CN106517270B - The preparation method of nano composite hydroxide - Google Patents

The preparation method of nano composite hydroxide Download PDF

Info

Publication number
CN106517270B
CN106517270B CN201610994642.7A CN201610994642A CN106517270B CN 106517270 B CN106517270 B CN 106517270B CN 201610994642 A CN201610994642 A CN 201610994642A CN 106517270 B CN106517270 B CN 106517270B
Authority
CN
China
Prior art keywords
cation
low price
hydroxide
preparation
cationic
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
Application number
CN201610994642.7A
Other languages
Chinese (zh)
Other versions
CN106517270A (en
Inventor
樊发英
迟立群
邓小川
唐志雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qinghai Institute of Salt Lakes Research of CAS
Original Assignee
Qinghai Institute of Salt Lakes Research of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Qinghai Institute of Salt Lakes Research of CAS filed Critical Qinghai Institute of Salt Lakes Research of CAS
Priority to CN201610994642.7A priority Critical patent/CN106517270B/en
Publication of CN106517270A publication Critical patent/CN106517270A/en
Application granted granted Critical
Publication of CN106517270B publication Critical patent/CN106517270B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • 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
    • C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a kind of preparation methods of nano composite hydroxide, the nano composite hydroxide includes low price main layer board cation, high price main layer board cation and interlayer anion, wherein, low price main layer board cation and high price main layer board cation include at least one metal cation；The preparation method with the water soluble salt of high-valence cationic comprising steps of S1, mix the hydroxide of the cation at a low price of nanoscale first and soluble in water, acquisition mixture；S2, mixture is reacted into 4h~100h at 60 DEG C~300 DEG C, for reaction product through being separated by solid-liquid separation, solid phase obtains nano composite hydroxide through dry.The preparation method of nano composite hydroxide according to the present invention is avoided using sodium hydroxide and other matter, will not generate by-product, and Atom economy is close to 100%；The nano composite hydroxide size Control obtained by the preparation method is in 100nm hereinafter, being a kind of nano material, with better application effect.

Description

The preparation method of nano composite hydroxide
Technical field
The invention belongs to inorganic non-metallic technical field of function materials, in particular, being related to a kind of nano composite hydrogen The preparation method of oxide.
Background technique
Complex metal hydroxide (abbreviation LDHs) is a kind of stratified material, and LDHs is by positively charged metal hydroxides Laminate and negatively charged interlayer anion assemble, with the metal sun with different charges in layers of metal hydroxides plate Ion.In existing LDHs, metal cation is mainly divalent metal and trivalent metal cation, thus the LDHs General structure may be expressed as: [M+M2+ 1-y-0.5x-2zM3+ yM4+ z(OH)2](An-)y/n·mH2O, wherein M+、M2+、M3+And M4+Respectively Indicate the monovalent metal cation being located on layers of metal hydroxides plate, divalent metal, trivalent metal cation and four Valence metal cation, An-Expression interlayer anion, 0≤x≤0.4,0≤y≤0.7,0≤z≤0.5,0≤y+0.5x+2z≤1, Wherein y, cannot be simultaneously the substance that 0, m is interlayer hydrone amount.
LDHs have the characteristics that Subjective and Objective element species and quantity is adjustable, laminate it is elastic it is adjustable, size and shape is adjustable, LDHs is ground due to the particularity of its structure and performance are greatly strengthened in catalysis, the energy, biosensor, absorption, drug etc. Study carefully field and cause broad interest and great attention, interrelationship between industries is big, permeability is strong, and it is numerous to can be widely applied to national economy Field and industry.
LDHs is widely used as lead-free PVC heat stabilizer, Halogen height suppression cigarette as a kind of excellent polymer builder material Fire retardant, selective infrared absorbing material, ultraviolet blocking material and spandex anti-chlorine agent etc..However since the surface LDHs oleophobic is hydrophilic Characteristic, with polymer compatibility it is poor, to will affect the dispersibility of LDHs in the polymer, polymer performance is caused to drop It is low, it is therefore desirable to the LDHs material of ultrafine nanometer to be prepared, to increase the unit dispersibility of LDHs in the polymer, to mention The performance of high composite material.
The preparation method of traditional LDHs mainly has hydro-thermal method, the precipitation method, in-situ synthesis, ion-exchange, roasting also Former method etc..The method for being used to prepare nano-LDHs more mature at present is nucleation crystallization isolation method, is belonged in the precipitation method The small LDHs material of particle size can be prepared in one kind；However use this method during the preparation process, it needs using hydroxide Sodium, ammonium hydroxide, sodium carbonate, ammonium carbonate etc. are used as raw material, can introduce by-product, and the water of tens times of even hundreds of times is needed to be washed It washs, while the LDHs of small size increases the difficulty of washing, to further increase washing times and difficulty, causes water resource A large amount of wastes, further increase production cost.
Summary of the invention
To solve the above-mentioned problems of the prior art, the present invention provides a kind of systems of nano composite hydroxide Preparation Method, the preparation method avoid can be obtained size using sodium hydroxide and other matter in 100nm composition metal hydrogen-oxygen below Compound, will not generate by-product, and Atom economy is a kind of clean preparation method close to 100%.
In order to achieve the above object of the invention, present invention employs the following technical solutions:
A kind of preparation method of nano composite hydroxide, the nano composite hydroxide include main at a low price Body laminate cation, high price main layer board cation and interlayer anion, wherein the low price main layer board cation and institute Stating high price main layer board cation includes at least one metal cation；The preparation method comprising steps of S1, by nanoscale The hydroxide of one low price cation is mixed with the water soluble salt of high-valence cationic and soluble in water, acquisition mixture；S2, by institute It states mixture and reacts 4h~100h at 60 DEG C~300 DEG C, for reaction product through being separated by solid-liquid separation, gained solid phase obtains institute through drying State nano composite hydroxide.
Further, described first is cationic identical as the low price main layer board cation at a low price；The high price sun from It is sub identical as the high price main layer board cation.
Further, described first is cationic selected from Li at a low price+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、 Cd2+And Be2+At least one of；The high-valence cationic is selected from Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3 +、Ga3+、Sn4+、Ti4+And Zr4+At least one of；Anion in the water soluble salt of the high-valence cationic is selected from Cl-、 SO4 2-、CO3 2-、NO3 -In any one.
Further, the water soluble salt of the hydroxide of the first low price of nanoscale cation and the high-valence cationic The ratio between the amount of substance be 2:1~4:1.
Further, in the step S1 further include: by second, the water soluble salt of cation and the high price are positive at a low price The hydroxide of ion is added into the mixture.
Further, the water soluble salt of the hydroxide of the first low price of nanoscale cation, the second low price cation The amount of total material be with the ratio between the water soluble salt of the high-valence cationic, the amount of total material of hydroxide of high-valence cationic 1:2~6:1.
Further, described second is cationic identical as the low price main layer board cation at a low price.
Further, described second is cationic selected from Li at a low price+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、 Cd2+And Be2+At least one of；Anion in the water soluble salt of the second low price cation is selected from Cl-、SO4 2-、CO3 2-、 NO3 -In any one.
Another object of the present invention, which also resides in, provides a kind of preparation method of nano composite hydroxide, the nanometer Complex metal hydroxide includes low price main layer board cation, high price main layer board cation and interlayer anion, wherein The low price main layer board cation and the high price main layer board cation include at least one metal cation；The preparation Method comprising steps of Q1, by the water soluble salt of cation and high at a low price of the hydroxide of cation, second at a low price of nanoscale first The water soluble salt mixing of the hydroxide and/or the high-valence cationic of valence cation is simultaneously soluble in water, obtains mixture；Q2, The mixture is reacted into 4h~100h at 60 DEG C~300 DEG C, through being separated by solid-liquid separation, gained solid phase obtains reaction product through drying Obtain the nano composite hydroxide.
Further, it is described first at a low price cation and it is described second at a low price cation and the low price main layer board sun from Son is identical；The high-valence cationic is identical as the high price main layer board cation.
Further, the first low price cation and the second low price cation are selected from Mg2+、Zn2+、Ca2+、Cu2 +、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of；The high-valence cationic is selected from Al3+、Ni3+、Co3+、Fe3+、 Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+At least one of；The water solubility of the second low price cation Anion in salt is selected from Cl-、SO4 2-、CO3 2-、NO3 -In any one.
Further, the water soluble salt of the hydroxide of the first low price of nanoscale cation, the second low price cation The amount of total material and the ratio between the amount of substance of the high-valence cationic be 1:2~6:1.
The present invention is by reasonably selecting reactant, passing through the ratio rationally controlled between each reactant simultaneously, so that finally The nano composite hydroxide including predetermined ion is only obtained, without other by-products of association；What is obtained is nano combined Metal hydroxides can be used directly, and without the operation such as washing, reduces the use of the freshwater resources such as slurry, reaches simultaneously To 100% Atom economy, the requirement of Green Chemistry is met.At the same time, preparation method according to the present invention obtains Nano composite hydroxide size in 100nm hereinafter, nanoscale size is more advantageous to it to apply well In technical fields such as catalysis, absorption, there is better application effect.
