CN115259201B - Preparation method of nano thorium dioxide - Google Patents

Preparation method of nano thorium dioxide Download PDF

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CN115259201B
CN115259201B CN202210891631.1A CN202210891631A CN115259201B CN 115259201 B CN115259201 B CN 115259201B CN 202210891631 A CN202210891631 A CN 202210891631A CN 115259201 B CN115259201 B CN 115259201B
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thorium
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thorium dioxide
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CN115259201A (en
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于婷
钱正华
刘小峰
乔延波
何辉
叶国安
李斌
卢宗慧
张烨
黄小红
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China Institute of Atomic of Energy
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors

Abstract

The application provides a preparation method of nano thorium dioxide, which comprises the steps of preparing solid powder by heating thorium nitrate, an organic ligand and N, N-dimethylformamide, soaking and washing the solid powder by using a low-boiling point organic solvent, filtering and drying to obtain a MOF precursor, and calcining the MOF precursor to obtain the nano thorium dioxide, wherein the organic ligand is selected from the group consisting of 1, 4-di (4-carboxyphenyl) benzene, 1,3, 5-tri (4-carboxyphenyl) benzene and 1,2,4, 5-tetra (4-carboxyphenyl) benzene. The thorium dioxide particles with nanometer size can be directly prepared by adopting the method.

Description

Preparation method of nano thorium dioxide
Technical Field
The application belongs to the technical field of nano materials, and relates to a preparation method of nano thorium dioxide.
Background
Nanoscale materials exhibit many physical and chemical properties that differ from bulk materials, and size limitations often lead to abrupt changes in the physical properties of the material, such as optical, electrical, magnetic, thermal, etc. From the following componentsThe nano material has a plurality of novel performances and has wide application space in the fields of national defense, energy, aerospace and the like. Thus, the preparation of actinide nano-oxides has important practical significance. Thorium dioxide (ThO) 2 ) As an actinide metal oxide, it is not only an important nuclear fuel, but also widely used in the fields of adsorption, catalysis, and the like.
At present, the preparation method of the nano thorium dioxide comprises the following steps: oxalic acid precipitation calcination, hydrothermal synthesis, molten salt method, and the like.
In the nuclear fuel cycle process, thorium dioxide is mainly prepared by adopting an oxalic acid precipitation calcination process: by converting the thorium nitrate solution into thorium oxalate and subsequently into thorium dioxide. The technological process comprises the steps of pretreatment of precipitation feed liquid, thorium oxalate precipitation, thorium oxalate filtration, thorium oxalate drying and roasting, thorium dioxide product pouring, weighing, packaging and the like. The whole process is complicated and inconvenient to operate, and can cause radioactive dust pollution and a large amount of thorium loss. In addition, thorium oxalate is usually precipitate with different sizes, and the thorium dioxide formed by roasting is difficult to reach the nano-scale, is uneven in particles and is easy to agglomerate and harden. If the nano-scale is to be achieved, grinding is needed, and radioactive aerosol is often generated when the nano thorium dioxide is prepared by grinding, so that potential safety hazards are caused.
CN 111439772a discloses a method for preparing nano thorium dioxide by mixing thorium nitrate solution and sodium hydroxide solution and then performing hydrothermal reaction, which avoids the process of converting thorium nitrate into thorium oxalate, directly prepares thorium dioxide, but still needs grinding, so there is still the danger of generating radioactive aerosol.
CN 113860350a discloses a method for directly preparing nano thorium dioxide with average particle size of 50-150 nm by dispersing thorium nitrate into molten salt and heating and reacting, which has simple operation and avoids grinding process, but requires high-temperature molten salt of lithium chloride and potassium chloride group, and a large amount of water is needed in post-treatment process to dissolve and remove lithium chloride and potassium chloride doped in cooling products, which is uneconomical and environment-friendly.
Accordingly, there is a need to provide an improved process for the preparation of nano thorium dioxide.
