CN113104857A - Low-temperature preparation method of transition metal boride - Google Patents
Low-temperature preparation method of transition metal boride Download PDFInfo
- Publication number
- CN113104857A CN113104857A CN202110397867.5A CN202110397867A CN113104857A CN 113104857 A CN113104857 A CN 113104857A CN 202110397867 A CN202110397867 A CN 202110397867A CN 113104857 A CN113104857 A CN 113104857A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- nitrate
- anhydrous
- metal chloride
- low temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021381 transition metal chloride Inorganic materials 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- 239000012153 distilled water Substances 0.000 claims abstract description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 235000010344 sodium nitrate Nutrition 0.000 claims description 11
- 239000004317 sodium nitrate Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims description 5
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 3
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 3
- 229960000359 chromic chloride Drugs 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 2
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 2
- 229910019918 CrB2 Inorganic materials 0.000 abstract description 10
- 229910003862 HfB2 Inorganic materials 0.000 abstract description 10
- 229910033181 TiB2 Inorganic materials 0.000 abstract description 10
- 229910007948 ZrB2 Inorganic materials 0.000 abstract description 10
- 229910015173 MoB2 Inorganic materials 0.000 abstract description 9
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
- C01B35/04—Metal borides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Products (AREA)
- Catalysts (AREA)
Abstract
A low-temperature preparation method of transition metal boride belongs to the technical field of inorganic functional materials. Taking transition metal chloride as a metal source, amorphous boron powder as a boron source and a reducing agent, nitrate as a molten salt and an oxidizing agent, mixing the above substances, fully grinding the mixture under the irradiation of an infrared lamp, calcining the mixture in inert gas at 400-500 ℃ for 30-120 min, centrifugally washing the calcined product for 2-6 times by using secondary distilled water and ethanol respectively, and drying the calcined product in vacuum at 40-60 ℃ for 2-4 h to obtain pure-phase transition metal boride comprising VB2、TiB2、CrB2、ZrB2、MoB2And HfB2And the like. The methodCompared with the traditional methods (a carbothermic method, a metallothermic method, an inorganic molten salt method and the like), the method has the advantages of obviously reducing the reaction temperature, along with simple operation, good repeatability and good controllability, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to a low-temperature preparation method of a transition metal boride.
Background
The transition metal boride has the characteristics of low cost, high melting point, high hardness, excellent chemical stability, good thermal conductivity, electric conductivity and the like, and has wide application prospects in the fields of superconductivity, super hardness, magnetocaloric effect, corrosion resistance and the like (J.Am.Ceram.Soc.,2020, 103, 719). In particular their low cost, superconductivity and good stability, make them an alternative catalyst to noble metal catalysts in the field of electrocatalysis. For example, alpha-MoB2As an electrochemical hydrogen evolution catalyst (j.am.chem.soc., 139, 12370, 2017), NiXB as an electrochemical oxygen evolution catalyst (j. mater. chem. a, vol 7, 2019, page 5288).
The synthesis of transition metal boride mainly comprises methods such as a metal and boron high-temperature synthesis method, a carbothermic reduction method, a metallothermic reduction method, an inorganic molten salt method and the like, but because of the high melting point of boron element, the methods generally need high temperature and high pressure to realize pure phase synthesis of boride (more than 800 ℃). However, high temperature synthesis undoubtedly results in a series of problems of large particle size, uncontrollable crystal form, product mixing, etc. (adv. mater.,2018, 30, page 1704181). Thus, the production of transition metal borides using low temperature, mild conditions is a very challenging task.
Disclosure of Invention
The invention aims to overcome the problem of overhigh synthesis temperature of the transition metal boride and provides a low-temperature and universal preparation method of the transition metal boride. The invention uses nitrate with oxidability, boron powder with reducibility and transition metal chloride as raw materials, and uses a large amount of heat released by redox reaction to reduce the synthesis temperature of the transition metal boride to obtain a series of transition metal borides (VB)2、TiB2、CrB2、ZrB2、HfB2、MoB2Etc.).
The invention provides a low-temperature preparation method of transition metal boride, which is characterized by comprising the following steps: the method comprises the steps of taking transition metal chloride as a metal source, amorphous boron powder as a boron source and a reducing agent, nitrate as a molten salt and an oxidizing agent, mixing the materials, fully grinding the materials under the irradiation of an infrared lamp, calcining the materials in inert gas at the calcining temperature of 400-500 ℃ for 30-120 min, centrifugally washing calcined products for 2-6 times by using secondary distilled water and ethanol respectively, and drying the calcined products in vacuum for 2-4 h at the temperature of 40-60 ℃ to obtain pure-phase transition metal boride.
In the above method, the transition metal chloride is a transition metal chloride of the fourth subgroup, the fifth subgroup and the sixth subgroup, specifically anhydrous titanium trichloride, anhydrous vanadium trichloride, anhydrous chromium trichloride, anhydrous zirconium tetrachloride, anhydrous hafnium tetrachloride, anhydrous molybdenum pentachloride, anhydrous niobium pentachloride, anhydrous tantalum pentachloride, etc. The nitrate is sodium nitrate, potassium nitrate or lithium nitrate.
In the above method, the mass of the nitrate is 0.5 to 1 g.
In the above method, the ratio of the amount of the substance of the metal chloride to the amount of the substance of the boron powder is 1: 5-15, wherein the ratio of the amount of the metal chloride to the amount of the nitrate is 1: 6 to 20.
In the method, the grinding time of the transition metal chloride, the boron powder and the nitrate is 10-30 min, and the inert gas is argon.
The invention has the following beneficial effects:
1. the method does not need any complex and expensive synthesis technology, has simple operation, good repeatability and good controllability, and can be suitable for synthesizing the transition metal borides of the fourth subgroup, the fifth subgroup and the sixth subgroup.
2. Compared with the conventional method for preparing the metal boride (a carbothermic reduction method, a metallothermic reduction method and an inorganic molten salt method), the nitrate molten salt used in the method has the function of an oxidant, and reacts with metal chloride and boron powder to release a large amount of heat, so that the synthesis temperature of the metal boride is greatly reduced.
Drawings
FIG. 1: example 1 preparation ofMoB2X-ray diffraction (XRD) pattern of (a).
FIG. 2: example 1 MoB prepared2Electron micrograph of (a). FIG. A shows the MoB prepared in example 12The Transmission Electron Microscope (TEM) photograph of (2) is shown with a scale of 100 nm. FIG. B shows the MoB prepared in example 12High Resolution Transmission Electron Microscopy (HRTEM) with a scale of 5 nm.
FIG. 3: XRD patterns of other transition metal borides prepared in examples 5-9 were VB2、TiB2、CrB2、ZrB2、HfB2。
FIG. 4: SEM photographs of other transition metal borides prepared in examples 5-9, VB2、TiB2、CrB2、ZrB2、HfB2。
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the scope of the present invention is not limited to the following examples, and alterations and modifications made by those skilled in the art in light of the common knowledge and practice in the art will be within the scope of the present invention without departing from the spirit and scope of the present invention.
Example 1
MoB2The preparation of (1): fully grinding 0.5g of sodium nitrate, 0.14g of anhydrous molybdenum pentachloride and 0.17g of boron powder for 10min under the irradiation of an infrared lamp, then transferring the fully ground mixture into a clean corundum magnetic boat, heating to 500 ℃ from room temperature at the heating rate of 5 ℃/min under the protection of inert gas argon, maintaining at the temperature for 30min, after the reaction is finished, respectively centrifugally washing the obtained black powder for three times by using secondary water and ethanol, and finally transferring to a vacuum drying oven at 60 ℃ for drying for 2 hours to obtain the MoB2Catalyst powder, product mass about 200 mg.
