CN108083315B - Preparation method of spherical thorium dioxide nano material with sheet surface structure and spherical thorium dioxide particles obtained by preparation method - Google Patents

Preparation method of spherical thorium dioxide nano material with sheet surface structure and spherical thorium dioxide particles obtained by preparation method Download PDF

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CN108083315B
CN108083315B CN201810130042.5A CN201810130042A CN108083315B CN 108083315 B CN108083315 B CN 108083315B CN 201810130042 A CN201810130042 A CN 201810130042A CN 108083315 B CN108083315 B CN 108083315B
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thorium dioxide
urea
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CN108083315A (en
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崔荣荣
窦强
刘艳成
王晨阳
程治强
李晴暖
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Shanghai Institute of Applied Physics of CAS
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/36—Spheres fragmented
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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Abstract

The invention provides a preparation method of a spherical thorium dioxide nano material with a sheet surface structure, which comprises the following steps: dissolving thorium nitrate in water to form a thorium nitrate solution; dissolving urea in water to form a urea solution; transferring the thorium nitrate solution and the urea solution into a reaction kettle, wherein the molar ratio of thorium to urea is 1: 1-10; placing the reaction kettle in a microwave reactor, selecting the reaction temperature of 120-; and drying the precipitate to obtain the spherical thorium dioxide nano material with the sheet surface structure. The invention also provides the spherical thorium dioxide particles prepared by the method. In a word, the preparation method provided by the invention has the advantages of simple process and good reproducibility, and the used raw materials are inorganic compounds, so that the preparation method is cheap and easy to obtain, low in cost, environment-friendly and easy for industrial production.

Description

Preparation method of spherical thorium dioxide nano material with sheet surface structure and spherical thorium dioxide particles obtained by preparation method
Technical Field
The invention belongs to the technical field of preparation processes of rare earth oxide materials with special morphologies, and particularly relates to a preparation method of a spherical thorium dioxide nano material with a flaky surface structure and spherical thorium dioxide particles obtained by the preparation method.
Background
The preparation method of the nanometer rare earth oxide material has various common hydrothermal methods, and is a liquid phase reaction with relatively high temperature and high pressure in a closed container, so that the material reacts, grows and nucleates at a certain temperature and pressure to prepare the nanometer material with special morphology. The material generally has the characteristics of high surface area, high activity and the like and is widely applied to the aspects of adsorption catalysis and the like. The nano thorium oxide also has the application, but the research on preparing the nano thorium oxide by using a hydrothermal method is less compared with other rare earth oxides at present.
At present, methods for preparing thorium oxide by using a hydrothermal method mainly comprise a common hydrothermal method and a special hydrothermal method. The common hydrothermal method generally has the reaction time of more than ten hours to several days except high temperature and high pressure; compared with the common hydrothermal method, the special hydrothermal method is adopted to add conditions such as a direct current electric field, a magnetic field, a microwave electromagnetic field and the like under the hydrothermal reaction condition, so that the conventional growth nucleation mode of the material can be changed easily, the nano material with the special morphology is prepared, and compared with the common hydrothermal method, the hydrothermal synthesis time can be shortened, and the reaction temperature can be reduced. The invention relates to spherical nano thorium dioxide prepared by a microwave-assisted hydrothermal method. In addition, in recent years, the preparation of nano thorium oxide by using special environment is also disclosed, such as the following documents: moeini M, Malekzadeh A, Ahmadi S J, et al, Synthesis of nanoparticles via the hydrothermal method in supercritical conditions [ J ]. Materials Letters,2012,81(11):99-101, but the synthesis temperature used in this method is 450 ℃ higher and the critical conditions are critical. The microwave hydrothermal method has the characteristics that the reaction time can be obviously shortened, the reaction temperature is reduced, so that the formation and the growth of crystal nuclei can be carried out at lower temperature and in shorter time in the hydrothermal process, the reduction of the reaction temperature and the reaction time limits the further growth of product microcrystal, and the preparation of the superfine powder material is facilitated. At present, no case of preparing the special-shaped nano thorium oxide by using a microwave-assisted hydrothermal method is reported.
Disclosure of Invention
In order to solve the problem of long time for preparing a precursor by a hydrothermal/solvothermal method, the invention aims to provide a preparation method of a spherical thorium dioxide nano material with a sheet-shaped surface structure and spherical thorium dioxide particles obtained by the preparation method.
The invention provides a preparation method of a spherical thorium dioxide nano material with a sheet surface structure, which comprises the following steps: s1, dissolving thorium nitrate in water to form a thorium nitrate solution; s2, dissolving urea in water to form a urea solution; s3, transferring the thorium nitrate solution and the urea solution into a reaction kettle, wherein the molar ratio of thorium to urea is 1: 1-10; s4, placing the reaction kettle in a microwave reactor, selecting the reaction temperature of 120-200 ℃, heating for reaction for 30-60min, and performing centrifugal separation on the microwave product obtained in the reaction kettle to obtain a precipitate; and S5, drying the precipitate to obtain the spherical thorium dioxide nano material with the flaky surface structure.
In particular, the thorium dioxide nano-material obtained by the preparation method has relatively uniform morphology and a flaky surface structure, which is completely different from the powder obtained by the conventional precipitation method. Moreover, the process of preparing thorium dioxide is shortened to dozens of minutes by the aid of microwaves in the step S4, so that pure phase is achieved in a short time, and the crystal form is good. Wherein, if the microwave time is too short, the crystal structure of the material is not good, and if the microwave time is too long, the crystal structure is easy to be damaged, and the microwave time is finally determined to be 30-60min after a plurality of experiments.
Preferably, the molar ratio of thorium to urea in step S3 is 2:3 or 3: 3.
Preferably, the reaction kettle in the step S3 is a 100ml polytetrafluoroethylene reaction kettle.
Preferably, the microwave power in step S4 is 400-1000W. Specifically, the reaction kettle in step S3 is placed in the microwave reactor after being sleeved in an outer tank, and at this time, a plurality of outer tanks may be placed in the microwave reactor, and of course, the power is set higher correspondingly as the number of tanks is larger. It will be appreciated that power is a temperature-dependent parameter and that microwave power needs to be increased in order to raise the temperature. Typically, at least 100W is required for one outer tank, and 4-16 tanks can be placed in the microwave reactor at a time.
The step S1 specifically includes: general formula Th (NO)3)4·6H2Dissolving O in deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution.
The step S2 specifically includes: adding CO (NH)2)2Dissolving in deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain uniform transparent solution.
It should be understood that the concentrations of the thorium nitrate solution and the urea solution are preferably not too low, otherwise the volumes are too large after the measurement. Generally, the total volume of the two mixed materials transferred into the reaction kettle does not exceed 1/3 of the volume of the reaction kettle.
The step S4 includes: washing the precipitate with absolute ethanol. Preferably, the precipitate is washed 2-3 times with absolute ethanol, centrifuged, and the ethanol rinse removed.
The step S5 specifically includes: drying the precipitate at 60-80 deg.C for 6-10 hr. It should be understood that the temperature is selected here because drying in the centrifuge tube prevents the centrifuge tube from deforming by burning, and can be over 100 ℃ and done in a shorter time if the batch is taken out and dried in a glass.
The preparation method further comprises the step S6 of roasting the spherical thorium dioxide nano material in a muffle furnace at 350-600 ℃ for 60-120 min in an air atmosphere.
The invention also provides the spherical thorium dioxide particles prepared by the method.
The diameter of the spherical thorium dioxide particles is about 10-80 nm. It should be understood that the diameter of the spherical thorium dioxide is a distribution range which can be directly obtained by a TEM spectrum.
In a word, the preparation method provided by the invention has the advantages of simple process and good reproducibility, and the used raw materials are inorganic compounds, so that the preparation method is cheap and easy to obtain, low in cost, environment-friendly and easy for industrial production. Moreover, the thorium dioxide particles have a flaky spherical shape on the surface, and the stacking of the flakes enables the thorium dioxide particles to have larger specific surface area and porosity than common thorium dioxide powder, so that the thorium dioxide particles can be well applied to the aspects of adsorption and catalysis, and lay a good foundation for the research, application and development of functional materials.
Drawings
Fig. 1 shows the preparation process according to the invention, the molar ratio of thorium: thorium dioxide (ThO) obtained with urea 2:3 (or 1:1.5) at different temperatures2) An X-ray diffractometer (XRD) spectrum of the powder;
FIG. 2 shows the preparation process according to the invention, at 180 ℃ and 1h, but with the differenceThorium dioxide (ThO) of materials prepared with a molar ratio of thorium to urea (neither calcined)2) XRD pattern of the powder;
FIG. 3 shows thorium dioxide (ThO) prepared at 200 ℃ and a thorium-urea molar ratio of 1:1.5 and at different reaction times according to the preparation method of the invention2) XRD pattern of the powder;
fig. 4a shows the preparation process according to the invention, at 180 ℃, 1h, thorium: urea molar ratio of 2: thorium dioxide (ThO) obtained at 32) A Transmission Electron Microscope (TEM) image of the powder;
fig. 4b shows the preparation process according to the invention, at 180 ℃, 1h, thorium: urea molar ratio 3: thorium dioxide (ThO) obtained at 32) A Transmission Electron Microscope (TEM) image of the powder;
FIG. 4c is an enlarged view of a sample prepared under the same conditions as for thorium dioxide in FIG. 4 b;
fig. 4d is a graph showing the preparation process according to the invention, at 180 ℃, 1h, thorium: urea molar ratio 3: thorium dioxide (ThO) obtained at 32) The picture of the edge of the thorium dioxide flake nanosphere and the selected area diffraction pattern (SAED) of the thorium dioxide flake nanosphere observed under a high-resolution transmission electron microscope (HRTEM) of the powder are shown in an inset picture;
fig. 5a-5 e show the preparation process according to the invention, with a reaction time of 1h (0.5 h at 120 ℃), thorium: when the molar ratio of urea is 2:3, obtaining the nano thorium dioxide (ThO) at different reaction temperatures (120-200℃)2) A TEM image of (B);
FIG. 5f is an HR-TEM image of the arrowed region of FIG. 5e with a selected area diffractogram (SAED) shown as an inset, from which the ring plot shows that the product is also polycrystalline;
fig. 6a-6 e show the preparation process according to the invention, 180 ℃, different Th: TEM image of the product after 1 hour of hydrothermal reaction at urea ratio (1: 1-1: 7);
fig. 6f shows a preparation process according to the invention, 200 ℃, Th: the ratio of urea is 1:10, TEM images of products of hydrothermal reaction for 1 hour show that the nano thorium dioxide obtained in the different ratio ranges is also in a flaky surface sphere structure, and the diameter of the sphere is in a range of about 10-80nm as shown in the appearance of FIGS. 6 a-f.
Fig. 7a shows a preparation process according to the invention, 120 ℃, Th: TEM image of product of 1:10 urea ratio and 30min hydrothermal reaction;
fig. 7b shows a preparation process according to the invention, 180 ℃, Th: TEM image of product of 1:1.5 urea ratio and 30min hydrothermal reaction;
fig. 7c shows a preparation process according to the invention, 200 ℃, Th: TEM image of product of 1:1.5 urea ratio and 30min hydrothermal reaction.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and preferred embodiments thereof so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following embodiments.
Example 1
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, mixing 2mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 3mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 180 ℃ and the microwave power of 600W, and heating for reaction for 60 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 2 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 60 ℃ for 8 hours to remove water and ethanol to obtain the spherical thorium dioxide nano material with the sheet surface structure;
s6, the spherical thorium dioxide nano material obtained in the step S5 is roasted for 60min in the air atmosphere at 500 ℃ in a muffle furnace, and spherical nano thorium dioxide white powder with a relatively pure sheet surface structure (observed under a TEM lens, see figure 4a) is obtained. In addition, the calcination in this step can not only burn off the uncleaned reactant thorium nitrate and the like remaining in the thorium dioxide powder, but also make the crystal structure denser. That is, the calcined micro-crystalline form is better, and the calcined peak intensity is stronger as seen by the XRD pattern, which shows a sharper peak shape (see the apparent higher peak intensities at 180 and 200 ℃ C. in FIG. 1). It is noteworthy that if the firing temperature is too high, it may have an effect on the morphology and may cause partial sphere breakage. It is understood that spherical thorium dioxide nanomaterials with sheet-like surface structures can be prepared without roasting, and actually, the spherical thorium dioxide nanomaterials with the sheet-like surface structures are not roasted, and are shown in TEM morphology photographs in FIGS. 4 a-4 d, 5a-5f, 6a-6f and 7a-7 c.
Example 2
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, mixing 2mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 3mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 200 ℃ and the microwave power of 400W, and heating for reaction for 60 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
and S5, drying the precipitate obtained in the step S4 at 60 ℃ for 8 hours to obtain the spherical thorium dioxide nano material with the platy surface structure (observed under a TEM lens, and shown in a figure 5 e).
Example 3
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, adding 3mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 3mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 180 ℃ and the microwave power of 800W, and heating for reaction for 60 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 60 ℃ for 10 hours to obtain the spherical thorium dioxide nano-material with the platy surface structure (observed under a TEM lens, see figure 4 b).
Example 4
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, adding 1mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 10mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 200 ℃ and the microwave power of 600W, and heating for reaction for 60 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 60 ℃ for 8 hours to obtain the spherical thorium dioxide nano-material with the platy surface structure (observed under a TEM lens, see figure 6 f).
Example 5
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, mixing 2mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 3mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 120 ℃ and the power of 600W, and heating for reaction for 60 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 60 ℃ for 6 hours to obtain the spherical thorium dioxide nano-material with the platy surface structure (observed under a TEM lens, see figure 5 a).
Example 6
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, adding 1mmol of Th (NO)3)4·6H2Dissolving O in 10ml deionized water under stirring or ultrasonic wave at room temperature, and stirring to obtain uniform transparent solutionThe solution of (1);
s2, adding 7mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 180 ℃ and the microwave power of 800W, and heating for reaction for 60 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 60 ℃ for 8 hours to obtain the spherical thorium dioxide nano-material with the flaky surface structure (the spherical thorium dioxide nano-material is ground into powder by using a mortar and then observed by a TEM lens, and the powder is shown in figure 6 e).
Example 7
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, adding 1mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 10mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 120 ℃, the microwave power of 800W, and heating for reaction for 30 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 80 ℃ for 8 hours to obtain the spherical thorium dioxide nano-material with the platy surface structure (observed under a TEM lens, see figure 7 a).
Example 8
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, adding 1mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 1.5mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 180 ℃ and the microwave power of 800W, and heating for reaction for 30 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 80 ℃ for 8 hours to obtain spherical thorium dioxide white powder of the spherical thorium dioxide nano material with the flaky surface structure (observed under a TEM lens, see figure 7 b).
Example 9
A preparation method of a spherical thorium dioxide nano material with a sheet surface structure comprises the following steps:
s1, adding 1mmol of Th (NO)3)4·6H2Dissolving O in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to form a uniform and transparent solution;
s2, adding 1.5mmol of urea (CO (NH)2)2) Dissolving in 10ml of deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain a uniform and transparent solution;
s3, transferring the thorium nitrate solution in the step S1 and the urea solution in the step S2 into a clean 100mL polytetrafluoroethylene reaction kettle, screwing a kettle cover tightly, and sleeving an outer tank;
s4, placing the reaction kettle in the step S3 in a microwave reactor, selecting the reaction temperature of 200 ℃ and the microwave power of 800W, and heating for reaction for 30 min; after the reaction is finished, cooling, collecting the microwave product, performing centrifugal separation to obtain a precipitate, and washing for 3 times by using absolute ethyl alcohol;
s5, drying the precipitate obtained in the step S4 at 80 ℃ for 8 hours to obtain the spherical thorium dioxide nano-material with the platy surface structure (observed under a TEM lens, see figure 7 c).
