CN105439188B - The preparation method of acrylic/hydrotalcite-like nano piece - Google Patents
The preparation method of acrylic/hydrotalcite-like nano piece Download PDFInfo
- Publication number
- CN105439188B CN105439188B CN201510769754.8A CN201510769754A CN105439188B CN 105439188 B CN105439188 B CN 105439188B CN 201510769754 A CN201510769754 A CN 201510769754A CN 105439188 B CN105439188 B CN 105439188B
- Authority
- CN
- China
- Prior art keywords
- hydrotalcite
- acrylic
- preparation
- nano piece
- solution
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
-
- 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
- C01F7/00—Compounds of aluminium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/36—Spheres fragmented
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of preparation method of acrylic/hydrotalcite-like nano piece.Step is as follows:First mixed metal salt and sodium hydroxide cocurrent are added in amphoteric surfactant solution, after completion of the reaction, is put into water heating kettle and carries out hydro-thermal process, intercalation houghite is made;Intercalation houghite is put into acid solution again, acrylic/hydrotalcite-like nano piece is made.This method technological operation is simple, is adapted to large-scale production.The present invention does not use other organic matters and used solvent is aqueous phase in addition to using two kinds of organic matters of amphoteric surfactant and organic acid, small to environmental hazard;Simple to operate, cost is low.
Description
Technical field
The present invention relates to hydrotalcite-like materials, a kind of hydrothermal preparing process of acrylic/hydrotalcite-like nano piece is particularly belonged to.
Background technology
Houghite (HTlc), also known as layered double hydroxide (LDHs), be a class high-sequential two dimension it is cloudy from
Sub- clay material, it has regular octahedron structure, and adjacent is octahedra by common side forming layer, and layer is asked with layer is stacked in one to top
Rise, interlayer passes through hydrogen bond association;Due to the interchangeability and the collocation property of laminate cation of its anion, and it can synthesize each
Plant the houghite compound of different compositions.Being calcined the composite oxides prepared with houghite compound typically has than surface
Product is big, and heat endurance is high, and Active components distribution is uniform, the features such as can suppressing to sinter, have good stability, at present in oxidation also
Original, shows excellent catalytic performance, so as to cause people more and more widely to pay close attention in the reaction such as acid-base catalysis.But,
Due to being filled with anion between laminate and laminate spacing is smaller, so reactant cannot be introduced into interlayer in catalytic process, and nothing
Method makes all laminate faces of houghite all fully be utilized.The laminate that houghite is stacked is made up of lift-off technology
The acrylic/hydrotalcite-like nano piece of individual layer, is exposed the laminate face filled originally by interlayer anion, provides and urge for catalytic reaction
Change site, can so greatly improve the utilization rate of catalyst, the catalyst cost in reduction reaction.
On houghite lift-off technology, it is initially to be found by Adachi-Pagano et al., is repaiied with long-chain organic anion
The hydrotalcite of decorations shows peeling behavior in some organic solvents, in butanol environment, is existed under certain temperature using acrylic acid
The Zn/Al-LDH for modifying lauryl sodium sulfate in reflux course is peeled off.But this process needs to heat and organic solvent.
Subsequent Naik et al. realizes the delamination of the hydrotalcite-like materials to lauryl sodium sulfate intercalation using toluene.
Hibino et al. successfully successfully peels off amino acid modified Mg/Al-LDH in formamide afterwards.Wu et al.
Also with formamide under conditions of ultrasonic wave by Mg/Al-LDH success delamination.Subsequent Liu Zhao equalitys people also utilizes formamide
Successfully obtain the nanometer sheet of large-size.Although the process without any heating and backflow, these methods are still organic
Carried out in solvent, although using formamide delamination be a kind of effective stripping means, but acrylic/hydrotalcite-like nano piece is in formamide
Middle long-time storage can be dissolved.
In summary report, intercalation houghite is made currently with amphoteric surfactant and directly occurs in water
Peeling behavior has no report to prepare this method of acrylic/hydrotalcite-like nano piece.
