CN103949201B - A kind of efficient organic dyestuff sorbing material easily reclaimed and preparation method thereof - Google Patents
A kind of efficient organic dyestuff sorbing material easily reclaimed and preparation method thereof Download PDFInfo
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- CN103949201B CN103949201B CN201410204424.XA CN201410204424A CN103949201B CN 103949201 B CN103949201 B CN 103949201B CN 201410204424 A CN201410204424 A CN 201410204424A CN 103949201 B CN103949201 B CN 103949201B
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Abstract
The invention provides a kind of preparation method of the efficient organic dyestuff sorbing material easily reclaimed.The method take metal nano material as raw material, by silane coupler, magnetic nano particle sub-surface is modified, coated in magnetic nano particle sub-surface of silica is realized at ambient temperature by the hydrolysis in silicon source, recycling surfactant is template, realizes the secondary self assembly of surface mesoporous silica.Advantage of the present invention is to adopt self-assembling technique to synthesize, method is easy, be effectively prevent the reunion between the nano particle caused due to the character of nano particle itself and the magnetic interaction power of magnetic nanometer by the way of secondary self assembly, make again the material prepared possess the uniform loose structure of high-ratio surface sum of porous material and the magnetic performance of magnetic material excellence simultaneously.
Description
Technical field
The invention belongs to nano material and field of nanometer technology, particularly a kind of efficient organic dyestuff sorbing material easily reclaimed and preparation method thereof.
Background technology
Originally inorganic Porous materials and being compounded in of nano metal mainly utilize slaine immersion reduction method to be supported on Porous materials by nano metal.But the nano metal that this method supports easily blocks duct, easily reunites between particle, specific area reduces, and application have also been obtained restriction.Someone proposed the method at nano metal Surface coating inorganic hole shell afterwards, and not only achieve the stable of nano metal, the characteristic that also can make full use of Porous materials carries out catalysis.One is more widely used to be silica in the sheathing material of inorganic hole, the advantage of silica is: the stability of special water-borne dispersions, there is the simple and easy surface modification of the preparation allowing nonaqueous colloid, by controlling the particles' interaction that shell thickness is easy to control.By carrying out involucrum to magnetic nano-particle, there is following advantage: the dispersiveness 1. improving or change nano particle; 2. the compatibility between nano particle and other material is improved; 3. the surface-active of nano particle is improved; 4. nanoparticle surface is made to produce new physics, chemical property and new function.Surface modification has surface physics modification and surface chemical modification two kinds of methods usually.Physical modification has again surfactant modified method and surface deposition.Adopt surfactant by Van der Waals force, dissimilar materials can be adsorbed on the surface of nano particle to magnetic particle finishing, the reunion of nano particle can be prevented.But for nano metallic nickel granular material, first the easy agglomeration of nano particle adds difficulty to involucrum, secondly there is magnetic interaction power between magnetic nano-particle, increase the possibility of reunion further.Can be stoped to a certain extent between particle by the method for finishing organo-functional group and reunite, but add hydrophilic silicon oxides in surface coated difficulty, therefore, the sorbing material how stoping nano particle reunion also simultaneously to have high specific surface area becomes the focus of people's research.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of technique simple, efficient organic dyestuff sorbing material easily reclaimed with good adsorption properties and preparation method thereof can be produced.
The present invention for solving the problems of the technologies described above taked technical scheme is:
A preparation method for the efficient organic dyestuff sorbing material easily reclaimed, it is characterized in that, it comprises the following steps:
1) solution of preparation containing transition metal nanoparticles;
2) by step 1) solution that obtains pours in the mixed liquor of ethanol, silane coupler and tetraethyl orthosilicate (hereinafter referred to as TEOS), stir 5-10min, collect the product obtained with magnet, be the nano particle of transition metal nanoparticles core/silica shell structure;
3) by step 2) again disperse to obtain in ethanol the alcohol dispersion liquid of product after the product cleaning that obtains, wherein the mass ratio of product and ethanol is 1:150-1:200;
4) surfactant is added in the mixed liquor of second alcohol and water, the described surfactant of 0.002-0.0025g is added in the mixed liquor of the described second alcohol and water of every milliliter, then adding ammoniacal liquor regulates pH within the scope of 10-11, by step 3) alcohol dispersion liquid of product that obtains adds in described mixed liquor, stir 0.5-1h, add tetraethyl orthosilicate again, stir 5-7h, wash products also puts into baking oven drying, obtain described organic dyestuff sorbing material, the wherein alcohol dispersion liquid of product: ethanol: water: the volume ratio of tetraethyl orthosilicate is 2:30:40:0.5.
In such scheme, described surfactant is softex kw (hereinafter referred to as CTAB).
In such scheme, described silane coupler is 3-aminopropyl triethoxysilane (hereinafter referred to as APTES).
In such scheme, described step 1) in transition metal nanoparticles be cobalt nanometer particle.
