CN108502910A - Insoluble inorganic salts micro Nano material and its preparation method and application - Google Patents
Insoluble inorganic salts micro Nano material and its preparation method and application Download PDFInfo
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- CN108502910A CN108502910A CN201810170785.5A CN201810170785A CN108502910A CN 108502910 A CN108502910 A CN 108502910A CN 201810170785 A CN201810170785 A CN 201810170785A CN 108502910 A CN108502910 A CN 108502910A
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- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention belongs to New Chemical Materials technical field, specially insoluble inorganic salts micro Nano material and its preparation method and application.The present invention, at room temperature with water-soluble inorganic salt solution reaction, synthesizes using " metal ion thiocyanate radical " system as precursor and obtains insoluble inorganic salts micro Nano material；Wherein, water-soluble inorganic salt uses sodium carbonate；When metal ion uses calcium ion, inorganic salts micro Nano material obtained is the Calcium carbonate micro-nano material of specific form；When metal ion uses indium ion, insoluble inorganic salts micro Nano material obtained is indium salts nano material.The Calcium carbonate micro-nano material of specific form can be used as chemical materials and filler, for fields such as rubber, plastics, coating, cosmetics；Insoluble indium salts nano material can be used as functional form added material and dopant material, be used for the fields such as functional material and photoelectric functional device.
Description
Technical field
The invention belongs to New Chemical Materials technical fields, and in particular to the insoluble inorganic salts of specific form micro-nano-scale
Material and its preparation method and application.
Background technology
Simple inorganic salts can be widely used field.Many carbonate are insoluble in water, or in water
Solubility is extremely low, and this kind of insoluble inorganic salts can maintain its structural form well.Calcium carbonate（CaCO3）It is typical example.
Calcium carbonate is widely present in nature and a kind of function admirable, the cheap raw material of industry.Calcium carbonate is common to fill
Agent is widely used in field of compound material such as rubber, plastics, coating, cosmetics.The application performance of calcium carbonate not only with scale
It is related, it is also related with the configuration of surface of particle and structure.Such as calcium carbonate and resin compounded, the size of one side calcium carbonate granule
The performance of composite material can be influenced, the surface texture of another aspect calcium carbonate granule also can greatly influence performance.Such as surface
The adhesion effect of smooth calcium carbonate and resin can be poor, has the calcium carbonate of special construction level since there is also mechanical snaps
With a variety of interactions such as adhesive force, the performance of composite material can be enhanced.Therefore scale is combined to the calcium carbonate of specific form
Micro Nano material still has important value.[（1）Zhang Qun, Zhu Wanhua, Wang Xuwu, Zhang Qing, the preparation of calcium carbonate superfine powder microballoon, people
Work crystal journal, 2014,43 (2): 438;（2）Yue Linhai, Jin Dalai, Xu Zhude, Co deposited synthesis composite calcium carbonate and
The research of its pattern and crystal form, chemical journal, 2003,61 (10): 1587~1591;（3）The poles Luo Ying, land-sea is diligent, Jiao Bo, changes
Influence of the additive to calcium carbonate crystal is learned,《Food industry》, 2013,34 (5): 78-181].
Many phosphate are also insoluble inorganic salts.With going deep into for research, the functional character of simple inorganic salts and application
Field is constantly opened up.Indium phosphate, calcium phosphate etc. are exactly very representational substance, in fields such as poromerics, magnetics, catalysis
There is potential application value.But the material for wanting low-coat scale to be combined to nanoscale is not easy to.
Inventor has found that " metal ion-thiocyanate radical " system can be used for liquid-phase precipitation method early period, prepares metal oxidation
Object nano material. [（4）Xuwei, Tian Guo, Xiao Xingxing, a kind of preparation of trimanganese tetroxide nano granular materials of Xia Peng, Sun Qian
Method applications for a patent for invention number：2014100314102；（5）Xuwei, Sun Qian, Xiao Xingxing, Xia Peng, a kind of sheet oxygen of field fruit
Change the simple preparation method applications for a patent for invention number of zinc nano material：2014100412374；（6）Xuwei, Tian Guo, Sun Qian, Xiao
Star, a kind of simple preparation method applications for a patent for invention number of aluminum hydroxide nanoparticle materials of Xia Peng：
2014100413076]。
By continuing to study, present invention discover that " metal ion-thiocyanate radical " system can be used for synthesis specific form
Insoluble inorganic salts micro Nano material.
Invention content
Present invention aims at a kind of insoluble inorganic salts micro Nano materials of proposition and its preparation method and application.
The preparation method of insoluble inorganic salts micro Nano material proposed by the present invention, with " metal ion-thiocyanate radical " body
System is precursor, at room temperature with water-soluble inorganic salt solution reaction, synthesizes and obtains insoluble inorganic salts micro Nano material.
In the present invention, calcium ion can be used in the metal ion；Water-soluble inorganic salt uses sodium carbonate（NaCO3）；It is made
Insoluble inorganic salts micro Nano material be specific form Calcium carbonate micro-nano material.
In the present invention, the calcium ion source can be calcium chloride（CaCl2）.
In the present invention, indium ion can be used in the metal ion；Water-soluble inorganic salt uses sodium phosphate（NaCO3）；It is made
Insoluble inorganic salts micro Nano material be indium salts nano material.
In the present invention, the indium ion source can be indium nitrate.
In the present invention, the preparation flow of Calcium carbonate micro-nano material is as follows：
By calcium chloride（CaCl2）Aqueous solution and sodium sulfocyanate（NaSCN）Aqueous solution is uniformly mixed, and prepares " calcium ion-thiocyanic acid
Aqueous sodium carbonate is added as precursor, then in the system in root " system, after stirring evenly, stands 2 ~ 24 hours.By reaction solution
It is separated by filtration, precipitation is washed with deionized 3-4 times, is placed in baking oven（Temperature can be 60 DEG C）Middle drying is to get calcium carbonate micro-nano
Rice material.
A concentration of 0.1 ~ 5 mol/L of the calcium chloride water.
A concentration of 0.1 ~ 5 mol/L of the sodium thiocyanate water solution.
A concentration of 0.1 ~ 5 mol/L of the aqueous sodium carbonate.
The amount ratio of the substance of sodium sulfocyanate and calcium chloride is 3 ~ 30；The amount ratio of the substance of sodium carbonate and calcium chloride is 3 ~ 20.
The study found that different reactant concentrations can influence product CaCO3Grain size and pattern, further change molten
Liquid concentration combination can further regulate and control the appearance structure of product.Under determining formula and concentration conditions, the pattern knot of product
Structure can remain stable.Illustrate specific modality calcium carbonate product can controlledly synthesis, including：The more smooth cube in surface is micro-
It scale particles, shaggy pseudo-cubic particle made of being stacked by laminated structure and is stacked by flake nano level structure
Made of torispherical and elliposoidal micron particles etc..The calcium carbonate of this multilayered structure is due to big mechanical snap power, attachment
Power and complicated surface texture, can enhance the performance of composite material, improve the additive effect of mixture.
Compared with the method that document has been reported, the method proposed by the present invention for preparing calcium carbonate need not add organic table
Face activating agent and polymer builder, it is simple for process, it is environmentally protective.
In the present invention, the preparation flow of insoluble indium salts nano material is as follows：
Indium nitrate aqueous solution is poured into sodium thiocyanate water solution, is uniformly mixed, and " indium ion-thiocyanate radical " system conduct is prepared
Precursor, then sodium phosphate aqueous solution is added into the system, after stirring evenly, stand 2 ~ 24 hours.Reaction solution is separated by filtration (or
Centrifuge), precipitation is washed with deionized 3-4 times, is placed in baking oven（Temperature can be 60 DEG C）Middle drying is to get insoluble indium salts
Nano material.
A concentration of 0.5 mol/L of the sodium thiocyanate water solution.
A concentration of 0.5 ~ 1 mol/L of the indium nitrate aqueous solution.
A concentration of 0.1 ~ 0.5 mol/L of the sodium phosphate aqueous solution.
The amount ratio of the substance of sodium sulfocyanate and indium nitrate is 3 ~ 4；The amount ratio of the substance of sodium phosphate and indium nitrate is 1 ~ 3.
Preparation method proposed by the present invention is very simple, is easy production.It in the actual production process, can be according to specific feelings
Condition amplifies production scale, including improves solution concentration.
Product powder x-ray diffraction prepared by the present invention（XRD）And scanning electron microscope（SEM）To be analyzed and characterized.
The calcium carbonate of specific form produced by the present invention is used as new type chemical material and filler, in rubber, plastics, painting
It is widely used in the field of compound material such as material, cosmetics.
Insoluble indium salts nano material produced by the present invention is used as functional form added material and dopant material, is applied to work(
It can material and photoelectric functional devices field.
Description of the drawings
Fig. 1 is the preparation flow schematic diagram of specific form Calcium carbonate micro-nano material.
Fig. 2 is the preparation flow schematic diagram of insoluble indium salts nano material.
Fig. 3 is the XRD curves of calcium carbonate.Wherein, curve a is the calcium carbonate of common method synthesis；Curve b, c and d are this
Invent the three kinds of specific form Calcium carbonate micro-nano materials prepared.
Fig. 4 is the SEM image of synthetic calcium carbonate.Wherein, b, c and d label on three width images and three XRD in Fig. 3
Curve（B, c and d）It is corresponding.
Fig. 5 is the SEM image of insoluble indium salts nano material.
Specific implementation mode
The insoluble inorganic salts micro Nano material of specific form that the invention is further illustrated by the following examples proposes
Preparation method.
Embodiment 1
The CaCl of 50 milliliters of 0.1 a concentration of mol/Ls2The NaSCN water of aqueous solution and 150 milliliters of a concentration of 0.1 mol/Ls
Solution in beaker after mixing, then by 100 milliliters of a concentration of 0.1 mol/L Na2CO3Aqueous solution is added dropwise in beaker, is put
It sets 2~4 hours, product is separated by filtration, be washed with deionized three times, it is dry in 60 DEG C of baking oven, it is spare.
Powder x-ray diffraction（XRD）Analytical proof product is calcium carbonate.As shown in the curve b in Fig. 3.
SEM image shows that calcium carbonate is the more smooth cube micron particles in surface, as shown in the b images in Fig. 4.
Embodiment 2
The CaCl of 50 milliliters of 0.5 a concentration of mol/Ls2The NaSCN water of aqueous solution and 150 milliliters of a concentration of 0.5 mol/Ls
Solution in beaker after mixing, then by 100 milliliters of a concentration of 0.5 mol/L Na2CO3Aqueous solution is added dropwise in beaker, is put
It sets 2~4 hours, product is separated by filtration, be washed with deionized three times, it is dry in 60 DEG C of baking oven, it is spare.
Powder x-ray diffraction（XRD）Analytical proof product is calcium carbonate.As shown in the curve c in Fig. 3.
SEM image shows that calcium carbonate is shaggy pseudo-cubic micron particles, is stacked by laminated structure
, as shown in the c images in Fig. 4.
Embodiment 3
The CaCl of 50 milliliters of 2 a concentration of mol/Ls2The NaSCN aqueous solutions of aqueous solution and 150 milliliters of a concentration of 2 mol/Ls
In beaker after mixing, then by 100 milliliters of a concentration of 2 mol/L Na2CO3Aqueous solution is added dropwise in beaker, places 2~4
Hour, product is separated by filtration, is washed with deionized three times, it is dry in 60 DEG C of baking oven, it is spare.
Powder x-ray diffraction（XRD）Analytical proof product is calcium carbonate.As shown in the curve d in Fig. 3.
SEM image shows in calcium carbonate a large amount of torisphericals and elliposoidal micron particles occur, by flake nano level structure heap
Made of folded, as shown in the d images in Fig. 4.
Embodiment 4
The nitric acid solution of indium of 20 milliliter of 0.5 mol/L is added to the beaker for the NaSCN solution for filling 120 milliliter of 0.5 mol/L
In, after mixing, add the sodium phosphate aqueous solution of 120 milliliter of 0.5 mol/L.After stirring evenly, 1 hour is stood, then from
It is centrifuged again after heart separation, washing, is placed in drying in 60 DEG C of baking ovens, be powder body material.
Fig. 5 is the SEM image of the powder body material, is shown as typical nano-particle material, and particle can be found by examining
Most of size is less than 50 nanometers.Some larger particles in figure are actually also made of minimum nanoparticle aggregate.
This clustering phenomena may be to be extruded from centrifugal separation processes.
Powder x-ray diffraction（XRD）There is not diffraction maximum in analysis.Reason unknown.May be nano material size too
It is small, and it is in amorphous normality.The accurate structural of this insoluble indium salts nano material can't be determined at present.But particle size
It is affirmative in nanoscale.
This nano-particle material is mainly used as functional additive and dopant material, is applied to functional material and photoelectric functional
Devices field.
Claims (7)
1. a kind of preparation method of insoluble inorganic salts micro Nano material, which is characterized in that with " metal ion-thiocyanate radical " body
System is precursor, at room temperature with water-soluble inorganic salt solution reaction, synthesizes and obtains insoluble inorganic salts micro Nano material；Wherein：
The metal ion uses calcium ion；Water-soluble inorganic salt uses sodium carbonate；The micro-nano material of insoluble inorganic salts obtained
Material is the Calcium carbonate micro-nano material of specific form；
The metal ion uses indium ion；Water-soluble inorganic salt uses sodium phosphate；The micro-nano material of insoluble inorganic salts obtained
Material is indium salts nano material.
2. preparation method according to claim 1, which is characterized in that the calcium ion source is calcium chloride；The indium from
Component is indium nitrate.
3. preparation method according to claim 2, which is characterized in that the preparation flow of Calcium carbonate micro-nano material is as follows：
Calcium chloride water and sodium thiocyanate water solution are uniformly mixed, " calcium ion-thiocyanate radical " system is prepared, as preceding
Body, then aqueous sodium carbonate is added in the system, after stirring evenly, stand 2 ~ 24 hours；Reaction solution is separated by filtration, is precipitated
It is washed with deionized 3-4 times, is placed in baking oven and dries to get Calcium carbonate micro-nano material；Wherein：
A concentration of 0.1 ~ 5 mol/L of the calcium chloride water；
A concentration of 0.1 ~ 5 mol/L of the sodium thiocyanate water solution；
A concentration of 0.1 ~ 5 mol/L of the aqueous sodium carbonate；
The amount ratio of the substance of sodium sulfocyanate and calcium chloride is 3 ~ 30；The amount ratio of the substance of sodium carbonate and calcium chloride is 3 ~ 20.
4. preparation method according to claim 3, which is characterized in that the form of Calcium carbonate micro-nano material is surface relatively light
Sliding cube micron particles, shaggy pseudo-cubic particle made of being stacked by laminated structure, or received by sheet
Torispherical and elliposoidal micron particles made of meter level build stack.
5. preparation method according to claim 2, which is characterized in that the preparation flow of insoluble indium salts nano material is such as
Under：
Indium nitrate aqueous solution is poured into sodium thiocyanate water solution, is uniformly mixed, " indium ion-thiocyanate radical " system is prepared, and is made
For precursor, then sodium phosphate aqueous solution is added into the system, after stirring evenly, stands 2 ~ 24 hours；Reaction solution is separated by filtration
Or centrifuge, precipitation is washed with deionized 3-4 times, is placed in baking oven and dries to get insoluble indium salts nano material；Its
In：
A concentration of 0.5 mol/L of the sodium thiocyanate water solution；
A concentration of 0.5 ~ 1 mol/L of the indium nitrate aqueous solution；
A concentration of 0.1 ~ 0.5 mol/L of the sodium phosphate aqueous solution；
The amount ratio of the substance of sodium sulfocyanate and indium nitrate is 3 ~ 4；The amount ratio of the substance of sodium phosphate and indium nitrate is 1 ~ 3.
6. by the insoluble inorganic salts micro Nano material of specific form that the preparation method described in one of claim 1-5 obtains, packet
Include the Calcium carbonate micro-nano material and indium salts nano material of specific form.
7. the application of the insoluble inorganic salts micro Nano material of specific form as claimed in claim 6, wherein specific form
Calcium carbonate micro-nano material is as chemical materials and filler, for rubber, plastics, coating, cosmetic field；Insoluble indium salts
Nano material is used for functional material and photoelectric functional devices field as functional form added material and dopant material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110015682A (en) * | 2019-04-30 | 2019-07-16 | 复旦大学 | The environment-friendly preparation method thereof of form controllable oxidization zinc nano material |
| CN111302320A (en) * | 2020-02-01 | 2020-06-19 | 复旦大学 | Nano chemical material and its general synthetic method |
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| CN101983924A (en) * | 2010-11-24 | 2011-03-09 | 鲁东大学 | Method for preparing calcium carbonate with controllable topography by using calcium sulfate |
| CN102741458A (en) * | 2009-09-08 | 2012-10-17 | 西安大略大学 | Electrochemical method of producing copper indium gallium diselenide (cigs) solar cells |
| CN104758955A (en) * | 2015-03-26 | 2015-07-08 | 湖北大学 | Method for preparing supermolecule capsule with multiple drug release stimulation and MRI radiography ability |
| CN107308966A (en) * | 2017-07-11 | 2017-11-03 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of nanometer of indium phosphate photochemical catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103754913B (en) * | 2014-01-28 | 2016-08-17 | 复旦大学 | A kind of simple method for preparing of aluminum hydroxide nanoparticle material |
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Patent Citations (4)
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| CN102741458A (en) * | 2009-09-08 | 2012-10-17 | 西安大略大学 | Electrochemical method of producing copper indium gallium diselenide (cigs) solar cells |
| CN101983924A (en) * | 2010-11-24 | 2011-03-09 | 鲁东大学 | Method for preparing calcium carbonate with controllable topography by using calcium sulfate |
| CN104758955A (en) * | 2015-03-26 | 2015-07-08 | 湖北大学 | Method for preparing supermolecule capsule with multiple drug release stimulation and MRI radiography ability |
| CN107308966A (en) * | 2017-07-11 | 2017-11-03 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of nanometer of indium phosphate photochemical catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110015682A (en) * | 2019-04-30 | 2019-07-16 | 复旦大学 | The environment-friendly preparation method thereof of form controllable oxidization zinc nano material |
| CN110015682B (en) * | 2019-04-30 | 2022-04-12 | 复旦大学 | Green preparation method of zinc oxide nano material with controllable form |
| CN111302320A (en) * | 2020-02-01 | 2020-06-19 | 复旦大学 | Nano chemical material and its general synthetic method |
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