The content of the invention
It is to shell in organic solvent it is an object of the invention to the acrylic/hydrotalcite-like nano piece for preparing existed for prior art
From easily causing environmental pollution, there is provided a kind of hydrothermal preparing process of acrylic/hydrotalcite-like nano piece, this method for the problem of cost is higher
Without using organic solvent, cost is relatively low, and the acrylic/hydrotalcite-like nano piece of preparation may be implemented in pair of catalyst laminate in catalytic reaction
Face is fully utilized.
To achieve the above object, the technical scheme taken of the present invention is:
A kind of preparation method of acrylic/hydrotalcite-like nano piece, comprises the following steps:
(1) preparation of intercalation houghite:Mixed salt solution and sodium hydroxide solution cocurrent are added to both sexes table
In the activator solution of face, pH=8~11 are kept, after completion of the reaction, is put into water heating kettle and carries out hydro-thermal process, production is taken out afterwards
Product, drying removes water, produces intercalation houghite;The concentration of amphoteric surfactant solution is dense less than the critical micell of itself
Degree;
(2) prepared by acrylic/hydrotalcite-like nano piece:In whipping process, intercalation houghite obtained above is put into and matched somebody with somebody in advance
In the acid solution put, after completion of the reaction, a moment is stood, take upper strata translucent liquid, carried out high speed centrifugation, produce houghite
Nanometer sheet.
Salt-mixture described in step (1) can be at least two in aluminum nitrate, zinc nitrate, magnesium nitrate, copper nitrate, and
The mol ratio of trivalent metal cation and divalent metal is 0.25~0.67 ︰ 1 in mixed metal salt.
Amphoteric surfactant described in step (1) can be betaine type amphoteric surfac-tant, imidazoline type two
One or more in property surfactant, amino acid type amphoteric surfactant.
Amphoteric surfactant solution, mixed salt solution and NaOH solution described in step (1) are preferably used
Without CO2Water be formulated.
The acid in acid solution described in step (2) can be hydrochloric acid, nitric acid, acetic acid, sulfuric acid or citric acid.
Acid solution described in step (2) is preferably with without CO2Water be formulated.
Step (2) whole process is preferably without CO2Environment in carry out.
Material purity grade of the present invention can be technical pure, and chemistry is pure, analyze pure etc..
The principle of the present invention is:When preparing houghite with hydro-thermal method, solution is alkaline environment, will can now be shown
Show that the amphoteric surfactant of anion characteristic is intercalation into the middle of houghite laminate;Intercalation houghite is then put into acid molten
In liquid, amphoteric surfactant shows cationic surfactant characteristic, can be shelled houghite laminate by electrostatic repulsion
From having directly obtained acrylic/hydrotalcite-like nano piece in aqueous.
Compared with prior art it is an advantage of the invention that:The present invention is except utilizing amphoteric surfactant and organic acid two
Plant beyond organic matter, other organic matters are not used and used solvent is aqueous phase, it is small to environmental hazard;Peeled off
Cheng Jun is to carry out under normal temperature and pressure and the reaction time is shorter, and simple to operate, cost is low.
Brief description of the drawings
Fig. 1 is the forming process schematic diagram of acrylic/hydrotalcite-like nano piece
Fig. 2 is the XRD spectra of intercalation hydrotalcite-like nanometer piece
Fig. 3 is the XRD spectra after acrylic/hydrotalcite-like nano piece is recombinated
Embodiment
The present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment 1 (by taking Cu/Al acrylic/hydrotalcite-like nano pieces as an example)
1) preparation of intercalation houghite
What the lauryl imidazoline for weighing 0.28g was put into 40mL removes CO2Under water wiring solution-forming, normal temperature, it is by 50mL concentration
(each material mol ratio is Cu to 0.5mol/L metal nitrate mixed salt solution:Al=1:0.25) with the hydrogen that concentration is 0.5mol/L
Sodium hydroxide solution, cocurrent adds logical N2Octyl group aqueous solutions of betaine in, be stirred vigorously, control pH=8 or so.Salt to be mixed is molten
Liquid completion of dropping, stops the dropwise addition of alkali lye.Continue to be stirred vigorously after 0.5h, be put into water heating kettle, 75 DEG C, 24h is carried out at hydro-thermal
Reason.Reaction is finished, product centrifugation, spends CO2Several times, to neutrality, suction filtration, vacuum drying obtains intercalation class water to water washing
Talc materials.
