CN112844444A - Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle - Google Patents
Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle Download PDFInfo
- Publication number
- CN112844444A CN112844444A CN202110099115.0A CN202110099115A CN112844444A CN 112844444 A CN112844444 A CN 112844444A CN 202110099115 A CN202110099115 A CN 202110099115A CN 112844444 A CN112844444 A CN 112844444A
- Authority
- CN
- China
- Prior art keywords
- cerium
- catalytic
- cerium dioxide
- drying
- catalytic material
- 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.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention discloses a method for preparing a cerium dioxide catalytic material by utilizing a carrier pore passage self-adsorption principle, belonging to the technical field of catalytic material preparation. The preparation process comprises the following steps: and (2) taking a cerium salt water solution as a precursor, taking an SBA-15 molecular sieve material as a hard template, fully stirring and mixing to enable metal ions to be fully adsorbed into carrier pore channels, drying and calcining, and carrying out corrosion treatment on the obtained powder by using a strong acid solution to obtain the cerium dioxide material with uniform morphology. The cerium dioxide material prepared by the method has the performance characteristics of uniform appearance and granularity, excellent reducibility and the like, can be used as a catalytic oxidation auxiliary agent, an oxygen storage material and the like, and is used in the fields of catalytic oxidation of carbon monoxide or alkanes, three-way catalytic purification of automobile exhaust, catalytic combustion and the like.
Description
Technical Field
The invention belongs to the field of preparation of catalytic materials, and particularly relates to a method for preparing a cerium dioxide catalytic material by utilizing a carrier pore channel self-adsorption principle.
Background
Rare earth catalytic materials represented by cerium dioxide are widely applied to the aspects of motor vehicle exhaust treatment, industrial flue gas denitration and catalytic combustion of volatile organic pollutants (VOCs). A requirement in the design of catalytic materials is to increase the overall life of the catalytic material while ensuring that the activity remains at a high level. Therefore, how to further improve the stability of ceria and its composite oxide itself has been a focus of research in this field. The preparation of cerium dioxide materials with high specific surface area and high thermal stability by means of different synthesis methods, optimized synthesis processes and the like is a common technical route. The synthesis method of the cerium dioxide material is various, and the common powder material synthesis method can be used for preparing the cerium dioxide and the composite oxide thereof. In consideration of industrialization, cost and other factors, the liquid phase method, especially the coprecipitation method, is mainly adopted for large-scale preparation in the current practical production. In laboratory research, with the continuous development of material preparation technology, synthesis methods such as a sol-gel method, a template method, a high-energy ball milling method and the like have been applied to the preparation of cerium dioxide and composite oxides thereof.
The coprecipitation method has the characteristics of simple operation, controllable process and the like, and has high industrial application value. The method is the most widely applied preparation process in the industry at present, and cerium dioxide and composite oxide products thereof with different specific surface areas can be obtained by adjusting process parameters such as a washing mode, a drying mode, a surfactant adding condition, an aging time and the like. In the preparation process of the sol-gel method, the raw materials are uniformly dispersed in the solvent on the molecular level, which is beneficial to improving the component uniformity of the synthesized sample. However, the cost of some organic salts is high, which leads to an increase in the production cost of the sol-gel process. Although the products prepared by the coprecipitation method and the sol-gel method have fine particles, the agglomeration state is not uniform, so that the powder is easy to sinter. The high-energy ball milling method mixes the powder raw materials according to the required metering ratio, then places the mixture and the milling balls into a ball milling tank, and obtains products with different particle sizes and specific surface areas by utilizing the equivalent effect of crushing and diffusion in the ball milling process. The high-energy ball milling method is simple and convenient, but impurities are easily introduced in the high-energy ball milling process, and the synthesized powder material is generally uneven in component distribution and generally low in specific surface area.
The template method is a kind of wet chemical preparation method emerging in recent years, and carriers with special structures such as surfactants, high molecular compounds, inorganic materials and the like are usually used as templates, so that the precise regulation and control of the morphology, size and structure of the materials in the synthesis process can be realized. But has the disadvantages of complex process and long synthesis period.
1) Patent CN111362295A reports a high specific surface area ordered large mesoporous cerium oxide material and a preparation method thereof, and specifically relates to a material for controllably synthesizing ordered large mesoporous cerium oxide by using mesoporous silicon oxide as a hard template and a preparation method thereof. The method is characterized in that mesoporous silicon oxide with larger hole wall connecting holes is prepared by a hydrothermal method, a solvent is adopted for assisting impregnation to enable a precursor to enter a pore channel, a mesoporous structure is reserved after a template is etched, and the mesoporous structure is used for adsorbing heavy metal ions.
2) Patent CN 107827141B provides a nano ceria and a preparation method thereof, specifically, silane coupling agent is used as a soft template and added into cerium nitrate solution, and the reaction is performed in a closed system to obtain a product, and the product is dried to obtain the nano spherical ceria.
3) Patent CN 110975857 a discloses a three-dimensional ordered macroporous oxygen defect type ceria catalyst, its preparation method and application. Specifically, the catalyst is prepared by adopting a polymethyl methacrylate (PMMA) colloidal crystal template method and performing reduction/oxidation atmosphere calcination and water vapor treatment, and the prepared catalyst shows excellent activity and stability in photothermal catalytic purification of typical atmospheric pollutants such as styrene, normal hexane and cyclohexane.
4) Patent CN 104587949B discloses a method for preparing cerium dioxide for treating fluorine-containing wastewater in lead-zinc smelting by a biological template and organic template double-template method. Specifically, the cerium modified material can be obtained by adding an organic template into an algae template and carrying out the processes of dipping, cerium modification and calcination. The prepared material is used for removing fluorine.
5) CN 109534383A provides a synthesis method of ultrathin cerium dioxide nanosheets, which is characterized in that a precipitator and a nonionic surfactant are added into a cerium salt solution, an oxidant is added after the cerium salt solution is fully stirred and is uniformly stirred, the mixture is heated in a water bath circularly and is continuously stirred, and the cerium dioxide nanosheets are obtained after the processes of precipitation, suction filtration, washing and airflow grinding.
6) Patent CN1837053A discloses a method for preparing mesoporous ceria, which specifically comprises adding a surfactant as a template agent into a cerium salt solution, adding a precipitant at the same time, forming a precipitate, and then filtering, drying and roasting to obtain the material. The reaction condition and the roasting condition are changed to obtain materials with different grain sizes and pore size ranges.
7) Patent CN100567160C discloses a preparation method of mesoporous ceria microspheres with high specific surface area. Specifically, ammonium ceric nitrate is used as a cerium source, N-dimethylformamide is used as a surfactant, and a precursor obtained after hydrothermal reaction for several hours is sintered to form spherical and hemispherical mesoporous cerium dioxide.
8) Patent CN103342378B discloses a method for preparing ceria with a hierarchical pore structure, which mainly uses a surfactant or a block copolymer as a soft template, and artemia cysts as a hard template to prepare the ceria material with hierarchical pores.
In the preparation method in the prior art, the template type adopts a soft template or a biological template, or the template is prepared by a surfactant and a hydrothermal method, or a precursor enters the template through solvent-assisted impregnation; in addition, the method for preparing the ceria catalytic material by using the self-adsorption principle of the carrier pore channels is needed to be provided based on the above problems.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing a cerium dioxide catalytic material by utilizing a carrier pore channel self-adsorption principle, which comprises the following steps:
1) mixing cerium salt and deionized water according to a mass ratio of 1: 10-20 to obtain a precursor solution A containing cerium ions;
2) adding an SBA-15 molecular sieve carrier into the precursor solution A, and fully stirring for 1-5 hours to enable metal ions to be fully adsorbed into carrier channels to obtain a suspension B;
3) putting the suspension B into a drying oven for drying, and then putting the suspension B into a muffle furnace for calcining at a high temperature to obtain a powder sample C;
4) mixing the powder sample C with a strong acid solution, fully stirring and corroding;
5) and after the corrosion is finished, performing centrifugal treatment to obtain corroded powder, adding deionized water, centrifuging, and performing secondary drying in an oven to obtain the cerium dioxide catalytic material.
The SBA-15 molecular sieve material has a highly ordered two-dimensional hexagonal through hole structure, and a stronger electrostatic field exists in the interior of a pore channel, so that polar molecules with the diameter smaller than that of the pore channel can be adsorbed into the interior of the pore channel from an aqueous solution spontaneously only in the stirring process. The cerium salt solution absorbed into the pore channels can be decomposed to form CeO in the drying and calcining processes2Is fixed in the pore canal of the molecular sieve, and the size of the pore canal limits the sintering growth of cerium dioxide particles in the calcining process. The molecular sieve skeleton made of aluminosilicate compound is dissolved in strong acid, CeO2Is substantially insoluble. Therefore, the SBA-15 molecular sieve framework is completely removed by using a strong acid dissolution mode, and pure CeO is reserved2。
In the step 1), the cerium salt is one or a mixture of two of hydrated cerium nitrate, cerium nitrate and cerium acetate.
In the step 2), the SBA-15 molecular sieve material is of a mesoporous structure, and the aperture size is 5-20 nm.
In the step 3), the drying temperature is 100-120 ℃, and the drying time is 12-24 h.
In the step 3), the calcining temperature is 500-600 ℃, and the calcining time is 3-5 h.
In the step 4), the strong acid solution is one or a mixture of nitric acid, hydrochloric acid, sulfuric acid and hydrofluoric acid.
In the step 4), the mass ratio of the powder sample C to the strong acid solution is 1: 5-10.
In the step 4), the acid corrosion process is carried out at 20-30 ℃, and the corrosion time is 10-30 min.
The centrifugation time after the deionized water in the step 5) is 2-3 times, the secondary drying time is 10-15 h, and the secondary drying temperature is 100-.
The prepared cerium dioxide catalytic material is applied to the fields of catalytic oxidation auxiliaries and oxygen storage materials, and is suitable for catalytic oxidation of carbon monoxide or alkanes, three-way catalytic purification of automobile tail gas and catalytic combustion.
The invention has the beneficial effects that:
1. the preparation method of the nano cerium dioxide is a simple method for preparing the cerium dioxide based on the pore self-adsorption principle by taking an inorganic oxide material with a mesoporous structure as a hard template and taking a commercially available SBA-15 molecular sieve material with a unique hexagonal pore electrostatic field.
2. In the invention, the SBA-15 molecular sieve material sold in the market is directly soaked in the cerium salt aqueous solution, and then the template is corroded after drying and sintering, so that the process is simpler and easier to operate, and the reliability is higher. The method solves the problems that the traditional template method only adopts a soft template, a biological template or a surfactant, the process is complex and the synthesis period is long, and can also realize the uniformity of the size and the appearance of the material in the synthesis process. The preparation method has the advantages of wide raw material source, simple preparation process, easy operation, good repeatability, high reliability, and good batch production and application prospect.
3. The cerium dioxide catalytic material prepared by the method has uniform particle size and better performance than the commercial cerium dioxide system commonly used at present. TPR test shows that the reduction peaks of the CeO are reduced within the range of 300-550 ℃ and above 550 ℃, and are far lower than those of common commercial pure CeO2The reduction peak at the temperature of 700-800 ℃ has more excellent reducibility, is applied to the fields of catalytic oxidation auxiliaries and oxygen storage materials, is suitable for the fields of catalytic oxidation of carbon monoxide or alkanes, three-way catalytic purification of automobile tail gas and catalytic combustion, and is used as a catalytic auxiliary in catalytic purification of waste gas.
Drawings
Fig. 1 is an XRD pattern of the cerium oxide material in example 1. The experimental conditions and parameters were as follows: cu target and Cu K as X-ray sourceα1 
The accelerating voltage is 40kV, the working current is 40mV, the 2 theta range is 10-90 degrees in a theta-2 theta linkage scanning mode, and the scanning step length is0.02 DEG, and a scanning speed of 4 DEG/min.
Fig. 2 is a Scanning Electron Micrograph (SEM) of the cerium oxide material in example 1.
Fig. 3 is a Scanning Electron Micrograph (SEM) of the cerium oxide material in example 2.
Fig. 4 is an XRD pattern of the cerium oxide material in example 3. The experimental conditions and parameters were as follows: cu target and Cu K as X-ray sourceα1 
The acceleration voltage is 40kV, the working current is 40mV, the 2 theta range is 10-90 degrees in a theta-2 theta linkage scanning mode, the scanning step length is 0.02 degree, and the scanning speed is 4 degrees/min.
Fig. 5 is a Transmission Electron Micrograph (TEM) of a cerium oxide material embodying example 4. The magnification is 8000 times.
FIG. 6 is a hydrogen temperature programmed reduction (H) of a ceria material of example 42TPR) curve. Temperature programming reduction test conditions: h2Concentration 10 vol%, N2Balance, flow rate is 50mL/min, test temperature range is 20-1000 ℃, and heating speed is 10 ℃/min.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
example 1:
mixing 37.86g of cerium nitrate hexahydrate and 500mL of deionized water to obtain a precursor solution A containing cerium ions; adding 49.44g of mesoporous molecular sieve SBA-15 into the solution A, and fully stirring for 5 hours to enable cerium ions to be fully adsorbed into a carrier pore channel to obtain suspension B; and then transferring to an oven, drying for 12h at 120 ℃ to obtain dry powder, sending into a muffle furnace, and calcining for 5h at 500 ℃ to obtain a powder sample C. Putting the powder C into 180mL of 0.2M HF solution for corrosion for 10 min; after the corrosion is finished, obtaining corroded powder through centrifugal treatment, adding deionized water for washing for multiple times, and then drying in a 120 ℃ oven for 12 hours to obtain a catalytic material sample, wherein the chemical formula of the catalytic material sample is CeO2。
From the XRD pattern of the cerium oxide material in fig. 1, it is shown that its phase is a cubic fluorite structure and has no other hetero-phase.
Fig. 2 is an SEM image of the ceria material prepared in the present embodiment, which can be observed from the figure, and the microstructure of the ceria material is formed by stacking rod-shaped particles, the diameter of the rod is about 50 to 200nm, the original microstructure of the via hole structure of the SBA-15 molecular sieve template material is retained, and it is further demonstrated that the metal cations in the cerium nitrate are spontaneously adsorbed into the interior of the via hole from the aqueous solution during the stirring process. During the drying and calcining process of the cerium salt solution absorbed into the pore canal, the size of the pore canal limits the sintering growth of cerium dioxide particles in the calcining process to form CeO fixed in the pore canal of the molecular sieve2。
Example 2:
mixing 18.93g of cerous nitrate hexahydrate and 200mL of deionized water to obtain a precursor solution A containing cerium ions; adding 24.94g of mesoporous molecular sieve SBA-15 into the solution A, and fully stirring for 3 hours to enable cerium ions to be fully adsorbed into carrier channels to obtain suspension B; and then transferring to an oven, drying for 12h at 120 ℃ to obtain dry powder, sending into a muffle furnace, and calcining for 5h at 500 ℃ to obtain a powder sample C. Putting the powder C into 180mL of 0.2M HF solution for corrosion for 20 min; after the corrosion is finished, obtaining corroded powder through centrifugal treatment, adding deionized water for washing for multiple times, and then drying in a 120 ℃ oven for 12 hours to obtain a catalytic material sample, wherein the chemical formula of the catalytic material sample is CeO2。
FIG. 3 is an SEM image of the ceria material prepared according to the present embodiment, wherein the microstructure of the ceria material is formed by stacking rod-shaped particles, the diameter of the rod is about 50-200 nm, and the original microstructure of the template material is substantially maintained.
Example 3:
mixing 27.66g of cerium acetate with 300mL of deionized water to obtain a precursor solution A containing cerium ions; adding 49.44g of mesoporous molecular sieve SBA-15 into the solution A, and fully stirring for 5 hours to enable cerium ions to be fully adsorbed into a carrier pore channel to obtain suspension B; and then transferring to an oven, drying for 16h at 100 ℃ to obtain dry powder, sending into a muffle furnace, and calcining for 5h at 500 ℃ to obtain a powder sample C.Putting the powder C into 180mL of 0.2M HF solution for corrosion for 20 min; after the corrosion is finished, obtaining corroded powder through centrifugal treatment, adding deionized water for washing for multiple times, and then drying in a drying oven at 100 ℃ for 16 hours to obtain a catalytic material sample, wherein the chemical formula of the catalytic material sample is CeO2。
Fig. 4 is an XRD pattern of the cerium oxide material prepared in this example, which shows that its phase is a cubic fluorite structure and has no other hetero-phase.
Example 4:
mixing 37.86g of cerium nitrate hexahydrate and 500mL of deionized water to obtain a precursor solution A containing cerium ions; adding 49.44g of mesoporous molecular sieve SBA-15 into the solution A, and fully stirring for 5 hours to enable cerium ions to be fully adsorbed into a carrier pore channel to obtain suspension B; and then transferring to an oven, drying for 12h at 120 ℃ to obtain dry powder, sending into a muffle furnace, and calcining for 5h at 600 ℃ to obtain a powder sample C. Putting the powder C into 180mL of 0.2M HF solution for corrosion for 30 min; after the corrosion is finished, obtaining corroded powder through centrifugal treatment, adding deionized water for washing for multiple times, and then drying in a 120 ℃ oven for 12 hours to obtain a catalytic material sample, wherein the chemical formula of the catalytic material sample is CeO2。
FIG. 5 is a TEM image of the cerium dioxide material prepared by the example, which can be seen more clearly that the micro-morphology still retains the micro-morphology of SBA-15, and the fine nano-CeO2The particles are stacked along the direction of a regular pore channel, grow into a rod shape from a spherical shape gradually, the wall of the pore channel is corroded to be completely removed, and the nano CeO2The radial size distribution of the particles is 5-20 nm, the transverse size is 5nm, and the growth process is further proved to be related to the size of the pore channel of the SBA-15.
In the field of gas phase catalysis, CeO2As an important catalytic promoter, the catalyst does not have strong catalytic activity per se. However, the reversible redox ability of the catalyst can be utilized to regulate the supply and storage of active oxygen during the catalytic process, thereby promoting the catalytic reaction. The lower the redox temperature is, the larger the reducible amount is, and the more easily the reducible amount participates in various redox catalytic reactions to play a role. So we pass through H2TPR test, examining the cerium oxide material preparedThe reducible capability of the material, the results are shown in FIG. 6. The result shows that two small reduction peaks exist in the range of 300-550 ℃, an obvious reduction peak exists above 550 ℃, the peak value is 634 ℃, and the common commercial pure CeO exists2The reduction peak is usually found in the 800 ℃ region of 700-2The reducible capability of the material is better than that of the commercial CeO2。
Claims (10)
1. A method for preparing a cerium dioxide catalytic material by utilizing a carrier pore channel self-adsorption principle is characterized by comprising the following steps:
1) mixing cerium salt and deionized water according to a mass ratio of 1: 10-20 to obtain a precursor solution A containing cerium ions;
2) adding an SBA-15 molecular sieve carrier into the precursor solution A, and fully stirring for 1-5 hours to enable metal ions to be fully adsorbed into carrier channels to obtain a suspension B;
3) putting the suspension B into a drying oven for drying, and then putting the suspension B into a muffle furnace for calcining at a high temperature to obtain a powder sample C;
4) mixing the powder sample C with a strong acid solution, fully stirring and corroding;
5) and after the corrosion is finished, performing centrifugal treatment to obtain corroded powder, adding deionized water, centrifuging, and performing secondary drying in an oven to obtain the cerium dioxide catalytic material.
2. The method as claimed in claim 1), wherein in the step 1), the cerium salt is one or a mixture of two of hydrated cerium nitrate, cerium nitrate and cerium acetate.
3. The method as claimed in claim 1, wherein in the step 2), the SBA-15 molecular sieve material has a mesoporous structure and a pore size of 5-20 nm.
4. The method as claimed in claim 1, wherein the drying temperature in step 3) is 100 ℃ and 120 ℃, and the drying time is 12-24 h.
5. The method according to claim 1, wherein in the step 3), the calcination temperature is 500-600 ℃ and the calcination time is 3-5 h.
6. The method according to claim 1, wherein in the step 4), the strong acidic solution is one or more of nitric acid, hydrochloric acid, sulfuric acid and hydrofluoric acid.
7. The method according to claim 1, wherein in the step 4), the mass ratio of the powder sample C to the strongly acidic solution is 1: 5-10.
8. The method as claimed in claim 1, wherein in the step 4), the acid etching process is performed at 20-30 ℃ for 10-30 min.
9. The method as claimed in claim 1, wherein the centrifugation time after de-ionized water in step 5) is 2-3 times, the secondary drying time is 10-15 h, and the secondary drying temperature is 100-120 ℃.
10. The application of the cerium dioxide catalytic material prepared by the method of any one of claims 1 to 9 is characterized by being applied to the fields of catalytic oxidation auxiliaries and oxygen storage materials, and being suitable for catalytic oxidation of carbon monoxide or alkanes, three-way catalytic purification of automobile exhaust and catalytic combustion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110099115.0A CN112844444A (en) | 2021-01-25 | 2021-01-25 | Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110099115.0A CN112844444A (en) | 2021-01-25 | 2021-01-25 | Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112844444A true CN112844444A (en) | 2021-05-28 |
Family
ID=76008751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110099115.0A Pending CN112844444A (en) | 2021-01-25 | 2021-01-25 | Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112844444A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505046A (en) * | 2022-02-28 | 2022-05-17 | 武汉工程大学 | Cerium dioxide nanocrystalline composite material and preparation method and application thereof |
| CN114904506A (en) * | 2022-04-28 | 2022-08-16 | 济南市环境研究院(济南市黄河流域生态保护促进中心) | Ozone catalyst and preparation method and application thereof |
| CN114940509A (en) * | 2022-07-06 | 2022-08-26 | 四川大学 | Method for preparing hierarchical porous structure cerium dioxide material by re-dissolving after doping zinc |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924144A (en) * | 2012-11-30 | 2013-02-13 | 浙江师范大学 | Method for preparing mesoporous cerium praseodymium composite oxide |
| CN103008015A (en) * | 2011-09-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Preparation method of fuel battery catalyst carrier WO3 (Tungsten Trioxide) |
| WO2015149499A1 (en) * | 2014-04-04 | 2015-10-08 | 同济大学 | Low-temperature and highly efficient denitration catalyst and preparation method therefor |
| 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 |
-
2021
- 2021-01-25 CN CN202110099115.0A patent/CN112844444A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103008015A (en) * | 2011-09-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | Preparation method of fuel battery catalyst carrier WO3 (Tungsten Trioxide) |
| CN102924144A (en) * | 2012-11-30 | 2013-02-13 | 浙江师范大学 | Method for preparing mesoporous cerium praseodymium composite oxide |
| WO2015149499A1 (en) * | 2014-04-04 | 2015-10-08 | 同济大学 | Low-temperature and highly efficient denitration catalyst and preparation method therefor |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 马鹏起等: "《冶金工业出版社》", 31 October 2017 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114505046A (en) * | 2022-02-28 | 2022-05-17 | 武汉工程大学 | Cerium dioxide nanocrystalline composite material and preparation method and application thereof |
| CN114904506A (en) * | 2022-04-28 | 2022-08-16 | 济南市环境研究院(济南市黄河流域生态保护促进中心) | Ozone catalyst and preparation method and application thereof |
| CN114940509A (en) * | 2022-07-06 | 2022-08-26 | 四川大学 | Method for preparing hierarchical porous structure cerium dioxide material by re-dissolving after doping zinc |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112844444A (en) | Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle | |
| CN107207274B (en) | A kind of micron cerium oxide particle and preparation method thereof being total to shell structure with multicore | |
| CN108722433B (en) | Preparation and application of shape-adjustable hollow cage-shaped Mn/Fe oxide nano material | |
| CN111545192B (en) | MOFs-derived perovskite catalyst, preparation method thereof and application of MOFs-derived perovskite catalyst in catalytic degradation of organic pollutants | |
| CN111333127B (en) | Hierarchical porous honeycomb nickel oxide microsphere and preparation method thereof | |
| CN106904649B (en) | In-situ control method for form and crystal face of nano cerium oxide | |
| Han et al. | Controlled synthesis of double-shelled CeO 2 hollow spheres and enzyme-free electrochemical bio-sensing properties for uric acid | |
| JP2008081392A (en) | Porous zirconia-based powder and its manufacture method | |
| CN111320198A (en) | Preparation method of hollow cerium dioxide | |
| CN113830826A (en) | Method for preparing shell-core structure mesoporous quantum titanium oxide by precipitation-self-assembly method | |
| CN111362295A (en) | Ordered large-mesoporous cerium oxide material with high specific surface area and preparation method thereof | |
| CN108380203B (en) | Mesoporous wall hollow core-shell spherical LaMnO3Perovskite catalyst and preparation method thereof | |
| CN113877586B (en) | Preparation method and application of cerium-iron bimetallic composite oxide with hierarchical structure and controllable morphology | |
| CN110950421B (en) | MgO micro-sphere with high specific surface area and preparation method and application thereof | |
| CN101269832A (en) | Process for producing nano-cerium dioxide with high-specific surface area and high hole capacity | |
| CN113772710B (en) | Preparation method and application of cerium dioxide nanowire | |
| CN110980789B (en) | Copper-based two-dimensional sheet cerium oxide nanomaterial and synthesis method and application thereof | |
| CN103466721B (en) | Cobalt molybdate hollow ball powder body material preparation method and cobalt molybdate hollow ball powder body material | |
| CN114367271B (en) | Load type MnO X Preparation method of @ NiCo-MOF composite material | |
| CN105236464A (en) | Preparation method of zero-dimensional cerium oxide hollow spheres | |
| Xu et al. | Template-free synthesis of mesoporous CeO 2 powders by integrating bottom-up and top-down routes for acid orange 7 adsorption | |
| CN111686757B (en) | Platinum-loaded nano cage-shaped zirconia-cobaltosic oxide solid solution, preparation thereof and application thereof in toluene thermal catalysis treatment | |
| CN110559983B (en) | Preparation method of cobalt-doped porous ZnO for pollutant adsorption | |
| CN110918101B (en) | Ultralow-content Pt composite catalyst for catalytic decomposition of formaldehyde gas at room temperature and preparation method thereof | |
| CN113058542A (en) | Preparation method and application of copper oxide @ hydrotalcite hybrid material |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210528 |
|
| WD01 | Invention patent application deemed withdrawn after publication |