CN114836205B - 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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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 74
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- -1 nitrogen-containing organic compound Chemical class 0.000 claims abstract description 46
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004327 boric acid Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 229910052582 BN Inorganic materials 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 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
- 238000002441 X-ray diffraction Methods 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
- 238000003746 solid phase reaction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000694 effects Effects 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
- 239000011812 mixed powder 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0646—Preparation by pyrolysis of boron and nitrogen containing compounds
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Abstract
The invention relates to rare earth doped boron nitride nano powder and a preparation method thereof. The technical proposal is as follows: and (3) mixing the ingredients according to the mol 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. Adding rare earth nitrate compound into the solution A according to the mol ratio of boric acid to 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, suction filtering and drying to obtain the rare earth doped boron nitride nano powder. The preparation method has the advantages of simple process, mild condition, high safety, controllable doping amount and doping sites of the rare earth elements, and the prepared rare earth doped boron nitride nano powder has high purity, good crystallinity and excellent luminescence property.
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-function materials and devices, the electronic structure and transport properties (carrier mobility) of semiconductor materials are two critical parameters. High carrier mobility can reduce the power consumption of the device in practical applications, and proper electronic structure is a necessary condition for responding to external fields. Therefore, effective regulation of the electronic structure and transport properties of semiconductor materials has become a major concern for those skilled in the art. The low-dimensional Boron Nitride (BN) nanomaterial is a wide-band-gap semiconductor material, and the electronic structure and transport property of the low-dimensional Boron Nitride (BN) nanomaterial can be correspondingly changed under the conditions of layer number change, edge structure configuration change and defect existence. Zhang Zhiwei et al (Zhang Zhiwei, first principles study the effect of rare earth doping on the hydrogen storage and surface catalytic activity of nanomaterials, 2012, jilin university doctor's treatise) have found, through first principles prediction, that rare earth doping can adjust and optimize the electronic structure of BN nanomaterials and their transport properties.
The high chemical stability/inertness of low-dimensional BN nanomaterials makes it very difficult to achieve exotic doping. Chen et al (H.Chen, Y.Chen, C.P.Li, et al), eu-doped boron nitride nanotubes as a nanometer-sized visible-light source, advanced Materials,19 (2007) 1845-1848.) mixed powder B with Yb followed by ball milling in an ammonia atmosphere for 50 hours, adding iron and chromium as catalysts during ball milling, and adding nitrogen and hydrogen (5%H 2 +95％N 2 ) Heating the mixed gas to 1050 ℃ and preserving heat for 2 hours to obtain the Yb doped BN nanotube. The method has the defects that: the raw materials are toxic and explosive, the preparation process is long, the energy consumption is high, and the doping amount and the doping site cannot be effectively controlled. E.M. Shishonok et al (E.M.Shishonok, A.R.Philipp, N.A.Shishonok, et al, luminescence in cubic boron nitride doped by rare-earth impurity 242 (2005), 1700-1704) by mixing Eu micropowder with c-BN, treating at high temperature and high pressure of 4GPa and 1800 ℃ and then acid washing and alkali washing, and finally vacuum heat treating to obtain Eu-doped c-BN material, although the material hasExcellent luminescence properties, but the disadvantages of the synthetic method are: high temperature, high pressure and vacuum heat treatment are needed, the process is complex, the cost is high, and the doping amount and the doping site of the rare earth can not be controlled; the doping amount, the doping site and the doping element species directly influence the electronic structure and the transport property of the BN nano material, thereby influencing the performance of the BN nano material.
At present, although remarkable progress is made in the research on the preparation of rare earth doped boron nitride nano powder, the following technical defects still exist: 1) The doping amount and the doping sites cannot be controlled effectively, and the performance of the BN nano material is affected; 2) The process for synthesizing the rare earth doped boron nitride nano powder is complex, the condition is harsh, the danger is high, and the application of the material is greatly influenced.
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 which has the advantages of simple preparation process, mild condition, high safety, controllable doping amount of rare earth elements and doping sites, and the rare earth doped boron nitride nano powder prepared by the method has high purity, good crystallinity and excellent luminescence property.
In order to achieve the above purpose, the invention adopts the following technical scheme:
step one, mixing boric acid and a nitrogen-containing organic compound according to the mol ratio 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 step two, adding the rare earth nitric acid compound into the solution A according to the molar ratio of the boric acid to the rare earth nitric acid compound of 2:0.01-0.05 at the temperature of 90-100 ℃, stirring for 2-3 h, and then drying for 30-36 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And thirdly, mixing 15-40 wt% of the composite precursor with 60-85 wt% of molten salt to obtain a mixture.
Step four, heating to 1000-1200 ℃ at a speed of 4-6 ℃/min under the condition of nitrogen or ammonia gas atmosphere, preserving heat for 3-4 h, and naturally cooling; and then washing with deionized water for 2-3 times, carrying out suction filtration, and drying at 100-120 ℃ for 8-16 h to obtain the rare earth doped boron nitride nano powder.
