CN109879305B - Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles - Google Patents
Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles Download PDFInfo
- Publication number
- CN109879305B CN109879305B CN201910235484.0A CN201910235484A CN109879305B CN 109879305 B CN109879305 B CN 109879305B CN 201910235484 A CN201910235484 A CN 201910235484A CN 109879305 B CN109879305 B CN 109879305B
- Authority
- CN
- China
- Prior art keywords
- spherical particles
- lanthanum aluminate
- micron
- laalo
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000012798 spherical particle Substances 0.000 title claims abstract description 36
- 229910002244 LaAlO3 Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 57
- -1 lanthanum aluminate Chemical class 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 36
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 10
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 10
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 81
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000003937 drug carrier Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000012856 packing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910021117 Sm(NO3)3 Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(III) nitrate Inorganic materials [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Abstract
The invention belongs to the field of material science, and provides a method for preparing micron-sized monodisperse LaAlO3:xMm+A novel process for the preparation of spherical particles. Wherein M is one of Mn, Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr and Sm, and a hydrothermal method is adopted to add certain amount of the above-mentioned materialsThe additive of (2) prepares ultra-large monodisperse lanthanum aluminate spherical particles doped with rare earth elements or transition metal elements, and the size of the ultra-large monodisperse lanthanum aluminate spherical particles can reach micron level (1-20 mu m). The spherical particles have high light emission efficiency and have indispensable functions in photocatalysis, drug carriers and the like. The spherical particles obtained in the experiment are all in the micron level, the particle surfaces are smooth, the technical scheme of the invention is simple and feasible, a good theoretical basis is shown for the preparation of the novel commercial fluorescent powder (the particle size of the commercial fluorescent powder is in the micron level), and the method has extremely high guiding significance and application prospect.
Description
Technical Field
The invention belongs to the field of material science, and particularly relates to a method for preparing micron-sized monodisperse LaAlO3:xMm+(M ═ Mn, Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr, Sm) spherical particles.
Background
Lanthanum aluminate has the advantages of good chemical stability, high thermal stability and the like, and has wide application in the aspects of electronic devices, catalysis, high-temperature fuel cells, ceramics, sewage treatment, substrate materials and the like. Lanthanum aluminate is a typical perovskite structure, is a cubic structure, La sites and Al sites can be replaced by other metal ions with similar radiuses, but the crystal structure of the lanthanum aluminate is kept unchanged, and various defects such as La vacancies, Al vacancies, O vacancies, charge compensation defects and the like can be generated in the replacement process, so that the photoelectric property of the lanthanum aluminate can be improved, and a transient fluorescent material, a long afterglow material or an up-conversion luminescent material can be prepared.
To synthesize lanthanum aluminate fluorescent powder with good fluorescent property, the reflectivity and refractive index of the fluorescent powder need to be reduced, the absorptivity and conversion rate need to be improved, and the size, the morphology and the surface morphology of fluorescent powder particles determine the luminescent property of the fluorescent powder particles. The granulometry studies have demonstrated that the lower the sphericity (defined as the ratio of the surface area of a sphere to the surface area of an irregular particle of the same volume) of a particle, whether it is loosely packed or tightly packed, the higher the packing porosity. The spherical luminescent particles can obtain higher packing density, thereby reducing the scattering of the luminophor, and because the spherical luminescent particles have high packing density and reduced porosity, the loss of transmitted light is less, and the optimal particle form is spherical for the luminophor. The existing method for preparing lanthanum aluminate powder is a solid phase method, a molten salt method and the like, the formed particles are not in the shape and are seriously agglomerated, the calcining temperature is high, and the preparation process is complex. Hydrothermal method is a test method for carrying out chemical reaction in fluid under certain temperature and pressure conditions. The method can overcome some inevitable hard agglomeration and the like during high-temperature preparation by using a hydrothermal method, and has the characteristics of high purity, good dispersibility, uniformity, narrow distribution, no agglomeration, good crystal form, controllable shape, environmental purification and the like. Therefore, the lanthanum aluminate particles doped with rare earth ions (Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr and Sm) or transition metal ions (Mn) are prepared by a hydrothermal method, and the micron-sized spherical fluorescent powder particles with high luminous efficiency can be obtained.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing monodisperse LaAlO3:xMm+A novel process for the preparation of spherical particles.