2) preparation of acrylic/hydrotalcite-like nano piece
0.30g intercalation hydrotalcite-like materials are weighed, the 100mL pH=1.5 configured in advance hydrochloric acid solution is put into rapidly
In, without CO2Environment in be stirred vigorously after 24h, stand a moment, take upper strata translucent liquid to be centrifuged at a high speed
(10000rpm, 15min), that is, obtain houghite metal oxide nano-sheet.
Embodiment 2 (by taking Mg/Al acrylic/hydrotalcite-like nano pieces as an example)
1) preparation of intercalation houghite
What the octyl group glycine betaine for weighing 0.30g was put into 80mL removes CO2Under water wiring solution-forming, normal temperature, it is by 100mL concentration
(each material mol ratio is Mg to 0.1mol/L metal nitrate mixed salt solution:Al=3:2) with the hydrogen-oxygen that concentration is 0.1mol/L
Change sodium solution, cocurrent adds logical N2Octyl group aqueous solutions of betaine in, be stirred vigorously, control pH=10 or so.Salt to be mixed is molten
Liquid completion of dropping, stops the dropwise addition of alkali lye.Continue to be stirred vigorously after 1h, be put into water heating kettle, 85 DEG C, 20h carries out hydro-thermal process.
Reaction is finished, product centrifugation, spends CO2Several times, to neutrality, suction filtration, vacuum drying obtains intercalation houghite to water washing
Material.
2) preparation of acrylic/hydrotalcite-like nano piece
Weigh in 0.15g intercalation hydrotalcite-like materials, the salpeter solution that 50mL pH=2 are put into rapidly, without CO2Ring
It is stirred vigorously in border after 2 days, stands a moment, take the translucent solution in upper strata to be centrifuged at a high speed (10000rpm, 20min),
Obtain houghite metal oxide nano-sheet.
Embodiment 3 (by taking Zn/Al acrylic/hydrotalcite-like nano pieces as an example)
1) preparation of intercalation houghite
What the dodecyl alanine for weighing 6.91g was put into 120mL removes CO2Under water wiring solution-forming, normal temperature, by 150mL
(each material ratio is Zn to the metal nitrate mixed salt solution that concentration is 1mol/L:Al=7:3) with the hydrogen-oxygen that concentration is 0.5mol/L
Change sodium solution, cocurrent adds logical N2The dodecyl alanine aqueous solution in, be stirred vigorously, control pH=11 or so.Wait to mix
Salting liquid completion of dropping is closed, stops the dropwise addition of alkali lye.Continue to be stirred vigorously after 1.5h, be put into water heating kettle, 95 DEG C, 18h is carried out
Hydro-thermal process.Reaction is finished, product centrifugation, spends CO2Water washing several times, to neutrality, inserted by suction filtration, vacuum drying
Layer hydrotalcite-like materials.
2) preparation of acrylic/hydrotalcite-like nano piece
Weigh in 0.5g intercalation hydrotalcite-like materials, the sulfuric acid solution that 100mL pH=1 are put into rapidly, without CO2Ring
It is stirred vigorously in border after 5 days, stands a moment, take the translucent solution in upper strata to be centrifuged at a high speed (10000rpm, 10min),
Obtain houghite metal oxide nano-sheet.
Embodiment 4 (by taking Cu/Mg/Al acrylic/hydrotalcite-like nano pieces as an example)
1) preparation of intercalation houghite
What the octyl group amphoteric imidazoline for weighing 0.614g was put into 160mL removes CO2It is under water wiring solution-forming, normal temperature, 200mL is dense
(each material ratio is Cu to the metal nitrate mixed salt solution for spending for 0.1mol/L:Mg:Al=7:3:2.5) it is 2mol/L's with concentration
Sodium hydroxide solution, cocurrent adds logical N2The octyl group amphoteric imidazoline aqueous solution in, be stirred vigorously, control pH=8 or so.Wait to mix
Salting liquid completion of dropping is closed, stops the dropwise addition of alkali lye.Continue to be stirred vigorously after 0.5h, be put into water heating kettle, 105 DEG C, 24h is carried out
Hydro-thermal process.Reaction is finished, product centrifugation, spends CO2Water washing several times, to neutrality, inserted by suction filtration, vacuum drying
Layer hydrotalcite-like materials..
2) preparation of acrylic/hydrotalcite-like nano piece
Weigh in 0.15g intercalation hydrotalcite-like materials, the acetum that 100mL pH=1.5 are put into rapidly, without CO2's
Be stirred vigorously in environment after 12h, stand a moment, take the translucent solution in upper strata be centrifuged at a high speed (10000rpm,
20min), that is, houghite metal oxide nano-sheet is obtained.
Embodiment 5 (by taking Cu/Mg/Al acrylic/hydrotalcite-like nano pieces as an example)
1) preparation of intercalation houghite
What the octyldimethyl glycine betaine for weighing 3.48g was put into 500mL removes CO2It is under water wiring solution-forming, normal temperature, 50mL is dense
(each material ratio is Cu to the metal nitrate mixed salt solution for spending for 1.5mol/L:Mg:Al=7:3:3) it is 1.5mol/L's with concentration
Sodium hydroxide solution, cocurrent adds logical N2Octyldimethyl aqueous solutions of betaine in, be stirred vigorously, control pH=9 or so.Treat
Mixing salt solution completion of dropping, stops the dropwise addition of alkali lye.Continue to be stirred vigorously after 1h, be put into water heating kettle, 115 DEG C, 20h is carried out
Hydro-thermal process.Reaction is finished, product centrifugation, spends CO2Water washing several times, to neutrality, inserted by suction filtration, vacuum drying
Layer hydrotalcite-like materials.
2) preparation of acrylic/hydrotalcite-like nano piece
0.1g intercalation hydrotalcite-like materials are weighed, in the hydrochloric acid solution that the 200mL pH=5 configured in advance are put into rapidly,
Without CO2Environment in be stirred vigorously after 3 days, stand a moment, take the translucent solution in upper strata to be centrifuged at a high speed
(10000rpm, 15min), that is, obtain houghite metal oxide nano-sheet.
Embodiment 6 (by taking Cu/Zn/Al acrylic/hydrotalcite-like nano pieces as an example)
1) preparation of intercalation houghite
What the dodecyl ethyoxyl sulfobetaines for weighing 0.57g was put into 100mL removes CO2Under water wiring solution-forming, normal temperature,
By metal nitrate mixed salt solution that 50mL concentration is 1mol/L, (each material ratio is Cu:Zn:Al=7:3:4) it is with concentration
1.mol/L sodium hydroxide solution, cocurrent adds logical N2Dodecyl ethyoxyl sulfobetaines aqueous alkali in, acutely stir
Mix, control pH=10 or so.Salting liquid completion of dropping to be mixed, stops the dropwise addition of alkali lye.Continue to be stirred vigorously after 0.5h, be put into
In water heating kettle, 120 DEG C, 20h carries out hydro-thermal process.Reaction is finished, product centrifugation, spends CO2Water washing is several times, extremely neutral,
Suction filtration, vacuum drying obtains intercalation hydrotalcite-like materials..
2) preparation of acrylic/hydrotalcite-like nano piece
0.15g intercalation hydrotalcite-like materials are weighed, the 100mL pH=1.5 configured in advance salpeter solution is put into rapidly
In, without CO2Environment in be stirred vigorously after 3 days, stand a moment, take the translucent solution in upper strata to be centrifuged at a high speed
(10000rpm, 20min), that is, obtain houghite metal oxide nano-sheet.
Embodiment 7 (by taking Cu/Zn/Mg/Al acrylic/hydrotalcite-like nano pieces as an example)
1) preparation of intercalation houghite
What the stearamide propyl group amine oxide for weighing 1.66g was put into 80mL removes CO2Under water wiring solution-forming, normal temperature, by 100mL
(each material ratio is Cu to the metal nitrate mixed salt solution that concentration is 0.5mol/L:Zn:Mg:Al=4:3:3:6) it is with concentration
0.6mol/L sodium hydroxide solution, cocurrent adds logical N2Stearamide propyl group amine oxide aqueous solution in, be stirred vigorously, control
PH=9 or so.Salting liquid completion of dropping to be mixed, stops the dropwise addition of alkali lye.Continue to be stirred vigorously after 1h, be put into water heating kettle,
100 DEG C, 24h carries out hydro-thermal process.Reaction is finished, product centrifugation, spends CO2Water washing is several times, extremely neutral, suction filtration, vacuum
Drying, that is, obtain intercalation hydrotalcite-like materials.