Detailed description of the invention
What is carried out in conjunction with the accompanying drawings is described below, above and other aspect, features and advantages of the embodiment of the present invention It will become clearer, in attached drawing:
Fig. 1 is the XRD diagram piece of the nano composite hydroxide of embodiment according to the present invention 1.
Specific embodiment
Hereinafter, with reference to the accompanying drawings to detailed description of the present invention embodiment.However, it is possible to come in many different forms real The present invention is applied, and the present invention should not be construed as limited to the specific embodiment illustrated here.On the contrary, providing these implementations Example is in order to explain the principle of the present invention and its practical application, to make others skilled in the art it will be appreciated that the present invention Various embodiments and be suitable for the various modifications of specific intended application.
Term " first ", " second " etc. herein can be used to describe various substances although will be appreciated that, these Substance should not be limited by these terms.These terms are only used to separate a substance with another substance.
The invention discloses a kind of preparation method of nano composite hydroxide, the nano composite hydroxide Including low price main layer board cation, high price main layer board cation and interlayer anion, wherein low price main layer board sun from Son and high price main layer board cation include at least one metal cation.
The preparation method of nano composite hydroxide according to the present invention includes the following steps:
S1, the hydroxide of nanoscale the first low price cation is mixed, and soluble in water with high-valence cationic source, is obtained Mixture.
It preferably, further include the hydrogen-oxygen of the second low price cationic water soluble salt and/or high-valence cationic in the mixture Compound.
It is worth noting that when the second water soluble salt of cation at a low price is not present in mixture, the high-valence cationic Source is the mixture of the water soluble salt of high-valence cationic or the water soluble salt of high-valence cationic and its hydroxide；And when mixing There are when the water soluble salt of the second low price cation in object, which can be the water soluble salt of high-valence cationic And/or the hydroxide of high-valence cationic.
Specifically, first cationic at a low price, the second low price cation and the low price body layer in complex metal hydroxide Plate cation is identical, wherein the first low price cation and the second low price cation use X respectively1、X2It indicates.High-valence cationic and height Valence main layer board cation is identical, is indicated with Y.
First low price cation and the second low price cation are selected from Li+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2 +、Mn2+、Cd2+And Be2+At least one of；High-valence cationic is selected from Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、 In3+、Ga3+、Sn4+、Ti4+And Zr4+At least one of.
Anion in the water soluble salt of second low price cation and the water soluble salt of high-valence cationic is selected from Cl-、 SO4 2-、CO3 2-、NO3 -In any one.
More specifically, when the second water soluble salt of cation at a low price is not present in mixture, nanoscale first is at a low price Cation is total with the amount of the substance of the water soluble salt of high-valence cationic or the water soluble salt of high-valence cationic and its hydroxide The ratio between amount of substance is 1:2~6:1；When, there are when the second water soluble salt of cation at a low price, nanoscale first is low in mixture The amount of the total material of the water soluble salt of the hydroxide of valence cation and the second low price cation and the water solubility of high-valence cationic The ratio between amount of substance of hydroxide of salt and/or high-valence cationic is 1:2~6:1.In other words, i.e. cation (the at a low price One at a low price cation or first at a low price cation with second at a low price cation mixing) substance amount and high-valence cationic object The ratio between amount of matter is 1:2~6:1.
Preferably, the quality control of used water is the 1 of the quality of the hydroxide of nanoscale the first low price cation ~100 times.
S2, mixture is reacted into 4h~100h at 60 DEG C~300 DEG C, reaction product is through being separated by solid-liquid separation, gained solid phase warp It is dry, obtain nano composite hydroxide.
Before mixture reacts, 0.1h~4h is preferably stirred the mixture for, with abundant dissolution dispersion, forms one Even mixture.
Mixture carries out hydro-thermal reaction preferably in hydrothermal reaction kettle.
The solid phase of acquisition dry 12h preferably at 80 DEG C.
The pH value of the nano composite hydroxide obtained is measured, discovery is in neutrality, that is to say, that according to the present invention The nano composite hydroxide that the preparation method of nano composite hydroxide obtains will not generate other by-products, and Also fundamental reaction is complete for reactant, and needing not move through washing operation can be used directly, and it is light not only to have saved a large amount of slurries etc. Water resource reduces waste, reduces cost, and simplifies technique.
Hereinafter, by referring to specific embodiment to the preparation method of nano composite hydroxide according to the present invention into The detailed description of row, for convenience of comparing to each embodiment, analysis compares each embodiment in table form.Embodiment 1-11 In the comparing result under different experiments parameter it is as shown in table 1.
Comparison of the 1 embodiment according to the present invention 1-11 of table under different experiments parameter
Note: in table 1, when " molar ratio " refers to the water soluble salt that the second low price cation is not present in mixture, nanoscale First exist in the hydroxide of cation and the ratio between amount of substance of high-valence cationic or mixture at a low price second at a low price it is positive from When the water soluble salt of son, total object of the cationic water soluble salt of the hydroxide of nanoscale the first low price cation, the second low price The ratio between amount and the amount of substance of high-valence cationic of matter.
X-ray diffraction test (abbreviation XRD) has been carried out to the nano composite hydroxide that embodiment 1 is prepared, As a result such as Fig. 1.From figure 1 it appears that the nano composite hydroxide that embodiment 1 obtains is MgAl-Cl-LDHs, There is feature crystallographic plane diffraction peak in many places, and each diffraction maximum peak type is sharp, free from admixture peak, illustrates that sample crystal phase is single and has had Whole layered crystal structure.
Certainly, the preparation method of nano composite hydroxide according to the present invention is not limited to above-described embodiment 1-11 Described, such as first is cationic for Li at a low price+, second is cationic for Mg at a low price2+, high-valence cationic Al3+And Ti4+, then nanometer is multiple It closes and then exists simultaneously Li on the layers of metal hydroxides plate of metal hydroxides+、Mg2+、Al3+And Ti4+Four kinds of metal cations； In other words, the preparation method of nano composite hydroxide according to the present invention enables to prepare nano combined Metal cation on the layers of metal hydroxides plate of metal hydroxides be monovalent metal cation, divalent metal, At least two in trivalent metal cation, tetravalent metal cation；Meanwhile for the metal cation of identical valence state, may be used also With the cation comprising various metals.
Although the present invention has shown and described referring to specific embodiment, it should be appreciated by those skilled in the art that: In the case where not departing from the spirit and scope of the present invention being defined by the claims and their equivalents, can carry out herein form and Various change in details.

Claims (8)

1. a kind of preparation method of nano composite hydroxide, the nano composite hydroxide include low price main body Laminate cation, high price main layer board cation and interlayer anion, wherein the low price main layer board cation and described High price main layer board cation includes at least one metal cation；It is characterized in that, the preparation method comprising steps of
S1, the hydroxide of the cation at a low price of nanoscale first is mixed and soluble in water with the water soluble salt of high-valence cationic, Obtain mixture；Described first is cationic identical as the low price main layer board cation at a low price；The high-valence cationic and institute It is identical to state high price main layer board cation；Described first is cationic selected from Li at a low price+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、 Fe2+、Mn2+、Cd2+And Be2+At least one of；The high-valence cationic is selected from Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3 +、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+At least one of；Anion choosing in the water soluble salt of the high-valence cationic From Cl-、SO4 2-、CO3 2-、NO3 -In any one；
S2, the mixture is reacted into 4h~100h at 60 DEG C~300 DEG C, reaction product is through being separated by solid-liquid separation, gained solid phase warp It is dry, obtain the nano composite hydroxide.
2. preparation method according to claim 1, which is characterized in that the hydroxide of the first low price of nanoscale cation The ratio between amount of substance of water soluble salt of object and the high-valence cationic is 1:2~6:1.
3. preparation method according to claim 1, which is characterized in that in the step S1 further include: at a low price by second The water soluble salt of cation and the hydroxide of the high-valence cationic are added into the mixture.
4. preparation method according to claim 3, which is characterized in that the hydroxide of the first low price of nanoscale cation The amount of the total material of the cationic water soluble salt of object, the second low price and water soluble salt, the high-valence cationic of the high-valence cationic The ratio between the amount of total material of hydroxide be 1:2~6:1.
5. the preparation method according to claim 4, which is characterized in that the second low price cation and the low price main body Laminate cation is identical.
6. preparation method according to claim 5, which is characterized in that described second is cationic selected from Li at a low price+、Mg2+、Zn2 +、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of；The water soluble salt of the second low price cation In anion be selected from Cl-、SO4 2-、CO3 2-、NO3 -In any one.
7. a kind of preparation method of nano composite hydroxide, the nano composite hydroxide include low price main body Laminate cation, high price main layer board cation and interlayer anion, wherein the low price main layer board cation and described High price main layer board cation includes at least one metal cation；It is characterized in that, the preparation method comprising steps of
Q1, by the water soluble salt and high-valence cationic of the cation at a low price of the hydroxide of cation, second at a low price of nanoscale first Hydroxide and/or the high-valence cationic water soluble salt mixing and it is soluble in water, obtain mixture；Described first at a low price The cationic and described second low price cation is identical as the low price main layer board cation；The high-valence cationic and the height Valence main layer board cation is identical；The first low price cation and the second low price cation are selected from Li+、Mg2+、Zn2+、 Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of；The high-valence cationic is selected from Al3+、Ni3+、Co3 +、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+At least one of；The second low price cation Anion in water soluble salt is selected from Cl-、SO4 2-、CO3 2-、NO3 -In any one；
Q2, the mixture is reacted into 4h~100h at 60 DEG C~300 DEG C, reaction product is through being separated by solid-liquid separation, gained solid phase warp It is dry, obtain the nano composite hydroxide.
8. preparation method according to claim 7, which is characterized in that the hydroxide of the first low price of nanoscale cation Object, second at a low price amount of the total material of the water soluble salt of cation and the ratio between the amount of substance of the high-valence cationic for 1:2~ 6:1。
CN201610994642.7A 2016-11-11 2016-11-11 The preparation method of nano composite hydroxide Active CN106517270B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610994642.7A CN106517270B (en) 2016-11-11 2016-11-11 The preparation method of nano composite hydroxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610994642.7A CN106517270B (en) 2016-11-11 2016-11-11 The preparation method of nano composite hydroxide

Publications (2)

Publication Number Publication Date
CN106517270A CN106517270A (en) 2017-03-22
CN106517270B true CN106517270B (en) 2019-01-11

Family

ID=58350712

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610994642.7A Active CN106517270B (en) 2016-11-11 2016-11-11 The preparation method of nano composite hydroxide

Country Status (1)

Country Link
CN (1) CN106517270B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107555454A (en) * 2017-09-01 2018-01-09 中国科学院青海盐湖研究所 The preparation method of layered composite metal hydroxides with chlorion intercalation

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102815752A (en) * 2012-09-24 2012-12-12 湖南工业大学 Novel quaternary layered double hydroxide (LDHs), its preparation method and application thereof
US9656877B2 (en) * 2014-09-26 2017-05-23 Cobra Rahmani Nezhad Preparing layered double hydroxide nanostructures
CN105753022B (en) * 2016-03-28 2017-06-20 北京化工大学 A kind of preparation method of magnesium-base layer-shaped complex hydroxide

Also Published As

Publication number Publication date
CN106517270A (en) 2017-03-22

Similar Documents

Publication Publication Date Title
CN106517099B (en) The preparation method of complex metal hydroxide
CN105753022B (en) A kind of preparation method of magnesium-base layer-shaped complex hydroxide
CN106745116B (en) A kind of preparation method of complex metal hydroxide
CN105836769B (en) A kind of clean method for preparing of magnesium-aluminum-based layered double hydroxide
CN103274437B (en) Three-dimensional flower-like layered double hydroxide and preparation method thereof
CN105032342B (en) A kind of effective layered bi-metal oxide adsorbent preparation method for removing low phosphorus acid group
CN104944452A (en) High surface area layered double hydroxides and preparation method thereof
CN102910622A (en) Preparation method of two-dimensional nano-graphene
EP3245258B1 (en) Sio2-layered double hydroxide microspheres and methods of making them
CN101905861A (en) Preparation method of nanometer laminated composite metal hydroxide
Boytsova et al. Nanocrystalline manganese dioxide synthesis by microwave-hydrothermal treatment
CN104924706B (en) A kind of preparation method of brucite-montmorillonite laminate alternating structure composite
CN102701241B (en) Cleaning preparation method of laminated composite metal hydroxide
CN103101962A (en) Preparation method of zinc oxide/titanium dioxide composite nanorod
CN106517270B (en) The preparation method of nano composite hydroxide
CN103318933A (en) Method for preparing surface-modified hydrotalcite compound through adopting brucite
CN106517269B (en) A kind of method of comprehensive utilization of by-product magnesium hydroxide
CN106517261B (en) The preparation method of magnesium-based complex metal hydroxide
CN106517304B (en) The preparation method of three-dimensional complex metal hydroxide
CN107473187A (en) The preparation method of layered composite metal hydroxides with sulfate radical intercalation
CN107500320A (en) The preparation method of layered composite metal hydroxides
CN109502656A (en) A kind of spherical Co (II) Co (III) hydrotalcite-like materials and preparation method thereof
CN105148808B (en) A kind of method for preparing three-dimensional barium tantalate flower-shape microballoon
CN107572563A (en) A kind of preparation method of magnesium-base layer-shaped complex metal hydroxide
JP5339330B2 (en) Method for producing layered rare earth hydroxide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant