CN114836205A - Rare earth doped boron nitride nano powder and preparation method thereof - Google Patents
Rare earth doped boron nitride nano powder and preparation method thereof Download PDFInfo
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- boric acid
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 68
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- -1 nitrogen-containing organic compound Chemical class 0.000 claims abstract description 53
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004327 boric acid Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 3
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract 1
- 229910052582 BN Inorganic materials 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
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Abstract
The invention relates to rare earth doped boron nitride nano powder and a preparation method thereof. The technical scheme is as follows: mixing the materials according to the molar ratio of boric acid to the nitrogen-containing organic compound of 2: 1, adding deionized water into the mixed mixture, and stirring to obtain a solution A. And adding the rare earth nitrate compound into the solution A according to the molar ratio of boric acid to the rare earth nitrate compound of 2: 0.01-0.05, stirring and drying to obtain the composite precursor. Then mixing 15-40 wt% of the composite precursor with 60-85 wt% of molten salt, heating to 1000-1200 ℃ at a speed of 4-6 ℃/min under the condition of nitrogen or ammonia atmosphere, preserving heat for 3-4 h, and naturally cooling; washing, filtering, drying and obtaining the rare earth doped boron nitride nano powder. The preparation method has the advantages of simple preparation process, mild conditions, high safety, controllable rare earth element doping amount and doping sites, and high purity, good crystallinity and excellent luminescence property of the prepared rare earth doped boron nitride nano powder.
Description
Technical Field
The invention belongs to the field of boron nitride nano powder. In particular to rare earth doped boron nitride nano powder and a preparation method thereof.
Background
In modern information functional materials and devices, the electronic structure and transport properties (carrier mobility) of semiconductor materials are two crucial parameters. High carrier mobility can reduce the power consumption of the device in practical applications, and having a suitable electronic structure is a prerequisite for responding to an external field. Therefore, effective control of the electronic structure and transport properties of semiconductor materials has become a major concern to those skilled in the art. The low-dimensional Boron Nitride (BN) nano material is a wide-band-gap semiconductor material, and the electronic structure and the transport property of the low-dimensional Boron Nitride (BN) nano material can be correspondingly changed under the conditions of layer number change, edge structure configuration change and defects. The Zhang Shi et al (Zhang Shi, the first principle researches the influence of rare earth doping on the hydrogen storage and surface catalytic activity of the nano material, 2012, the doctrine college academic thesis) discovers that rare earth doping can adjust and optimize the electronic structure and the transport property of the BN nano material through the first principle prediction.
The high chemical stability/inertness of the low dimensional BN nano-material makes it very difficult to realize exo-type doping. Chen et al (H.Chen, Y.Chen, C.P.Li, e)t. Eu-doped boron nitride as a nano-meter-sized visible-light source, Advanced Materials,19(2007)1845-1848.) after B powder and Yb are mixed, ball milling is carried out in an ammonia atmosphere for 50 hours, iron and chromium are added as catalysts during ball milling, and nitrogen hydrogen (5% H) is added 2 +95％N 2 ) Heating the mixed gas to 1050 ℃ and preserving the temperature for 2h to obtain the BN nano tube doped with Yb. The disadvantages of this method are: the raw materials are toxic and explosive, the preparation process is long, the energy consumption is high, and the doping amount and the doping sites cannot be effectively controlled. E.M.Shishook et al (E.M.Shishook, A.R.Philipp, N.A.Shishook, et al.luminescences in cubic boron nitride treated by ray-earth electrical treatment, 242(2005), 1700-1704) mix Eu micropowder and c-BN, then treat at 4GPa and 1800 ℃ under high temperature and high pressure, then subject to acid washing and alkali washing, and finally subject to vacuum heat treatment to obtain Eu-doped c-BN material, which has excellent luminescence properties, but the defects of the synthesis method are that: high-temperature high-pressure and vacuum heat treatment is needed, the process is complex, the cost is high, and the doping amount and the doping site of the rare earth cannot be controlled; the doping amount, the doping sites and the doping element types directly influence the electronic structure and the transport property of the BN nano material, and further influence the performance of the BN nano material.
At present, although the research on the preparation of the rare earth doped boron nitride nano powder has made a remarkable progress, the following technical defects still exist: 1) the doping amount and the doping sites can not be effectively controlled, and the performance of the BN nano material is influenced; 2) the process for synthesizing the rare earth doped boron nitride nano powder is complex, has harsh conditions and high risk, and greatly influences the application of materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a preparation method of rare earth doped boron nitride nano powder with simple preparation process, mild conditions, high safety and controllable rare earth element doping amount and doping sites.