2) preparation of acrylic/hydrotalcite-like nano piece
1.5g intercalation hydrotalcite-like materials are weighed, the citric acid that the 500mL pH=1.5 configured in advance are put into rapidly is molten
In liquid, without CO2Environment in be stirred vigorously after 24h, stand a moment, take the translucent solution in upper strata to be centrifuged at a high speed
(10000rpm, 15min), that is, obtain houghite metal oxide nano-sheet.
Claims (7)
1. a kind of preparation method of acrylic/hydrotalcite-like nano piece, it is characterised in that as follows including step:
(1) preparation of intercalation houghite:Using hydro-thermal method, mixed salt solution and sodium hydroxide solution cocurrent are added to
In amphoteric surfactant solution, pH=8~11 are kept, after completion of the reaction, is put into water heating kettle and carries out hydro-thermal process, Zhi Houqu
Go out product, drying removes water, produces intercalation houghite;The concentration of amphoteric surfactant solution is less than the critical glue of itself
Beam concentration;The temperature of the hydro-thermal process is 75 DEG C, 85 DEG C, 95 DEG C, 105 DEG C, 115 DEG C, 120 DEG C or 100 DEG C, corresponding water
The time of heat treatment is 24 hours, 20 hours, 18 hours, 24 hours, 20 hours, 20 hours or 24 hours;
(2) prepared by acrylic/hydrotalcite-like nano piece:In whipping process, intercalation houghite obtained above is put into and configured in advance
Acid solution in, after completion of the reaction, stand a moment, take upper strata translucent liquid, carry out high speed centrifugation, produce acrylic/hydrotalcite-like nano
Piece.
2. a kind of preparation method of acrylic/hydrotalcite-like nano piece as claimed in claim 1, it is characterised in that described in step (1)
Mixed metal salt be in aluminum nitrate, zinc nitrate, magnesium nitrate, copper nitrate at least two, and trivalent metal in mixed metal salt
The mol ratio of cation and divalent metal is 0.25~0.67 ︰ 1.
3. a kind of preparation method of acrylic/hydrotalcite-like nano piece as claimed in claim 1, it is characterised in that described in step (1)
Amphoteric surfactant be betaine type amphoteric surfac-tant, imidazoline type amphoteric surfactant, amino acid type amphoteric
One or more in surfactant.
4. a kind of preparation method of acrylic/hydrotalcite-like nano piece as claimed in claim 1, it is characterised in that described in step (1)
Amphoteric surfactant solution, mixed salt solution and NaOH solution with without CO2Water be formulated.
5. a kind of preparation method of acrylic/hydrotalcite-like nano piece as claimed in claim 1, it is characterised in that described in step (2)
Acid solution in acid be hydrochloric acid, nitric acid, acetic acid, sulfuric acid or citric acid.
6. a kind of preparation method of acrylic/hydrotalcite-like nano piece as claimed in claim 1, it is characterised in that described in step (2)
Acid solution with without CO2Water be formulated.
7. a kind of preparation method of acrylic/hydrotalcite-like nano piece as claimed in claim 1, it is characterised in that step (2) whole mistake
Journey is without CO2Environment in carry out.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510769754.8A CN105439188B (en) | 2015-11-11 | 2015-11-11 | The preparation method of acrylic/hydrotalcite-like nano piece |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510769754.8A CN105439188B (en) | 2015-11-11 | 2015-11-11 | The preparation method of acrylic/hydrotalcite-like nano piece |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105439188A CN105439188A (en) | 2016-03-30 |
CN105439188B true CN105439188B (en) | 2017-10-17 |
Family
ID=55549909
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510769754.8A Active CN105439188B (en) | 2015-11-11 | 2015-11-11 | The preparation method of acrylic/hydrotalcite-like nano piece |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105439188B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105948085B (en) * | 2016-04-21 | 2017-08-25 | 巢湖学院 | A kind of preparation method of magnetic hydrotalcite |
GB201701382D0 (en) * | 2017-01-27 | 2017-03-15 | Turner Rhodri | Catalyst suitable for methonal synthesis |
CN110433764A (en) * | 2019-08-13 | 2019-11-12 | 浙江理工大学 | A kind of double-hydroxide preparation method for fluorine absorption |
CN110898796A (en) * | 2019-11-27 | 2020-03-24 | 清华大学深圳国际研究生院 | Preparation method of magnetic layered double hydroxide, magnetic layered double hydroxide and application thereof |
CN112176338A (en) * | 2020-09-04 | 2021-01-05 | 重庆大学 | Preparation method of ZnAL-LDHs film with amino acid ion intercalation |
CN113234254B (en) * | 2021-04-27 | 2022-09-09 | 台州学院 | Intercalated hydrotalcite flame-retardant smoke suppressant and preparation method thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102786927B (en) * | 2012-08-24 | 2013-12-25 | 北京化工大学 | 4-hydroxy coumarin intercalated hydrotalcite blue-light composite luminescence material and preparation method thereof |
-
2015
- 2015-11-11 CN CN201510769754.8A patent/CN105439188B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN105439188A (en) | 2016-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105439188B (en) | The preparation method of acrylic/hydrotalcite-like nano piece | |
CN105384148A (en) | Preparation method of hydrotalcite-like nano-sheet | |
CN103979596B (en) | The preparation method of the pillared rare-earth hydroxide nano-film sol of organic anion | |
CN105413688B (en) | A kind of method that microwave method prepares CuFeO2 metal composite oxides | |
CN107572566A (en) | A kind of preparation method of compounded amino modified layered double hydroxide | |
CN104148054B (en) | A kind of preparation method of pucherite nano rod bundle | |
CN102773110A (en) | Method for preparing SnS2/SnO2 composite photocatalyst material of numismatics-shaped hollow structure | |
CN107311243A (en) | A kind of preparation method of the nickel vanadium dual metal hydroxide of sheet | |
CN103241775B (en) | Preparation method of Fe2O3/BiOCl nano-composite powder | |
CN101279759A (en) | Synthetic method of micron cuprous oxide in ultrasonic field | |
CN105239130A (en) | High-antiseptic aluminum alloy anode oxide film non-nickel sealant and preparation method thereof | |
CN106025238B (en) | A kind of preparation method of the anode material for lithium-ion batteries of bulk phase-doped metallic element | |
CN102941110A (en) | Preparation method of nano-zinc oxide composite photocatalyst | |
CN104445364B (en) | A kind of synthetic method of ZnAl-layered double hydroxide | |
CN104860337A (en) | High pressure intercalation assembly method and application in preparation field of intercalation structure composite material | |
CN104449400A (en) | Corn-shaped nano lanthanum cerium oxide/graphene composite rare earth polishing powder and preparation method thereof | |
CN101407328B (en) | Method for preparing zinc aluminum oxide nano-powder | |
CN101367540B (en) | Hydrotalcite-like film with different orientation on two-side of substrate and blooming preparation in situ | |
CN105197994A (en) | Organic molten salt method for preparation of rod-assembled spherical BiOCl nanoparticles | |
CN105967236B (en) | A kind of preparation method of tubulose lead molybdate nano material | |
CN102373507A (en) | Method for hydrothermally synthesizing Bi2WO6 material under assistance of imidazole ionic liquids | |
CN104108739A (en) | Preparation method of particle size-controllable spherical copper oxide | |
CN102286739A (en) | Blackening agent for inner layer of multilayer board of printed circuit board and preparation method and application thereof | |
CN105133023A (en) | Low-volatility monocrystalline silicon slice texturing solution and preparation method thereof | |
CN105252017A (en) | Method for prepring three-dimensional dendritic magnetic cobalt nano material through self-assembly of two-dimensional lamellar constitutional units |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |