CN107555454A - The preparation method of layered composite metal hydroxides with chlorion intercalation - Google Patents
The preparation method of layered composite metal hydroxides with chlorion intercalation Download PDFInfo
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- CN107555454A CN107555454A CN201710781215.5A CN201710781215A CN107555454A CN 107555454 A CN107555454 A CN 107555454A CN 201710781215 A CN201710781215 A CN 201710781215A CN 107555454 A CN107555454 A CN 107555454A
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Abstract
The invention discloses a kind of preparation method of the layered composite metal hydroxides with chlorion intercalation, the layered composite metal hydroxides include 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, and interlayer anion is chlorion；The preparation method includes step：S1, the hydroxide of low price cation mixed and soluble in water with the hydroxide of high-valence cationic, obtain the first mixture；S2, add hydrochloric acid and/or water soluble chloride into the first mixture and be well mixed, obtain the second mixture；S3, the second mixture reacted into 4h~100h at 50 DEG C~300 DEG C, reaction product is through separation of solid and liquid, and gained solid phase is through drying.Preparation in accordance with the present invention compares existing method, without providing N2Atmosphere, reduce and prepare cost and equipment requirement, and be a kind of preparation method of cleaning in the absence of Keep Clear-High Voltage.
Description
Technical field
The invention belongs to inorganic non-metallic technical field of function materials, and specifically, being related to one kind has chlorion intercalation
Layered composite metal hydroxides preparation method.
Background technology
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, and the metal sun with different electric charges is carried 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 be represented by：[M+M2+ 1-y-0.5x-2zM3+ yM4+ z(OH)2](An-)y/n·mH2O, wherein M+、M2+、M3+And M4+Respectively
Represent monovalent metal cation, divalent metal, trivalent metal cation and four on layers of metal hydroxides plate
Valency 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, z can not be the amount for the material that 0, m is interlayer hydrone simultaneously.
LDHs has the characteristics that Subjective and Objective element species and quantity is adjustable, the elastic adjustable, size of laminate and pattern are adjustable,
LDHs is because the particularity of its structure and performance are greatly strengthened and are ground in catalysis, the energy, biology sensor, absorption, medicine 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.
Traditional LDHs preparation method mainly includes hydro-thermal method, the precipitation method, ion-exchange, roast reduction process etc., typically
Ground, the method for preparing the LDHs with chlorion intercalation generally has an ion-exchange and coprecipitation, but both sides
Method is required in N2Carried out under atmosphere protection, preparation condition is relatively harsh, and needs special equipment, there is that Keep Clear-High Voltage.
Therefore, it is critically important to explore a kind of suitable LDHs with chlorion intercalation preparation method.
The content of the invention
To solve the above-mentioned problems of the prior art, the invention provides a kind of composition metal with chlorion intercalation
The preparation method of hydroxide, the preparation method need not provide N2Atmosphere, reduce and prepare cost and equipment requirement, and in the absence of height
Pressure is dangerous, is a kind of preparation method of cleaning.
In order to reach foregoing invention purpose, present invention employs following technical scheme：
A kind of preparation method of the layered composite metal hydroxides with chlorion intercalation, layered composition metal hydrogen
Oxide includes low price main layer board cation, high price main layer board cation and interlayer anion, wherein, the low price master
Body laminate cation and the high price main layer board cation include at least one metal cation, and the interlayer anion is chlorine
Ion；The preparation method includes step：
S1, the hydroxide of low price cation mixed and soluble in water with the hydroxide of high-valence cationic, obtain the
One mixture；
S2, add hydrochloric acid and/or water soluble chloride into first mixture and be well mixed, obtain the second mixing
Thing；
S3, second mixture reacted into 4h~100h at 50 DEG C~300 DEG C, reaction product is through separation of solid and liquid, institute
Solid phase is obtained through drying, obtains the layered composite metal hydroxides with chlorion intercalation.
Further, the low price cation is identical with the low price main layer board cation；The high-valence cationic with
The high price main layer board cation is identical.
Further, the low price cation is selected from Li+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+
And Be2+At least one of.
Further, 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.
Further, the amount of the hydroxide of the low price cation and the material of the hydroxide of the high-valence cationic
The ratio between be 2:1~100:1.
Further, the amount of the material of the hydrochloric acid and/or water soluble chloride is the amount of the high-valence cationic material
0.01~50 times.
Further, in the step S1, the quality of water for the quality of the hydroxide of the low price cation 1~
1000 times.
Further, in the step S1, in addition to：First mixture stirring is no more than 4h.
Further, in the step S3, second mixture is placed in ultrasound, hydro-thermal, backflow, any ring of microwave
Reacted under border.
The present invention is by reasonable selection reactant while by rationally controlling the ratio between each reactant so that final
Only obtaining includes the layered composite metal hydroxides of predetermined ion, without other accessory substances of association, and the lamellar composite
Metal hydroxides is used as interlayer anion using chlorion；The layered composite metal hydroxides of acquisition can be used directly, and nothing
It the operation such as need to wash, reduce the use of the freshwater resources such as slurry, while reach 100% Atom economy, meet
The requirement of Green Chemistry.According to the present invention the layered composite metal hydroxides with chlorion intercalation preparation method,
Preparation method in compared with prior art, N need not be provided in preparation process2Atmosphere, operating process is easy, not only reduces system
Standby cost and equipment requirement, and in the absence of Keep Clear-High Voltage, preparation technology is safer.
Embodiment
Hereinafter, embodiments of the invention are described in detail in the future.However, it is possible to implement this hair in many different forms
It is bright, and the specific embodiment of the invention that should not be construed as limited to illustrate here.Conversely, there is provided these embodiments be for
The principle and its practical application of the present invention is explained, so that others skilled in the art are it will be appreciated that the present invention's is various
Embodiment and the various modifications for being suitable for specific intended application.
It will be appreciated that although can be used term " first ", " second " etc. to describe various materials herein, but these
Material should not be limited by these terms.These terms are only used for separating a material with another material.
The invention discloses a kind of preparation method of the layered composite metal hydroxides with chlorion intercalation, the stratiform
Complex metal 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/or high price main layer board cation include at least one metal cation, and interlayer anion
Specially chlorion.
Following steps are included according to the preparation method of the layered composite metal hydroxides with chlorion intercalation of the present invention
Suddenly：
S1, the hydroxide of low price cation mixed with the hydroxide of high-valence cationic, and soluble in water, obtain the
One mixture.
Specifically, low price cation is identical with the low price main layer board cation in layered composite metal hydroxides, low
Valency cation is represented with X；High-valence cationic is identical with high price main layer board cation, is represented with Y.
Low price cation is selected from Li+、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+In at least
One kind, high-valence cationic are selected from Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+In
At least one.
More specifically, in the first mixture, the hydroxide of low price cation and the hydroxide of high-valence cationic
The ratio between the amount of material be 2:1~100:1.
Preferably, the quality control of used water is 1~1000 times of quality of the hydroxide of low price cation.
S2, add hydrochloric acid and/or water soluble chloride into the first mixture and be well mixed, obtain the second mixture.
Specifically, it is 0.01 to control the ratio between hydrochloric acid and/or the amount of material of water soluble chloride and high-valence cationic:1
~50:1, and the cation in water soluble chloride may be selected from Na+、Li+、NH4 +、Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、
Fe2+、Mn2+、Cd2+、Be2+、Al3+、Ni3+、Co3+、Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+、Sn4+、Ti4+And Zr4+In
At least one, preferably Na+、Li+、NH4 +。
It is preferred that 4h will be no more than with the stirring of the mixture of hydrochloric acid and/or water soluble chloride in the first mixture, with abundant
Dissolve and disperse, and form uniform second mixture.
S3, the second mixture reacted into 4h~100h at 50 DEG C~300 DEG C, reaction product is solid through separation of solid and liquid, gained
Mutually through drying, the layered composite metal hydroxides with chlorion intercalation are obtained.
The solid phase of acquisition dries 12h preferably at 80 DEG C.
What deserves to be explained is the reaction of the second mixture can be in any ring such as ultrasound, hydro-thermal, backflow, microwave
Carried out under border, but reaction environment be not limited to it is above-mentioned listed.
The pH value of the layered composite metal hydroxides with chlorion intercalation obtained is determined, finds to be in neutrality, also
To say, according to the present invention the layered composite metal hydroxides with chlorion intercalation preparation method acquisition with chlorine from
The layered composite metal hydroxides of sub- intercalation will not produce other accessory substances, and also fundamental reaction is complete for reactant, without through
Cross washing operation to can be used directly, not only saved the freshwater resources such as a large amount of slurries, reduce and waste, reduce cost, and
And simplify technique.
Hereinafter, by reference specific embodiment to the layered composite metal hydrogen-oxygen with chlorion intercalation according to the present invention
The preparation method of compound is described in detail, and for convenience of being contrasted to each embodiment, analysis contrast is each in table form
Embodiment.The comparing result under different experiments parameter in embodiment 1-8 is as shown in table 1.
Contrasts of the 1-8 under different experiments parameter according to an embodiment of the invention of table 1
Note：In table 1, " the first mol ratio " refers to the hydroxide of low price cation and the hydroxide of high-valence cationic
The ratio between amount of material；" the second mol ratio " refers to the ratio between amount of material of hydrochloric acid and/or water soluble chloride and high-valence cationic.
Certainly, according to the preparation method of the layered composite metal hydroxides with chlorion intercalation of the present invention and unlimited
In described in above-described embodiment 1-8, such as low price cation is Li+And Mg2+, high-valence cationic Al3+And Ti4+, then it is final to be made
The layered composite metal hydroxides with chlorion intercalation layers of metal hydroxides plate on then simultaneously have above-mentioned four kinds
Metal cation；In other words, according to the preparation side of the layered composite metal hydroxides with chlorion intercalation of the present invention
It is monovalent metal cation, divalent metal, three that method, which enables to the metal cation on its layers of metal hydroxides plate,
At least two in valency metal cation, tetravalent metal cation, meanwhile, can be with for the metal cation of identical valence state
Cation comprising various metals.
Although the present invention has shown and described with reference 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 limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (9)
1. a kind of preparation method of the layered composite metal hydroxides with chlorion intercalation, layered composition metal hydrogen-oxygen
Compound includes low price main layer board cation, high price main layer board cation and interlayer anion, wherein, the low price main body
Laminate cation and the high price main layer board cation include at least one metal cation, the interlayer anion be chlorine from
Son；Characterized in that, the preparation method includes step：
S1, the hydroxide of low price cation mixed and soluble in water with the hydroxide of high-valence cationic, it is mixed to obtain first
Compound；
S2, add hydrochloric acid and/or water soluble chloride into first mixture and be well mixed, obtain the second mixture；
S3, second mixture reacted into 4h~100h at 50 DEG C~300 DEG C, reaction product is solid through separation of solid and liquid, gained
Mutually through drying, the layered composite metal hydroxides with chlorion intercalation are obtained.
2. preparation method according to claim 1, it is characterised in that the low price cation and the low price main layer board
Cation is identical；The high-valence cationic is identical with the high price main layer board cation.
3. preparation method according to claim 2, it is characterised in that the low price cation is selected from Li+、Mg2+、Zn2+、
Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+And Be2+At least one of.
4. preparation method according to claim 2, it is characterised in that 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.
5. according to any described preparation methods of claim 1-4, it is characterised in that the hydroxide of the low price cation with
The ratio between amount of material of hydroxide of the high-valence cationic is 2:1~100:1.
6. according to any described preparation methods of claim 1-4, it is characterised in that the hydrochloric acid and/or water soluble chloride
The amount of material be 0.01~50 times of amount of the high-valence cationic material.
7. preparation method according to claim 1, it is characterised in that in the step S1, the quality of water is described low
1~1000 times of the quality of the hydroxide of valency cation.
8. preparation method according to claim 1, it is characterised in that in the step S1, in addition to：By described first
Mixture stirring is no more than 4h.
9. preparation method according to claim 1, it is characterised in that in the step S3, by second mixture
It is placed under ultrasound, hydro-thermal, backflow, microwave any environment and is reacted.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994888A (en) * | 2007-01-12 | 2007-07-11 | 北京化工大学 | Cleaning preparation method of sheet-like composite oxide powder |
| CN105753022A (en) * | 2016-03-28 | 2016-07-13 | 北京化工大学 | Preparation method of LDHs (magnesium-based layered double hydroxides) |
| CN106517270A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method for nano-composite metal hydroxide |
| CN106517099A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method of LDHs (layered double hydroxides) |
-
2017
- 2017-09-01 CN CN201710781215.5A patent/CN107555454A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994888A (en) * | 2007-01-12 | 2007-07-11 | 北京化工大学 | Cleaning preparation method of sheet-like composite oxide powder |
| CN105753022A (en) * | 2016-03-28 | 2016-07-13 | 北京化工大学 | Preparation method of LDHs (magnesium-based layered double hydroxides) |
| CN106517270A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method for nano-composite metal hydroxide |
| CN106517099A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method of LDHs (layered double hydroxides) |
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Application publication date: 20180109 |