CN107032314B - A kind of preparation method of manganese phosphate nanocages - Google Patents
A kind of preparation method of manganese phosphate nanocages Download PDFInfo
- Publication number
- CN107032314B CN107032314B CN201611062017.5A CN201611062017A CN107032314B CN 107032314 B CN107032314 B CN 107032314B CN 201611062017 A CN201611062017 A CN 201611062017A CN 107032314 B CN107032314 B CN 107032314B
- Authority
- CN
- China
- Prior art keywords
- manganese phosphate
- preparation
- manganese
- nanocages
- phosphate nanocages
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
-
- 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
Abstract
The present invention relates to a kind of preparation methods of manganese phosphate nanocages, it is characterized in that, the preparation method is using cube silver orthophosphate as silver-colored source and template, using soft base thiosulfate anion as the complexometric reagent of soft acid silver ion, carry out the release of phosphate radical, and with the manganese ion reaction in-situ of addition, obtain manganese phosphate nanocages.The preparation method of the material includes the following steps：It is 1 that polyvinylpyrrolidone, four chloride hydrate Asia manganese, which are dissolved in ethyl alcohol and water volume ratio,:In 1 ethyl alcohol water mixed solution, cube silver orthophosphate is dispersed in the mixed liquor under stirring；The thiosulfate solution of 1 mol/L is added dropwise into the mixed liquor, until reaction solution gradually becomes white by faint yellow, continues stirring 1 hour, washing, drying obtain manganese phosphate nanocages.Manganese phosphate nanocages prepared by this method have certain application prospect in catalysis, photonic device, drug delivery carrier etc..
Description
Technical field
The present invention relates to a kind of preparation methods of nanocages, and in particular to a kind of preparation method of manganese phosphate nanocages belongs to
In function technologic material field.
Background technology
Hollow Nano basket structure has the unique knots such as inner space is big, density is small, large specific surface area and permeability are strong
Structure feature, in catalysis, photonic device, drug delivery carrier, active matter encapsulation, energy storage device and nano-reactor etc.
It has broad application prospects.In recent years, the preparation of hollow Nano basket structure material was increasingly becoming grinding for nano-functional material
Study carefully one of hot spot.Wherein, aspherical hollow Nano basket structure (such as hollow polyhedral, spheroid and conulite) is in addition to having
Outside the characteristic of ball shaped nano basket structure, symmetry reduces caused structural anisotropy and makes it in light, electricity, magnetic etc.
By with unusualr property, therefore, synthesis and property research are concerned.
Although anisotropic nanometer basket structure application prospect is bright, conventional method is used（For example, self assembly, by it is interior it
Outer Ostwald ripening）But it is difficult to prepare them.Template be conducive to prepare number of other, non-spherical shapes nano-hollow
Cage material.Although having had the report for successfully preparing aspherical nanometer basket structure using template at present, there are still some skills
Art problem needs scientific research personnel to capture, such as：(1) how to grasp synthesis material requested shell and go the reaction between removing template
Kinetic balance；(2) how uniform shell is obtained on the high curvature surface of aspherical template；(3) how high remaining
Ghost pattern is completely preserved under stress.In recent years, Kirkendall effects, Galvanic substitution reactions and chemical etch technique
The methods of all be applied to hollow Nano basket structure preparation.For example, scientific research personnel is also prepared using Kirkendall effects
Cu7S4、Fe2O3, the hollow basket structure of MnO, ZnO.But above-mentioned preparation process needs at further heat treatment and acid etch
Reason, process is complicated, manufacturing cost is high, and easily causes environmental pollution.Therefore, develop room temperature condition, environmental-friendly, one-step synthesis
The new way of hollow Nano basket structure has great importance.
