CN1762819A - Appearance controllable CeO2 precursor----- Ce2O(CO3)2 H2O powder preparation method - Google Patents
Appearance controllable CeO2 precursor----- Ce2O(CO3)2 H2O powder preparation method Download PDFInfo
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- CN1762819A CN1762819A CN 200510098336 CN200510098336A CN1762819A CN 1762819 A CN1762819 A CN 1762819A CN 200510098336 CN200510098336 CN 200510098336 CN 200510098336 A CN200510098336 A CN 200510098336A CN 1762819 A CN1762819 A CN 1762819A
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Abstract
The present invention belongs to the field of chemical preparation technology of RE powder material. The form of the precursor has certain genetic inheritance to the form of final particle after calcinations. Unlike available one-step CeO2 synthesizing process forming single spherical particles, the multiple-step process of the present invention results in CeO2 precursor particles of different forms. The multiple-step process includes the steps of: dissolving trivalent Ce salt in distilled water to compound solution, adding urea to the Ce salt solution to form clear mother liquid of certain Ce ion/urea molar ratio, adding surfactant, continuously stirring in water bath of 70-95 deg.c for full reaction to obtain precipitate, and separating, collecting, washing and drying the precipitate to obtain Ce2O(CO3)2.H2O powder of different forms. The Ce2O(CO3)2.H2O powder has monocrystal structure of orthorhombic system in micron level, different forms and high crystallization degree.
Description
One, technical field
The invention belongs to the chemical preparation technical field of rare earth powder body material.
Two, background technology
There is abundant rare earth resources in China, accounts for the world's more than 80% of proven reserve, and wherein the content of cerium is the richest.Rare earth oxide CeO
2Be the light rare earths product of outbalance, be widely used in luminescent material, catalyzer, electronic ceramics, UV light absorber, precise polishing materials etc.Because it has superior oxygen function and the quick oxygen of the high temperature room diffusibility stored, therefore become the catalytic cleaning of car tail gas material, Solid Oxide Fuel Cell (SOFC) anode material, the electrochemical reaction that have application prospect and promote material, chemically machinery polished material etc. again.
CeO
2The character that particle is new and the acquisition of purposes are not only relevant with its chemical constitution, purity, and and CeO
2Index such as pattern, size-grade distribution, size of particles relevant, this is just to CeO
2Control preparation process is had higher requirement, and makes people grasp control CeO
2On the basis of particle size technology, have to pay attention to control CeO
2The research of particulate form.Particle shape can not show a candle to size of particles and is easy to control like that, and this is because grain form is subjected to all multifactor influences such as thermodynamics and kinetics simultaneously.
Prepare CeO at present
2Ubiquitous problem is in numerous methods of particle:
(1) single stage method synthetic CeO
2The pattern of particle is more single, is sphere.
(2) CeO of different-shape in the multistep processes
2The synthetic report that yet there are no of particulate.
The existence of these problems has limited CeO
2The application of particle and development.Relevant studies show that, the pattern of presoma has hereditary inheritance with the pattern of final particle in calcination process.Therefore, pattern preparation just the becoming preparation different-shape CeO of control presoma
2The presoma that the important means of particle, preparation have different-shape becomes the focus that the various countries expert studies.
Three, summary of the invention
At existing problem, the present invention utilizes homogeneous precipitation method, select for use different types of tensio-active agent to comprise ionogenic surfactant cetyl trimethylammonium bromide (CTAB), Aerosol OT (A-OT), nonionic surface active agent polyoxyethylene glycol 19000 (PEG19000), polyvinyl alcohol (PVA-124), polyoxyethylene nonylphenol ether (OP-10) and polyoxyethylene sorbitan ester (tween-80), three block nonionic surface active agent polyethylene glycol-glycerol-polyoxyethylene glycol (P123), in the hope of changing reaction mechanism, prepare the different presoma Ce of multiple pattern
2O (CO
3)
2H
2The O powder is the CeO of synthetic different-shape
2Lay the foundation.
A hydration carbonic acid gas cerium Ce provided by the present invention
2O (CO
3)
2H
2The O powder is characterized by: have rhombic single crystal structure, be of a size of micron-sized multiple pattern particulate, and the adding of tensio-active agent obviously improves the crystalline crystallization degree.
The invention provides the controlled CeO of a kind of pattern
2Presoma---Ce
2O (CO
3)
2H
2The preparation method of O powder is characterized in that, step is as follows:
(1) the solid cerous salt is dissolved in is made into 0.05～0.5mol/L solution in the distilled water;
(2) urea is joined in the above-mentioned cerium solution, and make Ce
3+With the urea uniform mixing, be made into Ce
3+: urea mol ratio=1: 20-1: 50 clarified mother liquor;
(3) adding weight percent is that 0.1～1% tensio-active agent (ionogenic surfactant, nonionic surface active agent, three block nonionic surface active agent) is in above-mentioned mixing solutions;
(4) mixed solution is put into 70～95 ℃ water bath with thermostatic control continuously stirring, reacted fully and carry out, and obtain precipitation;
(5), promptly obtain having the white Ce of various patterns with precipitate and separate, collection, washing, drying
2O (CO
3)
2H
2The O powder.
Among the present invention, because the not adding of tensio-active agent of the same race, make white Ce
2O (CO
3)
2H
2The remarkable refinement of the crystal grain of O powder, the varied and degree of crystallization of its pattern obviously improves.This is because the chemical property of rare earth element is active, it is saturated to make that these compounds are difficult for reaching coordination on the saturability, on the directivity, in conjunction with possibility very much, in the synthetic and reaction of rare earth compound, the rearrangement of part, the variation that coordination is how much all becomes easily, causes the different powder of pattern to produce.
From the image of the transmission electron microscope of Fig. 1 as can be seen: it is sample fusiform, that size is uneven that surfactant-free adds the precursor powder for preparing, and size is at micron order; The selected area electron diffraction proof products therefrom of Fig. 2 is a single crystal structure; The X ray collection of illustrative plates of Fig. 3 can know that the degree of crystallization of gained powder is relatively poor.
From the image of the transmission electron microscope of Fig. 4 as can be seen: it is that shuttle shape, size are more even that tensio-active agent cetyl trimethylammonium bromide (CTAB) adds the resulting powder morphology in back, and size is at micron order; The X ray collection of illustrative plates of Fig. 5 can know that the degree of crystallization of gained powder is strengthened greatly.
From the image of the transmission electron microscope of Fig. 6, Fig. 9, Figure 12 as can be seen: after adding tensio-active agent Aerosol OT (A-OT), polyvinyl alcohol (PVA-124), polyoxyethylene sorbitan ester (tween-80), preparation-obtained powder morphology is respectively the bar-shaped of sheet, queueing discipline and the divergent shape flower shape of nucleus of condensation is arranged.
From the image of the transmission electron microscope of Fig. 7 as can be seen: surfactant polyethylene 19000 (PEG19000) adds the preparation-obtained powder in back for arranging orderly, bar-shaped sample of uniform size, and size is at micron order; The selected area electron diffraction proof products therefrom of Fig. 8 is a single crystal structure.
From the image of the transmission electron microscope of Figure 10 as can be seen: it is to have-the divergent shape flower shape sample of nucleus of condensation that tensio-active agent polyoxyethylene nonylphenol ether (OP-10) adds the preparation-obtained powder in back; The selected area electron diffraction proof products therefrom of Figure 11 is a single crystal structure.
From the image of Figure 13,14 transmission electron microscope as can be seen: surfactant polyethylene-polyglycerol-polyoxyethylene glycol (P123) adds the promising spheric of the preparation-obtained powder in back, the also promising divergent shape flower shape sample that a nucleus of condensation is arranged.
As seen, when not adding tensio-active agent, the product particle one hydration carbonic acid gas cerium Ce that homogeneous precipitation method generates
2O (CO
3)
2H
2O is easy to mutual reunion.Therefore, the TEM photo shows that product is the spindle shape, is of a size of micron order and size inhomogeneous (Fig. 1), and ED figure shows that products therefrom is monocrystalline (Fig. 2), and XRD confirms its crystallization degree weak (Fig. 3); Add tensio-active agent and changed powder Ce
2O (CO
3)
2H
2The formation mechanism of O has changed the growth velocity of each crystal face to some extent, finally cause the different-shape crystalline to generate, and its crystallization degree improves (Fig. 4～14).
Four, description of drawings
Fig. 1: preparation method's Comparative Examples Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Fig. 2: the monocrystalline Ce of preparation method's Comparative Examples of the present invention
2O (CO
3)
2H
2O powder ED photo
Fig. 3: preparation method's Comparative Examples Ce of the present invention
2O (CO
3)
2H
2The X diffracting spectrum of O powder
Fig. 4: preparation method's example 1Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Fig. 5: preparation method's example 1Ce of the present invention
2O (CO
3)
2H
2The X diffracting spectrum of O powder
Fig. 6: preparation method's example 2Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Fig. 7: preparation method's example 3Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Fig. 8: the monocrystalline Ce of preparation method's example 3 of the present invention
2O (CO
3)
2H
2O powder ED photo
Fig. 9: preparation method's example 4Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Figure 10: preparation method's example 5Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Figure 11: the monocrystalline Ce of preparation method's example 5 of the present invention
2O (CO
3)
2H
2O powder ED photo
Figure 12: preparation method's example 6Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Figure 13: preparation method's example 7Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Figure 14: preparation method's example 7Ce of the present invention
2O (CO
3)
2H
2The TEM picture of O powder
Embodiment
Comparative Examples: with the solid cerous salt 0.1molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 25.Mixed solution is put into water bath with thermostatic control continuously stirring a few hours of 85 ℃, use the centrifuging precipitation separation, with throw out water and washing with alcohol respectively.Be deposited in drying at room temperature, promptly obtain the uneven spindle shape white of grain-size Ce
2O (CO
3)
2H
2O powder, XRD be confirmed that it is monocrystalline and crystallization degree a little less than.
Example 1: with the solid cerous salt 0.1molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 40.Add weight percent and be 0.5% cationic surfactant cetyl trimethylammonium bromide (CTAB) in this mother liquor, mixed solution is put into water bath with thermostatic control continuously stirring a few hours of 80 ℃, reaction process produces abundant white foam.Use the centrifuging precipitation separation, with throw out with deionized water wash after, use washing with alcohol again.Be deposited in drying at room temperature, promptly obtain having the Ce of the uniform shuttle shape of pattern
2O (CO
3)
2H
2O white powder, XRD confirms that its crystallization degree is strong.
Example 2: with the solid cerous salt 0.2molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 50.The adding weight percent is 0.7% cationic surfactant Aerosol OT (A-OT) in this mother liquor, and mixed solution is put into 90 ℃ water bath with thermostatic control continuously stirring a few hours, and the reaction process non-foam produces.Use the centrifuging precipitation separation, with throw out with deionized water wash after, use washing with alcohol again.Be deposited in drying at room temperature, promptly obtain having the comparatively uniform flaky Ce of pattern
2O (CO
3)
2H
2O white powder, XRD confirms that its crystallization degree is stronger.
Example 3: with the solid cerous salt 0.1molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 25.The adding weight percent is 0.7% nonionic surface active agent polyoxyethylene glycol 19000 (PEG19000) in this mother liquor, and mixed solution is put into 85 ℃ water bath with thermostatic control continuously stirring a few hours, does not have abundant foam in the reaction process.Use the centrifuging precipitation separation, throw out is spent water washing after, use washing with alcohol again.Be deposited in drying at room temperature, promptly obtain arranging the high Ce of the regular degree of order
2O (CO
3)
2H
2O rod-shaped powder, XRD confirm that its crystallization degree is strong.
Example 4: with the solid cerous salt 0.2molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 25.The adding weight percent is 0.2～0.8% nonionic surface active agent polyvinyl alcohol (PVA-124) in this mother liquor.Mixed solution is put into 90 ℃ water bath with thermostatic control continuously stirring a few hours, and reaction process produces abundant white foam.Use the centrifuging precipitation separation, throw out is spent water washing after, use washing with alcohol again.Be deposited in drying at room temperature, promptly obtain arranging the high Ce of the regular degree of order
2O (CO
3)
2H
2O rhabdolith, XRD confirm that its crystallization degree is strong.
Example 5: with the solid cerous salt 0.3molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 40.The adding weight percent is 0.6% nonionic surface active agent polyoxyethylene nonylphenol ether (OP-10) in this mother liquor.Mixed solution is put into 90 ℃ water bath with thermostatic control continuously stirring a few hours, and reaction process produces abundant white foam.Use the centrifuging precipitation separation, throw out is spent water washing after, use washing with alcohol again.Be deposited in drying at room temperature, promptly obtain having the divergent shape flower shape Ce of condensation center
2O (CO
3)
2H
2O white powder, XRD confirms that its crystallization degree is strong.
Example 6: with the solid cerous salt 0.1molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 50.The adding weight percent is 0.7% the water-soluble polyoxyethylene sorbitan ester (tween-80) of tensio-active agent in this mother liquor, and mixed solution is put into 80 ℃ water bath with thermostatic control continuously stirring a few hours, and reaction process produces abundant white foam.Use the centrifuging precipitation separation, throw out is spent water washing after, use washing with alcohol again.Be deposited in drying at room temperature, promptly obtain having the divergent shape flower shape Ce of condensation center
2O (CO
3)
2H
2O white powder, XRD confirms that its crystallization degree is stronger.
Example 7: with the solid cerous salt 0.2molL that is made into soluble in water
-1Solution, in this solution, add urea and be made into Ce
3+: the clarified mother liquor of urea=1: 20.The adding weight percent is three block surfactant polyethylene-polyglycerol-polyoxyethylene glycol (P123) of 0.8% in this mother liquor, and mixed solution is put into 90 ℃ water bath with thermostatic control continuously stirring a few hours, and reaction process produces abundant white foam.Use the centrifuging precipitation separation, throw out is spent water washing after, use washing with alcohol again.Be deposited in drying at room temperature, promptly obtain having the white Ce of various spherical, flower-shaped, bar-shaped mixing patterns
2O (CO
3)
2H
2O powder, XRD confirm that its crystallization degree is strong.
Chart 1 has been listed the influence of different surfaces promoting agent to the product pattern.
Table 1 different surfaces promoting agent is to the influence of product pattern
| Kinds of surfactants | Pattern | Crystallization degree | |
| Do not have | The spindle shape, inhomogeneous | Difference | |
| Ionogenic surfactant | CTAB A-OT | The shuttle shape, evenly sheet is more even | Better good |
| Nonionic surface active agent | PEG19000 PVA-124 OP-10 Tween-80 | Bar-shaped, ordered arrangement is bar-shaped, ordered arrangement is flower-shaped, there is nucleus of condensation flower-shaped, nucleus of condensation is arranged | Good better carefully |
| Three block tensio-active agents | P123 | Mix pattern | Good |
Claims (2)
1 one kinds of CeO that pattern is controlled
2Presoma---Ce
2O (CO
3)
2H
2The preparation method of O powder is characterized in that, step is as follows:
1) the solid cerous salt is dissolved in is made into 0.05～0.5mol/L solution in the distilled water;
2) urea is joined in the above-mentioned cerium solution, and make Ce
3+With the urea uniform mixing, be made into Ce
3+: urea mol ratio=1: 20-1: 50 clarified mother liquor;
3) adding weight percent is that 0.1～1% tensio-active agent is in above-mentioned mixing solutions;
4) mixed solution is put into 70～95 ℃ water bath with thermostatic control continuously stirring, reacted fully and carry out, and obtain precipitation;
5), promptly obtain having the white Ce of various patterns with precipitate and separate, collection, washing, drying
2O (CO
3)
2H
2The O powder
2, the controlled CeO of pattern according to claim 1
2Presoma---Ce
2O (CO
3)
2H
2The preparation method of O powder is characterized in that, above-mentioned steps 2) tensio-active agent be ionogenic surfactant, nonionic surface active agent, three block nonionic surface active agent thrins.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284952B (en) * | 2007-04-12 | 2011-03-23 | 北京有色金属研究总院 | Abrasive grain CeO2 for chemical and mechanical buffing and method for preparing same |
| CN102502758A (en) * | 2011-10-28 | 2012-06-20 | 包头市京瑞新材料有限公司 | Method for preparing large-particle cerium oxide |
| CN103214015A (en) * | 2013-04-12 | 2013-07-24 | 内蒙古科技大学 | Method for regulating and controlling synthesized petaloid cerium oxide by utilizing cationic polyelectrolyte template |
| CN109110794A (en) * | 2018-10-12 | 2019-01-01 | 青岛科技大学 | A kind of preparation method of hydrated rare-earth carbonic acid oxonium salt |
| CN110255599A (en) * | 2019-07-11 | 2019-09-20 | 河北铭万精细化工有限公司 | A kind of preparation method of nano cerium oxide powder |
| CN112875741A (en) * | 2021-01-28 | 2021-06-01 | 浙江师范大学 | Broadband hydrated cerium oxycarbonate microwave absorbent, and preparation process and application thereof |
| CN115305053A (en) * | 2022-01-24 | 2022-11-08 | 浙江师范大学 | Cerium-based hollow nano wave-absorbing material and preparation method and application thereof |
-
2005
- 2005-09-09 CN CN 200510098336 patent/CN1762819A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284952B (en) * | 2007-04-12 | 2011-03-23 | 北京有色金属研究总院 | Abrasive grain CeO2 for chemical and mechanical buffing and method for preparing same |
| CN102502758A (en) * | 2011-10-28 | 2012-06-20 | 包头市京瑞新材料有限公司 | Method for preparing large-particle cerium oxide |
| CN103214015A (en) * | 2013-04-12 | 2013-07-24 | 内蒙古科技大学 | Method for regulating and controlling synthesized petaloid cerium oxide by utilizing cationic polyelectrolyte template |
| CN103214015B (en) * | 2013-04-12 | 2014-11-26 | 内蒙古科技大学 | Method for regulating and controlling synthesized petaloid cerium oxide by utilizing cationic polyelectrolyte template |
| CN109110794A (en) * | 2018-10-12 | 2019-01-01 | 青岛科技大学 | A kind of preparation method of hydrated rare-earth carbonic acid oxonium salt |
| CN110255599A (en) * | 2019-07-11 | 2019-09-20 | 河北铭万精细化工有限公司 | A kind of preparation method of nano cerium oxide powder |
| CN110255599B (en) * | 2019-07-11 | 2022-02-01 | 河北铭万精细化工有限公司 | Preparation method of nano cerium oxide powder |
| CN112875741A (en) * | 2021-01-28 | 2021-06-01 | 浙江师范大学 | Broadband hydrated cerium oxycarbonate microwave absorbent, and preparation process and application thereof |
| CN115305053A (en) * | 2022-01-24 | 2022-11-08 | 浙江师范大学 | Cerium-based hollow nano wave-absorbing material and preparation method and application thereof |
| CN115305053B (en) * | 2022-01-24 | 2023-08-11 | 浙江师范大学 | Cerium-based hollow nano wave-absorbing material and preparation method and application thereof |
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