CN108083315A - A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure and thus obtained spherical thorium anhydride particle - Google Patents
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure and thus obtained spherical thorium anhydride particle Download PDFInfo
- Publication number
- CN108083315A CN108083315A CN201810130042.5A CN201810130042A CN108083315A CN 108083315 A CN108083315 A CN 108083315A CN 201810130042 A CN201810130042 A CN 201810130042A CN 108083315 A CN108083315 A CN 108083315A
- Authority
- CN
- China
- Prior art keywords
- thorium
- preparation
- spherical
- urea
- solution
- 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
Classifications
-
- 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
- C01F15/00—Compounds of thorium
-
- 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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/36—Spheres fragmented
-
- 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)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure, includes the following steps：Thorium nitrate is dissolved in the water to form thorium nitrate solution；Urea is dissolved in the water to form urea solution；The thorium nitrate solution and the urea solution are transferred in reaction kettle, wherein, the molar ratio of thorium and urea is 1:1~10；The reaction kettle is placed in microwave reactor, selects reaction temperature as 120 200 DEG C, 30 60min are reacted in heating, and the microwave product obtained in reaction kettle is centrifuged to obtain sediment；The dry sediment, obtains the spherical thorium anhydride nano material of sheet surface structure.The present invention also provides a kind of spherical thorium anhydride particles being prepared according to the above method.In short, preparation in accordance with the present invention is not only simple for process but also favorable reproducibility, and raw materials used is inorganic compound, and cheap and easy to get, cost is relatively low, environmental-friendly and be easy to industrialized production.
Description
Technical field
The invention belongs to special appearance rare earth oxide material fabricating technology fields, relate more specifically to a kind of sheet table
The preparation method of the spherical thorium anhydride nano material of face structure and thus obtained spherical thorium anhydride particle.
Background technology
There are many preparation methods of oxide nano rare earth material, common hydro-thermal method, is relatively high in closed container
The liquid phase reactor of warm high pressure makes material react, grow under certain temperature, pressure, is nucleated to prepare the nanometer material of special appearance
Material.Such material typically is provided with the features such as high surface area, high activity and is widely used in adsoption catalysis etc..Nano oxidized thorium
With above application, but the research for preparing nano oxidized thorium using hydro-thermal method at present is less with respect to other rare earth oxides.
Mainly there are common hydro-thermal method and special hydro-thermal method with the method that hydro-thermal method prepares thorium oxide at present.Common hydro-thermal method is removed
Outside high temperature and pressure, General reactions longer ten a few houres differed by several days；It is outer under hydrothermal reaction condition using special hydro-thermal method
The relatively common hydro-thermal method of the conditions such as DC electric field, magnetic field, microwave electromagnetic field is added to be easier to change the routine growth nucleation side of material
Formula, is made the nano material of special appearance, and can reduce the hydrothermal synthesis time compared to common hydro-thermal method, reduces reaction temperature
Degree.The present invention is exactly the spherical nanometer titanium dioxide thorium prepared using microwave radiation technology hydro-thermal method.In addition also have in recent years using special
Environment prepares nano oxidized thorium, such as document：Moeini M,Malekzadeh A,Ahmadi S J,et al.Synthesis
of thoria nanoparticles via the hydrothermal method in supercritical
condition[J]. Materials Letters,2012,81(11):Super critical condition hydrothermal method system is used in 99-101
Standby, but the synthesis temperature used in this method is 450 DEG C higher, and the requirement to critical condition is harsh.And use microwave
The characteristics of hydro-thermal is can to substantially reduce the reaction time and reduce reaction temperature, thus can be with lower temperature in water-heat process
Degree and shorter time carry out the formation and growth of nucleus, the reduction of reaction temperature and time, limit product micromeritics into
One step-length is big, is conducive to prepare superfine powdery material.And it at present, has not been reported and prepares special form using microwave radiation technology hydro-thermal method
The case of the nano oxidized thorium of looks.
The content of the invention
In order to solve the problems, such as that it is longer that the hot method of hydrothermal/solvent prepares the presoma time, the present invention is intended to provide a kind of sheet
The preparation method of the spherical thorium anhydride nano material of surface texture and thus obtained spherical thorium anhydride particle.
The present invention provides a kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure, including walking as follows
Suddenly：Thorium nitrate is dissolved in the water to form thorium nitrate solution by S1；Urea is dissolved in the water to form urea solution by S2；S3, by described in
Thorium nitrate solution and the urea solution are transferred in reaction kettle, wherein, the molar ratio of thorium and urea is 1:1~10；S4, will be described anti-
Kettle is answered to be placed in microwave reactor, selects reaction temperature as 120-200 DEG C, 30-60min is reacted in heating, is obtained in reaction kettle
Microwave product is centrifuged to obtain sediment；S5, the dry sediment, obtains the spherical titanium dioxide of sheet surface structure
Thorium nano material.
Particularly, the thorium anhydride nano material that preparation in accordance with the present invention obtains have relatively uniform pattern and
With sheet surface structure, the powder obtained with the conventional precipitation method is entirely different.Moreover, pass through the microwave radiation technology in step S4
The process for preparing thorium anhydride is shortened into dozens of minutes, so as to reach pure phase in the short period of time, and crystal form is preferable.Its
In, the microwave time, material crystal structure was not grown also if too short, and if the time is too long, crystal structure is easy
It is destroyed, finally determine that the microwave time is 30-60min after many experiments of the present invention.
Preferably, the molar ratio of the thorium in step S3 and urea is 2:3 or 3:3.
Preferably, the reaction kettle in step S3 is 100ml polytetrafluoro reaction kettles.
Preferably, the microwave power in step S4 is 400-1000W.Specifically, the reaction kettle in step S3 is being inserted in
It is placed in one outer tank in microwave reactor, at this time can be by multiple outer tanks as in microwave reactor, certainly, tank number is more
If, power just correspondingly sets height a bit.It is appreciated that power is the parameter being temperature dependent, so that just raising temperature needs
Improve microwave power.In general, an outer tank needs at least 100W, 4-16 tanks can be once inserted in microwave reactor.
The step S1 is specially：By Th (NO3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in deionized water, stir
Mix the solution to form homogeneous transparent.
The step S2 is specially：By CO (NH2)2Be stirred at room temperature or ultrasound under be dissolved in from water water, stirring is formed
The solution of homogeneous transparent.
It should be understood that the concentration of the thorium nitrate solution and urea solution had better not be too low, volume is too big after otherwise measuring.It is logical
Often so that the mixed total volume being transferred in reaction kettle of the two is no more than the 1/3 of reaction kettle volume.
The step S4 includes：The sediment is washed using absolute ethyl alcohol.Preferably, described in being washed using absolute ethyl alcohol
Sediment 2-3 times after centrifugation, removes ethanol rinse.
The step S5 is specially：When by the sediment, drying 6-10 is small at 60-80 DEG C.It should be understood that it selects herein
It selects the temperature to determine to prevent centrifuge tube from crumpling because of dry in centrifuge tube, if batch takes out product simultaneously
Drying in glassware is placed in, can also be completed more than 100 DEG C and within the shorter time.
The preparation method further includes step S6, by the spherical thorium anhydride nano material in Muffle furnace 350~600
60~120min is roasted under DEG C air atmosphere.
The present invention also provides a kind of spherical thorium anhydride particles being prepared according to the above method.
The diameter of the spherical thorium anhydride particle is about 10~80nm.It should be understood that the diameter of the spherical thorium anhydride
For distribution, can be directly obtained by TEM spectrograms.
In short, preparation in accordance with the present invention is not only simple for process but also favorable reproducibility, and raw materials used is inorganic
Compound, cheap and easy to get, cost is relatively low, environmental-friendly and be easy to industrialized production.Moreover, the thorium anhydride particle of the present invention is
The spherical morphology of surface platelets, the stacking of sheet make it have larger specific surface area and hole than common thorium anhydride powder
Rate, therefore may have good application in terms of absorption and catalysis, establish good base for the research application and development of functional material
Plinth.
Description of the drawings
Fig. 1 shows preparation in accordance with the present invention, molar ratio thorium：Urea=2:3 (or 1:1.5) in different temperatures when
Under obtained thorium anhydride (ThO2) powder x-ray diffractometer (XRD) spectrogram；
Fig. 2 shows preparation in accordance with the present invention, and at 180 DEG C, when reacting 1h, prepared by different thoriums, urea mol ratio
Thorium anhydride (the ThO of material (not roasting)2) powder XRD spectrum；
Fig. 3 shows preparation in accordance with the present invention, at 200 DEG C, thorium, urea mol ratio 1:When 1.5, during different reactions
Between the lower thorium anhydride (ThO prepared2) powder XRD spectrum；
Fig. 4 a show preparation in accordance with the present invention, at 180 DEG C, 1h, thorium：Urea mol ratio is 2：Two obtained when 3
Thorium oxide (ThO2) powder transmission electron microscope (TEM) figure；
Fig. 4 b show preparation in accordance with the present invention, at 180 DEG C, 1h, thorium：Urea mol ratio is 3：Two obtained when 3
Thorium oxide (ThO2) powder transmission electron microscope (TEM) figure；
Fig. 4 c are the sample enlarged drawings under the similary preparation condition of thorium anhydride in same Fig. 4 b；
Fig. 4 d are to show preparation in accordance with the present invention, at 180 DEG C, 1h, thorium：Urea mol ratio is 3：It is obtained when 3
Thorium anhydride (ThO2) powder high resolution transmission electron microscopy (HRTEM) under the thorium anhydride flake nano ball side observed
The picture and its selected diffraction figure (SAED) of edge are shown in illustration；
Fig. 5 a- Fig. 5 e show preparation in accordance with the present invention, and the reaction time is 1h (120 DEG C are 0.5h), thorium：
Urea mol ratio is 2:When 3, at a temperature of differential responses (120 DEG C -200 DEG C), obtained nanometer titanium dioxide thorium (ThO2) TEM figure；
Fig. 5 f are that the HR-TEM figures in arrow region in Fig. 5 e and its selected diffraction figure (SAED) are shown in illustration, can from cricoid figure
To learn that product is also polycrystalline structure；
Fig. 6 a- Fig. 6 e show preparation in accordance with the present invention, 180 DEG C, different Th：Urea ratio (1:1~1:7), water
Product TEM figures when thermal response 1 is small；
Fig. 6 f show preparation in accordance with the present invention, 200 DEG C, Th：Urea ratio is 1:10, when hydro-thermal reaction 1 is small
Product TEM schemes, and can be seen that the nanometer titanium dioxide thorium obtained in the range of more than different proportion also all from the pattern in Fig. 6 a~f
It is schistose surface sphere structure, sphere diameter size is also in the range of about 10-80nm.
Fig. 7 a show preparation in accordance with the present invention, 120 DEG C, Th：Urea ratio is 1:10, hydro-thermal reaction 30min's
Product TEM schemes；
Fig. 7 b show preparation in accordance with the present invention, 180 DEG C, Th：Urea ratio is 1:1.5, hydro-thermal reaction 30min's
Product TEM schemes；
Fig. 7 c show preparation in accordance with the present invention, 200 DEG C, Th：Urea ratio is 1:1.5, hydro-thermal reaction 30min's
Product TEM schemes.
Specific embodiment
Below in conjunction with the accompanying drawings and presently preferred embodiments of the present invention is described in detail the present invention, so that people in the art
Member more fully understands the present invention, but the invention is not limited in following embodiments.
Embodiment 1
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 2mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 3mmol2)2) be stirred at room temperature or ultrasound under be dissolved in the going from water water of 10ml, stirring
It, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 180 DEG C, and microwave power is
600W, heating reaction 60min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 2 times；
S5 to remove water and ethyl alcohol when drying 8 is small at 60 DEG C by the sediment of gained in step S4, obtains schistose surface
The spherical thorium anhydride nano material of structure；
S6 roasts the spherical thorium anhydride nano material of gained in step S5 under 500 DEG C of air atmospheres of Muffle furnace
60min obtains the spherical nanometer titanium dioxide thorium white powder of purer sheet surface structure (the saturating Microscopic observations of TEM, see Fig. 4 a)
End.Moreover, the roasting of this step not only can with remaining not clean reactant thorium nitrate etc. in burning-off thorium anhydride powder, and
And make crystal structure finer and close.That is, baked microcosmic crystal form is more preferable, from XRD spectrum it can be seen that the peak intensity burnt
It spends stronger, it is more sharp (see the baked apparent peak intensity higher of 180 and 200 DEG C in Fig. 1) to show as peak shape.
Wherein it is worth noting that, if calcination temperature is too high to have an impact to pattern, part sphere may be made damaged.It can manage
The spherical thorium anhydride nano material of sheet surface structure can equally be made without roasting for solution, in fact, Fig. 4 a- Fig. 4 d,
Shown in TEM pattern photos in Fig. 5 a- Fig. 5 f, Fig. 6 a- Fig. 6 f, Fig. 7 a- Fig. 7 c is the sheet surface structure not roasted
Spherical thorium anhydride nano material.
Embodiment 2
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 2mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 3mmol2)2) be stirred at room temperature or ultrasound under be dissolved in the going from water water of 10ml, stirring
It, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 200 DEG C, and microwave power is
400W, heating reaction 60min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 3 times；
S5 when drying 8 is small at 60 DEG C by the sediment of gained in step S4, obtains the spherical dioxy of sheet surface structure
Change thorium nano material (the saturating Microscopic observations of TEM, see Fig. 5 e).
Embodiment 3
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 3mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 3mmol2)2) be stirred at room temperature or ultrasound under be dissolved in the going from water water of 10ml, stirring
It, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 180 DEG C, and microwave power is
800W, heating reaction 60min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 3 times；
S5 when drying 10 is small at 60 DEG C by the sediment of gained in step S4, obtains spherical the two of sheet surface structure
Thorium oxide nano material (the saturating Microscopic observations of TEM, see Fig. 4 b).
Embodiment 4
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 1mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 10mmol2)2) be stirred at room temperature or ultrasound under be dissolved in the going from water water of 10ml, stirring
It, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 200 DEG C, and microwave power is
600W, heating reaction 60min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 3 times；
S5 when drying 8 is small at 60 DEG C by the sediment of gained in step S4, obtains the spherical dioxy of sheet surface structure
Change thorium nano material (the saturating Microscopic observations of TEM, see Fig. 6 f).
Embodiment 5
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 2mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 3mmol2)2) be stirred at room temperature or ultrasound under be dissolved in the going from water water of 10ml, stirring
It, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 120 DEG C, power 600W,
Heating reaction 60min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use absolute ethyl alcohol
Washing 3 times；
S5 when drying 6 is small at 60 DEG C by the sediment of gained in step S4, obtains the spherical dioxy of sheet surface structure
Change thorium nano material (the saturating Microscopic observations of TEM, see Fig. 5 a).
Embodiment 6
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 1mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 7mmol2)2) be stirred at room temperature or ultrasound under be dissolved in the going from water water of 10ml, stirring
It, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 180 DEG C, and microwave power is
800W, heating reaction 60min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 3 times；
S5 when drying 8 is small at 60 DEG C by the sediment of gained in step S4, obtains the spherical dioxy of sheet surface structure
Change thorium nano material (using the finely ground TEM lens inspections after being pelletized powder samples of mortar, seeing Fig. 6 e).
Embodiment 7
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 1mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 10mmol2)2) be stirred at room temperature or ultrasound under be dissolved in the going from water water of 10ml, stirring
It, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 120 DEG C, and microwave power is
800W, heating reaction 30min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 3 times；
S5 when drying 8 is small at 80 DEG C by the sediment of gained in step S4, obtains the spherical dioxy of sheet surface structure
Change thorium nano material (the saturating Microscopic observations of TEM, see Fig. 7 a).
Embodiment 8
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 1mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 1.5mmol2)2) be stirred at room temperature or ultrasound under be dissolved in 10ml and go, from water water, to stir
It is mixed, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 180 DEG C, and microwave power is
800W, heating reaction 30min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 3 times；
S5 when drying 8 is small at 80 DEG C by the sediment of gained in step S4, obtains the spherical dioxy of sheet surface structure
Change the spherical nanometer titanium dioxide thorium white powder of thorium nano material (the saturating Microscopic observations of TEM, see Fig. 7 b).
Embodiment 9
A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure is to carry out as steps described below：
S1, by the Th (NO of 1mmol3)4·6H2O be stirred at room temperature or ultrasound under be dissolved in the deionized water of 10ml, stir
It is mixed, forms the solution of homogeneous transparent；
S2, by the urea (CO (NH of 1.5mmol2)2) be stirred at room temperature or ultrasound under be dissolved in 10ml and go, from water water, to stir
It is mixed, forms the solution of homogeneous transparent；
It is anti-to be transferred to clean 100mL polytetrafluoros by S3 for urea solution in thorium nitrate solution and step S2 in step S1
It answers and kettle cover is screwed in kettle, put on outer tank；
Reaction kettle in step S3 is placed in microwave reactor by S4, selects reaction temperature as 200 DEG C, and microwave power is
800W, heating reaction 30min；After completion of the reaction, cool down, collect microwave product and be centrifuged to obtain sediment, and use nothing
Water-ethanol washs 3 times；
S5 when drying 8 is small at 80 DEG C by the sediment of gained in step S4, obtains the spherical dioxy of sheet surface structure
Change thorium nano material (the saturating Microscopic observations of TEM, see Fig. 7 c).
As shown in Figure 1, the obtained substance XRD collection of illustrative plates of 1h is reacted at 120,140,160,180,200 DEG C and ThO2Mark
Quasi- card (42-1462) matches, and is being schemed crystal plane therein and species dotted line according to the information that standard card provides
In mark.That is, diffraction maximum position that preparation in accordance with the present invention obtains and relative intensity with JCPDS (powder
Diffraction standard joint committee) card (42-1462) matches, and does not have other diffraction miscellaneous peaks in XRD spectrum, illustrate this hair
The bright thorium anhydride object prepared is mutually pure.
As shown in figure 3, the thorium anhydride obtained under different material ratio and different time is also and ThO2Standard card
(42-1462) unanimously, it is all the thorium anhydride of pure phase to illustrate what is obtained under conditions above.Particularly, TEM tests table at room temperature
The a diameter of 10-50nm of thorium anhydride sheet ball particle that is bright, being prepared by microwave radiation technology hydro-thermal method；HR-TEM test results show by
Thorium anhydride prepared by microwave radiation technology hydro-thermal method is polycrystalline structure.
Different temperatures under optimum condition, shown in Fig. 5 a-5f, different material shown in Fig. 6 a-6f compare item as shown in Figure 4 a- shown in Figure 4 d
Under part and Fig. 7a-7c shortened knowable to the hydro-thermal time to the TEM figures of the nanometer titanium dioxide thorium obtained by 30min：The method of the present invention obtains
Thorium anhydride be a diameter of 10-80nm schistose surface sphere structure, and piece interlayer hole is apparent；Wherein Fig. 4 d and 5f
Picture for the thorium anhydride sheet surface structure nanosphere edge observed under high resolution transmission electron microscopy (HRTEM)
And its selected diffraction figure (SAED) is shown in illustration, as can be seen from the figure diffraction pattern is that the prepared thorium anhydride of annular explanation is more
Jingjing body.
It is above-described, it is only the section Example of the present invention, is not limited to the scope of the present invention, of the invention is upper
Stating embodiment can also make a variety of changes.What i.e. every claims and description according to the present patent application were made
Simply, equivalent changes and modifications falls within the claims of patent of the present invention.The not detailed description of the present invention is
Routine techniques content.
Claims (9)
1. the preparation method of the spherical thorium anhydride nano material of a kind of sheet surface structure, which is characterized in that including walking as follows
Suddenly：
Thorium nitrate is dissolved in the water to form thorium nitrate solution by S1；
Urea is dissolved in the water to form urea solution by S2；
The thorium nitrate solution and the urea solution are transferred in reaction kettle by S3, wherein, the molar ratio of thorium and urea is 1:1~
10；
The reaction kettle is placed in microwave reactor by S4, selects reaction temperature as 120-200 DEG C, heating reaction 30-60min,
The microwave product obtained in reaction kettle is centrifuged to obtain sediment；
S5, the dry sediment, obtains the spherical thorium anhydride nano material of sheet surface structure.
2. preparation method according to claim 1, which is characterized in that the step S1 is specially：By Th (NO3)4·6H2O
Be stirred at room temperature or ultrasound under be dissolved in deionized water, stirring forms the solution of homogeneous transparent.
3. preparation method according to claim 1, which is characterized in that the step S2 is specially：By CO (NH2)2In room temperature
It is dissolved under stirring or ultrasound from water water, stirring forms the solution of homogeneous transparent.
4. preparation method according to claim 1, which is characterized in that the microwave power in the step S4 is 400-
1000W。
5. preparation method according to claim 1, which is characterized in that the step S4 includes：It is washed using absolute ethyl alcohol
The sediment.
6. preparation method according to claim 1, which is characterized in that the step S5 is specially：The sediment is existed
When drying 6-10 is small at 60 DEG C -80 DEG C.
7. preparation method according to claim 1, which is characterized in that the preparation method further includes step S6, by described in
Spherical thorium anhydride nano material roasts 60~120min under 350~600 DEG C of air atmospheres of Muffle furnace.
8. a kind of spherical thorium anhydride particle that preparation method according to any one of the claims 1-7 obtains.
9. spherical thorium anhydride particle according to claim 8, which is characterized in that the spherical thorium anhydride particle it is straight
Footpath is about 10~80nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810130042.5A CN108083315B (en) | 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810130042.5A CN108083315B (en) | 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108083315A true CN108083315A (en) | 2018-05-29 |
| CN108083315B CN108083315B (en) | 2020-05-08 |
Family
ID=62194315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810130042.5A Active CN108083315B (en) | 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108083315B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111439772A (en) * | 2020-03-10 | 2020-07-24 | 中国原子能科学研究院 | Preparation method of thorium dioxide nano material |
| CN111620361A (en) * | 2020-05-27 | 2020-09-04 | 西安交通大学 | Preparation method of thorium dioxide nano material |
| CN113860350A (en) * | 2021-11-03 | 2021-12-31 | 中国科学院上海应用物理研究所 | Method for preparing thorium dioxide nano material based on molten salt method and thorium dioxide nano material obtained by method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103081A (en) * | 1983-11-25 | 1986-10-22 | 考姆海克斯 | From the aqueous solution of the nitrate of metal or the method that solid mixture is produced mealy metallic oxide |
-
2018
- 2018-02-08 CN CN201810130042.5A patent/CN108083315B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103081A (en) * | 1983-11-25 | 1986-10-22 | 考姆海克斯 | From the aqueous solution of the nitrate of metal or the method that solid mixture is produced mealy metallic oxide |
Non-Patent Citations (2)
| Title |
|---|
| LIN WANG ET AL.: "Size-tunable synthesis of monodisperse thorium dioxide nanoparticles and their performance on the adsorption of dye molecules"", 《CRYSTENGCOMM》 * |
| 苏显云等: "《大学普通化学实验》", 31 December 2001, 高等教育出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111439772A (en) * | 2020-03-10 | 2020-07-24 | 中国原子能科学研究院 | Preparation method of thorium dioxide nano material |
| CN111620361A (en) * | 2020-05-27 | 2020-09-04 | 西安交通大学 | Preparation method of thorium dioxide nano material |
| CN113860350A (en) * | 2021-11-03 | 2021-12-31 | 中国科学院上海应用物理研究所 | Method for preparing thorium dioxide nano material based on molten salt method and thorium dioxide nano material obtained by method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108083315B (en) | 2020-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108083315A (en) | A kind of preparation method of the spherical thorium anhydride nano material of sheet surface structure and thus obtained spherical thorium anhydride particle | |
| CN101717122B (en) | Method for preparing ferroferric oxide nano-piece through microwave method | |
| CN102491417B (en) | Method for preparing ball-flower-shaped gamma-bismuth trioxide powder | |
| CN110203969A (en) | A kind of high dispersive cubic phase nano zirconium oxide and preparation method thereof | |
| CN107671280B (en) | A kind of york-shell structure C oNi@TiO2Nanosphere and preparation method thereof | |
| CN103288136A (en) | Hydrothermal synthesis method of shape-controllable molybdenum dioxide submicrocrystals | |
| CN106082306A (en) | A kind of aluminum-doped zinc oxide nanometer powder and microwave-assisted preparation method thereof and application | |
| CN1528706A (en) | Y2O3 stable tetragonal phase ZrO2 monodisperse nano posder hydrothermal preparation method | |
| Sugimoto et al. | Formation mechanism of uniform spindle-type titania particles in the gel-sol process | |
| CN107512707B (en) | Fusiform g-C3N4And preparation method thereof | |
| CN110040770A (en) | A kind of method that microchannel continuity method prepares nano-level sphere barium titanate | |
| CN107032406B (en) | A kind of micro-nano beam of manganese molybdate and preparation method thereof | |
| CN108785690A (en) | A kind of tumour diagnosis and treatment integration nano material and preparation method thereof | |
| CA1066873A (en) | Process for the hydrolysis of titanium sulphate solutions | |
| CN103922421A (en) | Method for preparing alpha-Fe2O3 | |
| CN111747441A (en) | Method for solid-phase synthesis of nano zinc oxide by utilizing alcohol amine compound | |
| CN110386613A (en) | A kind of preparation method for the mesoporous alumina hydrate microspherical of graduation that crystal form is controllable | |
| CN110563036A (en) | bismuth oxide nano material rich in oxygen vacancy and preparation method thereof | |
| CN105753060A (en) | Process for preparing spindle-shaped iron tungstate microcrystal | |
| CN108946812A (en) | Alkali tungsten bronze nanometer rods and its preparation method and application | |
| CN106745218B (en) | A kind of high-temperature stable titania nanotube raw powder's production technology | |
| CN110042423A (en) | The preparation method of the cobalt hydroxide of gold point battle array modification | |
| CN106379949B (en) | A kind of preparation method of nickel tungstate nano wire | |
| CN101255601A (en) | Method for synthesizing spindle-shaped and bar-shaped La2CuO4 by using copper oxide as crystal seed | |
| CN102040246A (en) | Method for synthesizing manganous-manganic oxide nano material at room temperature by using mild path |
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 |