As shown in figure 1, XRD patterns of substances obtained by reaction at 120, 140, 160, 180 and 200 ℃ for 1h are all equal to those of ThO2The standard card (42-1462) is fitted, and the positions and kinds of crystal faces are marked by broken lines according to the information provided by the standard card. That is, the positions and relative intensities of diffraction peaks obtained by the preparation method are consistent with JCPDS (Joint Committee for powder diffraction standards) card (42-1462), and no other diffraction peaks exist in an XRD (X-ray diffraction) spectrum, which indicates that the thorium dioxide phase prepared by the method is pure.
As shown in FIG. 3, thorium dioxide obtained at different raw material ratios and different time periods is also similar to ThO2Standard card (42-1462) was identical, indicating that pure phase thorium dioxide was obtained under the above conditions. Particularly, TEM room temperature tests show that the particle diameter of the thorium dioxide flaky spheres prepared by the microwave-assisted hydrothermal method is 10-50 nm; HR-TEM test results show that thorium dioxide prepared by a microwave-assisted hydrothermal method is of a polycrystalline structure.
As shown in the TEM images of the nano thorium dioxide obtained by shortening the hydrothermal time to 30min under the preferred conditions shown in FIGS. 4a to 4d, different temperatures shown in FIGS. 5a to 5f, different raw material ratios shown in FIGS. 6a to 6f and FIGS. 7a to 7c, the following results can be obtained: thorium dioxide obtained by the method is of a spherical structure with a flaky surface with the diameter of 10-80nm, and the inter-lamellar pores are obvious; wherein, fig. 4d and 5f are pictures of the edges of the nano-sphere with the thorium dioxide sheet-like surface structure observed under a high-resolution transmission electron microscope (HRTEM) and a selected area diffraction pattern (SAED) thereof are shown in an inset, and the diffraction pattern can be seen in the figures as a ring shape, so that the prepared thorium dioxide is a polycrystalline crystal.
The above embodiments are only some of the embodiments of the present invention, and are not intended to limit the scope of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.

Claims (5)

1. A preparation method of spherical thorium dioxide particles with a sheet surface structure is characterized by comprising the following steps:
s1, converting Th (NO)3)4·6H2Dissolving O in the deionized water under stirring at room temperature or under ultrasonic wave, and stirring to form a uniform and transparent thorium nitrate solution;
s2, adding CO (NH)2)2Dissolving in deionized water under stirring or ultrasonic treatment at room temperature, and stirring to obtain uniform and transparent urea solution;
s3, transferring the thorium nitrate solution and the urea solution into a reaction kettle, wherein the molar ratio of thorium to urea is 1: 1-10;
s4, placing the reaction kettle in a microwave reactor, selecting the microwave power of 400-;
and S5, drying the precipitate to obtain spherical thorium dioxide particles with a flaky surface structure and the diameter of 10-80 nm.
2. The method for preparing a composite material according to claim 1, wherein the step S4 includes: washing the precipitate with absolute ethanol.
3. The preparation method according to claim 1, wherein the step S5 specifically comprises: drying the precipitate at 60-80 deg.c for 6-10 hr.
4. The preparation method according to claim 1, further comprising a step S6 of roasting the spherical thorium dioxide particles in a muffle furnace at 350-600 ℃ for 60-120 min in an air atmosphere.
5. Spherical thorium dioxide particles obtained by the preparation process according to any one of claims 1 to 4.
CN201810130042.5A 2018-02-08 2018-02-08 Preparation method of spherical thorium dioxide nano material with sheet surface structure and spherical thorium dioxide particles obtained by preparation method Active CN108083315B (en)

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