Example 2
VB2The preparation of (1): 0.1700g of anhydrous vanadium trichloride, 0.19g of boron powder and 0.5g of sodium nitrate are fully ground for 10min under the irradiation of an infrared lamp, and then the fully ground mixture is transferred to be cleanIn the corundum magnetic boat, under the protection of inert gas argon, the temperature is increased from room temperature to 400 ℃ at the temperature rising rate of 5 ℃/min, the temperature is maintained for 30min, after the reaction is finished, the obtained black powder is respectively centrifugally washed by secondary water and ethanol for three times, and finally the black powder is transferred to a vacuum drying oven at 60 ℃ for drying for 2 hours to obtain VB2Catalyst powder, product mass about 150 mg.
Example 3
TiB2The preparation of (1): fully grinding 0.120g of anhydrous titanium trichloride, 0.130g of boron powder and 0.5g of sodium nitrate for 10min under the irradiation of an infrared lamp, then transferring the fully ground mixture into a clean corundum magnet boat, heating to 450 ℃ from room temperature at the heating rate of 5 ℃/min under the protection of inert gas argon, maintaining at the temperature for 30min, after the reaction is finished, respectively centrifugally washing the obtained black powder for three times by using secondary water and ethanol, and finally transferring to a vacuum drying oven at 60 ℃ for drying for 2 hours to obtain TiB2Catalyst powder, product mass about 50 mg.
Example 4
CrB2The preparation of (1): fully grinding 0.123g of anhydrous chromium trichloride, 0.15g of boron powder and 0.5g of sodium nitrate for 10min under the irradiation of an infrared lamp, then transferring the fully ground mixture into a clean corundum magnet boat, heating to 500 ℃ from room temperature at the heating rate of 5 ℃/min under the protection of inert gas argon, maintaining at the temperature for 30min, after the reaction is finished, respectively centrifugally washing the obtained black powder for three times by using secondary water and ethanol, and finally transferring to a vacuum drying oven at 60 ℃ for drying for 2 hours to obtain CrB2Catalyst powder, product mass about 150 mg.
Example 5
ZrB2The preparation of (1): fully grinding 0.1864g of anhydrous zirconium tetrachloride, 0.162g of boron powder and 0.5g of sodium nitrate under the irradiation of an infrared lamp for 10min, then transferring the fully ground mixture into a clean corundum magnet boat, raising the temperature from room temperature to 500 ℃ at the temperature raising rate of 5 ℃/min under the protection of inert gas argon, maintaining the temperature for 30min, and after the reaction is finished, respectively using secondary water and ethanol to obtain black powderCentrifugally washing for three times, and finally transferring to a vacuum drying oven at 60 ℃ for drying for 2 hours to obtain ZrB2Catalyst powder, product mass about 250 mg.
Example 6
HfB2The preparation of (1): fully grinding anhydrous 0.27g of hafnium tetrachloride, 0.162g of boron powder and 0.5g of sodium nitrate for 10min under the irradiation of an infrared lamp, then transferring the fully ground mixture into a clean corundum magnetic boat, heating to 500 ℃ from room temperature at the heating rate of 5 ℃/min under the protection of inert gas argon, maintaining the temperature for 30min, after the reaction is finished, respectively centrifugally washing the obtained black powder for three times by using secondary water and ethanol, and finally transferring to a vacuum drying oven at 60 ℃ for drying for 2 hours to obtain HfB2Catalyst powder, product mass about 250 mg.
Example 7
As with examples 1-6, the mass of the raw material sodium nitrate was changed from 0.5g to 1g, and pure-phase transition metal boride was obtained without any significant change in the product mass under otherwise unchanged conditions.
Example 8
In the same way as in examples 1-6, the nitrate is changed from sodium nitrate to potassium nitrate or lithium nitrate, and the pure-phase transition metal boride can still be obtained under the same other conditions, and the quality of the product has no obvious change.
Example 9
The same as the examples 1-6, the grinding time of the raw materials of transition metal chloride, boron powder and sodium nitrate is increased from 10min to 30min, and the pure-phase transition metal boride can still be obtained without changing other conditions, and the quality of the product is not obviously changed.
