CN117902898A - Preparation method and application of rare earth molybdate ceramic material synthesized by molten salt method - Google Patents
Preparation method and application of rare earth molybdate ceramic material synthesized by molten salt method Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 62
- -1 rare earth molybdate Chemical class 0.000 title claims abstract description 62
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 53
- 150000003839 salts Chemical class 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000011833 salt mixture Substances 0.000 claims description 25
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 19
- 235000015393 sodium molybdate Nutrition 0.000 claims description 19
- 239000011684 sodium molybdate Substances 0.000 claims description 19
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 4
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 4
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 4
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 description 9
- 230000005496 eutectics Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
- C09K11/7765—Vanadates; Chromates; Molybdates; Tungstates
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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Abstract
The invention relates to the technical field of new materials, in particular to a preparation method and application of a rare earth molybdate ceramic material synthesized by a molten salt method. The method has the advantages of low reaction temperature, simple process, short synthesis time, less impurity residue, no pollution, low cost and the like, and can also synthesize luminescent rare earth ion doped rare earth molybdate material, and compared with pure rare earth molybdate, the luminescent property of the luminescent rare earth ion doped rare earth molybdate material is further improved.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method and application of a rare earth molybdate ceramic material synthesized by a molten salt method.
Background
The rare earth molybdate family compounds have the characteristics of luminescence, catalysis, semiconductors and the like due to the characteristics of crystal and electronic structure, and the application of the compounds in luminescent materials, environment-friendly dyes, ferroelectric materials, microwave ceramics, catalysis and the like attracts attention, so that the compounds are widely and deeply studied in the past. The pure RE xMoO(3x+6)/2 and the doped RE xMoO(3x+6)/2 have potential application prospects in catalysis, high-performance luminescent materials, solid oxide fuel cells and the like due to good catalytic performance, luminescent performance and oxygen ion and proton conductivity.
Most of the preparation methods reported at present for RE xMoO(3x+6)/2 ceramic materials are solid phase sintering (solid-state reactions method), the sintering temperature is generally 1200-1600 ℃, the sintering temperature is high, the reaction time is long, and the control of the morphology and the maintenance of uniformity of the product are not facilitated. Thus, domestic and foreign scientists developed a synthetic method of "soft chemistry", such as: RE xMoO(3x+6)/2 ceramic materials with different shapes and sizes are prepared by a hydrothermal method (hydrothermal method), a sol-gel method (sol-gel process) and the like, but organic matters are introduced due to the complex synthesis method, and the reaction temperature is high, so that the method is not beneficial to industrial production.
In view of this, the present invention has been proposed.
Disclosure of Invention
The molten salt method uses different types of inorganic molten salts as reaction medium, and compared with the conventional solvent, the molten salt method has enough electric conductivity, high thermal stability and certain viscosity, so that the molten salt method has higher reactivity on different inorganic components, and the eutectic salt has lower melting point, so that the molten salt method can be used for preparing inorganic ceramic materials. Compared with the method, the molten salt method has the advantages of simple synthesis method, low synthesis temperature, short reaction time and less impurity residue, and is a more economic synthesis method.
The invention provides a preparation method and application of a rare earth molybdate ceramic material synthesized by a molten salt method, wherein a lithium molybdate and sodium molybdate binary salt mixture is used as a molten salt system, a rare earth oxide is used as an RE source, and a binary salt mixture and/or MoO 3 is used as a Mo source, so that the RE xMoO(3x+6)/2 ceramic material is simply and efficiently synthesized at a lower temperature.
Specifically, the invention provides a preparation method of a rare earth molybdate ceramic material, which comprises the following steps: RE source and Mo source are reacted in molten salt system by molten salt method to synthesize RE-molybdate ceramic material with chemical formula RE xMoO(3x+6)/2, wherein RE is more than one kind selected from La, nd, sm, eu, gd, dy, ho, er and Yb, x is more than 0 and less than or equal to 6.
According to the preparation method of the rare earth molybdate ceramic material provided by the invention, a binary salt mixture mainly composed of lithium molybdate and sodium molybdate is used as the molten salt system;
Compared with other salt substances, the lithium molybdate and the sodium molybdate adopted by the invention can be used as Mo sources, so that the use of other Mo raw materials is reduced, and compared with the single use of lithium molybdate or sodium molybdate, the preparation temperature of rare earth molybdate can be effectively reduced by using the mixture of the lithium molybdate and the sodium molybdate.
Preferably, the mass ratio of the lithium molybdate to the sodium molybdate is 1:10-10:1; more preferably, the mass ratio of the lithium molybdate to the sodium molybdate is 22:25.
According to the preparation method of the rare earth molybdate ceramic material provided by the invention, rare earth oxide is used as an RE source;
Preferably, the RE source comprises one or more of La2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Dy2O3、Ho2O3、Er2O3 and Yb 2O3;
More preferably, the RE sources are two of La2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Dy2O3、Ho2O3、Er2O3 and Yb 2O3;
Most preferably, the RE source is a mixture of Sm 2O3 and Gd 2O3; or the RE source is a mixture of Eu 2O3 and Gd 2O3.
When a mixture of Sm 2O3 and Gd 2O3 or a mixture of Eu 2O3 and Gd 2O3 is used, the luminescent rare earth ion doped rare earth molybdate material can be synthesized with further improved luminescent properties over pure rare earth molybdate compared to single RE sources.
According to the preparation method of the rare earth molybdate ceramic material, the binary salt mixture and/or MoO 3 are used as Mo sources;
Preferably, the binary salt mixture is used as a Mo source.
The preparation method of the rare earth molybdate ceramic material provided by the invention comprises the following steps:
Heating and melting a binary salt mixture mainly formed by mixing lithium molybdate and sodium molybdate; then adding the raw materials containing RE sources into the molten binary salt mixture, and reacting at 462-1000 ℃ to obtain rare earth molybdate ceramic materials; the raw materials containing RE sources mainly comprise RE sources and MoO 3 in a molar ratio of 1:0-10;
More specifically, the dried binary salt mixture is put into high-temperature equipment, heated to 462-1000 ℃, kept at the constant temperature for several hours (such as more than 1 hour) to enable the binary salt mixture to be completely melted, then raw materials containing RE sources are added, and the mixture is cooled after being kept at the temperature of 462-1000 ℃ for several hours (such as more than 2 hours) to obtain rare earth molybdate ceramic materials;
Or mixing a binary salt mixture mainly formed by mixing lithium molybdate and sodium molybdate with a raw material containing an RE source, and reacting at 462-1000 ℃ to obtain a rare earth molybdate ceramic material; the raw material containing the RE source mainly comprises RE source and MoO 3 with the molar ratio of 1:0-10.
In the heating process, the reaction system can be reacted in an air atmosphere or a protective gas atmosphere.
The preparation method of the rare earth molybdate ceramic material provided by the invention comprises the following steps:
The binary salt mixture mainly formed by mixing lithium molybdate and sodium molybdate is subjected to pretreatment and then is heated and melted, and the pretreatment comprises the following steps: uniformly mixing lithium molybdate and sodium molybdate to obtain a binary salt mixture, putting the binary salt mixture into a corrosion-resistant crucible (such as a corundum crucible), and then drying at a temperature of below 200 ℃ to remove water;
Or the product after the reaction is subjected to post-treatment to obtain rare earth molybdate ceramic powder;
Preferably, the post-treatment comprises: washing the product with water, and filtering to obtain a precipitate; and drying the precipitate at a temperature of 200 ℃ or below to obtain rare earth molybdate ceramic powder.
The high temperature apparatus in the present invention means a device which can provide a sufficient temperature and heat the reaction system under the action of an air atmosphere or a protective gas, such as a muffle furnace, an atmosphere furnace, etc., and is preferably used in the present invention.