Disclosure of Invention
Accordingly, the present application is directed to a method for preparing nano thorium dioxide, which can solve at least some of the above problems.
The present disclosure provides a method for preparing a nano thorium dioxide, comprising heating thorium nitrate, an organic ligand and N, N-dimethylformamide to prepare solid powder, soaking and washing the solid powder with a low boiling point organic solvent, filtering, drying to obtain a MOF precursor, and calcining the MOF precursor to obtain the nano thorium dioxide, wherein the organic ligand is selected from the group consisting of 1, 4-di (4-carboxyphenyl) benzene, 1,3, 5-tri (4-carboxyphenyl) benzene and 1,2,4, 5-tetra (4-carboxyphenyl) benzene.
According to some embodiments of the disclosure, the thorium nitrate is thorium nitrate pentahydrate.
According to some embodiments of the disclosure, the molar ratio of the thorium nitrate to the organic ligand is from 1:1 to 1.2.
According to some embodiments of the present disclosure, the heating reaction is at a temperature of 100 to 130 ℃ for a period of 24 to 48 hours.
According to some embodiments of the present disclosure, the low boiling point organic solvent is selected from ethanol, methanol and tetrachloromethane, preferably ethanol.
According to some embodiments of the present disclosure, the soaking wash temperature is 20-25 ℃ and the duration is 3-6 hours.
According to some embodiments of the disclosure, the drying is performed under reduced pressure.
According to some embodiments of the present disclosure, the drying temperature is 60 to 100 ℃ and the duration is 2 to 4 hours.
According to some embodiments of the present disclosure, the calcination temperature is 500 to 800 ℃ and the duration is 6 to 10 hours.
According to some embodiments of the present disclosure, the MOF precursor is warmed to the calcination temperature at a rate of 5 to 10 ℃/min.
The present disclosure prepares nano thorium dioxide by first synthesizing a MOF precursor and then calcining the MOF precursor at 500-800 ℃ for 6-10 hours. The inventors found that by screening suitable MOF precursors and controlling the temperature and time of pyrolysis, nano thorium dioxide with average particle size between 10 and 200nm can be produced, and agglomeration among particles is significantly inhibited, and in addition the present disclosure achieves the following significant advances:
(1) Compared with a molten salt method, the scheme avoids using high-temperature molten salt, and reduces energy consumption and consumption of molten salt;
(2) Compared with an oxalic acid precipitation calcination method and a hydrothermal method, the scheme avoids a grinding process and reduces the generation of radioactive aerosol.
Drawings
FIG. 1 is an XRD pattern of nano-thorium dioxide prepared based on MOF precursors in examples 11-15;
FIG. 2 is a TEM image of nano-thorium dioxide prepared based on MOF precursors in example 11;
FIG. 3 is an XRD pattern of nano-thorium dioxide prepared based on MOF precursors in examples 21-25; and
fig. 4 is a TEM image of nano-thorium dioxide prepared based on the MOF precursor in example 21.
Detailed Description
The following description of the embodiments of the present disclosure will be made clearly and fully with reference to the embodiments of the present disclosure and the accompanying drawings, it being apparent that the described embodiments are only some, but not all, of the embodiments of the present disclosure. All other embodiments, which can be made by one of ordinary skill in the art without inventive effort, are within the scope of the present application based on the embodiments in this disclosure.
As described above, the present disclosure is directed to providing a method for preparing nano thorium dioxide based on a MOF precursor, specifically, a two-step method is used to prepare nano thorium dioxide, that is, a class of organic ligands is first used to synthesize the MOF precursor at normal pressure and mild temperature, and then the MOF precursor is calcined to obtain nano thorium dioxide. According to an embodiment of the present disclosure, wherein the synthesizing the MOF precursor comprises heating the reaction with thorium nitrate, an organic ligand and N, N-dimethylformamide to produce a solid powder, the calcining comprises a step of calcining at 500-800 ℃ for 6-10 hours to obtain nano thorium dioxide with uniform particles.
MOF precursors of thorium
The metal-organic framework (metal organic framework, MOF) is a coordination polymer crystal with a three-dimensional pore structure, and generally forms a crystal with a periodic network structure by self-assembling transition metal ions and organic ligands, has the advantages of high porosity, large specific surface area, adjustable pore channel shape and the like, and is an important novel porous material.
Thorium (thorium) belongs to the actinide group and is radioactive. Thorium has a predominantly oxidation state of +4, such as thorium nitrate (Th (NO 3 ) 4 ) Is very soluble in water and ethanol, has toxicity, and is slightly soluble in acetone and diethyl ether. +4 valent thorium shows high coordination number and diverse coordination environments, and some studies of MOFs of thorium have been reported, but no report of preparing nano thorium dioxide by MOFs of thorium has been reported. The inventors found that the MOF of thorium provided by the present disclosure, as a precursor for preparing nano thorium dioxide, is micron-sized crystals, and has relatively uniform particles, so that the precursor with uniform particle size can be utilized to prepare nano thorium dioxide with uniform particle size by pyrolysis.
According to a preferred embodiment, the MOF of thorium is prepared by a heated reaction of thorium nitrate, an organic ligand and N, N-Dimethylformamide (DMF), wherein DMF as a highly polar organic solvent, both dissolves the organic ligand and also dissolves small amounts of inorganic salts, is the most suitable MOF preparation solvent. The organic ligand is selected from the group consisting of 1, 4-bis (4-carboxyphenyl) benzene, 1,3, 5-tris (4-carboxyphenyl) benzene, and 1,2,4, 5-tetrakis (4-carboxyphenyl) benzene. The inventors have found that by using such ligands, micrometer sized, uniformly dispersed MOF particles can be obtained.
Preferably, the molar ratio of the thorium nitrate to the organic ligand is from 1:1 to 1.2, and beyond this range, one reactant cannot effectively participate in the reaction, resulting in a reduced yield. Preferably, the temperature of the heating reaction is 100-130 ℃ and the duration is 24-48 hours. Too short a time or too low a temperature to form MOFs of suitable particle size; too long or too high a temperature leads to an increase in energy consumption on the one hand and to an uneven particle size of the MOF on the other hand.
The solid powder produced by the heating reaction is a MOF containing DMF and preferably the DFM is washed by soaking in a low boiling organic solvent. The low boiling point organic solvent may be selected from ethanol, methanol and tetrachloromethane, preferably ethanol is used, which is more economical and environmentally friendly. The soaking and washing process is not particularly limited in the present disclosure, and preferably soaking and washing at 20 to 25 ℃ for 3 to 6 hours may be performed with appropriate stirring, or may be repeated several times to achieve a better substitution effect.
The MOF containing the low boiling organic solvent is preferably dried under reduced pressure at a temperature of 60 to 100℃for a period of 2 to 4 hours. The drying condition can ensure the stability of the MOF structure and realize the rapid drying of the MOF.
Preparation of thorium dioxide
Thorium dioxide (ThO) 2 ) Is a crystalline solid which can be identified according to its XRD standard pattern. Thorium dioxide can be used as an alloy additive and has application prospect in catalysis, radiocontrast agents and the like. Th-232 is not fissionable, but under neutron bombardment, it eventually produces fissionable U-233, which is converted to nuclear fuel. Thorium dioxide can be used as a ceramic fuel pellet in a nuclear reactor. In order to obtain high quality thorium dioxide ceramics, catalysts or radiocontrast agents, it is necessary to control the thorium dioxide to uniform nanoparticles.
According to a preferred embodiment, the present disclosure uses a suitable MOF precursor of thorium, which is calcined at a rate of 5-10 ℃/min up to 500-800 ℃ for 6-10 hours. Calcination not only burns off the residual, unwashed reactant thorium nitrate, etc., in the thorium dioxide powder, but also results in a denser crystal structure. Because the crystallinity of the MOF precursor is very high, the pyrolysis temperature range of 500-800 ℃ is relatively low, and agglomeration among particles is remarkably inhibited. The calcination time is too short, and impurities cannot be removed sufficiently to form a crystal structure; too long calcination time can lead to crystal decomposition and too small particles. The temperature rising rate is too slow, so that the process time and the energy consumption are increased; too fast a heating rate can exacerbate the irregularities in crystal morphology.
In the range of the dosage proportion and the reaction condition, the MOF precursor is synthesized by using an organic ligand, and then the MOF precursor is calcined to obtain the nano thorium dioxide, so that the nano thorium dioxide with the average particle size of 10-200 nm is prepared, and agglomeration among particles is obviously inhibited. In the scheme of the disclosure, the MOF precursor is prepared by reacting in a common reaction kettle at 100-130 ℃, so that the use of a molten salt reaction device or a high-pressure hydrothermal kettle is avoided, and the operation is simple and safe; in the scheme of the disclosure, the MOF precursor is calcined to directly obtain the nanoscale thorium dioxide, so that the grinding process is avoided, and the generation of radioactive aerosol is reduced.
The disclosure is further illustrated with reference to specific examples.
The purity of thorium nitrate pentahydrate in the following examples is not less than 95% by weight; the purity of the organic ligand is more than or equal to 95 weight percent.
Example 1
Step one, taking DMF as a solvent, reacting thorium nitrate pentahydrate and 1, 4-di (4-carboxyphenyl) benzene at a molar ratio of 1:1 at 100 ℃ for 24 hours, cooling to room temperature, filtering, washing the product with DMF, and drying to obtain white powder.
And step two, soaking and washing the white powder in ethanol at 25 ℃ for 3 hours, replacing an organic solvent DMF or redundant organic ligands in the pore canal with ethanol, and filtering to obtain a precipitate.
And thirdly, placing the precipitate in a vacuum drying oven at the temperature of 100 ℃ for drying for 2 hours under reduced pressure, and removing ethanol in the precipitate to obtain the MOF precursor.
And fourthly, placing the MOF precursor into an alumina crucible, placing the alumina crucible into a box-type resistance furnace, heating to 500 ℃ at a speed of 5 ℃/min, calcining for 6 hours, and obtaining the nano thorium dioxide after complete cooling.
Example 2
In this example, the same procedure as in example 1 was followed except that the molar ratio of thorium nitrate pentahydrate to 1, 4-bis (4-carboxyphenyl) benzene in step one was 1:1.2.
Example 3
In this example, the procedure of example 1 was followed except that step one was conducted at 100℃for 48 hours.
Example 4
In this example, the procedure of example 1 was followed except that step one was conducted at 130℃for 24 hours.
Example 5
In this example, the procedure of example 1 was followed except that step one was conducted at 130℃for 48 hours.
Example 6
In this example, the procedure of example 1 was followed except that in step four, the temperature was raised to 800℃at a rate of 10℃per minute, and calcination was conducted for 6 hours.
Example 7
In this example, the procedure of example 1 was followed except that in step four, the temperature was raised to 500℃at a rate of 5℃per minute, and the calcination was carried out for 10 hours.
Example 8
In this example, the procedure of example 1 was followed except that in step four, the temperature was raised to 800℃at a rate of 10℃per minute, and the calcination was carried out for 10 hours.
Example 9
In this example, the procedure of example 1 was followed except that the white powder was immersed in ethanol at 20℃for washing for 6 hours.
Example 10
In this example, the same procedure as in example 1 was followed except that the precipitate in step three was dried under reduced pressure in a vacuum oven at 60℃for 4 hours.
Example 11
Step one, taking DMF as a solvent, enabling the mole ratio of thorium nitrate pentahydrate and 1,3, 5-tri (4-carboxyphenyl) benzene to be 1:1, reacting for 24 hours at 100 ℃, cooling to room temperature, filtering, washing the product with DMF, and drying to obtain white powder.
And step two, soaking and washing the white powder in ethanol at 25 ℃ for 3 hours, replacing an organic solvent DMF or redundant organic ligands in the pore canal with ethanol, and filtering to obtain a precipitate.
And thirdly, placing the precipitate in a vacuum drying oven at the temperature of 100 ℃ for drying for 2 hours under reduced pressure, and removing ethanol in the precipitate to obtain the MOF precursor.
And fourthly, placing the MOF precursor into an alumina crucible, placing the alumina crucible into a box-type resistance furnace, heating to 500 ℃ at a speed of 5 ℃/min, calcining for 6 hours, and obtaining the nano thorium dioxide after complete cooling.
Example 12
In this example, the same procedure as in example 11 was followed except that the molar ratio of thorium nitrate pentahydrate to 1,3, 5-tris (4-carboxyphenyl) benzene in step one was 1:1.2.
Example 13
In this example, the procedure of example 11 was followed except that step one was conducted at 100℃for 48 hours.
Example 14
In this example, the procedure of example 11 was followed except that step one was conducted at 130℃for 24 hours.
Example 15
In this example, the procedure of example 11 was followed except that step one was conducted at 130℃for 48 hours.
Example 16
In this example, the procedure of example 11 was followed except that in step four, the temperature was raised to 800℃at a rate of 10℃per minute, and calcination was conducted for 6 hours.
Example 17
In this example, the procedure of example 11 was followed except that in step four, the temperature was raised to 500℃at a rate of 5℃per minute, and the calcination was performed for 10 hours.
Example 18
In this example, the procedure of example 11 was followed except that in step four, the temperature was raised to 800℃at a rate of 10℃per minute, and the calcination was performed for 10 hours.
Example 19
In this example, the procedure of example 11 was followed except that the white powder was immersed in ethanol at 20℃for washing for 6 hours.
Example 20
In this example, the same procedure as in example 11 was followed except that the precipitate in step three was dried under reduced pressure in a vacuum oven at 60℃for 4 hours.
Example 21
Step one, taking N, N-Dimethylformamide (DMF) as a solvent, reacting thorium nitrate pentahydrate and 1,2,4, 5-tetra (4-carboxyphenyl) benzene for 24 hours at 100 ℃ according to the molar ratio of 1:1, cooling to room temperature, filtering, washing the product with DMF, and drying to obtain white powder.
And step two, soaking and washing the white powder in ethanol at 25 ℃ for 3 hours, replacing an organic solvent DMF or redundant organic ligands in the pore canal with ethanol, and filtering to obtain a precipitate.
And thirdly, placing the precipitate in a vacuum drying oven at the temperature of 100 ℃ for drying for 2 hours under reduced pressure, and removing ethanol in the precipitate to obtain the MOF precursor.
And fourthly, placing the MOF precursor into an alumina crucible, placing the alumina crucible into a box-type resistance furnace, heating to 500 ℃ at a speed of 5 ℃/min, calcining for 6 hours, and obtaining the nano thorium dioxide after complete cooling.
Example 22
In this example, the same procedure is as in example 21 except that the molar ratio of thorium nitrate pentahydrate to 1,2,4, 5-tetrakis (4-carboxyphenyl) benzene is 1:1.2.
Example 23
In this example, the procedure of example 21 was followed except that step one was conducted at 100℃for 48 hours.
Example 24
In this example, the procedure of example 21 was followed except that step one was conducted at 130℃for 24 hours.
Example 25
In this example, the procedure of example 21 was followed except that step one was conducted at 130℃for 48 hours.
Example 26
In this example, the procedure of example 21 was followed except that in step four, the temperature was raised to 800℃at a rate of 10℃per minute, and calcination was conducted for 6 hours.