Example 10
As with examples 1-6, the calcination time was increased from 30min to 120min, and pure-phase transition metal boride was still obtained without significant change in product quality under otherwise unchanged conditions.
Example 11
As with examples 1-6, the vacuum drying time is increased from 2h to 4h, and the pure-phase transition metal boride can still be obtained without obvious change in product quality under the same other conditions.
Some structural characterization and studies were performed on the materials prepared by the above methods.
FIG. 1 shows the XRD spectrum of the obtained material, in which the position assignment is MoB2(PDF #06-0682) indicating that the material is a pure phase MoB2；
FIG. 2 shows the MoB prepared in example 12Transmission electron micrograph (c). FIG. A shows the MoB prepared in example 12The TEM photograph of the obtained MoB shows that the MoB was synthesized2The structure of the nano particles is ensured, and the size of the nano particles is 50-150 nm. FIG. B shows the MoB prepared in example 12The lattice spacing of the nanoparticles is 0.23nm, corresponding to MoB2Further proving that we synthesized pure phase MoB2。
FIG. 3 shows other transition metal borides (VB) prepared in examples 5-92、TiB2、CrB2、ZrB2And HfB2) The XRD result shows that VB with good crystallinity is synthesized2、TiB2、CrB2、ZrB2And HfB2。
FIG. 4 shows other transition metal borides (VB) prepared in examples 5-92、TiB2、CrB2、ZrB2And HfB2) SEM photograph of (figure), SEM result shows that we synthesized nanometer-scale VB2、TiB2、CrB2、ZrB2And HfB2The size of the nano particles is 100 nm-300 nm.
Claims (6)
1. A low-temperature preparation method of transition metal boride is characterized by comprising the following steps: the method comprises the steps of taking transition metal chloride as a metal source, amorphous boron powder as a boron source and a reducing agent, nitrate as a molten salt and an oxidizing agent, mixing the materials, fully grinding the materials under the irradiation of an infrared lamp, calcining the materials in inert gas at the calcining temperature of 400-500 ℃ for 30-120 min, centrifugally washing calcined products for 2-6 times by using secondary distilled water and ethanol respectively, and drying the calcined products in vacuum for 2-4 h at the temperature of 40-60 ℃ to obtain pure-phase transition metal boride.
2. A process for the low temperature production of transition metal borides according to claim 1, wherein: the transition metal chloride is a transition metal chloride of fourth, fifth and sixth sub-groups.
3. A process for the low temperature production of transition metal borides according to claim 2, characterized by: the transition metal chloride is anhydrous titanium trichloride, anhydrous vanadium trichloride, anhydrous chromium trichloride, anhydrous zirconium tetrachloride, anhydrous hafnium tetrachloride, anhydrous molybdenum pentachloride, anhydrous niobium pentachloride or anhydrous tantalum pentachloride.
4. A process for the low temperature production of transition metal borides according to claim 1, wherein: the nitrate is sodium nitrate, potassium nitrate or lithium nitrate.
5. A process for the low temperature production of transition metal borides according to claim 1, wherein: in the method, the mass of the nitrate is 0.5-1 g; the ratio of the amount of metal chloride species to the amount of boron powder species is 1: 5-15, wherein the ratio of the amount of the metal chloride substance to the amount of the nitrate substance is 1: 6 to 20.
6. A process for the low temperature production of transition metal borides according to claim 1, wherein: the grinding time of the transition metal chloride, the boron powder and the nitrate is 10-30 min, and the inert gas is argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110397867.5A CN113104857B (en) | 2021-04-14 | 2021-04-14 | Low-temperature preparation method of transition metal boride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110397867.5A CN113104857B (en) | 2021-04-14 | 2021-04-14 | Low-temperature preparation method of transition metal boride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113104857A true CN113104857A (en) | 2021-07-13 |
| CN113104857B CN113104857B (en) | 2022-09-30 |
Family
ID=76716822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110397867.5A Active CN113104857B (en) | 2021-04-14 | 2021-04-14 | Low-temperature preparation method of transition metal boride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113104857B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114045546A (en) * | 2021-11-22 | 2022-02-15 | 安徽工业大学 | Method for preparing transition metal boride coating through fused salt in-situ synthesis and electrophoretic deposition |
| CN114506851A (en) * | 2022-03-14 | 2022-05-17 | 浙江理工大学 | Room-temperature ferromagnetic semiconductor and preparation method and application thereof |
| CN114717591A (en) * | 2022-03-25 | 2022-07-08 | 吉林大学 | Boride and preparation method and application thereof, oxygen evolution catalyst and preparation method thereof |
| CN114751753A (en) * | 2022-05-27 | 2022-07-15 | 中国科学院合肥物质科学研究院 | Method for preparing superfine ceramic powder by adopting liquid-phase ceramic precursor |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB477524A (en) * | 1936-06-29 | 1937-12-29 | Eastman Kodak Co | Improvements in and relating to colour photography |
| DE2523423A1 (en) * | 1975-02-03 | 1976-08-05 | Ppg Industries Inc | Refractory metal boride powders and the process for their manufacture |
| US4414188A (en) * | 1982-04-23 | 1983-11-08 | Aluminum Company Of America | Production of zirconium diboride powder in a molten salt bath |
| JPS62294435A (en) * | 1986-04-15 | 1987-12-21 | マ−チン・マリエツタ・コ−ポレ−シヨン | Cryogenic systesis |
| WO1996014268A1 (en) * | 1994-11-08 | 1996-05-17 | The Australian National University | Production of metal boride powders |
| WO2004041427A1 (en) * | 2002-11-08 | 2004-05-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Inorganic fine particles, inorganic raw material powder, and method for production thereof |
| CN102417188A (en) * | 2011-08-30 | 2012-04-18 | 中国科学院上海硅酸盐研究所 | Preparation method of submicron transition metal boride powder with low oxygen content |
| CN102464323A (en) * | 2010-11-04 | 2012-05-23 | 中国科学院过程工程研究所 | Method for preparing high-purity superfine zirconium boride powder by high-frequency plasma |
| CN103101922A (en) * | 2013-01-24 | 2013-05-15 | 浙江大学 | Preparation method of transition metal nano-boride |
| CN104211062A (en) * | 2014-09-05 | 2014-12-17 | 哈尔滨工业大学 | Preparation method of non-oxide eutectic ceramic amorphous powder via reaction spraying |
| CN105268449A (en) * | 2014-07-18 | 2016-01-27 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof in hydrodeoxygenation |
| CN107305838A (en) * | 2016-04-21 | 2017-10-31 | Asm Ip控股有限公司 | The deposition of metal boride and metal silicide |
| CN109821533A (en) * | 2019-02-25 | 2019-05-31 | 吉林大学 | A kind of transition metal boride catalyst, preparation method and applications |
| CN110156025A (en) * | 2019-05-27 | 2019-08-23 | 吉林大学 | A kind of preparation method of the metal silicide of pure phase |
| US20190393496A1 (en) * | 2018-06-21 | 2019-12-26 | Nanotek Instruments, Inc. | Method of extending cycle-life of a lithium metal secondary battery |
| CN111943218A (en) * | 2020-08-10 | 2020-11-17 | 中科合成油技术有限公司 | Preparation method of nano transition metal boride |
| CN112408410A (en) * | 2020-12-07 | 2021-02-26 | 郑州轻工业大学 | Method for preparing boride through low-temperature melting reaction, prepared boride and application of boride |
-
2021
- 2021-04-14 CN CN202110397867.5A patent/CN113104857B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB477524A (en) * | 1936-06-29 | 1937-12-29 | Eastman Kodak Co | Improvements in and relating to colour photography |
| DE2523423A1 (en) * | 1975-02-03 | 1976-08-05 | Ppg Industries Inc | Refractory metal boride powders and the process for their manufacture |
| US4414188A (en) * | 1982-04-23 | 1983-11-08 | Aluminum Company Of America | Production of zirconium diboride powder in a molten salt bath |
| JPS62294435A (en) * | 1986-04-15 | 1987-12-21 | マ−チン・マリエツタ・コ−ポレ−シヨン | Cryogenic systesis |
| US4751070A (en) * | 1986-04-15 | 1988-06-14 | Martin Marietta Corporation | Low temperature synthesis |
| WO1996014268A1 (en) * | 1994-11-08 | 1996-05-17 | The Australian National University | Production of metal boride powders |
| WO2004041427A1 (en) * | 2002-11-08 | 2004-05-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Inorganic fine particles, inorganic raw material powder, and method for production thereof |
| CN102464323A (en) * | 2010-11-04 | 2012-05-23 | 中国科学院过程工程研究所 | Method for preparing high-purity superfine zirconium boride powder by high-frequency plasma |
| CN102417188A (en) * | 2011-08-30 | 2012-04-18 | 中国科学院上海硅酸盐研究所 | Preparation method of submicron transition metal boride powder with low oxygen content |
| CN103101922A (en) * | 2013-01-24 | 2013-05-15 | 浙江大学 | Preparation method of transition metal nano-boride |
| CN105268449A (en) * | 2014-07-18 | 2016-01-27 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof in hydrodeoxygenation |
| CN104211062A (en) * | 2014-09-05 | 2014-12-17 | 哈尔滨工业大学 | Preparation method of non-oxide eutectic ceramic amorphous powder via reaction spraying |
| CN107305838A (en) * | 2016-04-21 | 2017-10-31 | Asm Ip控股有限公司 | The deposition of metal boride and metal silicide |
| US20190393496A1 (en) * | 2018-06-21 | 2019-12-26 | Nanotek Instruments, Inc. | Method of extending cycle-life of a lithium metal secondary battery |
| CN109821533A (en) * | 2019-02-25 | 2019-05-31 | 吉林大学 | A kind of transition metal boride catalyst, preparation method and applications |
| CN110156025A (en) * | 2019-05-27 | 2019-08-23 | 吉林大学 | A kind of preparation method of the metal silicide of pure phase |
| CN111943218A (en) * | 2020-08-10 | 2020-11-17 | 中科合成油技术有限公司 | Preparation method of nano transition metal boride |
| CN112408410A (en) * | 2020-12-07 | 2021-02-26 | 郑州轻工业大学 | Method for preparing boride through low-temperature melting reaction, prepared boride and application of boride |
Non-Patent Citations (4)
| Title |
|---|
| HUI CHEN等: ""Intermetallic borides: structures, synthesis and applications in electrocatalysis"", 《INORG. CHEM. FRONT》 * |
| SINA KHOSHSIMA ET.AL.: ""CoB-TiB2 crystalline powders: Synthesis, microstructural analysis and"", 《ADVANCED POWDER TECHNOLOGY》 * |
| YIPENG AN ET.AL.: ""MoB2:a new multifunctional transition metal diboride monolayer"", 《JONURNAL OF PHYSICS-CONDENSED MATTER》 * |
| 孙慧: "过渡金属硼化物粉体的制备", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114045546A (en) * | 2021-11-22 | 2022-02-15 | 安徽工业大学 | Method for preparing transition metal boride coating through fused salt in-situ synthesis and electrophoretic deposition |
| CN114045546B (en) * | 2021-11-22 | 2023-09-12 | 安徽工业大学 | Method for preparing transition metal boride coating by fused salt in-situ synthesis and electrophoretic deposition |
| CN114506851A (en) * | 2022-03-14 | 2022-05-17 | 浙江理工大学 | Room-temperature ferromagnetic semiconductor and preparation method and application thereof |
| CN114506851B (en) * | 2022-03-14 | 2023-08-18 | 浙江理工大学 | Room-temperature ferromagnetic semiconductor and preparation method and application thereof |
| CN114717591A (en) * | 2022-03-25 | 2022-07-08 | 吉林大学 | Boride and preparation method and application thereof, oxygen evolution catalyst and preparation method thereof |
| CN114717591B (en) * | 2022-03-25 | 2024-05-07 | 吉林大学 | Boride, preparation method and application thereof, oxygen evolution catalyst and preparation method thereof |
| CN114751753A (en) * | 2022-05-27 | 2022-07-15 | 中国科学院合肥物质科学研究院 | Method for preparing superfine ceramic powder by adopting liquid-phase ceramic precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113104857B (en) | 2022-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113104857B (en) | Low-temperature preparation method of transition metal boride | |
| CN109309214A (en) | The preparation method of carbon-coating nickel nanocomposite | |
| Ding et al. | The synthesis of titanium nitride whiskers on the surface of graphite by molten salt media | |
| Yuan et al. | A solid-state reaction route to prepare LaB6 nanocrystals in vacuum | |
| CN109437203B (en) | Preparation method of high-purity one-dimensional SiC nano material | |
| CN101857196B (en) | Method for preparing nano chrome/vanadium carbide composite powder | |
| Asgarian et al. | The effect of different sources of porous carbon on the synthesis of nanostructured boron carbide by magnesiothermic reduction | |
| CN113620712B (en) | High-entropy carbide ceramic nano powder and preparation method and application thereof | |
| CN108339562B (en) | Preparation method of iron ion doped carbon nitride nanotube and obtained product | |
| Zhang et al. | Morphology-controlled synthesis of Co3O4 crystals by soft chemical method | |
| Chen et al. | From high-yield Ti3AlCN ceramics to high-quality Ti3CNTx MXenes through eliminating Al segregation | |
| CN111039291A (en) | Method for preparing NbC and/or TaC powder in situ by molten salt disproportionation reaction | |
| WO2019227811A1 (en) | Ultrafine transition-metal boride powder, and preparation method therefor and application thereof | |
| CN110407213A (en) | One kind (Ta, Nb, Ti, V) C high entropy carbide nano powder and preparation method thereof | |
| CN106588018A (en) | Method for preparing superhigh temperature carbonized hafnium ceramic nano-powder | |
| Liu et al. | Fabrication of CdS-decorated mesoporous SiC hollow nanofibers for efficient visible-light-driven photocatalytic hydrogen production | |
| CN109499592B (en) | Preparation method of nanorod molybdenum carbide/molybdenum dioxide composite material | |
| CN114799191A (en) | Preparation method of rare earth oxide doped molybdenum-rhenium alloy powder | |
| Wang et al. | A universal method for the synthesis of refractory metal diborides | |
| CN114100648A (en) | Synthetic method of ZnMo-MOF-derived carbon-coated molybdenum carbide | |
| Hou et al. | Fabrication of TiO2/SiO2 hybrid fibers with tunable internal porous structures | |
| CN106549146A (en) | A kind of method that In-situ reaction prepares graphene-based lithium-rich manganic acid lithium electrode material | |
| CN110316752B (en) | Ytterbium oxychloride nanosheet and preparation method and application thereof | |
| CN112250080A (en) | Method for preparing refractory metal boride in two steps | |
| CN105692694B (en) | Ti3O5/TiO2The preparation method of mixed crystal nanofiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231011 Address after: 230000 Room 0103, Zone C, 2nd Floor, Building 3, Shuangfeng Zhigu Innovation and Entrepreneurship Technology Park, Northeast corner of Meichonghu Road and Wenming Road, Shuangfeng Economic Development Zone, Changfeng County, Hefei City, Anhui Province Patentee after: Hefei Conservation of Momentum Green Energy Co.,Ltd. Address before: 130012 No.2699 Qianjin Street, Changchun hi tech Industrial Development Zone, Changchun City, Jilin Province Patentee before: Jilin University |