The technical scheme of the invention is as follows:
preparation of micron-sized monodisperse LaAlO3:xMm+A method of forming spherical particles comprising the steps of:
step 1, quantitative Al (NO)3)3·9H2O、La(NO3)3And M (NO)3)mAdding the solution into a solution of deionized water and ethylene glycol, stirring, and simultaneously adding citric acid solid; stirring uniformly until the citric acid is completely dissolved, wherein the mixed solution is transparent; when M is one of Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr and Sm in rare earth elements, the molar ratio of Al to La to M is 1 (1-x) to x, wherein x is 0-1; when M is Mn, the molar ratio of Al to La to M is (1-x) 1 to x, x is 0-1, and the molar ratio of citric acid to total metal ions in the mixed solution is 0.5-3 to 1;
step 2: transferring the transparent mixed solution obtained in the step (1) to a hydrothermal reaction kettle, carrying out hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, removing supernatant in the reaction kettle, and cleaning and drying a precipitation product to obtain a lanthanum aluminate precursor; the hydrothermal reaction conditions are as follows: the temperature is 100-200 ℃, and the time is 1-168 h;
and step 3: calcining the lanthanum aluminate precursor obtained by the reaction in the step 2 to obtain micron-sized monodisperse spherical lanthanum aluminate particles; the calcination conditions are as follows: and (3) calcining for 2-8h in an oxygen atmosphere at the temperature of 900-1300 ℃.
The step 2: stirring for 10-60 min.
The step 2: the cleaning is three times of deionized water and two times of centrifugal cleaning of absolute ethyl alcohol.
The step 2: the drying condition is that the temperature is 40-80 ℃ and the time is 24-72 h.
The step 3: the grain diameter of the obtained micron-sized monodisperse spherical lanthanum aluminate particles is 1-20 mu m.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
the invention adopts a hydrothermal method and adds certain additives to prepare the ultra-large monodisperse lanthanum aluminate spherical particles doped with rare earth elements or transition metal elements, and the size of the ultra-large monodisperse lanthanum aluminate spherical particles can reach micron-sized (1-20 mu m). The spherical particles have high light emission efficiency and have indispensable functions in photocatalysis, drug carriers and the like. The spherical particles obtained in the experiment are all in the micron level, the particle surfaces are smooth, the technical scheme of the invention is simple and feasible, a good theoretical basis is shown for the preparation of the novel commercial fluorescent powder (the particle size of the commercial fluorescent powder is in the micron level), and the method has extremely high guiding significance and application prospect.
Drawings
FIG. 1(a) is LaAlO prepared in example 1 of the present invention3:0.1％Mn4+Scanning SEM photo of the precursor.
(b) Is LaAlO prepared in the embodiment 1 of the invention3:0.1％Mn4+SEM scanning photograph of (a).
FIG. 2(a) is a diagram of spherical LaAlO particles prepared in example 1 of the present invention3:0.1％Mn4+XRD pattern of (a).
(b) Is the spherical particle LaAlO prepared in the embodiment 2 of the invention3:0.5％Mn4+XRD pattern of (a).
(c) Is the spherical particle LaAlO prepared in the embodiment 3 of the invention3:1％Mn4+XRD pattern of (a).
(d) Is the spherical particle LaAlO prepared in the embodiment 4 of the invention3:1％Eu3+XRD pattern of (a).
(e) Is the spherical particle LaAlO prepared in the embodiment 5 of the invention3:2.5％Tb3+XRD pattern of (a).
(f) Is the spherical particle LaAlO prepared in the embodiment 6 of the invention3:5％Sm3+XRD pattern of (a).
