CN101007658A - Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template - Google Patents
Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template Download PDFInfo
- Publication number
- CN101007658A CN101007658A CN 200710036698 CN200710036698A CN101007658A CN 101007658 A CN101007658 A CN 101007658A CN 200710036698 CN200710036698 CN 200710036698 CN 200710036698 A CN200710036698 A CN 200710036698A CN 101007658 A CN101007658 A CN 101007658A
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- roasting
- hard template
- ferric oxide
- mesoporous carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a synthesizing method of dielectric hole ferric oxide, which comprises the following steps: adopting dielectric carbon as hard mould; stirring; leaching; dissolving ferric salt into pore path of dielectric carbon; disposing through sodium hydroxide; sintering protected by nitrogen; repeating the stirring and leaching course; sintering in the air; obtaining the product.
Description
Technical field
The invention belongs to the inorganic porous material technical field, being specifically related to a kind of is the method for the synthesizing ordered mesoporous iron oxide material of hard template with the mesoporous carbon.
Background technology
The scientist of Mobil in 1992 expands to mesoporous field for the synthetic regular aperture with material of M41S series silicon-based mesoporous material from range of micropores.Ordered mesoporous material has a class novel material of wide application prospect.Many research fields such as it is sent at the catalyzer, semi-conductor, optics, computer, senser element, the medicine that separate purification, biomaterial, chemosynthesis and conversion, gas and liquid adsorption have wide application prospect.
Matrix material [the Tolbert H of not siliceous in recent years various metal oxides and tensio-active agent, Sieger P, S tucky GD, et al.Control of Inorganic Layer Thick Self-A ssembled Iron O xide/Surfactant Composites.JAm Chem Soc, 1997,119 (37): 8 652～8 661] (as ferric oxide, plumbous oxide, aluminum oxide etc.) are owing to its special structure and performance receive much concern.In general, the skeleton structure of these composite oxides is supported by tensio-active agent, in case remove tensio-active agent, its structure [H itsunori Y that is easy to subside, Masato M, Tsuyoshi K.Synthesis and Deorganization of an Aluminium-Based Dodecyl Sulfate Mesophase with a Hexa2 gonalStructure.Chem Commun, 1996,769～772].This is to have certain limitation owing to the soft template method that utilizes tensio-active agent for structure directing agent must synthesize non-silicon system, transition metal oxide particularly, because its hydrolysis rate is difficult to control and the ionic that appraises at the current rate exists, making has very big difficulty with soft template method synthesizing ordered mesopore metal oxide and mixture thereof.Utilize the surfactant templates method synthetic street can metal oxide simultaneously, its hole wall be unbodied, and this has limited it greatly in catalysis, and the microcosmic device is as the application in fields such as light, electricity, magnetic and electromagnetism and photoelectric material.At above-mentioned situation, but the access method of another kind of synthesize meso-porous material occurred, utilized orderly mesoporous material exactly, obtained its anti-meso-hole structure by the nano-copy technology as hard template.The main process of hard template method is to utilize preformed order mesoporous solid hole, the desired inorganic salt precursor of interior dipping, the mineralising precursor makes it be transformed into target components at a certain temperature immediately, thereby removes the anti-meso-hole structure material that former solid template has obtained the component that requires at last.
Wherein, utilizing mesoporous carbon is a kind of effective means as the hard template synthesize meso-porous material.Meso-porous carbon material generally is to duplicate orderly mesoporous silicon by hard template method to obtain, and is that the template synthesize meso-porous material is two step nano-copy technology in fact with mesoporous carbon therefore.As the high [DongAG of research group of growing of Fudan University, RenN, Tang Y, etal.J.Am.Chem.Soc.2003,125 (17): 4976) 4977] at first synthesising mesoporous carbon bead is mesoporous solid or hollow beads such as the synthetic titanium oxide of template, zirconium white, aluminum oxide, zirconium phosphate and aluminum phosphate then with the mesoporous carbon.Tiemann etc. [RoggenbuckJ, TiemannM.J.Am.Chem.Soc., 2005,12 (4): 1096) 1097] utilizes mesoporous carbon CMK-3 successfully to synthesize mesoporous orderly magnesium oxide for template similarly.
Utilize mesopore silicon oxide to be template and back reductive method at present, successfully obtained the mesoporous iron oxide of superparamagnetism, but the relatively low (86m of specific surface area
2/ g).And utilize mesoporous carbon also not see bibliographical information for the synthetic method of hard template with mesoporous iron oxide of superparamagnetism.The mesoporous carbon of utilizing of present method success has directly been synthesized the high-specific-surface mesoporous iron oxide material of the crystallization of pore wall with superparamagnetism for hard template.
Summary of the invention
At the deficiency that prior art exists, the object of the present invention is to provide a kind of is hard template with the mesoporous carbon, the method for the orderly magnetic mesoporous iron oxide material of synthetic crystallization of pore wall, and this synthetic method novelty, the material order that obtains is good and the crystallization of pore wall degree is good.
Goal of the invention of the present invention is achieved through the following technical solutions:
A kind of is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, be to be hard template with the mesoporous carbon, make iron salt solutions enter the duct of mesoporous carbon by stirring dipping, roasting in the nitrogen after sodium-hydroxide treatment, repeat to stir steeping process, roasting in the last air and obtain the mesoporous iron oxide material.Concrete steps are as follows:
1) with the mesoporous carbon is hard template, mesoporous carbon joined fully stir dipping in the iron salt solutions;
2) filter the back and add the sodium hydroxide solution stirring, filter back roasting in air atmosphere;
3) repeating step 1) and step 2) once or once;
4) roasting in air atmosphere after the roasting in nitrogen atmosphere obtains the pore size distribution value at 2～20nm, and specific surface area surpasses 190m
2The sorrel mesoporous iron oxide material of/g.
Described mesoporous carbon is CMK-3[Jun, S.; Joo, S.H.; Ryoo, R.; Kruk, M.; Jaroniec, M.; Liu, Z.; Ohsuna, T.; Terasaki, O.J.Am.Chem.Soc.2000,122,107 12-10713.] or CMK-8[Kamil P.Gierszal, Tae-Wan Kim, Ryong Ryoo, and Mietek Jaroniec J.Phys.Chem.B 2005,109,23263-23268] etc.;
Described molysite is an iron nitrate etc.
Described iron salt concentration is 0.1mol/L～saturated iron salt solutions.
Above-mentioned steps 2) temperature of roasting is 200 ℃～275 ℃ in air, and the speed of heating is 1 ℃～5 ℃/min.
Above-mentioned steps 4) maturing temperature in nitrogen atmosphere is 300 ℃～500 ℃, and maturing temperature is 300～400 ℃ in air gas, and the speed of heating is 1 ℃～5 ℃/min.
Above-mentioned stirring dipping time is 1～10 hour.
The multiplicity of step 3) is 1 time or 2 times.
Advantage of the present invention is:
1, develop a kind of synthetic high-ratio surface and had the method for the mesoporous iron oxide of crystallization hole wall.
2, the order mesoporous ferric oxide of synthetic of the present invention has the hole wall of crystallization and good superparamagnetism.
3, this synthetic method process only needs low-temperature bake can obtain mesoporous iron oxide, save energy and to environment-friendly.
4, mesoporous carbon not only is a template but also be reductive agent in present method, need not the back reduction and handles.
Embodiment
Pore size distribution and specific surface area obtain by BET (specific surface area tester) test result among the embodiment.
Embodiment 1
0.5g CMK-3 is joined in the iron nitrate solution of 0.1mol/L of 5ml and fully stirred dipping 2 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 4 hours, filter 200 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 1 hour, filter then, the sodium hydroxide solution that adds 20ml0.8mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 350 ℃, roasting to 350 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 198m
2/ g.