Invention content
The present invention uses thiosulfate anion using cube silver orthophosphate as silver-colored source and template（Soft base）To silver ion（Soft acid）
It is complexed, phosphate radical is made to discharge, and reacted in situ with the manganese ion of addition, be prepared for manganese phosphate nanocages.With conventional template
Method is compared, and accompanying method of the present invention has the characteristics that：(1) template silver orthophosphate is cube pattern, the nanometer cage tool of preparation
There is cubic morphology；(2) silver ion is complexed using sodium thiosulfate as complexometric reagent, is on the one hand in situ generated
Manganese phosphate shell, while being the etching realized to remaining phosphoric acid galactic nucleus, finally obtain manganese phosphate nanocages；（3）Preparation method
Simply, entire reaction carries out at room temperature.
The manganese phosphate nanocages, specific preparation process include the following steps：
（1）It is 1 that polyvinylpyrrolidone, four chloride hydrate Asia manganese, which are dissolved in ethyl alcohol and water volume ratio,:1 alcohol-water is mixed
It closes in liquid, cube silver orthophosphate is dispersed in the mixed liquor under stirring；
（2）Under stirring, 1 mol/L is added dropwise in above-mentioned solution（M）Thiosulfate solution, until reaction solution by
Gradually become white from faint yellow, continues stirring 1 hour；
（3）Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
The preparation method of manganese phosphate nanocages according to claim 1, which is characterized in that polyvinylpyrrolidone exists
Mass percent concentration in ethanol-water mixture is 2% ~ 6%, and the molar ratio of four chloride hydrate Asia manganese and silver orthophosphate is 1:10~
1:1.5.The thiosulfate used is sodium thiosulfate or potassium thiosulfate, and the dosage of 1.0 M thiosulfates is 1 ~ 6 milli
It rises.
Description of the drawings
Fig. 1 is the X-ray line diffraction for the manganese phosphate nanocages that embodiment 1 obtains（XRD）Collection of illustrative plates；
Fig. 2 is the scanning electron microscope for the manganese phosphate nanocages that embodiment 1 obtains（SEM）Picture；
Fig. 3 is the transmission electron microscope for the manganese phosphate nanocages that embodiment 1 obtains（TEM）Picture.
Specific implementation mode
The present invention is discussed further below in conjunction with example.
Embodiment 1
0.33 gram of PVP K30 and 2.0 milligram of four chloride hydrate Asia manganese are dissolved in 10 milliliters of ethyl alcohol and water body
Product is than being 1:In 1 ethanol-water mixture；Under stirring, 10 milligrams of cube silver orthophosphates are scattered in the mixed liquor, then dropwise
The hypo solution of 4 milliliter of 1 M is added, until reaction solution gradually becomes pink from faint yellow, continues stirring 1 hour.
Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
The XRD spectrum of manganese phosphate nanocages prepared by example 1 is as shown in Figure 1, the diffraction maximum at 2 θ=10.8 ° belongs to
In Mn3(PO4)2·1.5H2O（110）Diffraction maximum (the JCPDS of crystal face:50-0231), the nanocages shown are manganese phosphate；
Fig. 2 be manganese phosphate nanocages SEM pictures, as can be seen from the figure manganese phosphate nanocages have tens nanometers particle aggregation and
At；Fig. 3 is the TEM pictures for preparing manganese phosphate nanocages, it can be seen from the figure that manganese phosphate nanocages are hollow-core construction.
Embodiment 2
0.20 gram of PVP K30 and 2.0 milligram of four chloride hydrate Asia manganese are dissolved in 10 milliliters of ethyl alcohol and water body
Product is than being 1:In 1 ethanol-water mixture；Under stirring, 10 milligrams of cube silver orthophosphates are scattered in the mixed liquor, then dropwise
The hypo solution of 4 milliliter of 1 M is added, until reaction solution gradually becomes pink from faint yellow, continues stirring 1 hour.
Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
Embodiment 3
0.33 gram of PVP K30 and 1 milligram of four chloride hydrate Asia manganese are dissolved in 10 milliliters of ethyl alcohol and water volume
Than being 1:In 1 ethanol-water mixture；Under stirring, 10 milligrams of cube silver orthophosphates are scattered in the mixed liquor, then are added dropwise
Enter the hypo solution of 4 milliliter of 1 M, until reaction solution gradually becomes pink from faint yellow, continues stirring 1 hour.It will
Obtained sample centrifugation, is washed with water 5 times, dry, obtains manganese phosphate nanocages.
Embodiment 4
0.33 gram of PVP K30 and 0.6 milligram of four chloride hydrate Asia manganese are dissolved in 10 milliliters of ethyl alcohol and water body
Product is than being 1:In 1 ethanol-water mixture；Under stirring, 10 milligrams of cube silver orthophosphates are scattered in the mixed liquor, then dropwise
The hypo solution of 4 milliliter of 1 M is added, until reaction solution gradually becomes pink from faint yellow, continues stirring 1 hour.
Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
Embodiment 5
0.33 gram of PVP K30 and 2.0 milligram of four chloride hydrate Asia manganese are dissolved in 10 milliliters of ethyl alcohol and water body
Product is than being 1:In 1 ethanol-water mixture；Under stirring, 10 milligrams of cube silver orthophosphates are scattered in the mixed liquor, then dropwise
The thiosulfuric acid potassium solution of 4 milliliter of 1 .0 M is added, until reaction solution gradually becomes pink from faint yellow, it is small to continue stirring 1
When.Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
Embodiment 6
0.33 gram of PVP K30 and 2.0 milligram of four chloride hydrate Asia manganese are dissolved in 10 milliliters of ethyl alcohol and water body
Product is than being 1:In 1 ethanol-water mixture；Under stirring, 10 milligrams of cube silver orthophosphates are scattered in the mixed liquor, then dropwise
The hypo solution of 2 milliliter of 1.0 M is added, until reaction solution gradually becomes pink from faint yellow, it is small to continue stirring 1
When.Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
Embodiment 7
0.33 gram of PVP K30 and 2.0 milligram of four chloride hydrate Asia manganese are dissolved in 10 milliliters of ethyl alcohol and water body
Product is than being 1:In 1 ethanol-water mixture；Under stirring, 10 milligrams of cube silver orthophosphates are scattered in the mixed liquor, then dropwise
The hypo solution of 6 milliliter of 1.0 M is added, until reaction solution gradually becomes pink from faint yellow, it is small to continue stirring 1
When.Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
Claims (5)
1. a kind of preparation method of manganese phosphate nanocages, which is characterized in that the preparation method is using cube silver orthophosphate as silver-colored source
And template carries out the release of phosphate radical using soft base thiosulfate anion as the complexometric reagent of soft acid silver ion, and with addition
Manganese ion reaction in-situ, obtains manganese phosphate nanocages, and specific preparation process includes the following steps：
（1）It is 1 that polyvinylpyrrolidone, four chloride hydrate Asia manganese, which are dissolved in ethyl alcohol and water volume ratio,:1 ethanol-water mixture
In, cube silver orthophosphate is dispersed in the mixed liquor under stirring；
（2）Under stirring, 1 mol/L is added dropwise in above-mentioned solution（M）Thiosulfate solution, until reaction solution gradually by
It is faint yellow to become white, continue stirring 1 hour；
（3）Obtained sample is centrifuged, is washed with water 5 times, it is dry, obtain manganese phosphate nanocages.
2. the preparation method of manganese phosphate nanocages according to claim 1, which is characterized in that polyvinylpyrrolidone is in second
Mass percent concentration in alcohol-water mixtures is 2% ~ 6%.
3. the preparation method of manganese phosphate nanocages according to claim 1, which is characterized in that four chloride hydrate Asia manganese and phosphorus
The molar ratio of sour silver is 1:10~1:1.5.
4. the preparation method of manganese phosphate nanocages according to claim 1, which is characterized in that the thiosulfate used is
Sodium thiosulfate or potassium thiosulfate.
5. the preparation method of manganese phosphate nanocages according to claim 1, which is characterized in that 1.0 M thiosulfates
Dosage is 1 ~ 6 milliliter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611062017.5A CN107032314B (en) | 2016-11-26 | 2016-11-26 | A kind of preparation method of manganese phosphate nanocages |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611062017.5A CN107032314B (en) | 2016-11-26 | 2016-11-26 | A kind of preparation method of manganese phosphate nanocages |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107032314A CN107032314A (en) | 2017-08-11 |
| CN107032314B true CN107032314B (en) | 2018-07-17 |
Family
ID=59530621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611062017.5A Expired - Fee Related CN107032314B (en) | 2016-11-26 | 2016-11-26 | A kind of preparation method of manganese phosphate nanocages |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107032314B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011056816A1 (en) * | 2011-12-21 | 2013-08-01 | Chemische Fabrik Budenheim Kg | Manganese-containing metal phosphates and process for their preparation |
| CN103539097B (en) * | 2013-10-30 | 2015-05-27 | 渤海大学 | Preparation method of multi-shape alkaline manganese phosphate microcrystal |
| CN105609765A (en) * | 2015-12-25 | 2016-05-25 | 中钢集团安徽天源科技股份有限公司 | Preparation method of manganese phosphate and manganese phosphate product |
-
2016
- 2016-11-26 CN CN201611062017.5A patent/CN107032314B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN107032314A (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Rice husks as a sustainable silica source for hierarchical flower-like metal silicate architectures assembled into ultrathin nanosheets for adsorption and catalysis | |
| CN101559951B (en) | Method for preparing nanoscale silica hollow microspheres | |
| CN107096494A (en) | A kind of preparation and application method of magnetic core-shell nano-compound adsorbent | |
| CN103500622A (en) | Magnetism inorganic nanoparticle/ordered mesopore silica nuclear shell composite microsphere and preparing method thereof | |
| CN102153094B (en) | Method for preparing ordered mesoporous hollow silica spheres | |
| CN105458295B (en) | A kind of multi-pore micron copper ball and preparation method thereof | |
| CN103157441A (en) | Fluorine removal agent with fluorine ion absorption/desorption function through pH value regulation and control and preparation method thereof | |
| Liu et al. | Building on size-controllable hollow nanospheres with superparamagnetism derived from solid Fe 3 O 4 nanospheres: preparation, characterization and application for lipase immobilization | |
| CN102764617A (en) | Method for preparing silver-carried silica microsphere functional materials | |
| CN101618895A (en) | Multi-level structure alpha type nickel hydroxide prepared by microwave auxiliary and method thereof | |
| CN102649046A (en) | Nanometer ferroferric oxide core-carbon meso pore hollow shell complex, as well as preparation method and application thereof | |
| An et al. | Facile template-free synthesis and characterization of elliptic α-Fe2O3 superstructures | |
| CN106495119B (en) | A kind of preparation method of cube cobalt phosphate nanocages | |
| CN109678137B (en) | Preparation method of hollow carbon nanospheres | |
| Azhar et al. | Synthesis of hollow Co–Fe Prussian blue analogue cubes by using silica spheres as a sacrificial template | |
| CN105597714A (en) | Preparation of phenyl-modified magnetic graphene/mesoporous silicon dioxide composite material and application of phenyl-modified magnetic graphene/mesoporous silicon dioxide composite material as solid-phase extracting agent | |
| CN107021498B (en) | Hollow silicic acid manganese material and preparation method thereof | |
| CN107032315B (en) | A kind of preparation method of trbasic zinc phosphate nanocages | |
| CN106698381B (en) | A kind of preparation method of cube nickel phosphate nanocages | |
| CN106075470B (en) | The application of gold-nano-piece synthetic method and gold-nano-piece in terms of breast cancer diagnosis and treatment | |
| CN107032314B (en) | A kind of preparation method of manganese phosphate nanocages | |
| CN102389771A (en) | Method for preparing bell type magnetic mesoporous silica-microsphere absorbent | |
| CN110302764A (en) | A kind of surface improved microballoon of superelevation and its preparation method and application | |
| CN106010500A (en) | Magnetic nano-luminescent material with core-shell structure and preparation method of magnetic nano-luminescent material | |
| CN105950148A (en) | Preparation method for preparing ferroferric oxide hollow ball-based fluorescent magnetic composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180717 Termination date: 20181126 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |