CN104556162B - Sheet polycrystalline gama-alumina and preparation method thereof - Google Patents
Sheet polycrystalline gama-alumina and preparation method thereof Download PDFInfo
- Publication number
- CN104556162B CN104556162B CN201310495781.1A CN201310495781A CN104556162B CN 104556162 B CN104556162 B CN 104556162B CN 201310495781 A CN201310495781 A CN 201310495781A CN 104556162 B CN104556162 B CN 104556162B
- Authority
- CN
- China
- Prior art keywords
- low
- alumina
- carbon
- gama
- alcohol
- 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of sheet polycrystalline gama-alumina and preparation method thereof, sheet polycrystalline gama-alumina median size is 100-600nm, and thickness is 40-100nm, is made up of the gama-alumina crystal grain of 5-40nm.The preparation method of sheet polycrystalline gama-alumina of the present invention, comprises following content: (1) inorganic aluminate, low-carbon alcohol and/or water, low-carbon (LC) epoxy alkane mix, and forms gel, is then undertaken aging by gel; (2) the gel low-carbon alcohol that step (1) obtains is soaked, then dry, roasting; (3) material that step (2) obtains immerses in ammoniacal liquor and carries out airtight hydrothermal treatment consists, solid-liquid separation, and dry, roasting, obtains product.Polycrystalline gamma-alumina preparation method of the present invention is simple, with low cost, the operability that tool is stronger.Have broad application prospects in heavy, residual oil hydrocatalyst preparation field.
Description
Technical field
The present invention relates to a kind of sheet polycrystalline gama-alumina and preparation method thereof, belong to field of inorganic material preparing technology.
Background technology
Active gama-alumina, as a kind of solid support material widely used in field of hydrogenation, has the catalytic activity that high pore volume, high-specific surface area etc. are higher usually.Research finds: active gama-alumina powder is normally made up of the once oxidation aluminum nanocrystalline grain being not more than 100nm on microcosmic, these little crystal grain due to the reason of interfacial energy reunite formed together size micron order and above irregular, without the second particle of solid shape, and form polycrystalline gamma phase.Pore structure character is the important controling parameters of of active gama-alumina, and the hole of activated alumina is divided three classes by [Industrial Catalysis, the 6th phase, 14-18 page in 2000]: the intercrystalline hole of the primary particle of coalescing particle; Micropartical intercrystalline hole (offspring); And alumina product shaping time formed defective hole.Wherein, the intercrystalline hole of primary particle belongs to the less micropore of size, mesoporous, for hydrogenation catalyst especially heavy resid hydrogenation, belong to inactive pore; The micropartical intercrystalline hole that offspring is formed belongs to relatively large hole, is important material mass transfer and the reaction duct of the catalyzer taking aluminum oxide as carrier.Originated as can be seen from the duct of above-mentioned activated alumina, the irregular and ununiformity of aluminum oxide secondary particle can cause the ununiformity of pore dimension between second particle, i.e. the dispersivity of pore distribution.This will produce adverse influence to the performance of monolith catalytic performance.
The aluminum hydroxide gel that CN200910011627.6, CN200910206229.X and CN200910011626.1 adopt fused salt titania nanoparticle legal system standby is raw material, after shaping and roasting, obtain comparatively regular rod-like nano aluminum oxide secondary particle, this bar-shaped nanoparticle is piled up and is formed skeleton construction, there is aperture large, porosity is high, and outer surface orifice is comparatively large, the advantages such as duct penetrability is good.
Above-mentioned three patent describes and can produce larger impact to the pore structure of material by the adjustment of aluminum oxide secondary particle form.But the process of this fused salt titania nanoparticle method regulation and control second particle pattern and size is comparatively loaded down with trivial details, is unconventional preparation method.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of sheet polycrystalline gama-alumina and preparation method thereof, the aluminum oxide secondary particle that polycrystalline gama-alumina of the present invention is made up of nano level gama-alumina crystal grain, the inventive method does not need special equipment, simple, with low cost, there is stronger operability.
