate (SDBS).
As a further improvement of the invention, the surfactant in the step (1) is a mixed solution of cetyl trimethyl ammonium bromide and ethanol or sodium dodecyl benzene sulfonate, and the proportion relationship of the cetyl trimethyl ammonium bromide and the ethanol is 0.5-2g:5 mL.
As a further improvement of the invention, the cleaning in the step (3) is firstly cleaning with deionized water and then cleaning with a mixed solution of acetone and ethanol with the volume fraction of 1: 1.
In order to achieve the above object, the present invention provides a flower-like microspherical structure potassium yttrium tungstate material obtained by the preparation method as described above, the flower-like microspherical structure potassium yttrium tungstate material is prepared from flaky KY (WO)4)2The composition is in a flower ball shape, the flower ball size is 2-8.5 mu m, and the specific surface area is 31.677 m2/g。
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the flower-like microsphere structure potassium yttrium tungstate is prepared by using a hydrothermal method to assist a surfactant, the surfactant is added to change the interfacial tension, and the self-assembly of the nanosheets is assisted by using a surfactant ordered aggregate microenvironment as a template to synthesize the flower-like microsphere structure potassium yttrium tungstate. The prepared potassium yttrium tungstate with the flower-like microsphere structure has larger specific surface area, and the surface activity, the surface adsorption capacity, the catalytic capacity, the luminous intensity and the like are enhanced, so that the photoelectric function of the material can be effectively improved; the material prepared by the invention has the characteristics of high purity, good crystal form, good monodispersity and the like. The preparation method has the advantages of simple process, low cost, good repeatability, convenient post-treatment, no need of high-temperature sintering, energy conservation and environmental protection. Can be widely applied to the fields of high-definition display equipment, photocatalysis, agricultural sunlight conversion, photoelectric devices, biological fluorescent markers and the like as a luminescent material.
Drawings
FIG. 1 is a scanning electron microscope photograph of potassium yttrium tungstate having a flower-like microsphere structure prepared in example 1;
FIG. 2 is a scanning electron microscope photograph of potassium yttrium tungstate in flower-like microsphere structure prepared in example 2;
FIG. 3 is a scanning electron microscope photograph of potassium yttrium tungstate in flower-like microsphere structure prepared in example 3;
FIG. 4 is a scanning electron microscope photograph of potassium yttrium tungstate in flower-like microsphere structure prepared in example 4;
FIG. 5 is a scanning electron microscope photograph of potassium yttrium tungstate in flower-like microsphere structure prepared in example 5;
FIG. 6 is a comparison of the X-ray diffraction analysis pattern of potassium yttrium tungstate with flower-like microsphere structure prepared in example 5 with standard PDF card;
FIG. 7 is a graph showing the adsorption and desorption curves of potassium yttrium tungstate with flower-like microsphere structure prepared in example 5;
FIG. 8 is an emission spectrum of potassium yttrium tungstate with flower-like microsphere structure prepared in example 5 under 464nm excitation.
Detailed Description
In order that those skilled in the art will be able to better understand the technical solutions provided by the present invention, the following description is provided in connection with specific embodiments.
Example 1:
weighing 8mmol of K2WO42.2mmol of Y (NO)3)3·6H2O is respectively dissolved in deionized water to prepare WO with the concentration of 0.16mol/L4 2-Solution and 0.044mol/L of Y3+Ionic solution of Y3+The ionic solution was added dropwise to WO4 2-Mixing the solutions, and stirring for 10 min. Weighing 1.8mmol of Eu (NO)3)3Dissolving in deionized water to prepare 0.036mol/L Eu3+The solution was then added dropwise to the above mixed solution, and stirred for 10 min. Then the pH value of the mixed solution is adjusted to 7.8, and then 0.5g of 1.37m mol of hexadecyl trimethyl ammonium bromide (and K)2WO4The ratio of the amount of the substances is 1: 6) and 5ml of ethanol are mixed and then added into the mixed solution, and the mixture is stirred for 1 hour on a magnetic stirrer to prepare a precursor solution. And standing the prepared precursor solution in a hydrothermal kettle at 130 ℃ for 18 hours, filtering the solution subjected to hydrothermal heat preservation, cleaning the filtered substance, drying and grinding to obtain the flower-like microsphere structure potassium yttrium tungstate. As shown in FIG. 1, the size of the microspheres is around 8.1. mu.m.
