CN103752240B - A kind of preparation method of basic copper sulfate/metal organic framework core-shell microsphere - Google Patents
A kind of preparation method of basic copper sulfate/metal organic framework core-shell microsphere Download PDFInfo
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- CN103752240B CN103752240B CN201410047897.3A CN201410047897A CN103752240B CN 103752240 B CN103752240 B CN 103752240B CN 201410047897 A CN201410047897 A CN 201410047897A CN 103752240 B CN103752240 B CN 103752240B
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Abstract
The invention discloses a kind of preparation method of basic copper sulfate/metal organic framework core-shell microsphere, belong to advanced Nano-composite materials technical field.Its preparation method first prepares the basic copper sulfate microballoon with nucleocapsid structure, is then metal-organic framework materials by its shell converted in-situ, obtained basic copper sulfate/metal organic framework core-shell microsphere.The invention has the advantages that: 1) at room temperature prepared basic copper sulfate/metal organic framework core-shell microsphere by simple two-step method; 2) with basic copper sulfate microballoon prepared by method provided by the invention, by regulate add organic ligand kind can prepare different metal organic backbone shell; 3) with method reaction condition provided by the invention is gentle, technique is simple, the cycle is short, suitability for industrialized production is applicable to.
Description
Technical field
The invention belongs to advanced Nano-composite materials technical field, particularly a kind of preparation method of basic copper sulfate/metal organic framework core-shell microsphere.
Background technology
Metal-organic framework materials (metal-organicframeworks, MOFs) be a kind of novel nano porous material, by the self assembly of transition metal ions or metal cluster and organic ligand, what formed has periodically infinite network structure one class novel crystalline material, has had the advantage of inorganic compound and organic polymer concurrently.Metal-organic framework materials demonstrates physics and the chemical property of its uniqueness in all many-sides such as catalysis, battery, Chu Qing, fluorescence, separation and absorption, and is widely used in these fields.
In recent years, using the clad of metal-organic framework materials as micro-and nano-particles, utilize the nano pore structure of its extra specific surface area, rule and hybrid inorganic-organic characteristic etc. to improve the combination property of Core-shell structure material, become the important study hotspot of material science one and development trend.At present, the method preparing micro-and nano-particles/metallic organic framework Core-shell structure material mainly contains two kinds.The first, using metal-organic framework materials as matrix material, nano particle is embedded in its pore passage structure and prepare composite.But the method reaction condition is general comparatively harsh, and the load capacity of nano particle is also lower.Second, first finishing is carried out and adsorbing metal ions to micro-and nano-particles, then in reaction system, organic ligand is added, metal ion and organic ligand form metallic organic framework on micro-and nano-particles surface, have certain thickness metallic organic framework shell through multiple adsorb, the formation of coated process.But finishing and the layer by layer loaded down with trivial details process such as coated limit its mass production and application.
In sum, the problem such as there is severe reaction conditions in current preparation method or technique is loaded down with trivial details, therefore develops a kind of gentlenessization, simplification, rapid preparation method is significant for development micro-and nano-particles/metallic organic framework Core-shell structure material.
Summary of the invention
The object of the invention is to propose the preparation method of a kind of mild condition, technique is simple, the cycle is short basic copper sulfate/metal organic framework core-shell microsphere, to overcome the shortcoming of prior art.By regulate add organic ligand kind can prepare the core-shell particles with different metal organic backbone shell.
In order to realize object of the present invention, following technical scheme is proposed:
A preparation method for basic copper sulfate/metal organic framework core-shell microsphere, described preparation method comprises step:
1) first in the aqueous solution of copper sulphate, add amine, then at room temperature leave standstill a period of time, through filtering, the basic copper sulfate microballoon of washing, dry obtained nucleocapsid structure;
2) the basic copper sulfate microballoon of obtained nucleocapsid structure is scattered in the mixed solution of second alcohol and water, add the ethanolic solution of organic ligand under agitation, the shell converted in-situ of basic copper sulfate microballoon is metal-organic framework materials, obtained basic copper sulfate/metal organic framework core-shell microsphere.