Embodiment 2
0.5g CMK-3 is joined in the iron nitrate solution of 8ml 0.5mol/L and fully stirred dipping 3 hours, filter, the sodium hydroxide solution that adds 20ml 2mol/L stirred 3 hours, filter 250 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.6mol/L of 10ml fully stirred dipping 4 hours, filter then, the sodium hydroxide solution that adds 10ml0.6mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 350 in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 190m
2/ g.
Embodiment 3
1g CMK-3 joined in the saturated iron nitrate solution of 10ml fully stirred dipping 2 hours, filter, the sodium hydroxide solution that adds 10ml0.5mol/L stirred 4 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 3 hours, filter then, the sodium hydroxide solution that adds 8ml 0.4mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 200m
2/ g.
Embodiment 4
2g CMK-3 is joined in the iron nitrate solution of 0.1mol/L of 15ml and fully stirred dipping 10 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 4 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 8 hours, filter then, the sodium hydroxide solution that adds 10ml2mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 400 ℃ can obtain sorrel mesoporous iron oxide material in the air atmosphere, pore size distribution is 2-20nm, and specific surface area is 200m
2/ g.
Embodiment 5
1.5g CMK-3 is joined in the iron nitrate solution of 0.1mol/L of 20ml and fully stirred dipping 3 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 1 hour, filter 275 ℃ of roastings in the air atmosphere of back, place the saturated iron nitrate solution of 5ml fully to stir dipping 10 hours once more in the powder that obtains after the roasting, filter then, the sodium hydroxide solution that adds 15ml0.1mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 500 ℃, roasting to 400 ℃ can obtain sorrel mesoporous iron oxide material in the air atmosphere, pore size distribution is 2-20nm, and specific surface area is 200m
2/ g.
Embodiment 6
1g CMK-3 is joined in the iron nitrate solution of 0.1mol/L of 20ml and fully stirred dipping 10 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 4 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 1 hour, filter then, the sodium hydroxide solution that adds 10ml1.5mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 210m
2/ g.
Embodiment 7
1.2g CMK-8 is joined in the iron nitrate solution of 0.1mol/L of 20ml and fully stirred dipping 8 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 4 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 7 hours, filter then, the sodium hydroxide solution that adds 10ml1.5mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 200m
2/ g.
Embodiment 8
1g CMK-8 is joined in the iron nitrate solution of 5ml 0.1mol/L and fully stirred dipping 6 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 1 hour, filter 275 ℃ of roastings in the air atmosphere of back, place the saturated iron nitrate solution of 5ml fully to stir dipping 5 hours once more in the powder that obtains after the roasting, filter then, the sodium hydroxide solution that adds 15ml 0.1mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 200m
2/ g.
Embodiment 9
1.8g CMK-8 is joined in the iron nitrate solution of 0.1mol/L of 15ml and fully stirred dipping 9 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 4 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 1 hour, filter then, the sodium hydroxide solution that adds 10ml2mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 400 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 198m
2/ g.
Embodiment 10
1g CMK-8 joined in the saturated iron nitrate solution of 10ml fully stirred dipping 3 hours, filter, the sodium hydroxide solution that adds 10ml0.5mol/L stirred 4 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 5 hours, filter then, the sodium hydroxide solution that adds 8ml 0.4mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 350 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 190m
2/ g.
Embodiment 11
1.2g CMK-8 is joined in the iron nitrate solution of 0.5mol/L of 8ml and fully stirred dipping 7 hours, filter, the sodium hydroxide solution that adds 5ml 2mol/L stirred 3 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.6mol/L of 10ml fully stirred dipping 6 hours, filter then, the sodium hydroxide solution that adds 10ml0.6mol/L stirred 4 hours, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 212m
2/ g.
Embodiment 12
0.5g CMK-3 is joined in the iron nitrate solution of 0.1mol/L of 5ml and fully stirred dipping 7 hours, filter, the sodium hydroxide solution that adds 10ml 2mol/L stirred 4 hours, filter 275 ℃ of roastings in the air atmosphere of back, the powder that obtains after the roasting is placed once more the iron nitrate solution of the 0.1mol/L of 5ml fully stirred dipping 7 hours, filter then, the sodium hydroxide solution that adds 10ml0.8mol/L stirred 0.5 hour, in the nitrogen atmosphere after the roasting to 300 ℃, roasting to 400 ℃ in the air atmosphere, can obtain sorrel mesoporous iron oxide material, pore size distribution is 2-20nm, and specific surface area is 210m
2/ g.
Claims (8)
1, a kind of is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, and concrete steps are as follows:
1), be hard template with the mesoporous carbon, mesoporous carbon is joined fully stirs dipping in the iron salt solutions;
2), filtering the back adds the sodium hydroxide solution stirring, filtration back roasting in air atmosphere;
3), repeating step 1) and step 2) once or once;
4), in nitrogen atmosphere after the roasting, roasting in air atmosphere again obtains sorrel mesoporous iron oxide material.
2, according to claim 1 is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, it is characterized in that: mesoporous carbon is CMK-3 or CMK-8;
3, according to claim 1 is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, it is characterized in that: described molysite is an iron nitrate.
4, according to claim 1 is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, it is characterized in that: described iron salt concentration is 0.1mol/L～saturated iron salt solutions.
5, according to claim 1 is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, it is characterized in that: step 2) temperature of roasting in air is 200 ℃～275 ℃, the speed of heating is 1 ℃～5 ℃/min.
6, according to claim 1 is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, it is characterized in that: the maturing temperature in the step 4) in nitrogen atmosphere is 300 ℃～500 ℃, maturing temperature is 300～400 ℃ in air gas, and the speed of heating is 1 ℃～5 ℃/min.
7, according to claim 1 is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, it is characterized in that: stirring dipping time is 1～10 hour.
8, according to claim 1 is the method for the synthesising mesoporous ferric oxide of hard template with the mesoporous carbon, it is characterized in that: the multiplicity of step 3) is 1 time or 2 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100366982A CN100467388C (en) | 2007-01-22 | 2007-01-22 | Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100366982A CN100467388C (en) | 2007-01-22 | 2007-01-22 | Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101007658A true CN101007658A (en) | 2007-08-01 |
| CN100467388C CN100467388C (en) | 2009-03-11 |
Family
ID=38696366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100366982A Expired - Fee Related CN100467388C (en) | 2007-01-22 | 2007-01-22 | Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100467388C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823777A (en) * | 2010-04-20 | 2010-09-08 | 上海大学 | Method for removing phenol in aqueous solution with magnetic mesoporous carbon material |
| CN101468817B (en) * | 2007-12-25 | 2010-12-08 | 中国科学院过程工程研究所 | Mesoporous nanocrystalline assembled porous bengala microsphere and preparation thereof |
| CN102110506A (en) * | 2010-11-17 | 2011-06-29 | 安徽工业大学 | Carbon-based magnetic mesoporous composite microsphere and preparation method thereof |
| CN101531771B (en) * | 2009-04-02 | 2011-06-29 | 华东师范大学 | Method for using metallic copper to carry out in-situ modification on mesoporous organic polymer or carbon material |
| CN102054575B (en) * | 2009-11-06 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Method for preparing magnetic mesoporous carbon by co-pouring |
| CN105842288A (en) * | 2016-03-22 | 2016-08-10 | 苏州捷德瑞精密机械有限公司 | Porous gas sensitive nanomaterial and preparation method thereof |
-
2007