Example 2:
weighing 8mmol of K2WO41.8mmol of Y (NO)3)3·6H2O is respectively dissolved in deionized waterIn the preparation, 0.16mol/L of WO is prepared4 2-Solution and 0.036mol/L of Y3+Ionic solution of Y3+The ionic solution was added dropwise to WO4 2-Mixing the solutions, and stirring for 10 min. Weighing 2.2mmol of Eu (NO)3)3Dissolving in deionized water to prepare 0.044mol/L Eu3+The solution was then added dropwise to the above mixed solution, and stirred for 10 min. The pH of the mixture was adjusted to 8, and 1g of 2.74 mmol of cetyltrimethylammonium bromide (with K)2WO4The ratio of the amount of the substances is 1: 3) and 5ml of ethanol are mixed and then added into the mixed solution, and the mixture is stirred for 1 hour on a magnetic stirrer to prepare a precursor solution. And standing the prepared precursor solution in a hydrothermal kettle at 100 ℃ for heat preservation for 16 hours, filtering the solution subjected to hydrothermal heat preservation, cleaning the filtered matter, drying and grinding to obtain the flower-like microsphere structure potassium yttrium tungstate. As shown in FIG. 2, the microsphere size was around 4.4. mu.m.
Example 3:
weighing 8mmol of K2WO4WO dissolved in deionized water to prepare 0.16mol/L4 2-Solution 1.5mmol of Y was weighed2O3Dissolving in dilute nitric acid to obtain 0.06mol/L Y (NO)3)3Solution of Y (NO)3)3The solution was added dropwise to WO4 2-Mixing the solutions, and stirring for 10 min. Weighing 0.5mmol of Eu2O3Dissolving in dilute nitric acid to prepare 0.02mol/L Eu3+The solution was then added dropwise to the above mixed solution, and stirred for 10 min. Then the pH value of the mixed solution is adjusted to 7.2, and then 0.06g of 0.172 mmol sodium dodecyl benzene sulfonate (and K)2WO4The ratio of the amount of the substances is 1: 47) is added into the mixed solution, and the mixture is stirred for 1 hour on a magnetic stirrer to prepare a precursor solution. And standing the prepared precursor solution in a hydrothermal kettle at 100 ℃ for 19 hours, filtering the solution subjected to hydrothermal heat preservation, cleaning the filtered substance, drying and grinding to obtain the potassium yttrium tungstate with a flower-like microsphere structure. As shown in FIG. 3, the microsphere size was around 3.2 μm.
Example 4:
4mmol of K are weighed out separately2WO4And 1.7mmol of Y (NO)3)3·6H2O is dissolved in deionized water to prepare WO 0.08mol/L4 2-Solution and 0.034mol/L of Y3+Ionic solution of Y3+The ionic solution was added dropwise to WO4 2-Mixing the solutions, and stirring for 10 min. 0.075mmol of Eu was weighed2O3Dissolving in dilute nitric acid to prepare Eu of 0.003mol/L3+Dropwise adding the solution into the mixed solution, and stirring for 10 min; after adjusting the pH of the mixture to 7.5, 2g of 5.49mmol cetyltrimethylammonium bromide (with K)2WO4The ratio of the amount of the substances is 1.4: 1) and 5ml of ethanol are evenly mixed and then added into the mixed solution, and the mixture is stirred for 1 hour on a magnetic stirrer to prepare precursor solution. And standing the prepared precursor solution in a hydrothermal kettle at 120 ℃ for 19 hours, filtering the solution subjected to hydrothermal heat preservation, cleaning the filtered substance, drying and grinding to obtain the potassium yttrium tungstate with a flower-like microsphere structure. As shown in FIG. 4, the microsphere size was around 5.7 μm.
Example 5:
4mmol of K are weighed out separately2WO4And 2mmol of Y (NO)3)3·6H2O is dissolved in deionized water to prepare WO 0.08mol/L4 2-Solution and 0.04mol/L of Y3+Ionic solution of Y3+The ionic solution was added dropwise to WO4 2-Mixing the solutions, and stirring for 10 min. 0.075mmol of Eu was weighed2O3Dissolving in dilute nitric acid to prepare 0.003mol/L Eu3+ solution, dropwise adding into the mixed solution, and stirring for 10 min; after adjusting the pH of the mixture to 8, 2g of 5.49mmol of cetyltrimethylammonium bromide (with K)2WO4The ratio of the amount of the substances is 1.4: 1) and 5ml of ethanol are evenly mixed and then added into the mixed solution, and the mixture is stirred for 1 hour on a magnetic stirrer to prepare precursor solution. And standing the prepared precursor solution in a hydrothermal kettle at 100 ℃ for 19 hours, filtering the solution subjected to hydrothermal heat preservation, cleaning the filtered substance, drying and grinding to obtain the potassium yttrium tungstate with a flower-like microsphere structure. As shown in FIG. 5, the microsphere size was around 2.3 μm.
The prepared flower-shaped microsphere structureWhen the potassium yttrium tungstate material is subjected to X-ray diffraction analysis and compared with a standard PDF card, as shown in figure 6, all diffraction peak crystal faces correspond to a monoclinic system KY (WO)4)2Diffraction of each crystal face (PDF NO 45-0472) does not have other impurity peaks, and the prepared product is determined to be potassium yttrium tungstate.