(g) Is the spherical particle LaAlO prepared in the embodiment 7 of the invention3:0.1％Mn4+XRD pattern of (a).
FIG. 3(a) is LaAlO prepared in example 2 of the present invention3:0.5％Mn4+Scanning SEM photo of the precursor.
FIG. 3(b) is LaAlO prepared in example 2 of the present invention3:0.5％Mn4+SEM scanning photograph of (a).
FIG. 4(a) is LaAlO prepared in example 3 of the present invention3:1％Mn4+SEM scanning photographs of the precursors.
FIG. 4(b) is LaAlO prepared in example 3 of the present invention3:1％Mn4+SEM scanning photograph of (a).
FIG. 5(a) is LaAlO prepared in example 4 of the present invention3:1％Eu3+SEM scanning photographs of the precursors.
FIG. 5(b) is LaAlO prepared in example 4 of the present invention3:1％Eu3+SEM scanning photograph of (a).
FIG. 6(a) is LaAlO prepared in example 5 of the present invention3:2.5％Tb3+Scanning SEM photo of the precursor.
FIG. 6(b) is LaAlO prepared in example 5 of the present invention3:2.5％Tb3+SEM scanning photograph of (a).
FIG. 7(a) is LaAlO prepared in example 6 of the present invention3:5％Sm3+SEM scanning photographs of the precursors.
FIG. 7(b) is LaAlO prepared in example 6 of the present invention3:5％Sm3+SEM scanning photograph of (a).
FIG. 8(a) is L prepared in example 7 of the present inventionaAlO3:0.1％Mn4+Scanning SEM photo of the precursor.
FIG. 8(b) is LaAlO prepared in example 7 of the present invention3:0.1％Mn4+SEM scanning photograph of (a).
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
The chemical reagents adopted in the embodiment of the invention are all analytical pure-grade products; XRD phase analysis is carried out by adopting an X' Pert Pro X-ray diffractometer with the model number of PW 3040/60; and a JSM-7001F type JEOL field emission scanning electron microscope is adopted for appearance observation and analysis.
Example 1
Measuring Al (NO)3)3·9H2O、La(NO3)3And Mn (NO)3)2Putting the solution into a 100mL beaker, adding Al, La and Mn which are 0.999:1:0.001, stirring and mixing uniformly, adding citric acid, wherein the ratio of the citric acid to metal ions is 1:1, adding 20mL of deionized water and 40mL of ethylene glycol (the ratio is 1:2), stirring for 30min until the citric acid is completely dissolved and mixing uniformly, transferring the transparent solution into a 100mL hydrothermal reaction kettle, reacting for 8h, wherein the hydrothermal temperature is 180 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, removing supernatant, centrifugally cleaning precipitates (3 times of deionized water and 2 times of absolute ethyl alcohol), and drying for 24h at 70 ℃ to obtain a precursor of lanthanum aluminate. Calcining the precursor for 4h at 1000 ℃ in an oxygen atmosphere to obtain the ultra-large monodisperse spherical lanthanum aluminate particles with the diameter of about 2 mu m.
LaAlO3:0.1％Mn4+The precursor is an amorphous phase, which is monodisperse spherical particles with a diameter of about 2-3 μm, as shown in FIG. 1 (a). After calcination, spherical particles with good dispersibility and slightly reduced size with a diameter of about 2 μm were obtained, as shown in fig. 1(b), and the XRD pattern thereof is shown in fig. 2(a), demonstrating that it is a pure phase of lanthanum aluminate.
Example 2
Measuring Al (NO)3)3·9H2O、La(NO3)3And Mn (NO)3)2Dissolving in 100mIn a beaker, adding La, Mn and 0.995:1:0.005 of Al, stirring and mixing uniformly, adding citric acid, wherein the ratio of the citric acid to metal ions is 1:1, adding 60mL of deionized water and 0mL of ethylene glycol, stirring for 40min until the citric acid is completely dissolved, mixing uniformly, transferring the transparent solution into a 100mL hydrothermal reaction kettle, reacting for 18h at 180 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, removing supernatant, centrifugally cleaning precipitates (3 times of deionized water and 2 times of absolute ethyl alcohol), and drying for 24h at 70 ℃ to obtain a lanthanum aluminate precursor. And calcining the precursor for 4h at 1100 ℃ in an oxygen atmosphere to obtain the ultra-large lanthanum aluminate monodisperse spherical particles.
LaAlO3:0.5％Mn4+The precursor is an amorphous phase, which is monodisperse spherical particles with a diameter of about 10-13 μm, as shown in FIG. 3 (a). After calcination, spherical lanthanum aluminate particles with good dispersibility are obtained, the diameter is slightly reduced, the diameter is about 8-10 μm, as shown in figure 3(b), and an XRD pattern is shown in figure 2(b), which proves that the lanthanum aluminate particles are pure phase.
Example 3
Measuring Al (NO)3)3·9H2O、La(NO3)3And Mn (NO)3)2Putting the solution into a 100mL beaker, adding Al, La and Mn which are 0.99:1:0.01, stirring and mixing uniformly, adding citric acid, wherein the ratio of the citric acid to metal ions is 1:1, adding 50mL of deionized water and 10mL of ethylene glycol (the ratio is 5:1), stirring for 40min until the citric acid is completely dissolved and mixing uniformly, transferring the transparent solution into a 100mL hydrothermal reaction kettle, reacting for 4h at the reaction temperature of 160 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, removing supernatant, centrifugally cleaning precipitates (3 times of deionized water and 2 times of absolute ethyl alcohol), and drying for 72h at the temperature of 80 ℃ to obtain a precursor of lanthanum aluminate. Calcining the precursor for 4h at 1000 ℃ in an oxygen atmosphere to obtain the ultra-large monodisperse spherical lanthanum aluminate particles with the diameter of about 2 mu m.
LaAlO3:1％Mn4+The precursor is an amorphous phase, which is monodisperse spherical particles with a diameter of about 3-5 μm, as shown in fig. 4 (a). Calcining to obtain aluminate with good dispersibilityLanthanum spherical particles, slightly reduced in size and about 3 μm in diameter, are shown in fig. 4(b), and have an XRD pattern as shown in fig. 2(c), demonstrating that they are pure phase lanthanum aluminate.
Example 4
Measuring Al (NO)3)3·9H2O、La(NO3)3、Eu(NO3)3Putting the solution into a 100mL beaker, adding citric acid, wherein the ratio of the citric acid to metal ions is 1:1, adding 40mL of deionized water and 20mL of ethylene glycol (the ratio is 2:1), stirring for 40min until the citric acid is completely dissolved and uniformly mixed, transferring the transparent solution into a 100mL hydrothermal reaction kettle, reacting for 4h at the reaction temperature of 180 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, removing supernatant, centrifugally cleaning precipitates (3 times of deionized water and 2 times of absolute ethyl alcohol), and drying for 36h at 60 ℃ to obtain a precursor of lanthanum aluminate. Calcining the precursor for 4h at 1100 ℃ in an oxygen atmosphere to obtain the ultra-large monodisperse spherical lanthanum aluminate particles with the diameter of about 2.5 microns.
LaAlO3:1％Eu3+The precursor is an amorphous phase, which is monodisperse spherical particles with a diameter of about 3-5 μm, as shown in fig. 5 (a). After calcination, spherical lanthanum aluminate particles with good dispersibility are obtained, the diameter of the spherical lanthanum aluminate particles is slightly reduced, the diameter of the spherical lanthanum aluminate particles is about 2.5 microns, as shown in figure 5(b), and an XRD pattern of the spherical lanthanum aluminate particles is shown in figure 2(d), and the spherical lanthanum aluminate particles are proved to be pure phase lanthanum aluminate.
Example 5
Measuring Al (NO)3)3·9H2O、La(NO3)3、Tb(NO3)3Putting the solution into a 100mL beaker, adding Al, La and Tb which are 1:0.975:0.025, stirring and mixing uniformly, adding citric acid, wherein the ratio of the citric acid to the metal ions is 1.5:1, adding 30mL of deionized water and 30mL of ethylene glycol (the ratio is 1:1), stirring for 30min until the citric acid is completely dissolved and mixing uniformly, transferring the transparent solution into a 100mL hydrothermal reaction kettle, reacting for 6h at the reaction temperature of 200 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, removing the supernatant, centrifugally cleaning the precipitate (3 times of deionized water and 2 times of absolute ethyl alcohol), adding the solution into a 100mL beaker, and washing the precipitate with waterDrying the precursor for 24 hours at the temperature of 60 ℃ to obtain a precursor of lanthanum aluminate. Calcining the precursor for 4h at 1200 ℃ in an oxygen atmosphere to obtain the ultra-large monodisperse spherical lanthanum aluminate particles with the diameter of about 3 mu m.
LaAlO3:2.5％Tb3+The precursor is an amorphous phase, which is monodisperse spherical particles with a diameter of about 3-5 μm, as shown in fig. 6 (a). After calcination, lanthanum aluminate spherical particles with good dispersibility are obtained, the size is slightly reduced, the diameter is about 3 mu m, as shown in figure 6(b), and the XRD pattern is shown in figure 2(e), which proves that the lanthanum aluminate spherical particles are doped with Tb3+The lanthanum aluminate pure phase is still formed after the preparation.
Example 6
Measuring Al (NO)3)3·9H2O、La(NO3)3、Sm(NO3)3Putting the solution into a 100mL beaker, adding Al, La and Sm (1: 0.95: 0.05), stirring and mixing uniformly, adding citric acid, wherein the ratio of citric acid to metal ions is 2:1, adding 10mL of deionized water and 50mL of ethylene glycol (the ratio is 1:5), stirring for 25min until the citric acid is completely dissolved and mixing uniformly, transferring the transparent solution into a 100mL hydrothermal reaction kettle, reacting for 9h at the reaction temperature of 140 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, removing supernatant, centrifugally cleaning precipitates (3 times of deionized water and 2 times of absolute ethyl alcohol), and drying for 24h at the temperature of 60 ℃ to obtain a precursor of lanthanum aluminate. Calcining the precursor for 4h at 1300 ℃ under the oxygen atmosphere to obtain the ultra-large monodisperse spherical lanthanum aluminate particles with the diameter of about 3 mu m.
LaAlO3:5％Sm3+The precursor was amorphous and was monodisperse spherical particles with a diameter of about 3 μm, as shown in FIG. 7 (a). After calcination, spherical lanthanum aluminate particles with good dispersibility are obtained, the size is slightly reduced, the diameter is about 2 mu m, as shown in figure 7(b), and the XRD pattern is shown in figure 2(f), which proves that the lanthanum aluminate particles are doped with Sm3+The lanthanum aluminate pure phase is still formed after the preparation.
Example 7
Measuring Al (NO)3)3·9H2O、La(NO3)3And Eu (NO)3)3The solution was placed in a 100ml beaker, and Al: La: Eu: 0.999:1:0.001, stirring and mixing uniformly, adding citric acid at the same time, wherein the ratio of the citric acid to metal ions is 1:1, adding 20mL of deionized water and 40mL of ethylene glycol (the ratio is 1:2), stirring for 40min until the citric acid is completely dissolved, mixing uniformly, transferring a transparent solution into a 100mL hydrothermal reaction kettle, reacting for 4h, after the reaction is finished, naturally cooling the reaction kettle to room temperature, removing supernatant, centrifugally cleaning precipitates (3 times of deionized water and 2 times of absolute ethyl alcohol), and drying for 24h at 70 ℃ to obtain a precursor of lanthanum aluminate. Calcining the precursor for 4h at 1000 ℃ in an oxygen atmosphere to obtain the ultra-large monodisperse spherical lanthanum aluminate particles with the diameter of about 2 mu m.
The lanthanum aluminate precursor is an amorphous phase, which is monodisperse spherical particles with a diameter of about 2-3 μm, as shown in fig. 8 (a). After calcination, spherical lanthanum aluminate particles with good dispersibility are obtained, the size is slightly reduced, the diameter is about 2 mu m, as shown in figure 8(b), and an XRD pattern is shown in figure 2(g), which proves that when the particles are doped with Mn4+Still is a pure phase of lanthanum aluminate and does not contain other mixed phases.
Claims (4)
1. Preparation of micron-sized monodisperse LaAlO3:xMm+A method of forming spherical particles, comprising the steps of:
step 1, quantitative Al (NO)3)3·9H2O、La(NO3)3And M (NO)3)mAdding the solution into a solution of deionized water and ethylene glycol, stirring, and simultaneously adding citric acid solid; stirring uniformly until the citric acid is completely dissolved, wherein the mixed solution is transparent; when M is one of Yb, Dy, Nd, Eu, Ce, Tb, Er, Tm, Ho, Pr and Sm in the rare earth elements, the molar ratio of Al to La to M is 1 (1-x) to x, the x is 0-1, and the volume ratio of deionized water to ethylene glycol is 1:1 or 2: 1; when M is Mn, the molar ratio of Al to La to M is (1-x) 1 to x, x is 0-1, and the volume ratio of deionized water to ethylene glycol is 5: 1; the molar ratio of the citric acid to the total metal ions in the mixed solution is 0.5-3: 1;
step 2: transferring the transparent mixed solution obtained in the step (1) to a hydrothermal reaction kettle, carrying out hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, removing supernatant in the reaction kettle, and cleaning and drying a precipitation product to obtain a lanthanum aluminate precursor; the hydrothermal reaction conditions are as follows: the temperature is 100-200 ℃, and the time is 1-168 h;
and step 3: calcining the lanthanum aluminate precursor obtained by the reaction in the step 2 to obtain micron-sized monodisperse spherical lanthanum aluminate particles; the calcination conditions are as follows: calcining for 2-8h in an oxygen atmosphere at 900-1300 ℃; the grain diameter of the obtained micron-sized monodisperse spherical lanthanum aluminate particles is 1-20 mu m.
2. The method of claim 1 for preparing micron-sized monodisperse LaAlO3:xMm+A method of spherical particles, characterized by step 1: stirring for 10-60 min.
3. Preparation of micro-sized monodisperse LaAlO according to claim 1 or 23:xMm+A method of spherical particles, characterized by step 2: the cleaning is three times of deionized water and two times of centrifugal cleaning of absolute ethyl alcohol.
4. Preparation of micro-sized monodisperse LaAlO according to claim 1 or 23:xMm+A method of spherical particles, characterized by step 2: the drying condition is that the temperature is 40-80 ℃ and the time is 24-72 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910235484.0A CN109879305B (en) | 2019-03-27 | 2019-03-27 | Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910235484.0A CN109879305B (en) | 2019-03-27 | 2019-03-27 | Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109879305A CN109879305A (en) | 2019-06-14 |
| CN109879305B true CN109879305B (en) | 2020-03-31 |
Family
ID=66934485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910235484.0A Expired - Fee Related CN109879305B (en) | 2019-03-27 | 2019-03-27 | Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109879305B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841559B (en) * | 2020-07-28 | 2022-08-16 | 四川宇科思通环保科技有限公司 | Sr, Ni and Cr co-doped LaAlO 3 Application of photocatalyst in organic wastewater treatment |
| CN112608745A (en) * | 2020-12-29 | 2021-04-06 | 威海市泓淋电力技术股份有限公司 | Rare earth samarium element doped micron red long afterglow material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090208396A1 (en) * | 2005-05-12 | 2009-08-20 | Basf Catalysts Llc | Alumina-Based Perovskite Catalysts and Catalyst Supports |
| CN101786596B (en) * | 2010-03-04 | 2012-10-03 | 长春理工大学 | Polycrystalline nano-fiber with europium ion doped with lanthanum aluminate and preparation method thereof |
| CN101982418A (en) * | 2010-10-29 | 2011-03-02 | 北京化工大学 | Preparation method of perovskite LnCrO3 and LnAlO3 nanomaterials |
| CN102701723A (en) * | 2012-06-21 | 2012-10-03 | 上海大学 | Preparation method of Ce-doped LaAlO3 flickering ceramic material |
| CN103112881B (en) * | 2012-12-31 | 2014-09-03 | 内蒙古科技大学 | Method for preparing lanthanum aluminate powder efficiently |
-
2019
- 2019-03-27 CN CN201910235484.0A patent/CN109879305B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN109879305A (en) | 2019-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Uniform colloidal spheres for (Y1− x Gd x) 2O3 (x= 0–1): Formation mechanism, compositional impacts, and physicochemical properties of the oxides | |
| Li et al. | Monodispersed colloidal spheres for uniform Y2O3: Eu3+ red-phosphor particles and greatly enhanced luminescence by simultaneous Gd3+ doping | |
| CN101792164B (en) | Method for preparing nano aluminum oxide through vacuum freeze drying technology | |
| CN101234750B (en) | Method of preparing superfine micro-particle and nano granule | |
| CN101973569B (en) | Method for synthesizing fluorescent powder of yttrium aluminum garnet | |
| CN100543110C (en) | The oxalic acid non-homogeneous phase deposition prepares the method for rare earth doping yttrium aluminium garnet fluorescent powder | |
| CN109879305B (en) | Preparation of micron-sized monodisperse LaAlO3:xMm+Method for producing spherical particles | |
| CN108083316A (en) | A kind of preparation method of nano rareearth oxidate powder body | |
| Wu et al. | Low-temperature preparation of monodispersed Eu-doped CaTiO 3 LED phosphors with controllable morphologies | |
| Jinqing et al. | Preparation of nanoscaled yttrium oxide by citrate precipitation method | |
| Cheng et al. | Low-temperature solution synthesis and characterization of Ce-doped YAG nanoparticles | |
| Choi et al. | Spherical shape with fast decaying property of solvothermally grown (Y, Gd) BO3: Eu3+ nanophosphor | |
| Yan et al. | Preparation of YAG: Ce3+ phosphor by sol-gel low temperature combustion method and its luminescent properties | |
| CN105152192B (en) | A kind of preparation method of magnesia/rare earth oxide core shell structure flower-like nanometer composite | |
| CN108165269B (en) | Lutetium potassium fluoride nanocrystal with phase change delay and greatly improved up-conversion luminescence intensity and preparation method thereof | |
| CN101831292A (en) | Strontium aluminate luminous material and controllable synthesis method thereof | |
| Huang et al. | Morphology controllable synthesis of yttrium oxide-based phosphors from yttrium citrate precursors | |
| Jiu et al. | Preparation and luminescent properties of hollow Y2O3: Tb3+ microspheres | |
| CN102618279B (en) | Preparation method of shape-controllable aluminate luminous materials | |
| Zhang et al. | Shape-controlled synthesis and luminescence properties of yttria phosphors | |
| CN110124658B (en) | Controllable preparation method of cerium-aluminum oxide solid solution nanocubes | |
| Wang et al. | Synthesis of Y2O2SO4 submicron spheres and photoluminescence behaviour with Tb3+ doping | |
| CN102001696A (en) | Method for preparing magnesium-aluminum spinel nano particle powder | |
| CN1974715A (en) | Prepn of nanometer spherical red CaSiO3:Eu3+ phosphor | |
| Zhang et al. | Core/shell Y (OH) CO3: Eu3+/YBO3: Eu3+ phosphors with sphericity, submicrometre size and non-aggregation characteristics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200331 |