The shielding gas in the present invention is a gas capable of avoiding interference of external gas to the reaction of the present invention, and is generally inert gas such as helium, argon, etc. is introduced into the reaction equipment to isolate the reactant from the outside, preferably argon atmosphere.
The crucible of the present invention is used only as a reaction vessel, and needs to have properties such as corrosion resistance and high temperature resistance.
The preparation method of the rare earth molybdate ceramic material provided by the invention comprises the following steps:
The molar ratio of the RE source to MoO 3 in the RE source-containing raw material is 1:0-5; the RE source-containing raw material is obtained after agate mortar grinding;
Preferably, the mass of the raw material containing the RE source is 1-20% of that of the binary salt mixture.
According to the preparation method of the rare earth molybdate ceramic material, the heating rate in the heating process in the reaction process is 5-50 ℃/min.
In a second aspect, the invention also provides a rare earth molybdate ceramic material with a chemical formula of RE xMoO(3x+6)/2, which is prepared by the preparation method of the rare earth molybdate ceramic material, wherein RE is more than one of La, nd, sm, eu, gd, dy, ho, er and Yb, and x is more than 0 and less than or equal to 6;
preferably, the rare earth molybdate ceramic material has a chemical formula La2MoO6、Nd6MoO12、Sm2MoO6、Eu2MoO6、Gd1.8Sm0.2MoO6 or Gd 1.8Eu0.2MoO6.
In a third aspect, the invention also provides the use of a rare earth molybdate ceramic material as described above in an environmentally friendly dye, ferroelectric material, microwave ceramic material, catalytic material, luminescent material or solid oxide fuel cell.
The invention provides a preparation method and application of a rare earth molybdate ceramic material synthesized by a molten salt method, which adopts the rare earth molybdate ceramic material with a chemical formula of RE xMoO(3x+6)/2 by the molten salt method, specifically takes a binary salt mixture of lithium molybdate and sodium molybdate as a melt, has low reaction temperature, and has the advantages of simple process, short synthesis time, less impurity residue, no pollution, low cost and the like.
In addition, the melt is also one of the sources of Mo, and in some embodiments, the preparation of the rare earth molybdate ceramic material may be accomplished without the need to introduce MoO 3 powder.
Furthermore, in some embodiments, luminescent rare earth ion doped rare earth molybdate materials may also be synthesized that further improve luminescent performance relative to pure rare earth molybdates.
Therefore, the invention is expected to be used for preparing engineering-scale rare earth molybdate ceramic materials.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of La 2MoO6 prepared in example 1;
fig. 2 is an XRD pattern of Nd 6MoO12 prepared in example 2;
FIG. 3 is an XRD pattern for Sm 2MoO6 prepared in example 3;
FIG. 4 is an XRD pattern of Eu 2MoO6 prepared in example 4;
FIG. 5 is an XRD pattern for Gd 1.8Sm0.2MoO6 prepared in example 5;
FIG. 6 is an XRD pattern for Gd 1.8Eu0.2MoO6 prepared in example 6;
FIG. 7 is a fluorescence spectrum of the ceramic powders prepared in example 3 and example 5;
FIG. 8 is a fluorescence spectrum of the ceramic powders prepared in example 4 and example 6.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following describes a preparation method and application of the rare earth molybdate ceramic material synthesized by the molten salt method according to the present invention with reference to fig. 1 to 8.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
A preparation method for synthesizing rare earth molybdate ceramic material by molten salt method comprises the following specific steps:
Step 1: and (3) uniformly mixing lithium molybdate and sodium molybdate with the mass ratio of 22:25, then placing the mixture into a corundum crucible, and placing the corundum crucible into a vacuum oven at 150 ℃ for drying for more than 24 hours to obtain the binary eutectic salt.
Step 2: and (3) placing the crucible in the step (1) into a muffle furnace, introducing argon, heating to 550 ℃ at a speed of 5 ℃/min, keeping the temperature for 1 hour to completely melt the eutectic salt, then adding La 2O3, wherein the mass of La 2O3 is 1% of that of the binary eutectic salt, keeping the temperature at 550 ℃ for 5 hours, and naturally cooling to room temperature.
Step 3: washing the product obtained in the step 2 with deionized water at room temperature, filtering to obtain a precipitate, and drying the precipitate in a vacuum oven at 150 ℃ for more than 6 hours to obtain dried La 2MoO6 ceramic powder, wherein the XRD test result of the powder is shown in figure 1.
Example 2
The preparation method for synthesizing rare earth molybdate ceramic material by using molten salt method comprises the following steps, which are basically the same as those in example 1, and differ only in that: the equivalent mass of La 2O3 was replaced with Nd 2O3 to give a dried Nd 6MoO12 ceramic powder whose XRD test results are shown in fig. 2.
Example 3
The preparation method for synthesizing rare earth molybdate ceramic material by using molten salt method comprises the following steps, which are basically the same as those in example 1, and differ only in that: equal mass of La 2O3 was replaced by a 1:1 mixture of Sm 2O3 and MoO 3, the mass of which was 1% of the mass of the binary eutectic salt, resulting in a dry Sm 2MoO6 ceramic powder whose XRD test results are shown in FIG. 3.
FIG. 7 (solid line) shows the emission spectrum of the target sample prepared in example 3 under 319nm laser excitation and the excitation spectrum at 640 nm. It can be seen that the prepared sample exhibited red emission at 640nm under excitation at 319nm wavelength.
Example 4
The preparation method for synthesizing rare earth molybdate ceramic material by using molten salt method comprises the following steps, which are basically the same as those in example 1, and differ only in that: the equivalent mass of La 2O3 was replaced by a Eu 2O3 and MoO 3 mixture in a molar ratio of 1:1, the mass of which was 1% of the mass of the binary eutectic salt, to give a dry Eu 2MoO6 ceramic powder, the XRD test results of which are shown in FIG. 4.
FIG. 8 (solid line) shows the emission spectrum of the target sample prepared in example 4 at 306nm under excitation by a laser and the excitation spectrum at 614 nm. It can be seen that the prepared sample exhibited red emission at 614nm under 306nm wavelength excitation.
Example 5
The preparation method for synthesizing rare earth molybdate ceramic material by using molten salt method comprises the following steps, which are basically the same as those in example 1, and differ only in that: equal mass of La 2O3 was replaced by a mixture of Sm 2O3、Gd2O3 and MoO 3 (molar ratio of 0.1:0.9:1.0) with a mass of 1% of the mass of the binary eutectic salt, resulting in a dry Gd 1.8Sm0.2MoO6 ceramic powder whose XRD test results are shown in fig. 5.
FIG. 7 (dashed line) shows the emission spectrum of the target sample prepared in example 5 under 319nm laser excitation and the excitation spectrum at 640 nm. It can be seen that the prepared sample exhibited red emission at 640nm under 319nm wavelength excitation and its fluorescence intensity was stronger than that of example 3.
Example 6
The preparation method for synthesizing rare earth molybdate ceramic material by using molten salt method comprises the following steps, which are basically the same as those in example 1, and differ only in that: equal mass of La 2O3 was replaced by a mixture of Eu 2O3、Gd2O3 and MoO 3 (molar ratio of 0.1:0.9:1.0), the mass of which is 1% of the mass of the binary eutectic salt, resulting in a dry Gd 1.8Eu0.2MoO6 ceramic powder, the XRD test results of which are shown in fig. 6.
FIG. 8 (dashed line) shows the emission spectrum of the target sample prepared in example 6 at 306nm under excitation by a laser and the excitation spectrum at 614 nm. It can be seen that the prepared sample exhibited red emission at 614nm under 306nm wavelength excitation. Also, as can be seen from the excitation spectrum, the excitation band of the sample at 614nm is wider than that of example 4.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the rare earth molybdate ceramic material is characterized by comprising the following steps: RE source and Mo source are reacted in molten salt system by molten salt method to synthesize RE-molybdate ceramic material with chemical formula RE xMoO(3x+6)/2, wherein RE is more than one kind selected from La, nd, sm, eu, gd, dy, ho, er and Yb, x is more than 0 and less than or equal to 6.
2. The method for preparing a rare earth molybdate ceramic material according to claim 1, wherein a binary salt mixture mainly composed of lithium molybdate and sodium molybdate is used as the molten salt system;
preferably, the mass ratio of the lithium molybdate to the sodium molybdate is 1:10-10:1.
3. The method for preparing rare earth molybdate ceramic material according to claim 1 or 2, wherein rare earth oxide is used as RE source;
Preferably, the RE source comprises one or more of La2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Dy2O3、Ho2O3、Er2O3 and Yb 2O3;
More preferably, the RE sources are two of La2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Dy2O3、Ho2O3、Er2O3 and Yb 2O3;
Most preferably, the RE source is a mixture of Sm 2O3 and Gd 2O3; or the RE source is a mixture of Eu 2O3 and Gd 2O3.
4. A method for preparing a rare earth molybdate ceramic material according to any of claims 1 to 3, wherein the binary salt mixture and/or MoO 3 is used as a Mo source;
Preferably, the binary salt mixture is used as a Mo source.
5. The method for producing a rare earth molybdate ceramic material according to any one of claims 1 to 4, comprising:
Heating and melting a binary salt mixture mainly formed by mixing lithium molybdate and sodium molybdate; then adding the raw materials containing RE sources into the molten binary salt mixture, and reacting at 462-1000 ℃ to obtain rare earth molybdate ceramic materials; the raw materials containing RE sources mainly comprise RE sources and MoO 3 in a molar ratio of 1:0-10;
Or mixing a binary salt mixture mainly formed by mixing lithium molybdate and sodium molybdate with a raw material containing an RE source, and reacting at 462-1000 ℃ to obtain a rare earth molybdate ceramic material; the raw material containing the RE source mainly comprises RE source and MoO 3 with the molar ratio of 1:0-10.
6. The method for preparing a rare earth molybdate ceramic material according to claim 5, comprising:
The binary salt mixture mainly formed by mixing lithium molybdate and sodium molybdate is subjected to pretreatment and then is heated and melted, and the pretreatment comprises the following steps: uniformly mixing lithium molybdate and sodium molybdate to obtain a binary salt mixture, putting the binary salt mixture into a crucible, and then drying at a temperature of below 200 ℃ to remove water;
Or the product after the reaction is subjected to post-treatment to obtain rare earth molybdate ceramic powder;
Preferably, the post-treatment comprises: washing the product with water, and filtering to obtain a precipitate; and drying the precipitate at a temperature of 200 ℃ or below to obtain rare earth molybdate ceramic powder.
7. The method for preparing a rare earth molybdate ceramic material according to claim 6, comprising:
The molar ratio of the RE source to MoO 3 in the RE source-containing raw material is 1:0-5;
Preferably, the mass of the raw material containing the RE source is 1-20% of that of the binary salt mixture.
8. The method for preparing a rare earth molybdate ceramic material according to claim 6 or 7, wherein the heating rate at the time of heating in the reaction process is 5 to 50 ℃/min.
9. The rare earth molybdate ceramic material of the chemical formula RE xMoO(3x+6)/2 prepared by the preparation method of the rare earth molybdate ceramic material of any one of claims 1 to 8, wherein RE is more than one kind selected from La, nd, sm, eu, gd, dy, ho, er and Yb, x is more than 0 and less than or equal to 6;
preferably, the rare earth molybdate ceramic material has a chemical formula La2MoO6、Nd6MoO12、Sm2MoO6、Eu2MoO6、Gd1.8Sm0.2MoO6 or Gd 1.8Eu0.2MoO6.
10. The use of the rare earth molybdate ceramic material of claim 9 in an environmentally friendly dye, ferroelectric material, microwave ceramic material, catalytic material, luminescent material or solid oxide fuel cell.
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