Carrying out nitrogen isothermal adsorption and desorption test on the prepared flower-like microsphere structure potassium yttrium tungstate material, and obtaining a graph shown in FIG. 7, wherein the abscissa is relative pressure P/P0Ordinate is adsorption value cm3(ii)/g; as shown in FIG. 7, the adsorption/desorption curve pattern of the sample was a weak interaction, and the specific surface area of the sample was 31.677 m as calculated from the BET formula2/g。
Performing fluorescence test on the prepared potassium yttrium tungstate with the flower-like microsphere structure under 464nm exciting light to obtain an emission spectrum; FIG. 8 is an emission spectrum of potassium yttrium tungstate with a flower-like microsphere structure under excitation of 464 nm; wherein the abscissa is wavelength nm and the ordinate is intensity a.u.; as shown in fig. 8, at the 464nm excitation wavelength, the spectral line is mainly composed of peaks between 500nm and 750 nm. Respectively correspond to Eu3+Of ions5D0→7F1 (596nm) transition, converted to yellow light;5D0→7F2(614nm), converted to orange light and emitted with a high intensity;5D0→7F4(704nm) transition, converted to red light.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. A preparation method of potassium yttrium tungstate with a flower-like microsphere structure is characterized by comprising the following steps:
(1) dropwise adding an yttrium ion solution into a potassium tungstate solution to form a mixed solution, dropwise adding an europium ion solution into the mixed solution, adjusting the pH value to 7.5-8, uniformly stirring, adding a certain amount of surfactant, and performing ultrasonic stirring to obtain a precursor solution; the molar ratio of tungstate ions, yttrium ions and europium ions in the precursor solution is 2:1: 1;
(2) putting the precursor solution prepared in the step (1) into an autoclave, carrying out hydrothermal sealing and heat preservation on the precursor solution to obtain white precipitate, wherein the hydrothermal temperature is 100-135 ℃, the heat preservation time is 15-19 h, and naturally cooling the autoclave to room temperature after the reaction is finished;
(3) cleaning, centrifuging, drying and grinding the white precipitate obtained in the step (2) to obtain flower-like microsphere structure potassium yttrium tungstate; the surfactant in the step (1) is mixed solution of cetyl trimethyl ammonium bromide and ethanol or sodium dodecyl benzene sulfonate.
2. The method for preparing potassium yttrium tungstate with flower-like microsphere structure according to claim 1, wherein the molar ratio of the surfactant to tungstate ions in step (1) is 1.4: 1.
3. The method for preparing potassium yttrium tungstate with flower-like microsphere structure as claimed in claim 1, wherein the amount of cetyl trimethyl ammonium bromide and ethanol in the mixed solution of cetyl trimethyl ammonium bromide and ethanol in step (1) is 0.5-2g:5 mL.
4. The method for preparing potassium yttrium tungstate with flower-like microsphere structure according to claim 1, wherein the step (3) is carried out by washing with deionized water and then with a mixed solution of acetone and ethanol with a volume fraction of 1: 1.
5. Flower-like microspheres obtained by the preparation method according to any one of claims 1 to 4The structural potassium yttrium tungstate material is characterized in that the flower-like microsphere structural potassium yttrium tungstate material is prepared from flaky KY (WO)4)2The composition is in a flower ball shape, the flower ball size is 2-8.5 mu m, and the specific surface area is 31.677 m2/g。
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| CN1995492A (en) * | 2006-12-01 | 2007-07-11 | 暨南大学 | Nd-doped potassium yittrium tungstate laser crystal growth method and growth device |
| CN103332748A (en) * | 2013-08-01 | 2013-10-02 | 江苏大学 | Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof |
| CN104891572A (en) * | 2015-05-19 | 2015-09-09 | 江苏大学 | A micro-nano potassium yttrium tungstate film and a preparing method thereof |
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| CN101643935A (en) * | 2009-09-04 | 2010-02-10 | 长春理工大学 | 2mum-waveband K (Yb/Tm) W laser crystal |
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| CN1995492A (en) * | 2006-12-01 | 2007-07-11 | 暨南大学 | Nd-doped potassium yittrium tungstate laser crystal growth method and growth device |
| CN103332748A (en) * | 2013-08-01 | 2013-10-02 | 江苏大学 | Micro/nano potassium yttrium tungstate near-spherical particles and preparation method thereof |
| CN104891572A (en) * | 2015-05-19 | 2015-09-09 | 江苏大学 | A micro-nano potassium yttrium tungstate film and a preparing method thereof |
Non-Patent Citations (2)
| Title |
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| "Morphology-controlled synthesis of NaGd(WO4)2:Eu3+ microcrystals by hydrothermal process";Xiaomin Yang et al.;《Superlattices and Microstructures》;20150117;第80卷;第188-195页 * |
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