Sheet polycrystalline gama-alumina of the present invention, median size is 100-600nm, and thickness is 40-100nm, and polycrystalline gamma-alumina particle is made up of the gama-alumina crystal grain of 5-40nm.
The aperture of sheet polycrystalline gama-alumina of the present invention is between 8-50nm.
The preparation method of sheet polycrystalline gama-alumina of the present invention, comprises following content:
(1) inorganic aluminate, low-carbon alcohol and/or water, low-carbon (LC) epoxy alkane mix, and form gel, are then undertaken aging by gel;
(2) the gel low-carbon alcohol that step (1) obtains is soaked, then dry, roasting;
(3) material that step (2) obtains immerses in ammoniacal liquor and carries out airtight hydrothermal treatment consists, solid-liquid separation, and dry, roasting, obtains product.
In the inventive method, the inorganic aluminate described in step (1) is water-soluble inorganic aluminium salt, is selected from one or more in aluminum chloride, aluminum nitrate and Tai-Ace S 150, is preferably aluminum chloride; Low-carbon alcohol is C
5following alcohol, be selected from methyl alcohol, ethanol, n-propyl alcohol and Virahol one or more, be more preferably ethanol and/or propyl alcohol; Low-carbon alcohol can mix with arbitrary proportion with water, and the mass ratio being preferably water/low-carbon alcohol is 0.5-2.0.
In the inventive method, the carbon number of the low-carbon (LC) epoxy alkane described in step (1) is 2-4, is preferably oxyethane and/or propylene oxide.
In the inventive method, each component concentration in step (1) mixture, in percent mass: inorganic aluminate 10%-60%, be preferably 20%-35%, the total content of water and/or low-carbon alcohol is 30%-70%, and rest materials is low-carbon (LC) epoxy alkane.Low-carbon (LC) epoxy alkane and inorganic aluminate meet following relation: with molar amount, low-carbon (LC) epoxy alkane/Al
3+for 2.5-9, be preferably 3.5-7.
In the inventive method, the aging temperature described in step (1) is 20-90 DEG C, preferred 30-60 DEG C, and digestion time is 1-72 hour, preferred 12-60 hour.
In the inventive method, the low-carbon alcohol described in step (2) is C
5following alcohol, be preferably in methyl alcohol, ethanol, n-propyl alcohol and Virahol one or more, be preferably ethanol and/or propyl alcohol.
In the inventive method, the soaking conditions described in step (2) is: temperature 20-80 DEG C, time 1-72 hour.Be preferably 30-60 DEG C, time 12-60 hour.
In the inventive method, the drying temperature described in step (2) is not more than 200 DEG C, is preferably not more than 120 DEG C, and degree of drying is: material constant weight at this temperature.
In the inventive method, the roasting condition described in step (2) is: 400-750 DEG C of roasting 1-12 hour, preferred 500-650 DEG C roasting 3-6 hour.
In the inventive method, the ammonia concn described in step (3) is 0.01-0.5mol/L.In the present invention, with molar amount, ammoniacal liquor/Al
3+ratio 0.5-20, is preferably 1.0-5.0; The volume of ammoniacal liquor at least can the complete submergence by handled material.
In the inventive method, the airtight hydrothermal condition described in step (3) is: hydrothermal treatment consists 1-12 hour at 130-180 DEG C.
In the inventive method, the drying temperature described in step (3) is not more than 200 DEG C, is preferably not more than 120 DEG C, degree of drying: material constant weight at this temperature.
In the inventive method, the roasting condition described in step (3) is: 400-750 DEG C of roasting 1-12 hour, preferred 500-650 DEG C roasting 3-6 hour.
The application of sheet polycrystalline gama-alumina of the present invention in prepared by heavy, residual oil hydrocatalyst.
Compared with existing irregular gama-alumina second particle, gama-alumina second particle of the present invention has sheet-like morphology, sheet second particle by gama-alumina once little crystal grain form, form polycrystalline gama-alumina, therefore can keep the activity of the irregular alumina particle of conventional polysilicon.Tabular alumina of the present invention unity on pattern and size is relatively high, can be used as the raw material of shaped alumina alumina supporter, through suitably process, the centrality of the pore size distribution formed by offspring in solid support material can be significantly improved, thus improve the catalytic performance of catalyzer.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of sheet gama-alumina prepared by the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope photo of sheet gama-alumina prepared by the embodiment of the present invention 1.
Fig. 3 is X-ray diffraction (XRD) spectrogram of sheet gama-alumina prepared by the embodiment of the present invention 1.
Fig. 4 is the pore size distribution$ figure of sheet gama-alumina prepared by the embodiment of the present invention 1.
Embodiment
Below by embodiment to the inventive method detailed description in addition.Sheet gama-alumina particle size is measured according to scanning electron microscope image.Measure the maximum length in the face of 20 particles at random, get the size value of its mean value as particle; Measure 20 particles at random, measure its lateral thickness, get its mean value and make thickness.The little crystal grain of composition platy shaped particle, by transmission electron microscope observing, observes its size range.Crystal formation adopts X-ray diffraction to characterize.Pore distribution adopts low temperature nitrogen physisorphtion to measure.
Embodiment 1
By water, dehydrated alcohol, aluminum chloride mixing, then add propylene oxide and mix, by weight, content is respectively each component of mixture: water 23%, ethanol 23%, aluminum chloride 20%, propylene oxide 34%.After mixing, gained gel at 30 DEG C aging 60 hours, the gel after then using alcohol immersion aging, soaks 60 hours at 30 DEG C.After remove liquid phase, dry until obvious loss of weight no longer occurs product at 120 DEG C.Then roasting 6 hours at 500 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 0.01M that it floods completely to major general (with molar amount, ammoniacal liquor/Al
3+ratio is 5.0), then airtight and be warmed up to 135 DEG C of hydrothermal treatment consists 12 hours.By product dried at 120 DEG C roasting 3 hours at 650 DEG C, known through scanning electron microscopic observation after cooling, product morphology shows as sheet, and it is of a size of 151nm, and thickness is 36nm.After sample grinding also ultrasonic disperse, known with transmission electron microscope observing, platy shaped particle is made up of the less crystal grain of 8-30nm.Because simply grinding and supersound process can not destroy single crystal particle, therefore platy shaped particle is not large single crystal crystal grain.The XRD result of product shows, it is gama-alumina.Therefore, platy shaped particle is polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower mesoporous distribution of 8-20nm.
Embodiment 2
Under room temperature, by water, dehydrated alcohol, aluminum chloride mixing, then add propylene oxide and mix, by weight, content is respectively each component of mixture: water 15%, ethanol 20%, aluminum chloride 35%, propylene oxide 30%.After mixing, gained gel at 40 DEG C aging 48 hours, then with propyl alcohol soak aging after mixture, temperature is 40 DEG C, and the time is 48 hours, after remove liquid phase, dry until obvious loss of weight no longer occurs product at 100 DEG C.Then roasting 6 hours at 600 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 0.1M that it floods completely to major general (with molar amount, ammoniacal liquor/Al
3+ratio is 2.0), then airtight and be warmed up to 150 DEG C of hydrothermal treatment consists 5 hours.By product dried at 100 DEG C roasting 5 hours at 550 DEG C.After cooling, scanning electron microscopic observation is known, and product morphology is sheet, and it is of a size of 254nm, and thickness is 41nm.After sample grinding also ultrasonic disperse, known with transmission electron microscope observing, platy shaped particle is made up of the little crystal grain of 10-25nm.The XRD result of product shows, it is gama-alumina.So platy shaped particle is polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower mesoporous distribution of 10-21nm.
Embodiment 3
Under room temperature, by water, dehydrated alcohol, aluminum chloride mixing, then add propylene oxide and mix, by weight, content is respectively each component of mixture: water 30%, ethanol 23%, aluminum chloride 25%, propylene oxide 22%.After mixing, gained gel at 60 DEG C aging 12 hours, then with ethanol 60 DEG C soak aging after mixture 24 hours, remove liquid phase afterwards, dry until obvious loss of weight no longer occurs product at 120 DEG C.Then roasting 5 hours at 550 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 0.3M that it floods completely to major general (with molar amount, ammoniacal liquor/Al
3+ratio is 3.0), then airtight and be warmed up to 165 DEG C of hydrothermal treatment consists 9 hours.By product dried at 120 DEG C roasting 8 hours at 500 DEG C, after cooling, scanning electron microscopic observation is known, and product morphology is sheet, is of a size of 542nm, and thickness is 89nm.After sample grinding and ultrasonic disperse, known with transmission electron microscope observing, platy shaped particle is made up of the little crystal grain of 10-35nm.The XRD result of product shows, it is gama-alumina, and therefore platy shaped particle is polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower mesoporous distribution of 35-47nm.
Embodiment 4
Under room temperature, by water, dehydrated alcohol, aluminum chloride mixing, then add propylene oxide and mix, by weight, content is respectively each component of mixture: water 30.5%, ethanol 30.5%, aluminum chloride 20%, propylene oxide 19%.After mixing, gained gel at 55 DEG C aging 12 hours, then with ethanol 60 DEG C soak aging after mixture 12 hours, soak complete and after removing liquid phase, at 40 DEG C, dry until product is not
There is obvious loss of weight again, then roasting 3 hours at 650 DEG C, cool to room temperature, then to be immersed in the ammoniacal liquor of the excessive 0.5M of volume (with molar amount, ammoniacal liquor/Al
3+ratio is 1.0), then airtight and be warmed up to 180 DEG C of hydrothermal treatment consists 2 hours.By product dried at 80 DEG C roasting 6 hours at 550 DEG C, after cooling, scanning electron microscopic observation is known, and product morphology shows as sheet, and sheet is of a size of 159nm, and thickness is 42nm.After sample grinding and ultrasonic disperse, known with transmission electron microscope observing, platy shaped particle is made up of the little crystal grain of 10-30nm.Because simply grinding and supersound process can not destroy single crystal particle, therefore platy shaped particle is not large single crystal crystal grain.The XRD result of product shows, it is γ phase alumina, and therefore platy shaped particle is actually polycrystalline gama-alumina.Physical adsorption test shows, it has the narrower mesoporous distribution of 15-25nm.
Claims (9)
1. a sheet polycrystalline gama-alumina, is characterized in that: the median size of gama-alumina is 100-600nm, and thickness is 40-100nm, and polycrystalline gamma-alumina particle is made up of the gama-alumina of 5-40nm; The wherein preparation method of sheet polycrystalline gama-alumina, comprises following content: (1) inorganic aluminate, low-carbon alcohol and/or water, low-carbon (LC) epoxy alkane mix, and forms gel, is then undertaken aging by gel; (2) the gel low-carbon alcohol that step (1) obtains is soaked, then dry, roasting; (3) material that step (2) obtains immerses in ammoniacal liquor and carries out airtight hydrothermal treatment consists, solid-liquid separation, and dry, roasting, obtains product; Each component concentration in step (1) mixture, in percent mass: inorganic aluminate 10%-60%, the total content of water and/or low-carbon alcohol is 30%-70%, and rest materials is low-carbon (LC) epoxy alkane; Low-carbon (LC) epoxy alkane and inorganic aluminate meet following relation: with molar amount, low-carbon (LC) epoxy alkane/Al
3+for 2.5-9; Aging temperature described in step (1) is 20-90 DEG C, and digestion time is 1-72 hour; Step (2) and the drying temperature described in (3) are not more than 200 DEG C; Step (2) and the roasting condition described in (3) are: 400-750 DEG C of roasting 1-12 hour; Airtight hydrothermal condition described in step (3) is: hydrothermal treatment consists 1-12 hour at 130-180 DEG C; Ammonia concn described in step (3) is 0.01-0.5mol/L, and the consumption of ammoniacal liquor at least can the complete submergence by handled material; With molar amount, ammoniacal liquor/Al
3+ratio is 0.5-20.
2. according to gama-alumina according to claim 1, it is characterized in that: the aperture of gama-alumina is between 8-50nm.
3. the preparation method of the sheet polycrystalline gama-alumina described in claim 1 or 2, is characterized in that comprising following content: (1) inorganic aluminate, low-carbon alcohol and/or water, low-carbon (LC) epoxy alkane mix, and forms gel, is then undertaken aging by gel; (2) the gel low-carbon alcohol that step (1) obtains is soaked, then dry, roasting; (3) material that step (2) obtains immerses in ammoniacal liquor and carries out airtight hydrothermal treatment consists, solid-liquid separation, and dry, roasting, obtains product; Each component concentration in step (1) mixture, in percent mass: inorganic aluminate 10%-60%, the total content of water and/or low-carbon alcohol is 30%-70%, and rest materials is low-carbon (LC) epoxy alkane; Low-carbon (LC) epoxy alkane and inorganic aluminate meet following relation: with molar amount, low-carbon (LC) epoxy alkane/Al
3+for 2.5-9; Aging temperature described in step (1) is 20-90 DEG C, and digestion time is 1-72 hour; Step (2) and the drying temperature described in (3) are not more than 200 DEG C; Step (2) and the roasting condition described in (3) are: 400-750 DEG C of roasting 1-12 hour; Airtight hydrothermal condition described in step (3) is: hydrothermal treatment consists 1-12 hour at 130-180 DEG C; Ammonia concn described in step (3) is 0.01-0.5mol/L, and the consumption of ammoniacal liquor at least can the complete submergence by handled material; With molar amount, ammoniacal liquor/Al
3+ratio is 0.5-20.
4. in accordance with the method for claim 3, it is characterized in that: the inorganic aluminate described in step (1) is water-soluble inorganic aluminium salt, be selected from one or more in aluminum chloride, aluminum nitrate and Tai-Ace S 150.
5. in accordance with the method for claim 3, it is characterized in that: the low-carbon alcohol described in step (1) is C
5following alcohol, be selected from methyl alcohol, ethanol, n-propyl alcohol and Virahol one or more.
6. in accordance with the method for claim 3, it is characterized in that: the carbon number of the low-carbon (LC) epoxy alkane described in step (1) is 2-4.
7. in accordance with the method for claim 3, it is characterized in that: the low-carbon alcohol described in step (2) is C
5following alcohol, be selected from methyl alcohol, ethanol, n-propyl alcohol and Virahol one or more.
8. in accordance with the method for claim 3, it is characterized in that: the soaking conditions described in step (2) is: temperature 20-80 DEG C, time 1-72 hour.
9. the application of the gama-alumina described in claim 1 or 2 in prepared by heavy, residual oil hydrocatalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310495781.1A CN104556162B (en) | 2013-10-22 | 2013-10-22 | Sheet polycrystalline gama-alumina and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310495781.1A CN104556162B (en) | 2013-10-22 | 2013-10-22 | Sheet polycrystalline gama-alumina and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104556162A CN104556162A (en) | 2015-04-29 |
CN104556162B true CN104556162B (en) | 2016-04-13 |
Family
ID=53073367
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310495781.1A Active CN104556162B (en) | 2013-10-22 | 2013-10-22 | Sheet polycrystalline gama-alumina and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104556162B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108275709B (en) * | 2018-02-05 | 2020-11-03 | 广东四通集团股份有限公司 | Preparation method of nano aluminum oxide |
CN110935432B (en) * | 2018-09-25 | 2022-09-09 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide composite oxide and preparation method thereof |
CN111825112B (en) * | 2019-04-19 | 2023-06-02 | 中国石油化工股份有限公司 | Preparation method of flaky alumina |
CN112978776B (en) * | 2019-12-02 | 2023-01-10 | 中国石油化工股份有限公司 | Gamma-alumina octahedral particle and preparation method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2004759A6 (en) * | 1987-07-17 | 1989-02-01 | Espanola Alumina Sa | Method for the obtention of an especial alumina from the powder produced in metallurgical alumina calcination |
CN102107899B (en) * | 2011-01-11 | 2012-07-25 | 上海理工大学 | Preparation method of lamellar gamma-phase nano aluminum oxide |
CN102861616B (en) * | 2011-07-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of alumina supporter with concentrated hole distribution |
CN102515215A (en) * | 2011-10-09 | 2012-06-27 | 上海大学 | Preparation method for wormhole-like mesoporous gamma-Al2O3 with narrow pore size distribution |
CN102718236B (en) * | 2012-05-10 | 2014-08-27 | 华东理工大学 | Activated alumina with vane possessing oriented staging structure and preparation method |
-
2013
- 2013-10-22 CN CN201310495781.1A patent/CN104556162B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN104556162A (en) | 2015-04-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104556163B (en) | Prism-shaped polycrystalline gama-alumina and preparation method thereof | |
CN104556178B (en) | A kind of preparation method of polycrystalline gama-alumina | |
CN104556162B (en) | Sheet polycrystalline gama-alumina and preparation method thereof | |
Zhu et al. | Shape-controlled synthesis of porous Co 3 O 4 nanostructures for application in supercapacitors | |
Chen et al. | Templated synthesis of hierarchically porous manganese oxide with a crystalline nanorod framework and its high electrochemical performance | |
CN106140180B (en) | A kind of heavy-oil hydrogenation catalyst and preparation method thereof | |
Joo et al. | Simple preparation of hollow carbon sphere via templating method | |
CN101565210B (en) | Method for preparing cobaltosic oxide powders with high tapping density by combining nanostructure | |
CN104248990A (en) | Spherical attapulgite mesoporous composite carrier, supported catalyst, preparation methods of spherical attapulgite mesoporous composite carrier and supported catalyst, use of supported catalyst and preparation method of ethyl acetate | |
KR20090115714A (en) | Aerogel materials based on metal oxides and composites thereof | |
CN101433865B (en) | Residual oil hydrocatalyst carrier and preparation method thereof | |
CN110331310B (en) | Three-dimensional gradient pore foam metal and preparation method and application thereof | |
CN104248986A (en) | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate | |
CN108080000A (en) | A kind of hollow porous micro sphere catalysis material and preparation method thereof and degradation NO applications | |
Zhao et al. | Fabrication, characterization and photocatalytic activity of Gd3+-doped titania nanoparticles with mesostructure | |
CN107303484B (en) | A kind of preparation method and hydrotreating catalyst of siliceous macropore alumina supporter | |
Cao et al. | Synthesis, characterization, and electrochemical properties of ordered mesoporous carbons containing nickel oxide nanoparticles using sucrose and nickel acetate in a silica template | |
CN104437458B (en) | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof | |
CN104193397B (en) | Perovskite structure porous Ba 0.5sr 0.5co 0.8fe 0.2o 3-δmaterial and preparation method thereof | |
CN109516782A (en) | Lithium battery ceramic diaphragm easy dispersed alumina and preparation method thereof | |
CN100558638C (en) | Layer stephanoporate gamma-aluminum oxide and its production and use | |
CN108786833A (en) | A kind of heavy-oil hydrogenation catalyst and preparation method thereof | |
CN107601581A (en) | A kind of double pore dimension structure nano crystalline substance cobalt acetate powders and preparation method thereof | |
CN106582604A (en) | Cerium oxide fluorite cubic-structure cerium-lanthanum solid solution and preparation method thereof | |
Peng et al. | Preparation of porous TiO 2 photocatalyts with different crystal phases and high catalytic activity by simple calcination of titanate nanofibers |
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 |