In described step 1), compound concentration is the copper-bath of 0.1 ~ 5mol/L at normal temperatures, adds amine solution, and then at room temperature leave standstill 1 ~ 3h, filtration washing, obtains the basic copper sulfate microballoon of nucleocapsid structure at 60 DEG C after dry 12h.
Described step 2) in, the nucleocapsid structure basic copper sulfate microballoon of 0.0001 ~ 1mol is scattered in the mixed solution of second alcohol and water, then the organic ligand ethanolic solution of 0.01 ~ 3mol/L is added under agitation, at room temperature react 1 ~ 3h, filtration washing, obtains basic copper sulfate/metal organic framework core-shell microsphere after dry 12h at 60 DEG C.
In above-mentioned steps, the mol ratio of described amine and total metal ion is 0.01 ~ 5:1, and amine solution concentration is 0.001 ~ 5mol/L.
In the mixed solution of described second alcohol and water, the mol ratio of second alcohol and water is 0.5 ~ 10:1; The mol ratio of organic ligand and basic copper sulfate is 0.001 ~ 1:1.
Described amine comprises: the one in ethylenediamine, 1,3-propane diamine, Putriscine, wherein preferred 1,3-propane diamine.
Described organic ligand comprises: terephthalic acid (TPA), phthalic acid, trimesic acid, Pyromellitic Acid, mellitic acid.
The invention has the advantages that:
1) at room temperature basic copper sulfate/metal organic framework core-shell microsphere has been prepared by simple two-step method;
2) with basic copper sulfate microballoon prepared by method provided by the invention, by regulate add organic ligand kind can prepare different metal organic backbone shell;
3) with method reaction condition provided by the invention is gentle, technique is simple, the cycle is short, suitability for industrialized production is applicable to.
Accompanying drawing explanation
Fig. 1,2 is the stereoscan photograph of the basic copper sulfate/metal organic framework core-shell microsphere that the invention process case 2 obtains.
Fig. 3 is the stereoscan photograph of the basic copper sulfate/metal organic framework core-shell microsphere that the invention process case 3 obtains.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with the drawings and specific embodiments, the present invention is described in more detail.
Case study on implementation 1
1) prepare the copper-bath that 4mL concentration is 0.75mol/L under normal temperature, add 1, the 3-propane diamine solution of 0.024mol/L, then at room temperature leave standstill 2h, filtration washing, obtains the basic copper sulfate microballoon of nucleocapsid structure at 60 DEG C after dry 12h;
2) the nucleocapsid structure basic copper sulfate microballoon of 0.003mol is scattered in (mol ratio of second alcohol and water is 1:1) in the mixed solution of 4mL second alcohol and water, then the ethanolic solution that 3mL concentration is 0.05mol/L terephthalic acid (TPA) is added under agitation, at room temperature react 1h, filtration washing, at 60 DEG C, obtain basic copper sulfate/metal organic framework core-shell microsphere after dry 12h, its metallic organic framework shell is Cu-BDC.
Case study on implementation 2
1) prepare the copper-bath that 4mL concentration is 0.75mol/L under normal temperature, add 1, the 3-propane diamine solution of 0.024mol/L, then at room temperature leave standstill 2h, filtration washing, obtains the basic copper sulfate microballoon of nucleocapsid structure at 60 DEG C after dry 12h;
2) the nucleocapsid structure basic copper sulfate microballoon of 0.003mol is scattered in (mol ratio of second alcohol and water is 1:1) in the mixed solution of 4mL second alcohol and water, then the ethanolic solution that 3mL concentration is 0.05mol/L trimesic acid is added under agitation, at room temperature react 1h, filtration washing, at 60 DEG C, obtain basic copper sulfate/metal organic framework core-shell microsphere after dry 12h, its metallic organic framework shell is Cu-BTC.The stereoscan photograph of product as Fig. 1, shown in 2.
Case study on implementation 3
1) prepare the copper-bath that 4mL concentration is 0.75mol/L under normal temperature, add 1, the 3-propane diamine solution of 0.024mol/L, then at room temperature leave standstill 2h, filtration washing, obtains the basic copper sulfate microballoon of nucleocapsid structure at 60 DEG C after dry 12h;
2) the nucleocapsid structure basic copper sulfate microballoon of 0.003mol is scattered in (mol ratio of second alcohol and water is 1:1) in the mixed solution of 4mL second alcohol and water, then the ethanolic solution that 3mL concentration is 0.05mol/L Pyromellitic Acid is added under agitation, at room temperature react 1h, filtration washing, at 60 DEG C, obtain basic copper sulfate/metal organic framework core-shell microsphere after dry 12h, its metallic organic framework shell is Cu-BTEC.The stereoscan photograph of product as shown in Figure 3.
Above-described specific embodiment; further detailed description has been carried out to object of the present invention, technical scheme and beneficial effect; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a preparation method for basic copper sulfate/metal organic framework core-shell microsphere, is characterized in that, described preparation method comprises step:
1) first in the aqueous solution of copper sulphate, add amine solution, then at room temperature leave standstill a period of time, through filtering, the basic copper sulfate microballoon of washing, dry obtained nucleocapsid structure;
2) the basic copper sulfate microballoon of obtained nucleocapsid structure is scattered in the mixed solution of second alcohol and water, add the ethanolic solution of organic ligand under agitation, the shell converted in-situ of basic copper sulfate microballoon is metal-organic framework materials, obtained basic copper sulfate/metal organic framework core-shell microsphere.
2. the preparation method of basic copper sulfate/metal organic framework core-shell microsphere according to claim 1, it is characterized in that, described step 1) in, compound concentration is the copper-bath of 0.1 ~ 5mol/L at normal temperatures, add amine solution, then at room temperature leave standstill 1 ~ 3h, filtration washing, obtains the basic copper sulfate microballoon of nucleocapsid structure at 60 DEG C after dry 12h.
3. the preparation method of basic copper sulfate/metal organic framework core-shell microsphere according to claim 1, it is characterized in that, described step 2) in, the nucleocapsid structure basic copper sulfate microballoon of 0.0001 ~ 1mol is scattered in the mixed solution of second alcohol and water, then the organic ligand ethanolic solution of 0.01 ~ 3mol/L is added under agitation, at room temperature react 1 ~ 3h, filtration washing, at 60 DEG C, obtain basic copper sulfate/metal organic framework core-shell microsphere after dry 12h.
4. the preparation method of basic copper sulfate/metal organic framework core-shell microsphere according to claim 1 and 2, is characterized in that, the amine in described amine solution and the mol ratio of copper ion are 0.01 ~ 5:1, and amine solution concentration is 0.001 ~ 5mol/L.
5. the preparation method of basic copper sulfate/metal organic framework core-shell microsphere according to claim 4, is characterized in that, in the mixed solution of described second alcohol and water, the mol ratio of second alcohol and water is 0.5 ~ 10:1; The mol ratio of organic ligand and basic copper sulfate is 0.001 ~ 1:1.
6. the preparation method of basic copper sulfate/metal organic framework core-shell microsphere according to claim 5, is characterized in that, described amine comprises: the one in ethylenediamine, 1,3-propane diamine, Putriscine.
7. the preparation method of basic copper sulfate/metal organic framework core-shell microsphere according to claim 6, is characterized in that, described organic ligand comprises: terephthalic acid (TPA), phthalic acid, trimesic acid, Pyromellitic Acid, mellitic acid.
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| CN104549082B (en) * | 2014-12-19 | 2016-11-16 | 安徽建筑大学 | ZnO@ZIF-8 nucleocapsid structure microsphere and preparation method thereof |
| CN106268554A (en) * | 2016-08-16 | 2017-01-04 | 中国石油大学(北京) | A kind of core-shell type MOFs composite particles and its preparation method and application |
| CN106430282B (en) * | 2016-11-28 | 2018-05-25 | 青岛科技大学 | A kind of preparation method of basic copper sulfate |
| CN107328750B (en) * | 2017-06-19 | 2020-02-04 | 吉林大学 | High-activity high-uniformity surface enhanced Raman scattering substrate and preparation method thereof |
| CN107140674A (en) * | 2017-06-21 | 2017-09-08 | 南京逸柔蒂雯新材料科技有限公司 | A kind of preparation method of basic copper nitrate |
| CN114432979B (en) * | 2020-10-31 | 2023-04-07 | 中国石油化工股份有限公司 | Phase-change microcapsule with metal organic framework material as capsule wall |
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