In order to achieve the purpose, the invention adopts the technical scheme that:
step one, mixing boric acid and a nitrogen-containing organic compound according to the molar ratio of boric acid to the nitrogen-containing organic compound of 2: 1 to obtain a mixture; and adding the mixture into deionized water according to the mass ratio of boric acid to deionized water of 1: 20-25, and stirring to obtain a solution A.
The nitrogen-containing organic compound is one of cyanuric acid, melamine and urea.
And secondly, adding the rare earth nitrate compound into the solution A at the temperature of 90-100 ℃ according to the molar ratio of the boric acid to the rare earth nitrate compound of 2: 0.01-0.05, stirring for 2-3 h, and drying for 30-36 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And step three, mixing 15-40 wt% of the composite precursor with 60-85 wt% of molten salt to obtain a mixture.
Step four, under the condition of nitrogen or ammonia atmosphere, heating to 1000-1200 ℃ at the speed of 4-6 ℃/min, preserving heat for 3-4 h, and naturally cooling; and then washing the mixture for 2-3 times by using deionized water, carrying out suction filtration, and drying the mixture for 8-16 h at the temperature of 100-120 ℃ to obtain the rare earth doped boron nitride nano powder.
The boric acid is commercially pure.
The rare earth nitric acid compound is one of cerium nitrate hexahydrate, yttrium nitrate hexahydrate, europium nitrate hexahydrate and lanthanum nitrate.
The molten salt is one of magnesium chloride, sodium chloride and potassium chloride.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
mixing boric acid and a nitrogen-containing organic compound, adding deionized water, stirring, adding a rare earth nitric acid compound, stirring, and drying to obtain a composite precursor. Mixing 15-40 wt% of the composite precursor with 60-85 wt% of molten salt, and carrying out heat preservation, washing and drying at 1000-1200 ℃ in a nitrogen or ammonia atmosphere to obtain the rare earth doped boron nitride nano powder, wherein the preparation process is simple.
According to the invention, boric acid, a nitrogen-containing organic compound and a rare earth nitrate compound are used as raw materials, and a composite precursor is prepared by a wet chemical method, so that the composite precursor (a B source and an N source) can be effectively combined with inorganic metal salt (doped ions) within a molecular scale range, and the doping amount and the doping sites can be effectively controlled; the raw materials used in the invention are nontoxic, high in safety and environment-friendly.
According to the invention, the rare earth doped boron nitride nano powder is synthesized by taking the molten salt as a medium, the liquid phase formed by the molten salt at the temperature higher than the melting point can provide a good liquid phase environment for reactants, namely, the migration and diffusion speeds of the reactants in the liquid phase are higher, and the migration speed of ions in the molten salt is far higher than the ion migration speed in the solid phase reaction, so that the reaction can be completed at a relatively low temperature in a short time without high-pressure and vacuum heat treatment, and the condition is mild; in addition, the reaction process and the subsequent cleaning process of the molten salt method are also beneficial to removing impurities, namely the synthesized rare earth doped boron nitride nano powder has high purity, good crystallinity and high luminous intensity.
Therefore, the preparation method has the advantages of simple preparation process, mild conditions, high safety, controllable rare earth element doping amount and doping sites, and high purity, good crystallinity and excellent luminescence property of the prepared rare earth doped boron nitride nano powder.
Drawings
FIG. 1 is an XRD spectrum of a rare earth doped boron nitride nanopowder prepared in the present invention;
FIG. 2 is an SEM image of the rare earth-doped boron nitride nanopowder shown in FIG. 1;
FIG. 3 is a PL profile of the rare earth doped boron nitride nanopowder shown in FIG. 1.
Detailed Description
The invention is further described with reference to the following figures and detailed description, without limiting the scope of the invention.
In this embodiment: the boric acid is commercially pure. The detailed description is omitted in the embodiments.
Example 1
A rare earth doped boron nitride nanometer powder and a preparation method thereof. The preparation method comprises the following steps:
step one, mixing boric acid and a nitrogen-containing organic compound according to the molar ratio of boric acid to the nitrogen-containing organic compound of 2: 1 to obtain a mixture; and adding the mixture into deionized water according to the mass ratio of boric acid to deionized water of 1: 20-21, and stirring to obtain a solution A.
And secondly, adding the rare earth nitrate compound into the solution A at the temperature of 90-100 ℃ according to the molar ratio of the boric acid to the rare earth nitrate compound of 2: 0.04-0.05, stirring for 2-3 h, and drying for 30-32 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And step three, mixing 15-20 wt% of the composite precursor with 80-85 wt% of molten salt to obtain a mixture.
Step four, under the condition of nitrogen atmosphere, heating to 1150-1200 ℃ at the speed of 4-5 ℃/min, preserving heat for 3-4 h, and naturally cooling; and then washing the mixture for 2-3 times by using deionized water, carrying out suction filtration, and drying the mixture for 8-10 hours at the temperature of 100-120 ℃ to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is cyanuric acid.
The rare earth nitric acid compound is cerous nitrate hexahydrate.
The molten salt is magnesium chloride.
Example 2
A rare earth doped boron nitride nanometer powder and a preparation method thereof. The preparation method comprises the following steps:
step one, mixing boric acid and a nitrogen-containing organic compound according to the molar ratio of boric acid to nitrogen-containing organic compound of 2: 1 to obtain a mixture; and adding the mixture into deionized water according to the mass ratio of boric acid to deionized water of 1: 21-22, and stirring to obtain a solution A.
And secondly, adding the rare earth nitrate compound into the solution A at the temperature of 90-100 ℃ according to the molar ratio of the boric acid to the rare earth nitrate compound of 2: 0.03-0.04, stirring for 2-3 h, and drying for 31-33 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And step three, mixing 20-25 wt% of the composite precursor with 75-80 wt% of molten salt to obtain a mixture.
Heating to 1100-1150 ℃ at a speed of 4-5 ℃/min under the condition of a nitrogen atmosphere, preserving heat for 3-3.5 hours, and naturally cooling; and then washing the powder with deionized water for 2-3 times, carrying out suction filtration, and drying the powder for 10-12 hours at the temperature of 100-120 ℃ to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is melamine.
The rare earth nitric acid compound is yttrium nitrate hexahydrate.
The molten salt is sodium chloride.
Example 3
A rare earth doped boron nitride nanometer powder and a preparation method thereof. The preparation method comprises the following steps:
step one, mixing boric acid and a nitrogen-containing organic compound according to the molar ratio of boric acid to the nitrogen-containing organic compound of 2: 1 to obtain a mixture; and adding the mixture into deionized water according to the mass ratio of boric acid to deionized water of 1: 22-23, and stirring to obtain a solution A.
And secondly, adding the rare earth nitrate compound into the solution A at the temperature of 90-100 ℃ according to the molar ratio of the boric acid to the rare earth nitrate compound of 2: 0.02-0.03, stirring for 2-3 h, and drying for 32-34 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And step three, mixing 25-30 wt% of the composite precursor with 70-75 wt% of molten salt to obtain a mixture.
Step four, under the condition of nitrogen atmosphere, heating to 1050-1100 ℃ at the speed of 5-6 ℃/min, preserving heat for 3-3.5 h, and naturally cooling; and then washing the mixture for 2-3 times by using deionized water, carrying out suction filtration, and drying the mixture for 12-14 hours at the temperature of 100-120 ℃ to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is urea.
The rare earth nitric acid compound is europium nitrate hexahydrate.
The molten salt is potassium chloride.
Example 4
A rare earth doped boron nitride nanometer powder and a preparation method thereof. The preparation method comprises the following steps:
step one, mixing boric acid and a nitrogen-containing organic compound according to the molar ratio of boric acid to the nitrogen-containing organic compound of 2: 1 to obtain a mixture; and adding the mixture into deionized water according to the mass ratio of boric acid to deionized water of 1: 23-24, and stirring to obtain a solution A.
And secondly, adding the rare earth nitrate compound into the solution A at the temperature of 90-100 ℃ according to the molar ratio of the boric acid to the rare earth nitrate compound of 2: 0.01-0.02, stirring for 2-3 h, and drying for 33-35 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And step three, mixing 30-35 wt% of the composite precursor with 65-70 wt% of molten salt to obtain a mixture.
Step four, under the condition of ammonia atmosphere, heating to 1050-1100 ℃ at the speed of 5-6 ℃/min, preserving heat for 3.5-4 h, and naturally cooling; and then washing the powder with deionized water for 2-3 times, carrying out suction filtration, and drying the powder for 14-16 h at the temperature of 100-120 ℃ to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is melamine.
The rare earth nitric acid compound is lanthanum nitrate.
The molten salt is magnesium chloride.
Example 5
A rare earth doped boron nitride nanometer powder and a preparation method thereof. The preparation method comprises the following steps:
step one, mixing boric acid and a nitrogen-containing organic compound according to the molar ratio of boric acid to the nitrogen-containing organic compound of 2: 1 to obtain a mixture; and adding the mixture into deionized water according to the mass ratio of boric acid to deionized water of 1: 24-25, and stirring to obtain a solution A.
And secondly, adding the rare earth nitrate compound into the solution A at the temperature of 90-100 ℃ according to the molar ratio of the boric acid to the rare earth nitrate compound of 2: 0.01-0.02, stirring for 2-3 h, and drying for 35-36 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And step three, mixing 35-40 wt% of the composite precursor with 60-65 wt% of molten salt to obtain a mixture.
Step four, under the condition of ammonia atmosphere, heating to 1000-1050 ℃ at the speed of 5-6 ℃/min, preserving heat for 3.5-4 h, and naturally cooling; and then washing the powder with deionized water for 2-3 times, carrying out suction filtration, and drying the powder for 14-16 h at the temperature of 100-120 ℃ to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is melamine.
The rare earth nitric acid compound is yttrium nitrate hexahydrate.
The molten salt is sodium chloride.
Compared with the prior art, the specific implementation mode has the following positive effects:
mixing boric acid and a nitrogen-containing organic compound, adding deionized water, stirring, adding a rare earth nitric acid compound, stirring, and drying to obtain the composite precursor. Mixing 15-40 wt% of the composite precursor with 60-85 wt% of molten salt, and carrying out heat preservation, washing and drying at 1000-1200 ℃ in a nitrogen or ammonia atmosphere to obtain the rare earth doped boron nitride nano powder, wherein the preparation process is simple.
According to the specific embodiment, boric acid, a nitrogen-containing organic compound and a rare earth nitric acid compound are used as raw materials, and a composite precursor is prepared by a wet chemical method, so that the composite precursor (a B source and an N source) can be effectively combined with inorganic metal salt (doped ions) within a molecular scale range, and the doping amount and the doping sites can be effectively controlled; the raw materials used in the embodiment are nontoxic and high in safety.
According to the specific embodiment, the rare earth doped boron nitride nano powder is synthesized by taking the molten salt as a medium, a liquid phase formed by the molten salt at a temperature higher than a melting point can provide a good liquid phase environment for reactants, namely, the migration and diffusion speeds of the reactants in the liquid phase are higher, and the migration speed of ions in the molten salt is far higher than the ion migration speed in a solid phase reaction, so that the reaction can be completed at a relatively low temperature in a short time without high-pressure and vacuum heat treatment, and the condition is mild; in addition, the reaction process of the molten salt method and the subsequent cleaning process are also beneficial to removing impurities, namely the synthesized rare earth doped boron nitride nano powder has high purity and good crystallinity.
The rare earth doped boron nitride nanopowder synthesized in the present embodiment is shown in the accompanying drawing, and fig. 1 is an XRD pattern of the cerium doped boron nitride nanopowder prepared in example 1. As can be seen from figure 1, the prepared cerium-doped boron nitride nano powder has diffraction peaks at 26.75 degrees and 41.56 degrees, the two diffraction peaks sequentially correspond to a (002) crystal face and a (100) crystal face of h-BN, no impurity peak exists, and the synthesized cerium-doped boron nitride nano powder has high purity and good crystallinity. Fig. 2 is an SEM photograph of the cerium-doped boron nitride nanopowder shown in fig. 1, and it can be seen from fig. 2 that the prepared cerium-doped boron nitride material is nanoparticles, and the average particle size is calculated to be 200 nm. FIG. 3 is a PL spectrum of the cerium-doped boron nitride nanopowder shown in FIG. 1. As can be seen from FIG. 3, the cerium-doped boron nitride nanopowder has a strong emission peak near 400nm and an emission intensity of 200000. Therefore, the synthesized rare earth doped boron nitride nano powder has high purity, good crystallinity and high luminous intensity.
Therefore, the preparation method of the specific embodiment has the advantages of simple preparation process, mild conditions, high safety, controllable doping amount and doping sites of the rare earth elements, and high purity, good crystallinity and excellent luminescence of the prepared rare earth doped boron nitride nano powder.
Claims (5)
1. A preparation method of rare earth doped boron nitride nano powder is characterized by comprising the following steps:
step one, mixing boric acid and a nitrogen-containing organic compound according to the molar ratio of boric acid to the nitrogen-containing organic compound of 2: 1 to obtain a mixture; adding the mixture into deionized water according to the mass ratio of boric acid to deionized water of 1: 20-25, and stirring to obtain a solution A;
the nitrogen-containing organic compound is one of cyanuric acid, melamine and urea;
secondly, adding the rare earth nitrate compound into the solution A at the temperature of 90-100 ℃ according to the molar ratio of the boric acid to the rare earth nitrate compound of 2: 0.01-0.05, stirring for 2-3 h, and drying for 30-36 h at the temperature of 80-90 ℃ to obtain a composite precursor;
step three, mixing 15-40 wt% of the composite precursor with 60-85 wt% of molten salt to obtain a mixture;
step four, under the condition of nitrogen or ammonia atmosphere, heating to 1000-1200 ℃ at the speed of 4-6 ℃/min, preserving heat for 3-4 h, and naturally cooling; and then washing the mixture for 2-3 times by using deionized water, carrying out suction filtration, and drying the mixture for 8-16 h at the temperature of 100-120 ℃ to obtain the rare earth doped boron nitride nano powder.
2. The method according to claim 1, wherein the boric acid is commercially pure.
3. The method of claim 1, wherein the rare earth nitrate compound is one of cerium nitrate hexahydrate, yttrium nitrate hexahydrate, europium nitrate hexahydrate, and lanthanum nitrate.
4. The method for preparing rare earth-doped boron nitride nanopowder according to claim 1, wherein the molten salt is one of magnesium chloride, sodium chloride and potassium chloride.
5. A rare earth-doped boron nitride nanopowder characterized in that it is prepared according to the method of any one of claims 1 to 4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116116374A (en) * | 2023-03-09 | 2023-05-16 | 河北工业大学 | La (La) 2 O 3 Preparation method and application of BNNFs composite adsorbent |
| CN117586755A (en) * | 2024-01-19 | 2024-02-23 | 镧明材料技术(上海)有限公司 | Refrigerating material and preparation method and application thereof |
| CN117866513A (en) * | 2024-03-12 | 2024-04-12 | 海聚高分子材料科技（广州）有限公司 | Deep-curable UV solid-color coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894177A (en) * | 2014-04-01 | 2014-07-02 | 江西理工大学 | Method for synthesizing rare earth doped potassium titanate powder with photocatalytic activity |
| CN108483414A (en) * | 2018-04-16 | 2018-09-04 | 武汉科技大学 | One kind is based on molten-salt growth method low temperature synthesis rhombohedral boron nitride powder and preparation method thereof |
| CN109279642A (en) * | 2018-10-23 | 2019-01-29 | 绍兴文理学院 | A kind of preparation method of rare earth doping zinc oxide |
-
2022
- 2022-03-18 CN CN202210270306.3A patent/CN114836205B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894177A (en) * | 2014-04-01 | 2014-07-02 | 江西理工大学 | Method for synthesizing rare earth doped potassium titanate powder with photocatalytic activity |
| CN108483414A (en) * | 2018-04-16 | 2018-09-04 | 武汉科技大学 | One kind is based on molten-salt growth method low temperature synthesis rhombohedral boron nitride powder and preparation method thereof |
| CN109279642A (en) * | 2018-10-23 | 2019-01-29 | 绍兴文理学院 | A kind of preparation method of rare earth doping zinc oxide |
Non-Patent Citations (1)
| Title |
|---|
| JAE YONG JUNG等: ""Enhanced Crystallinity and Luminescence Characteristics of Hexagonal Boron Nitride Doped with Cerium Ions According to Tempering Temperatures"", 《MATERIALS》, vol. 14, no. 1, pages 1 - 8 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116116374A (en) * | 2023-03-09 | 2023-05-16 | 河北工业大学 | La (La) 2 O 3 Preparation method and application of BNNFs composite adsorbent |
| CN116116374B (en) * | 2023-03-09 | 2024-05-17 | 河北工业大学 | La (La)2O3Preparation method and application of BNNFs composite adsorbent |
| CN117586755A (en) * | 2024-01-19 | 2024-02-23 | 镧明材料技术(上海)有限公司 | Refrigerating material and preparation method and application thereof |
| CN117586755B (en) * | 2024-01-19 | 2024-04-09 | 镧明材料技术(上海)有限公司 | Refrigerating material and preparation method and application thereof |
| CN117866513A (en) * | 2024-03-12 | 2024-04-12 | 海聚高分子材料科技（广州）有限公司 | Deep-curable UV solid-color coating and preparation method thereof |
| CN117866513B (en) * | 2024-03-12 | 2024-05-31 | 海聚高分子材料科技（广州）有限公司 | Deep-curable UV solid-color coating and preparation method thereof |
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