- 2007-01-22 CN CNB2007100366982A patent/CN100467388C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468817B (en) * | 2007-12-25 | 2010-12-08 | 中国科学院过程工程研究所 | Mesoporous nanocrystalline assembled porous bengala microsphere and preparation thereof |
| CN101531771B (en) * | 2009-04-02 | 2011-06-29 | 华东师范大学 | Method for using metallic copper to carry out in-situ modification on mesoporous organic polymer or carbon material |
| CN102054575B (en) * | 2009-11-06 | 2012-06-27 | 中国科学院上海硅酸盐研究所 | Method for preparing magnetic mesoporous carbon by co-pouring |
| CN101823777A (en) * | 2010-04-20 | 2010-09-08 | 上海大学 | Method for removing phenol in aqueous solution with magnetic mesoporous carbon material |
| CN101823777B (en) * | 2010-04-20 | 2011-12-21 | 上海大学 | Method for removing phenol in aqueous solution with magnetic mesoporous carbon material |
| CN102110506A (en) * | 2010-11-17 | 2011-06-29 | 安徽工业大学 | Carbon-based magnetic mesoporous composite microsphere and preparation method thereof |
| CN102110506B (en) * | 2010-11-17 | 2013-01-09 | 安徽工业大学 | Carbon-based magnetic mesoporous composite microsphere and preparation method thereof |
| CN105842288A (en) * | 2016-03-22 | 2016-08-10 | 苏州捷德瑞精密机械有限公司 | Porous gas sensitive nanomaterial and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100467388C (en) | 2009-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100467388C (en) | Method for synthesizing mesoporous ferric oxide using mesoporous carbon as hard template | |
| Chen et al. | The Co3O4 catalyst derived from ZIF-67 and their catalytic performance of toluene | |
| CN104812469B (en) | One-pot method for the synthesis of cu-ssz-13, the compound obtained by the method and use thereof | |
| Peng et al. | Hollow metal–organic framework polyhedra synthesized by a CO2–ionic liquid interfacial templating route | |
| CN102060534B (en) | Preparation method of three-dimensional ordered macroporous La1-xSrxCrO3 with mesoporous pore wall | |
| WO2019109830A1 (en) | Method of preparing molybdate complex hollow microspheres and application thereof | |
| CN101314135B (en) | Method for preparing double-catalysis center molecular sieve nucleocapsid material with hydrothermal/solvent-thermal system | |
| Devika et al. | Selective oxidation of ethylbenzene over CeAlPO-5 | |
| CN106946282B (en) | A kind of preparation method of porous cerium-based composite oxides | |
| CN110668458B (en) | Al-SBA-15 mesoporous molecular sieve, denitration catalyst, preparation methods of Al-SBA-15 mesoporous molecular sieve and denitration catalyst, and application of Al-SBA-15 mesoporous molecular sieve and denitration catalyst | |
| CN101584981A (en) | Low-temperature preparation method of ceria nano-crystalline microsphere of graduation structure | |
| CN103949193A (en) | Universal method for preparation of inorganic hollow microspheres | |
| CN111333127A (en) | Hierarchical porous honeycomb nickel oxide microsphere and preparation method thereof | |
| CN100460314C (en) | Method for synthesizing metal oxide mesoporous material by one-step vacuum perfusion | |
| CN103071807A (en) | Preparation method of ultra-fine spherical cobalt powder | |
| CN104591178A (en) | Method for preparing graphene | |
| CN102303906B (en) | Ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4 | |
| CN102649575A (en) | Flower-shaped magnesium oxide nanostructure material, and preparation method and application thereof | |
| CN103664192B (en) | A kind of pure phase pyrochlore constitution Ce 2zr 2o 7preparation method | |
| CN108714426A (en) | A kind of nanocube perovskite type catalyst and its preparation method and application | |
| CN103979602A (en) | Preparation method of crystalline meso-porous tin dioxide material with high specific surface | |
| CN107500336A (en) | A kind of method for preparing rare earth layered hydroxide using template method is sacrificed certainly | |
| CN105312080A (en) | Molecular sieve catalyst modification method for nitrous oxide catalytic decomposition | |
| CN104437501A (en) | Cobalt-based catalyst and preparation method and application thereof | |
| Lian et al. | Template-free hydrothermal synthesis of Gd2O2SO4: Eu3+ hollow spheres based on urea-ammonium sulfate (UAS) system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090311 Termination date: 20140122 |