CN105948097A - Spherical cerium dioxide - Google Patents
Spherical cerium dioxide Download PDFInfo
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- CN105948097A CN105948097A CN201610260014.6A CN201610260014A CN105948097A CN 105948097 A CN105948097 A CN 105948097A CN 201610260014 A CN201610260014 A CN 201610260014A CN 105948097 A CN105948097 A CN 105948097A
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- cerium salt
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention discloses a spherical cerium dioxide. The average particle size of spherical cerium dioxide is 50 nm-300 nm, and the specific surface area after roasting at 1000 DEG C is 1.5-20 m<2>/g, preferably, the specific surface area after roasting at 350 DEG C is 102-153 m<2>/g, and the specific surface area after roasting at 550 DEG C is 80-120 m<2>/g. The preparation method of the spherical cerium dioxide disclosed in the invention has short reaction time and simple operation, and is easy to control. Moreover, the prepared cerium dioxide is spherical and has regular shape, good degree of crystallization, high heat stability, and big specific surface area.
Description
Technical field
The invention belongs to micro Nano material synthesis field, be specifically related to a kind of spherical ceria.
Background technology
Rare earth element has the 4f electronic shell of uniqueness, and the Different Exercise Mode of 4f electronics makes it have and is different from other element
The characteristic such as optics, magnetics, electricity physics and chemistry.Cerium oxide is the one in rare earth oxide, and it is abundant at China's deposit,
It is widely used.Such as it is the important component part of oxygen sensor, humidity sensor, solid fuel cell, is also good UV
Adsorbent, ceramic material, polishing material etc..+ 3 ,+4 two valence states are had additionally, due to it, and along with the change of extraneous partial pressure of oxygen,
The valence state of cerium converts the most between, special stores oxygen ability so having；In addition the feature that its specific surface is big, is suitable for
It is used as carrier or the auxiliary agent of heterogeneous catalysis, has at aspects such as water gas shift, alcohol reforming hydrogen production and catalytic purification of motor vehicle tail gas
Important application.
As the catalyst for motor-vehicle tail-gas, owing to the operating temperature of this type of catalyst is higher, and the gas that need to be catalyzed
Body complicated component, each constituent content are continually changing, and this has just had higher requirement to catalyst.It is generally of Large ratio surface, heat
The cerium oxide that stability is strong is the material in ideal.Mono-dispersed nano crystalline substance has the highest surface energy, but high temperature can cause
It spontaneously reunites to reduce surface energy, i.e. to the topographical transition that thermodynamics is more stable, is usually formed irregular bulk and reunites
Body, causes specific surface rapid drawdown.
The synthetic method of ceria is a lot, common for liquid-solid synthetic method, specifically include the sedimentation method, sol-gal process,
Water/solvent-thermal method, microemulsion method, template etc.；Gas-solid synthetic method, as CN200910089538.3 discloses a kind of as size
The cerium dioxide micro-balloon of standard substance, described cerium dioxide micro-balloon is an inorganic organic hybrid microsphere, by ceria and poly-second
Alkene pyrrolidone molecular composition, wherein the weight ratio of ceria and polyvinylpyrrolidone is 11-16:1, and this is inorganic one organic
Hybrid microspheres is polycrystalline structure, belongs to cubic system, and crystal structure is fluorite type, and structure cell is face-centred cubic structure, microsphere shape
The factor is less than 1.2, and size range is 90nm-450nm, and the relative uncertainty degree of size value is less than 5}0.The need of said method twice
Hydrothermal Synthesis, operational approach is loaded down with trivial details, and the cerium dioxide micro-balloon obtained its specific surface area after 1000 DEG C of high-temperature roastings is less than
1m2/g。
Additionally also has solid-solid synthesis method, such as ball-milling method.The product morphology multidigit of the sedimentation method and sol-gal process synthesis is without fixed
Shape, degree of crystallinity is poor, high temperature specific surface declines serious, vapor phase grafting response time length, yields poorly；And ball-milling method be generally only by
Many kinds of substance physically mixes, and performance is the most poor.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that a kind of response time is short, easy and simple to handle, easily-controllable
The spherical ceria of system, the ceria pattern globulate of preparation and regular shape, better crystallinity degree, heat stability is high, compare table
Area is big.
For reaching above-mentioned purpose, present invention employs following technical proposals:
The invention provides a kind of spherical ceria, the mean diameter of spherical ceria is 50nm-300nm,
At 1000 DEG C, the specific surface area after roasting is 1.5-20m2/g, it is preferred that specific surface area after roasting at 350 DEG C and 550 DEG C
It is respectively 102-153m2/g and 80-120m2/g.
Present invention also offers the preparation method of described spherical ceria, specifically include following steps:
(1) mixing cerium salt, water and ethylene glycol, polyvinylpyrrolidone and short chain organic acid, moves into hydro-thermal after stirring and dissolving
Still carries out hydro-thermal reaction；
(2) react 1-8 hour at 160-240 DEG C；Being centrifuged after cooling and be precipitated thing, dry sediment obtains spherical two
Cerium oxide.
Preferably, in described step (1), the volume ratio of water and ethylene glycol is 5:(60-80).
Preferably, cerium salt and polyvinylpyrrolidone mol ratio are (220-260): 1, short chain organic acid and water and ethylene glycol
The volume ratio of sum is 1:60-80, and cerium salt is 5.2:66-88 with the mass ratio of water and ethylene glycol sum.
Preferably, cerium salt is first dissolved in water and ethylene glycol in (1) by described step, is subsequently adding polyvinylpyrrolidone
Stirring, to the solution of transparent clarification, stirs the solution to transparent clarification after adding short chain organic acid.
Preferably, described polyvinylpyrrolidone (being called for short PVP) mean molecule quantity is 40000-80000.Further preferably
, described polyvinylpyrrolidone mean molecule quantity is 58000.
Preferably, described step (2) is centrifuged with the rotating speed of (8000-12000) r/min, is precipitated thing, then uses deionization
The alternately washing of water and ethanol, is dried in 60-90 DEG C subsequently.Dried product mortar grinder is become fine powder, respectively at 350 DEG C
With 550 DEG C of roasting 4h, 3 DEG C/min of heating rate, obtain fresh ccria powder.This fresh powder through 1000 DEG C of roasting 2h,
3 DEG C/min of heating rate, obtain aging after cerium oxide powder.
Preferably, described cerium salt is Ce (NO3)3·6H2O or CeCl3·7H2O；Described short chain organic acid selected from glacial acetic acid,
Propanoic acid and n-butyric acie.
The application in motor-vehicle tail-gas of the described spherical ceria.
Present invention also offers the another kind of preparation method of described spherical ceria, specifically include following steps:
(1) mixing cerium salt, water, polyvinylpyrrolidone and short chain organic acid and carbamide, moves into water heating kettle after stirring and dissolving
In；
(2) react 1-8 hour at 160-240 DEG C；Being centrifuged after cooling and be precipitated thing, dry sediment obtains spherical two
Cerium oxide.
Preferably, in described step (1), the mass ratio of water and carbamide is (60-80): 4.8；Cerium salt and polyvinylpyrrolidine
Ketone mol ratio is (220-260): 1, and the volume ratio of short chain organic acid and water is 1:(60-80) cerium salt is 4.5 with the mass ratio of water:
(60-80), described carbamide is 4.8:4.5 with the mass ratio of cerium salt.
Preferably, cerium salt is first dissolved in water and ethylene glycol in (1) by described step, is subsequently adding polyvinylpyrrolidone
Stirring, to the solution of transparent clarification, stirs the solution to transparent clarification after adding short chain organic acid and carbamide.
Preferably, described cerium salt is Ce (NO3)3·6H2O or CeCl3·7H2O；Described short chain organic acid selected from glacial acetic acid,
Propanoic acid and n-butyric acie.
The application in motor-vehicle tail-gas of the described spherical ceria.
Preferably, described polyvinylpyrrolidone (being called for short PVP) mean molecule quantity is 40000-80000.Further preferably
, described polyvinylpyrrolidone mean molecule quantity is 58000.
Preferably, described step (2) is centrifuged with the rotating speed of (8000-12000) r/min, is precipitated thing, then uses deionization
The alternately washing of water and ethanol, is dried in 60-90 DEG C subsequently.Dried product mortar grinder is become fine powder, respectively at 350 DEG C
With 550 DEG C of roasting 4h, 3 DEG C/min of heating rate, obtain fresh ccria powder.This fresh powder through 1000 DEG C of roasting 2h,
3 DEG C/min of heating rate, obtain aging after cerium oxide powder.
The generally amorphous ceria that traditional method obtains, its poor heat stability, after 1000 DEG C of roastings specific surface <
1m2/ g, it is common that improve surface area by the method for doping and improve heat stability.The present invention is prepared by morphology control
The ceria of undoped still has comparatively ideal specific surface after 1000 DEG C of roastings.The product that the present invention prepares is suitable as urging
Formed material, and have the biggest using value at high temperature gas phase catalysis, particularly motor-vehicle tail-gas catalysis aspect.
Compared with prior art, there is advantages that
1, to prepare response time of ceria short, easy and simple to handle, easy to control for the present invention, sintetics pattern globulate and
Regular shape, better crystallinity degree, heat stability are high, specific surface area is big.
2, the present invention uses ethylene glycol to be solvent, and ethylene glycol can occur stronger coordination with cerium so that it is on synthesis rank
Section controls nanocrystalline growth.Additionally, the viscosity of ethylene glycol is high, it is possible to decrease nucleation and growth rate so as to get product morphology
Evenly, rule.The spherical secondary structure with relatively low-surface-energy can also be formed so that the spherical ceria heat of preparation simultaneously
Stability is high.
The addition of water have adjusted viscosity, it is to avoid spheroidal particle sticks together.Meanwhile, the present invention uses PVP to live as surface
Property agent, and with water and ethylene glycol in the range of proper ratio, it is spherical for not only preparing lanthana, and it has more uniform
Pattern, better crystallinity degree, good dispersion, heat stability are high, specific surface area is big.The addition of PVP and short chain organic acid has regulated and controled pattern,
PVP is adsorbed in spherical surface, limits the size of particle diameter and prevents the adhesion between spheroidal particle；Short chain organic acid affects spheroidal particle
Size, short chain organic acid owing to there is carboxyl and alkyl, the carboxyl of one end can and Ce3+Coordination, the alkyl of the other end is permissible
Modify nanoparticle and affect the interaction between nanoparticle.
3, the reaction of the carbamide that the present invention adds occurs in the homogeneous environment of constant sealing, carbamide as precipitant,
Under hot conditions, hydrolysis slowly releases OH-and CO3 2-, it is ensured that each nucleus generates in the environment of equal, grows, for fall
The spontaneous reunion of low-surface-energy, generates two grades of spherical agglomerates that pattern reaches unanimity.
Accompanying drawing explanation
SEM Electronic Speculum figure after 550 DEG C of roastings of ceria in Fig. 1 embodiment 1
XRD diffraction analysis figure after 550 DEG C of roastings of ceria in Fig. 2 embodiment 2
SEM Electronic Speculum figure after 550 DEG C of roastings of ceria in Fig. 3 embodiment 2
SEM Electronic Speculum figure after 550 DEG C of roastings of sample in Fig. 4 comparative example 1-4
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, to the present invention
It is further elaborated, but the scope of protection of present invention is not limited to the scope that embodiment is expressed.
The composition of raw materials used that each embodiment and comparative example prepare ceria is as follows:
Embodiment 1
Prepare a kind of spherical ceria, have and comprise the steps:
(1) CeCl is weighed3·7H2O is dissolved in deionized water and ethylene glycol, and stirring, to being completely dissolved, adds polyethylene
Ketopyrrolidine (PVP, molecular weight M=58000), stir about 1h, obtain the solution of transparent clarification, add glacial acetic acid, stir about
0.5h obtains clear liquid；
(2) mixed liquor obtaining transparent clarification proceeds to, in 100ml polytetrafluoroethyllining lining, put into stainless steel cauldron, and 180
DEG C reaction 1h；
(3), after question response still is cooled to room temperature, product is centrifuged 5min with the rotating speed of 10000r/min, is precipitated thing,
Again with deionized water and ethanol alternately washing 3 times, obtain ceria in 80 DEG C of dry 12h subsequently.
Test prepares:
(1) BET specific surface area test: ceria prepared by embodiment 1 is dried, and become thin with mortar grinder
Powder, respectively at 350 DEG C and 550 DEG C of roasting 4h, 3 DEG C/min of heating rate, obtain fresh ccria powder, record BET and compare table
Area.The most respectively through 1000 DEG C of roasting 2h, 3 DEG C/min of heating rate, obtain aging after cerium oxide powder, record BET
Specific surface area.
(2) SEM test: ceria prepared by the embodiment 1 after 550 DEG C of roastings is carried out SEM sem test,
Its pattern is as it is shown in figure 1, it will be seen from figure 1 that the uniform ball that mean diameter is 200nm of ceria of embodiment 1 preparation
Body.
(3) particle diameter distribution instrument is used to carry out particle diameter distribution tests.
Comparative example 1-1
Prepare a kind of spherical ceria and be provided without the polyvinylpyrrolidone that molecular weight is 58000, remaining raw material and system
Preparation Method and BET specific surface area test and particle diameter distribution tests are with embodiment 1.
Comparative example 1-2
When preparing a kind of spherical ceria, deionized water and ethylene glycol is not in OK range, remaining raw material and preparation side
Method and BET specific surface area test and particle diameter distribution tests are with embodiment 1.
Comparative example 1-3
When preparing a kind of spherical ceria, deionized water and ethylene glycol and polyvinylpyrrolidone be not in OK range,
Remaining raw material is tested with particle diameter distribution tests with embodiment 1 with preparation method and BET specific surface area.
Comparative example 1-4
Dodecyl trimethyl ammonium chloride is used to replace polyvinylpyrrolidone when preparing a kind of spherical ceria, remaining
Raw material is tested with embodiment 1 with preparation method and BET specific surface area test, particle diameter distribution tests and SEM, and SEM test result is shown in
Fig. 4.
Embodiment 2
Prepare a kind of spherical ceria, have and comprise the steps:
(1) CeCl is weighed3·7H2O is dissolved in deionized water, and stirring, to being completely dissolved, adds polyvinylpyrrolidone
(PVP, molecular weight M=58000), stir about 1h, obtain the solution of transparent clarification, add glacial acetic acid, be eventually adding carbamide, stirring
About 0.5h obtains clear liquid；
(2) mixed liquor obtaining transparent clarification proceeds to, in 100ml polytetrafluoroethyllining lining, put into stainless steel cauldron, and 180
DEG C reaction 1h；
(3), after question response still is cooled to room temperature, product is centrifuged 5min with the rotating speed of 10000r/min, is precipitated thing,
Again with deionized water and ethanol alternately washing 3 times, obtain ceria in 80 DEG C of dry 12h subsequently.
Test prepares:
(1) BET specific surface area test: ceria prepared by embodiment 2 is dried, and become thin with mortar grinder
Powder, respectively at 350 DEG C and 550 DEG C of roasting 4h, 3 DEG C/min of heating rate, obtain fresh ccria powder, record BET and compare table
Area.Respectively through 1000 DEG C of roasting 2h, 3 DEG C/min of heating rate, obtain aging after cerium oxide powder, record BET and compare table
Area.
(2) XRD test: just the ceria of embodiment 1 preparation is at 550 DEG C of roasting 4h, and heating rate is 3 DEG C/min,
Ceria after roasting is carried out test and obtains X ray diffracting spectrum, as shown in Figure 2.The crystal formation that ceria is described is vertical
Side's fluorite type, PDF standard card number 43-1002, to the catalytic effect of motor-vehicle tail-gas more preferably.
(3) SEM test: ceria prepared by the embodiment 1 after 550 DEG C of roastings is carried out SEM sem test,
Its pattern is as it is shown on figure 3, from figure 3, it can be seen that the uniform ball that mean diameter is 150nm of ceria of embodiment 1 preparation
Body.
(4) particle diameter distribution instrument is used to carry out particle diameter distribution tests.
Comparative example 2
Prepare a kind of spherical ceria and be provided without carbamide, remaining raw material and preparation method and BET specific surface area test with
Particle diameter distribution tests is with embodiment 1.
The test result of all above embodiment and comparative example such as following table:
Data above shows, comparative example 1-1 is provided without polyvinylpyrrolidone that molecular weight is 58000 as surface activity
Agent, relative to the ceria of embodiment 1 preparation, its mean diameter is relatively big, through 350 DEG C, 550 DEG C, after 1000 DEG C of roastings, heat is steady
Qualitative property is worse relative to embodiment 1, and after especially 1000 DEG C roastings, its specific surface area is lower, relative to its discomfort of embodiment 1
For vehicle exhaust gas systems.
Comparative example 1-2 deionized water and ethylene glycol is not in OK range, relative to the ceria of embodiment 1 preparation,
Its mean diameter is relatively big, through 350 DEG C, 550 DEG C, after 1000 DEG C of roastings, heat stability is worse relative to embodiment 1, especially
After 1000 DEG C of roastings, its specific surface area is lower, and relative to embodiment 1, it is not suitable for vehicle exhaust gas systems.
Comparative example 1-3 deionized water and ethylene glycol and polyvinylpyrrolidone be not in OK range, relative to embodiment 1
The ceria of preparation, its mean diameter is relatively big, through 350 DEG C, 550 DEG C, after 1000 DEG C of roastings, heat stability is relative to enforcement
Example 1 is worse, and after especially 1000 DEG C roastings, its specific surface area is lower, and relative to embodiment 1, it is not suitable for motor-vehicle tail-gas and urges
Agent.
Comparative example 1-4 uses Dodecyl trimethyl ammonium chloride sodium to replace polyvinylpyrrolidone, makes relative to embodiment 1
Standby ceria, its mean diameter is relatively big, through 350 DEG C, 550 DEG C, after 1000 DEG C of roastings, heat stability is relative to embodiment
1 is worse, and after especially 1000 DEG C roastings, its specific surface area is lower, and relative to embodiment 1, it is not suitable for motor-vehicle tail-gas catalysis
Agent.
Embodiment 2 is provided without ethylene glycol, but have employed carbamide, and the ceria mean diameter that it is prepared is 200nm, for all
One is spherical.Through 350 DEG C, 550 DEG C, there is after 1000 DEG C of roastings higher specific surface area, heat stability is high, especially at 1000 DEG C
High temperature under after roasting, it still has preferable specific surface area, it is adaptable to as vehicle exhaust gas systems.
Comparative example 2 is provided without ethylene glycol, is also provided without carbamide, fails to prepare ceria, is not the most also suitable for
Vehicle exhaust gas systems.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula changes and revises.Therefore, the invention is not limited in detailed description of the invention disclosed and described above, to the present invention's
Some modifications and changes should also be as falling in the scope of the claims of the present invention.Although additionally, this specification using
Some specific terms, but these terms are merely for convenience of description, the present invention does not constitute any restriction.
Claims (10)
1. a spherical ceria, it is characterised in that the mean diameter of spherical ceria is 50nm-300nm, at 1000 DEG C
Specific surface area after lower roasting is 1.5-20m2/ g, it is preferred that the specific surface area after roasting is respectively at 350 DEG C and 550 DEG C
102-153m2/ g and 80-120m2/g。
Spherical ceria the most according to claim 1, it is characterised in that the preparation method bag of described spherical ceria
Include following steps:
(1) mixing cerium salt, water and ethylene glycol, polyvinylpyrrolidone and short chain organic acid, carry out hydro-thermal reaction after stirring and dissolving；
(2) react 1-8 hour at 160-240 DEG C；Being centrifuged after cooling and be precipitated thing, dry sediment obtains spherical titanium dioxide
Cerium.
Spherical ceria the most as claimed in claim 2, it is characterised in that water and the volume of ethylene glycol in described step (1)
Ratio is 5:(60-80).
Spherical ceria the most as claimed in claim 2, it is characterised in that cerium salt with polyvinylpyrrolidone mol ratio is
(220-260): 1, short chain organic acid is 1:60-80 with the volume ratio of water and ethylene glycol sum, cerium salt and water and ethylene glycol sum
Mass ratio be 5.2:66-88.
Spherical ceria the most as claimed in claim 2, it is characterised in that cerium salt is first dissolved in water in (1) by described step
With in ethylene glycol, it is subsequently adding the solution of polyvinylpyrrolidone stirring extremely transparent clarification, stirs after adding short chain organic acid
Solution to transparent clarification.
Spherical ceria the most according to claim 1, it is characterised in that the preparation method bag of described spherical ceria
Include following steps:
(1) mixing cerium salt, water, polyvinylpyrrolidone and short chain organic acid and carbamide, move in water heating kettle after stirring and dissolving；
(2) react 1-8 hour at 160-240 DEG C；Being centrifuged after cooling and be precipitated thing, dry sediment obtains spherical titanium dioxide
Cerium.
Spherical ceria the most as claimed in claim 6, it is characterised in that water and the mass ratio of carbamide in described step (1)
For (60-80): 4.8；Cerium salt and polyvinylpyrrolidone mol ratio are (220-260): 1, short chain organic acid and the volume ratio of water
For 1:(60-80) mass ratio of cerium salt and water is 4.5:(60-80), described carbamide is 4.8:4.5 with the mass ratio of cerium salt.
Spherical ceria the most as claimed in claim 6, it is characterised in that cerium salt is first dissolved in water in (1) by described step
With in ethylene glycol, it is subsequently adding the solution of polyvinylpyrrolidone stirring extremely transparent clarification, adds short chain organic acid and carbamide
The solution of rear stirring extremely transparent clarification.
9. the spherical ceria as described in any one of claim 2-8, it is characterised in that described cerium salt is Ce (NO3)3·
6H2O or CeCl3·7H2O；Described short chain organic acid is selected from glacial acetic acid, propanoic acid and n-butyric acie.
10. spherical ceria application in motor-vehicle tail-gas described in claim 1 or 2.
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| CN109721093A (en) * | 2017-10-30 | 2019-05-07 | 西安文理学院 | A kind of micro-nano ship shape ceria and preparation method thereof |
| CN110354799A (en) * | 2019-07-24 | 2019-10-22 | 济南大学 | A kind of cerium dioxide nano material possessing good low temperature NOx storage capacity |
| CN113651351A (en) * | 2021-08-16 | 2021-11-16 | 广东工业大学 | Samarium oxide and preparation and application thereof |
| CN113891924A (en) * | 2020-02-27 | 2022-01-04 | 碧德·奧利珍股份有限公司 | Spherical inorganic particles with surface bumps and preparation method thereof |
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| CN110354799A (en) * | 2019-07-24 | 2019-10-22 | 济南大学 | A kind of cerium dioxide nano material possessing good low temperature NOx storage capacity |
| CN113891924A (en) * | 2020-02-27 | 2022-01-04 | 碧德·奧利珍股份有限公司 | Spherical inorganic particles with surface bumps and preparation method thereof |
| CN113891924B (en) * | 2020-02-27 | 2023-03-31 | 碧德·奧利珍股份有限公司 | Spherical inorganic particles with surface bumps and preparation method thereof |
| CN113651351A (en) * | 2021-08-16 | 2021-11-16 | 广东工业大学 | Samarium oxide and preparation and application thereof |
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| CN105948097B (en) | 2018-09-07 |
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