CN112194169B - Preparation method of cerium oxide with specific mixed valence state - Google Patents
Preparation method of cerium oxide with specific mixed valence state Download PDFInfo
- Publication number
- CN112194169B CN112194169B CN202011075000.XA CN202011075000A CN112194169B CN 112194169 B CN112194169 B CN 112194169B CN 202011075000 A CN202011075000 A CN 202011075000A CN 112194169 B CN112194169 B CN 112194169B
- Authority
- CN
- China
- Prior art keywords
- cerium
- cerium oxide
- aqueous solution
- solution
- oxide powder
- 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.)
- Active
Links
Images
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
- 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
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Cosmetics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of cerium oxide with a specific mixed valence state, which comprises the following steps: (1) under the condition of continuously stirring, adding a complexing agent and a template agent into a trivalent cerium salt aqueous solution in sequence to obtain a mixed solution; then adding a pH value regulator into the mixed solution until the pH value of the mixed solution is 2-6; (2) continuously stirring for 10-60 minutes, carrying out solid-liquid separation, and drying to obtain a precursor of cerium oxide powder; (3) spray roasting the precursor of the cerium oxide powder at 200-500 ℃, and cooling the roasted product by adopting inert gas to obtain the cerium oxide powder with the mass content of trivalent cerium of 60% and tetravalent cerium of 40%. The invention can prepare cerium oxide with specific mixed valence state, and has better ultraviolet shielding effect.
Description
Technical Field
The invention belongs to the technical field of inorganic material preparation, and mainly relates to a preparation method of cerium oxide with a specific mixed valence state.
Background
The common cerium oxide is cerium oxide (Ce)2O3) And cerium oxide (CeO)2). Ce in cerium dioxide4+/Ce3+Has smaller oxidation-reduction potential (1.3-1.8V) and can be mutually switched under different oxidation-reduction atmospheres. For example, in a three-way catalytic system, ceria acts as an oxygen storage material, buffering the change in oxygen concentration, i.e., releasing oxygen to increase oxygen concentration during lean conditions and absorbing oxygen to decrease oxygen concentration during rich conditions. In the actual catalytic reaction, the atmosphere in which the catalyst is exposed may alternately have excess and deficiency of oxygen concentration, and in this case, ceria may be used in the atmosphere having excess oxygen concentration2NO and H2Absorption of storage of O in O2And releases oxygen in environments with insufficient oxygen concentration. Because cerium ions can form unstable oxygen vacancies in the process of valence change, the cerium ions can be used as catalysts and promotersThe catalyst and the solid oxide fuel cell have very unique application. Pure cerium oxide is white heavy powder or cubic crystal, and impure products are light yellow and even pink to reddish brown (because of containing trace lanthanum, praseodymium and the like), and are hardly soluble in water and acid.
At present, common preparation methods of cerium oxide include: combustion, complex precipitation, hydrothermal synthesis, microwave, direct precipitation and sol-gel.
The combustion method is that solid cerium nitrate and citric acid are fully ground for 1 hour to obtain a slurry-like mixture which is uniformly mixed, and the slurry-like mixture is dissolved by using a proper amount of deionized water, dried and roasted to obtain loose foam-like nano cerium dioxide powder.
The complex precipitation method is to add cerium carbonate into citric acid solution and adjust the pH value with ammonia water until the precipitate is dissolved. Adding hydrochloric acid to obtain precipitate, filtering, washing, drying and roasting to obtain the cerium oxide superfine powder.
The hydrothermal synthesis method is that a certain amount of template agent glucose is put into cerium salt solution until the template agent glucose is completely dissolved, and the mixture is stirred at constant temperature, and a certain amount of template agent ethylenediamine is added while stirring. Carrying out hydrothermal reaction in a reaction kettle, stirring, filtering, drying and roasting to obtain the nano cerium oxide with the mesoporous structure.
The microwave method is to add sodium hydroxide into ceric sulfate tetrahydrate and polyethylene glycol solution to generate precipitate, and the precipitate is crystallized, filtered, washed, re-microwaved, dried and ground to obtain nano cerium dioxide with the particle size of about 25 nm.
The direct precipitation method comprises the steps of adding polyethylene glycol serving as a dispersant into a cerium nitrate solution, adjusting the pH value to be 4-5 by using ammonia water, adjusting the pH value of the solution to be 7-8 by using ammonium bicarbonate, stirring, aging, filtering, cleaning with absolute ethyl alcohol, drying and roasting to obtain cerium oxide with the grain size of 8-34 nm.
The sol-gel method is to gradually add cerous nitrate solution into citric acid solution, add a certain amount of PEG2000, adjust pH, heat at constant temperature to obtain semi-dry gel, dry, grind and bake to obtain cerium dioxide nano-powder.
The content of trivalent cerium in the cerium oxide powder prepared by the conventional method generally does not exceed the content of tetravalent cerium, and few studies are currently made on the preparation of cerium oxide in a specific mixed valence state. The conventional cerium oxide powder has an ultraviolet shielding effect, the absorption limit is about 350nm, and the width of the absorption wavelength is narrow.
Disclosure of Invention
Technical problem to be solved
In order to solve the technical problems, the invention provides a preparation method of cerium oxide with a specific mixed valence state, which is characterized in that cerium ions are precipitated by a precipitator under the synergistic action of a plurality of additives, and then the cerium oxide with a fixed mass content of trivalent cerium is prepared by spray roasting and rapid decomposition. And the prepared cerium oxide has better ultraviolet shielding effect and wider ultraviolet absorption wavelength.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in one aspect, the present invention provides a method for preparing cerium oxide having a specific mixed valence state, comprising the steps of:
(1) under the condition of continuously stirring, adding a complexing agent and a template agent into a trivalent cerium salt aqueous solution in sequence to obtain a mixed solution; wherein the complexing agent is mixed with Ce3+The molar ratio of (a) to (b) is 0.3-3: 1, templating agent and Ce3+In a molar ratio of 0.01 to 1: 1; then adding a pH value regulator into the mixed solution until the pH value of the mixed solution is 2-6;
(2) continuously stirring for 10-60 minutes, carrying out solid-liquid separation, and drying to obtain a precursor of cerium oxide powder;
(3) spray roasting the precursor of the cerium oxide powder at 200-500 ℃, and cooling the roasted product by adopting inert gas to obtain the cerium oxide powder with the mass content of trivalent cerium of 60% and tetravalent cerium of 40%.
Optionally, the temperature of the trivalent cerium salt aqueous solution is maintained at 20-50 ℃.
Optionally, the trivalent cerium salt aqueous solution is 0.5-1.5 mol/L cerium chloride aqueous solution or cerium nitrate aqueous solution.
Optionally, the complexing agent is an aqueous EDTA solution, an aqueous citric acid solution, or an aqueous lactic acid solution.
Optionally, the concentration of the complexing agent is 0.05-3 mol/L.
Optionally, the templating agent is an aqueous glucose solution, an aqueous polyethylene glycol solution, or an aqueous polyacrylamide solution.
Optionally, the concentration of the template agent is 0.05-3 mol/L.
Optionally, the pH value regulator is a sodium hydroxide solution with the concentration of 10 mol/L.
In another aspect, the present invention also provides a cerium oxide prepared by the above method.
(III) advantageous effects
The invention has the beneficial effects that: the cerium oxide powder with high content of trivalent cerium has better ultraviolet shielding effect, and the absorption limit can generate red shift, so the cerium oxide powder prepared by the method has the ultraviolet shielding effect with wide wavelength, has small crystal grain size, and can be used as an ultraviolet shielding agent.
Drawings
Fig. 1 is an XRD pattern of cerium oxide prepared by the preparation method of example 1 of the present invention.
Fig. 2 is an SEM image of cerium oxide prepared by the preparation method of example 1 of the present invention.
Fig. 3 is a graph showing the ultraviolet transmittance of cerium oxide prepared by the preparation method of example 1 of the present invention.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of specific embodiments thereof.
The invention provides a preparation method of cerium oxide with a specific mixed valence state, which comprises the following steps:
(1) sequentially adding a complexing agent and a template agent into a trivalent cerium salt aqueous solution by using a peristaltic pump under the condition that the temperature of the trivalent cerium salt aqueous solution is 20-50 ℃ and stirring is carried out continuously to obtain a mixed solution; then adding a pH value regulator into the mixed solution by using a peristaltic pump until the pH value of the mixed solution is 2-6; wherein the complexing agent is mixed with Ce3+The molar ratio of (a) to (b) is 0.3-3: 1, templating agent and Ce3+In a molar ratio of 0.01 to 1: 1;
(2) after the pH value of the mixed solution is adjusted to the designated value, continuously stirring for 10-60 minutes, filtering and drying to obtain a precursor of cerium oxide powder;
(3) roasting a precursor of cerium oxide powder in a spray roaster at 200-500 ℃ in a spray roasting mode, and cooling a roasted product to normal temperature by adopting inert gas at a product collecting position of the spray roaster to obtain the cerium oxide powder with the mass content of trivalent cerium of 60% and the mass content of tetravalent cerium of 40%.
Specifically, the trivalent cerium salt aqueous solution is 0.5-1.5 mol/L cerium chloride aqueous solution or cerium nitrate aqueous solution.
Specifically, the complexing agent is an aqueous solution of EDTA, citric acid or lactic acid, and the concentration of the complexing agent is 0.05-3 mol/L.
Specifically, the template agent is an aqueous solution of glucose, polyethylene glycol or polyacrylamide, and the concentration of the template agent is 0.05-3 mol/L.
Specifically, the pH value regulator is a sodium hydroxide solution with the concentration of 10 mol/L.
The characteristics and technical effects of the preparation method of the present invention are described below with reference to specific examples. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In the embodiment of the invention, the drying is carried out by heating to 60 +/-2 ℃ and keeping the temperature to remove the moisture.
Example 1
Sequentially adding a citric acid solution with the concentration of 3mol/L and a glucose solution with the concentration of 3mol/L into a cerium chloride aqueous solution with the concentration of cerium ions of 0.5mol/L by using a peristaltic pump under the condition that the temperature of the cerium chloride aqueous solution is 20 ℃ and the stirring is carried out continuously to obtain a mixed solution; then, a sodium hydroxide solution with a concentration of 10mol/L was added to the above mixed solution by a peristaltic pump until the pH of the mixed solution became 6. Wherein, citric acid and Ce3+Is 0.3: 1, glucose and Ce3+In a molar ratio of 0.01: 1.
and after the pH value of the mixed solution is adjusted to 6, continuously stirring for 10 minutes, filtering and drying to obtain a precursor of the cerium oxide powder.
Roasting a precursor of cerium oxide powder in a spray roaster at 500 ℃ in a spray roasting mode, and cooling a roasted product to normal temperature by adopting inert gas at a product collecting position of the spray roaster to obtain the cerium oxide powder with the mass content of trivalent cerium of 60% and tetravalent cerium of 40%, wherein the grain size of the cerium oxide powder is about 5.2 nm. The average ultraviolet transmittance of the cerium oxide prepared by the embodiment is about 6% in the ultraviolet range of 315-400 nm through an ultraviolet spectrometer test. As can be seen from fig. 1, the product prepared in this example is cerium oxide. As can be seen from fig. 2, the product size is uniform and the grain size is small, about 5.2 nm. As can be seen from FIG. 3, the average ultraviolet transmittance of the prepared cerium oxide is about 6% at 315-400 nm.
The order of adding citric acid and glucose in this embodiment is not required, and citric acid may be added first and then glucose may be added, or glucose may be added first and then citric acid may be added. The method can be used for preparing the cerium oxide with a specific mixed valence state, glucose molecules can be aggregated in a hydrogen bonding mode due to the fact that the glucose molecules contain a plurality of hydroxyl groups to form aggregates with different shapes, and small aggregates formed by the glucose molecules can be subjected to hydrogen bonding with-OH in cerium citrate complex ions to form a cerium-citric acid-glucose polymer. In the roasting process, citric acid and glucose are easy to dehydrate to form carbon species at first and are removed by oxygen combustion, so that the oxidation of cerium by oxygen is prevented, and the formation of tetravalent cerium is avoided. Therefore, the valence state of cerium in the roasted product can be controlled by the synergistic action of glucose and citric acid, so that the mass content of trivalent cerium in the roasted product is larger than that of tetravalent cerium, and the ultraviolet shielding effect of the product cerium oxide powder can be effectively improved.
Example 2
Under the condition that the temperature of the cerous nitrate aqueous solution is 50 ℃, and the mixture is continuously stirred, an EDTA solution with the concentration of 0.05mol/L and a polyethylene glycol solution with the concentration of 0.05mol/L are successively added into the cerous nitrate aqueous solution with the cerium ion concentration of 0.5mol/L by a peristaltic pumpObtaining a mixed solution; then, a sodium hydroxide solution with a concentration of 10mol/L was added to the above mixed solution by a peristaltic pump until the pH value of the mixed solution was 2. Wherein, EDTA and Ce3+In a molar ratio of 3: 1, polyethylene glycol and Ce3+In a molar ratio of 1: 1.
and after the pH value of the mixed solution is adjusted to 2, continuously stirring for 60 minutes, filtering and drying to obtain a precursor of the cerium oxide powder.
Roasting a precursor of cerium oxide powder in a spray roaster at 200 ℃ in a spray roasting mode, and cooling a roasted product to normal temperature by adopting inert gas at a product collecting position of the spray roaster to obtain the cerium oxide powder with the trivalent cerium mass content of 60% and the tetravalent cerium mass content of 40%, wherein the grain size of the cerium oxide powder is about 5.5 nm. The average ultraviolet transmittance of the cerium oxide prepared by the embodiment is about 6% in the ultraviolet range of 315-400 nm through an ultraviolet spectrometer test.
The order of addition of EDTA and polyethylene glycol in this embodiment is not required, and EDTA may be added first, followed by addition of polyethylene glycol, or polyethylene glycol may be added first, followed by addition of EDTA.
Example 3
Sequentially adding a lactic acid solution with the concentration of 1mol/L and a polyacrylamide solution with the concentration of 1mol/L into a cerium chloride aqueous solution with the concentration of cerium ions of 0.5mol/L by using a peristaltic pump under the condition that the temperature of the cerium chloride aqueous solution is 30 ℃ and the stirring is carried out continuously to obtain a mixed solution; then, a sodium hydroxide solution with a concentration of 10mol/L was added to the above mixed solution by a peristaltic pump until the pH of the mixed solution was 4. Wherein, lactic acid and Ce3+In a molar ratio of 1: 1, polyacrylamide and Ce3+In a molar ratio of 0.5: 1.
and after the pH value of the mixed solution is adjusted to 4, continuously stirring for 30 minutes, filtering and drying to obtain a precursor of the cerium oxide powder.
Roasting a precursor of cerium oxide powder in a spray roaster at 350 ℃ in a spray roasting mode, and cooling a roasted product to normal temperature by adopting inert gas at a product collecting position of the spray roaster to obtain the cerium oxide powder with the mass content of trivalent cerium of 60% and tetravalent cerium of 40%, wherein the grain size of the cerium oxide powder is about 5.3 nm. The average ultraviolet transmittance of the cerium oxide prepared by the embodiment is about 6% in the ultraviolet range of 315-400 nm through an ultraviolet spectrometer test.
The order of adding lactic acid and polyacrylamide in this embodiment is not required, and lactic acid may be added first, and then polyacrylamide may be added, or polyacrylamide may be added first, and then lactic acid may be added.
In short, by adopting the preparation process of the invention, cerium oxide with a specific mixed valence state can be prepared, so that the mass content of trivalent cerium is larger than that of tetravalent cerium, and because cerium oxide powder with high content of trivalent cerium has better ultraviolet shielding effect and red shift of absorption limit can occur, the cerium oxide powder prepared by the invention has wide-wavelength ultraviolet shielding effect and small crystal grain size, and can be used as an ultraviolet shielding agent.
Although embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are illustrative and not restrictive, and that those skilled in the art may make changes, modifications, substitutions and alterations to the above embodiments without departing from the scope of the present invention.
Claims (7)
1. A method for preparing cerium oxide with a specific mixed valence state is characterized by comprising the following steps:
(1) under the condition of continuously stirring, adding a complexing agent and a template agent into a trivalent cerium salt aqueous solution in sequence to obtain a mixed solution; wherein the complexing agent is mixed with Ce3+The molar ratio of (a) to (b) is 0.3-3: 1, templating agent and Ce3+In a molar ratio of 0.01 to 1: 1; then adding a pH value regulator into the mixed solution until the pH value of the mixed solution is 2-6; the complexing agent is an EDTA aqueous solution, a citric acid aqueous solution or a lactic acid aqueous solution; the template agent is a glucose aqueous solution, a polyethylene glycol aqueous solution or a polyacrylamide aqueous solution;
(2) continuously stirring for 10-60 minutes, carrying out solid-liquid separation, and drying to obtain a precursor of cerium oxide powder;
(3) spray roasting the precursor of the cerium oxide powder at 200-500 ℃, and cooling the roasted product by adopting inert gas to obtain the cerium oxide powder with the mass content of trivalent cerium of 60% and tetravalent cerium of 40%.
2. The method of claim 1, wherein the temperature of the aqueous solution of the trivalent cerium salt is maintained at 20-50 ℃.
3. The method of claim 1 or 2, wherein the aqueous solution of trivalent cerium salt is 0.5-1.5 mol/L aqueous solution of cerium chloride or cerium nitrate.
4. The method according to claim 1, wherein the concentration of the complexing agent is 0.05-3 mol/L.
5. The method according to claim 1, wherein the concentration of the template agent is 0.05-3 mol/L.
6. The method according to claim 1, wherein the pH regulator is 10mol/L NaOH solution.
7. A cerium oxide prepared by the preparation method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011075000.XA CN112194169B (en) | 2020-10-09 | 2020-10-09 | Preparation method of cerium oxide with specific mixed valence state |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011075000.XA CN112194169B (en) | 2020-10-09 | 2020-10-09 | Preparation method of cerium oxide with specific mixed valence state |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112194169A CN112194169A (en) | 2021-01-08 |
| CN112194169B true CN112194169B (en) | 2021-10-01 |
Family
ID=74013535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011075000.XA Active CN112194169B (en) | 2020-10-09 | 2020-10-09 | Preparation method of cerium oxide with specific mixed valence state |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112194169B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578396A (en) * | 2021-08-18 | 2021-11-02 | 国能龙源催化剂江苏有限公司 | High-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak regulation and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7504356B1 (en) * | 2006-02-17 | 2009-03-17 | University Of Central Florida Research Foundation, Inc. | Nanoparticles of cerium oxide having superoxide dismutase activity |
| CN101550318A (en) * | 2008-04-03 | 2009-10-07 | 北京有色金属研究总院 | Ce<3+>-contained rare-earth polishing powder and preparation method thereof |
| CN102559138A (en) * | 2010-12-23 | 2012-07-11 | 北京有色金属研究总院 | Fluorine ion and metal ion-doped cerium oxide-based nanometer ultraviolet shielding material and preparation method thereof |
| CN110560033A (en) * | 2019-08-09 | 2019-12-13 | 山东国瓷功能材料股份有限公司 | Stable cerium-zirconium solid solution and preparation method and application thereof |
-
2020
- 2020-10-09 CN CN202011075000.XA patent/CN112194169B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7504356B1 (en) * | 2006-02-17 | 2009-03-17 | University Of Central Florida Research Foundation, Inc. | Nanoparticles of cerium oxide having superoxide dismutase activity |
| CN101550318A (en) * | 2008-04-03 | 2009-10-07 | 北京有色金属研究总院 | Ce<3+>-contained rare-earth polishing powder and preparation method thereof |
| CN102559138A (en) * | 2010-12-23 | 2012-07-11 | 北京有色金属研究总院 | Fluorine ion and metal ion-doped cerium oxide-based nanometer ultraviolet shielding material and preparation method thereof |
| CN110560033A (en) * | 2019-08-09 | 2019-12-13 | 山东国瓷功能材料股份有限公司 | Stable cerium-zirconium solid solution and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 氯化铈溶液喷雾焙烧制备纳米氧化铈实心粉体的研究;杨国胜等;《稀土》;20170228;第72-78页 * |
| 超细氧化铈制备工艺研究;吴文远等;《东北大学学报(自然科学版)》;20150630;第800-804页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112194169A (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021208596A1 (en) | Catalyst for ozone decomposition, preparation method therefor and use thereof | |
| CN108855109B (en) | Synthetic gas oxygen carrier prepared by oxidizing methane with chemical chain part and preparation method and application thereof | |
| EP1872851B1 (en) | Cerium oxide-zirconium oxide-based mixed oxide and method for the production thereof | |
| CN100488623C (en) | Solid solution composition of cerium zirconium compound oxide with high specific surface and method for preparing the same | |
| JP3251951B2 (en) | Zirconia with large surface area | |
| CN106824163B (en) | Composite oxides and preparation method thereof | |
| CN108380221A (en) | A kind of preparation method and products thereof of stratiform cobalt manganese bimetallic oxide | |
| CN110026179B (en) | Cerium-zirconium composite oxide with high oxygen storage capacity and preparation method thereof | |
| CN112194169B (en) | Preparation method of cerium oxide with specific mixed valence state | |
| CN108554398B (en) | Preparation method and application of wide-temperature-window denitration catalyst | |
| DE112011105502T5 (en) | Redox material for thermochemical water splitting and method for producing hydrogen | |
| CN110327909B (en) | Preparation method of cerium-zirconium composite oxide with high oxygen storage capacity | |
| CN114192149A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| JP4972868B2 (en) | Surface-modified ceria / zirconia hydrated oxide, oxide thereof, production method thereof, and use thereof | |
| CN110721706A (en) | Oxidation catalyst for purifying CO and preparation method and application thereof | |
| JPH10216522A (en) | Catalyst for methanol synthesis | |
| CN113262780A (en) | High-activity and high-stability manganese-based carbon smoke catalyst and preparation method and application thereof | |
| CN115974549B (en) | Preparation method of cerium-zirconium solid solution and method for regulating and controlling cerium valence ratio and oxygen vacancy concentration of cerium-zirconium solid solution | |
| CN110860296A (en) | Method for preparing crystal face-controllable nano cerium-based composite oxide based on cellulose | |
| CN114735730B (en) | High-purity zinc aluminate spinel and preparation method thereof | |
| CN113617345B (en) | Catalyst and preparation method and application thereof | |
| CN114870859A (en) | Copper-based catalyst for hydrogen production by methanol steam reforming and preparation method thereof | |
| CN104624203B (en) | Pb modified Co oxide matrix N2O decomposition catalyst as well as preparation method and application of catalyst | |
| CN117509724B (en) | Cerium-zirconium composite oxide and preparation method thereof | |
| JP4061679B2 (en) | Zirconia fine powder and method for producing the same |
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 |