The boric acid is industrially pure.
The rare earth nitrate 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.
By adopting the technical scheme, compared with the prior art, the invention has the following positive effects:
the invention mixes boric acid and nitrogen-containing organic compound, adds deionized water, stirs, adds rare earth nitrate compound, stirs, dries to obtain compound precursor. 15-40 wt% of the composite precursor is mixed with 60-85 wt% of molten salt, and the mixture is subjected to heat preservation, washing and drying under the conditions of 1000-1200 ℃ and nitrogen or ammonia atmosphere, so that the rare earth doped boron nitride nano powder is prepared, and the preparation process is simple.
The invention takes boric acid, a nitrogen-containing organic compound and a rare earth nitric acid compound as raw materials, prepares the composite precursor by a wet chemical method, can effectively combine the composite precursor (B source and N source) with inorganic metal salt (doping ions) in a molecular scale range, and realizes effective control of doping amount and doping sites; 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 speed of the reactants in the liquid phase are faster, and the migration speed of ions in the molten salt is far higher than that of ions 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 conditions are mild; in addition, the molten salt method is also beneficial to removing impurities in the reaction process and the subsequent cleaning process, namely the synthesized rare earth doped boron nitride nano powder has high purity, good crystallinity and high luminous intensity.
Therefore, the preparation process provided by the invention has the advantages of simplicity, mild conditions, high safety, controllable doping amount and doping sites of the rare earth elements, and the prepared rare earth doped boron nitride nano powder has the advantages of high purity, good crystallinity and excellent luminescence property.
Drawings
FIG. 1 is an XRD pattern of a rare earth doped boron nitride nanopowder prepared in accordance with 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 nano-powder shown in FIG. 1.
Detailed Description
The invention is further described in connection with the drawings and the detailed description which follow, without limiting the scope of the invention.
In this embodiment: the boric acid is industrially pure. The embodiments are not described in detail.
Example 1
A rare earth doped boron nitride nano 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 mol ratio 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 step two, adding the rare earth nitric acid compound into the solution A according to the molar ratio of the boric acid to the rare earth nitric acid compound of 2:0.04-0.05 at the temperature of 90-100 ℃, stirring for 2-3 h, and then drying for 30-32 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And thirdly, mixing 15-20wt% of the composite precursor with 80-85wt% of molten salt to obtain the mixture.
Step four, heating to 1150-1200 ℃ at a speed of 4-5 ℃/min under the condition of nitrogen atmosphere, preserving heat for 3-4 h, and naturally cooling; and then washing with deionized water for 2-3 times, carrying out suction filtration, and drying at 100-120 ℃ for 8-10 hours to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is cyanuric acid.
The rare earth nitrate compound is cerium nitrate hexahydrate.
The molten salt is magnesium chloride.
Example 2
A rare earth doped boron nitride nano 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 mol ratio 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 step two, adding the rare earth nitric acid compound into the solution A according to the molar ratio of the boric acid to the rare earth nitric acid compound of 2:0.03-0.04 at the temperature of 90-100 ℃, stirring for 2-3 h, and then 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.
Step four, heating to 1100-1150 ℃ at a speed of 4-5 ℃/min under the condition of nitrogen atmosphere, preserving heat for 3-3.5 h, and naturally cooling; and then washing with deionized water for 2-3 times, carrying out suction filtration, and drying at 100-120 ℃ for 10-12 hours to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is melamine.
The rare earth nitrate compound is yttrium nitrate hexahydrate.
The molten salt is sodium chloride.
Example 3
A rare earth doped boron nitride nano 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 mol ratio 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 solution A.
And step two, adding the rare earth nitric acid compound into the solution A according to the molar ratio of the boric acid to the rare earth nitric acid compound of 2:0.02-0.03 at the temperature of 90-100 ℃, stirring for 2-3 h, and then drying for 32-34 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And thirdly, mixing 25-30wt% of the composite precursor with 70-75wt% of molten salt to obtain the mixture.
Step four, heating to 1050-1100 ℃ at a speed of 5-6 ℃/min under the condition of nitrogen atmosphere, preserving heat for 3-3.5 h, and naturally cooling; and then washing with deionized water for 2-3 times, carrying out suction filtration, and drying at 100-120 ℃ for 12-14 h to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is urea.
The rare earth nitrate compound is europium nitrate hexahydrate.
The molten salt is potassium chloride.
Example 4
A rare earth doped boron nitride nano 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 mol ratio 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 step two, adding the rare earth nitric acid compound into the solution A according to the molar ratio of the boric acid to the rare earth nitric acid compound of 2:0.01-0.02 at the temperature of 90-100 ℃, stirring for 2-3 h, and then drying for 33-35 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And thirdly, mixing 30-35 wt% of the composite precursor with 65-70 wt% of molten salt to obtain a mixture.
Step four, heating to 1050-1100 ℃ at a speed of 5-6 ℃/min under the condition of ammonia atmosphere, preserving heat for 3.5-4 h, and naturally cooling; and then washing with deionized water for 2-3 times, carrying out suction filtration, and drying at 100-120 ℃ for 14-16 h to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is melamine.
The rare earth nitrate compound is lanthanum nitrate.
The molten salt is magnesium chloride.
Example 5
A rare earth doped boron nitride nano 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 mol ratio 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 step two, adding the rare earth nitric acid compound into the solution A according to the molar ratio of the boric acid to the rare earth nitric acid compound of 2:0.01-0.02 at the temperature of 90-100 ℃, stirring for 2-3 h, and then drying for 35-36 h at the temperature of 80-90 ℃ to obtain the composite precursor.
And thirdly, 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 gas atmosphere, heating to 1000-1050 ℃ at a speed of 5-6 ℃/min, preserving heat for 3.5-4 h, and naturally cooling; and then washing with deionized water for 2-3 times, carrying out suction filtration, and drying at 100-120 ℃ for 14-16 h to obtain the rare earth doped boron nitride nano powder.
The nitrogen-containing organic compound is melamine.
The rare earth nitrate compound is yttrium nitrate hexahydrate.
The molten salt is sodium chloride.
Compared with the prior art, the specific embodiment has the following positive effects:
in the specific embodiment, boric acid and a nitrogen-containing organic compound are mixed, deionized water is added, stirring is carried out, then a rare earth nitric acid compound is added, stirring is carried out, and drying is carried out, thus obtaining the composite precursor. 15-40 wt% of the composite precursor is mixed with 60-85 wt% of molten salt, and the mixture is subjected to heat preservation, washing and drying under the conditions of 1000-1200 ℃ and nitrogen or ammonia atmosphere, so that the rare earth doped boron nitride nano powder is prepared, and the preparation process is simple.
The preparation method of the compound precursor takes boric acid, a nitrogen-containing organic compound and a rare earth nitric acid compound as raw materials, and prepares the compound precursor by a wet chemical method, so that the compound precursor (B source and N source) and inorganic metal salt (doping ions) can be effectively combined in a molecular scale range, and the effective control of doping amount and doping sites is realized; the raw materials used in the specific embodiment are nontoxic and have high safety.
According to the embodiment, 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 speed of the reactants in the liquid phase are faster, and the migration speed of ions in the molten salt is far higher than that of ions 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 conditions are mild; in addition, the molten salt method is also beneficial to removing impurities in the reaction process and the subsequent cleaning process, namely the synthesized rare earth doped boron nitride nano powder has high purity and good crystallinity.
The rare earth doped boron nitride nano powder synthesized in the specific embodiment is shown in the accompanying drawing, and fig. 1 is an XRD pattern of cerium doped boron nitride nano powder prepared in example 1. As can be seen from the 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 correspond to the (002) crystal face and the (100) crystal face of h-BN in sequence, 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 nano powder shown in fig. 1, and as can be seen from fig. 2, the prepared cerium-doped boron nitride material is nano particles, and the average particle size is 200nm. The PL spectrum of the cerium-doped boron nitride nano powder shown in fig. 3 and fig. 1 shows that the cerium-doped boron nitride nano powder has a strong emission peak near 400nm, and the luminous intensity is 200000. Therefore, the synthesized rare earth doped boron nitride nano powder has high purity, good crystallinity and high luminous intensity.
Therefore, the preparation process of the specific embodiment is simple, the condition is mild, the safety is high, the doping amount and the doping position of the rare earth element are controllable, and the prepared rare earth doped boron nitride nano powder has high purity, good crystallinity and excellent luminescence property.
Claims (5)
1. The preparation method of the rare earth doped boron nitride nano powder is characterized by comprising the following steps of:
step one, mixing boric acid and a nitrogen-containing organic compound according to the mol ratio 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;
step two, adding the rare earth nitric acid compound into the solution A according to the molar ratio of the boric acid to the rare earth nitric acid compound of 2:0.01-0.05 at the temperature of 90-100 ℃, stirring for 2-3 h, and then 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, heating to 1000-1200 ℃ at a speed of 4-6 ℃/min under the condition of nitrogen or ammonia gas atmosphere, preserving heat for 3-4 h, and naturally cooling; and then washing with deionized water for 2-3 times, carrying out suction filtration, and drying at 100-120 ℃ for 8-16 h to obtain the rare earth doped boron nitride nano powder.
2. The method for preparing rare earth doped boron nitride nano-powder according to claim 1, wherein the boric acid is industrially pure.
3. The method for preparing rare earth doped boron nitride nano powder according to 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 nano-powder 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 nano-powder characterized in that the rare earth-doped boron nitride nano-powder is prepared by the preparation method of the rare earth-doped boron nitride nano-powder according to any one of claims 1 to 4.
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