Example 27
In this example, the procedure of example 21 was followed except that in step four, the temperature was raised to 500℃at a rate of 5℃per minute, and the calcination was carried out for 10 hours.
Example 28
In this example, the procedure of example 21 was followed except that in step four, the temperature was raised to 800℃at a rate of 10℃per minute, and the calcination was carried out for 10 hours.
Example 29
In this example, the procedure of example 21 was followed except that the white powder was immersed in ethanol at 20℃for washing for 6 hours.
Example 30
In this example, the same procedure as in example 21 was followed except that the precipitate in step three was dried under reduced pressure in a vacuum oven at 60℃for 4 hours.
FIG. 1 is an XRD pattern of the nano-thorium dioxide products prepared in examples 11-15, showing that the characteristic peak-to-average ratio of the products to ThO 2 The peak positions of the standard patterns are identical, and diffraction peaks of other substances do not appear, which shows that the sample is a single ThO with high purity 2 。
FIG. 2 is a TEM image of thorium dioxide nano-particles prepared in example 11, in which ThO 2 The particle size distribution of the particles is between 10 and 50 nm.
FIG. 3 is an XRD pattern of the nano-thorium dioxide products prepared in examples 21-25, again as can be seen, the characteristic peak-to-average of the products is comparable to ThO 2 The peak positions of the standard patterns are identical, and diffraction peaks of other substances do not appear, which shows that the sample is a single ThO with high purity 2 。
FIG. 4 is a TEM image of thorium dioxide nano-particles prepared in example 21, in which ThO 2 The particle size distribution of the particles is between 10 and 200 nm.
The foregoing description of the embodiments of the present disclosure is provided for illustration only, and is not intended to limit the scope of the application, which is modified, substituted or directly/indirectly applied in other related technical fields under the inventive concept of the present disclosure, and is included in the scope of the application.

Claims (8)

1. A preparation method of nano thorium dioxide comprises the following steps:
thorium nitrate, organic ligand and N, N-dimethylformamide are heated to react to prepare solid powder,
soaking and washing the solid powder with a low boiling point organic solvent, filtering, drying to obtain a MOF precursor, and
calcining the MOF precursor to obtain the nano thorium dioxide,
wherein the organic ligand is selected from the group consisting of 1, 4-bis (4-carboxyphenyl) benzene, 1,3, 5-tris (4-carboxyphenyl) benzene and 1,2,4, 5-tetrakis (4-carboxyphenyl) benzene, the temperature of the heating reaction is 100-130 ℃, the duration is 24-48 hours, the calcining temperature is 500-800 ℃, the duration is 6-10 hours, and the MOF precursor is heated to the calcining temperature at a rate of 5-10 ℃/min.
2. The process of claim 1, wherein the thorium nitrate is thorium nitrate pentahydrate.
3. The preparation method according to claim 1 or 2, wherein the molar ratio of the thorium nitrate to the organic ligand is 1:1-1.2.
4. The production method according to claim 1 or 2, wherein the low boiling point organic solvent is selected from ethanol, methanol and tetrachloromethane.
5. The process according to claim 4, wherein the low boiling point organic solvent is ethanol.
6. The preparation method according to claim 1 or 2, wherein the soaking and washing temperature is 20-25 ℃ and the duration is 3-6 hours.
7. The production method according to claim 1 or 2, wherein the drying is performed under reduced pressure.
8. The preparation method of claim 7, wherein the drying temperature is 60-100 ℃ and the duration is 2-4 hours.
CN202210891631.1A 2022-07-27 2022-07-27 Preparation method of nano thorium dioxide Active CN115259201B (en)

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Publication number Priority date Publication date Assignee Title
CN107381616A (en) * 2017-09-15 2017-11-24 福州大学 A kind of method that active porous nano ceric oxide is prepared based on organic formwork
CN113248727A (en) * 2021-05-31 2021-08-13 中国原子能科学研究院 Thorium-based metal organic framework material and synthetic method thereof

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