In such scheme, the preparation method of described cobalt nanometer particle is: by raw material cobalt chloride hexahydrate, and monohydrate potassium and sodium borohydride mix under nitrogen protection condition, obtain cobalt nanometer particle after stirring.
In such scheme, described step 1) in transition metal nanoparticles be Fe nanometer particles or nickel nano particle.
The organic dyestuff sorbing material that above-mentioned preparation method obtains, described organic dyestuff sorbing material is take transition metal nanoparticles as the double-shell structure of core, and the outer shell in described double shells is mesoporous silicon oxide.
In such scheme, described mesoporous pore size is 2.5nm, and the particle diameter of nanoparticle core is 15nm, and the gross thickness of double shells is
20nm。
Preparation principle of the present invention is: the metal nanoparticle being obtained the homogeneous good dispersion of granular size by the method for sodium borohydride and citric acid reducing metal salt, modified in surfaces of metal nanoparticles by silane coupler again, make silicon source can form coated with silica layer in surfaces of metal nanoparticles hydrolysis.With surfactant, finishing is carried out to the Core-shell structure material obtained again, regulate pH to control the hydrolysis rate in silicon source, silicon source is hydrolyzed and forms uniform meso-porous titanium dioxide silicon layer in material surface self assembly.By realizing this secondary modification to surfaces of metal nanoparticles, successfully obtain the porous functional composite material in the present invention.
Beneficial effect of the present invention is: the present invention obtains double-deck silica shell structure by carrying out self assembly with surfactant after Nanosurface coated silica, and its ectomesoderm is mesoporous silicon oxide.The LBL self-assembly method wherein adopted achieves silicon dioxide layer secondary on the surface of metal nanoparticle builds, effectively prevent the reunion between the nano particle that causes due to the character of nano particle itself and the magnetic interaction power of magnetic nanometer, make again the material prepared possess the uniform loose structure of high-ratio surface sum of porous material and the magnetic performance of magnetic material excellence simultaneously.Demonstrate by carrying out Dye Adsorption performance test to material the efficient adsorption that material can realize organic dyestuff, the magnetic of material can be utilized to reclaim fast and recycle simultaneously.
Accompanying drawing explanation
Fig. 1 is ConSiO
2a) the low power TEM of material schemes, b) high power TEM figure;
Fig. 2 is ConSiO
2a) the low power SEM of material schemes, b) high power SEM figure;
Fig. 3 is ConSiO
2mSiO
2a) the low power TEM of porous functional composite material schemes, b) high power TEM figure;
Fig. 4 is ConSiO
2mSiO
2the little angle XRD of porous functional composite material schemes;
Fig. 5 is ConSiO
2mSiO
2the nitrogen adsorption curve map of porous functional composite material;
Fig. 6 is ConSiO
2mSiO
2porous functional composite material is schemed over time to rhodamine absorbance;
Fig. 7 is cobalt and silicon dixoide nucleocapsid structure magnetic chart, (a) CoSiO
2core-shell structure magnetic figure, (b) ConSiO
2mSiO
2core-shell structure magnetic figure.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with drawings and Examples, but content of the present invention is not only confined to the following examples.
The present embodiment provides a kind of preparation method of the efficient organic dyestuff sorbing material (i.e. cobalt mesoporous SiO 2 porous silica organic dyestuff sorbing material) easily reclaimed, and it comprises the following steps:
1) raw material cobalt chloride hexahydrate is added in the aqueous solution of monohydrate potassium and sodium borohydride under nitrogen protection condition, be specially: cobalt chloride hexahydrate 0.019g injects 0.014g monohydrate potassium, and the 200ml of 0.016g sodium borohydride is in the aqueous solution of deoxygenation process;
2) cobalt magnetic nano-particle is obtained after reacting 1min;
3) by step 2) solution that obtains adds in the ethanolic solution of APTES and TEOS, stir 5min, be specially 200ml step 2) solution that obtains is added to 800ml containing in the ethanolic solution of 14.4 μ lAPTES and 170 μ lTEOS;
4) step 3 is collected with magnet) nano particle in the solution that obtains;
5) by step 4) again disperse to obtain in ethanol the alcohol dispersion liquid of product after the product cleaning that obtains, wherein the mass ratio of product and ethanol is 1:200;
6) CTAB is added in the mixed liquor of second alcohol and water, the CTAB of 0.0025g is added in the mixed liquor of the described second alcohol and water of every milliliter, then adding ammoniacal liquor regulates pH within the scope of 10-11, by step 5) alcohol dispersion liquid of product that obtains adds in described mixed liquor, stir, add tetraethyl orthosilicate again, stir 6h, wash products is also dry, obtain described cobalt mesoporous SiO 2 porous silica organic dyestuff sorbing material, the wherein alcohol dispersion liquid of product: ethanol: water: the volume ratio of tetraethyl orthosilicate is 2:30:40:0.5.
The TEM figure and SEM figure of cobalt earth silicon material is shown in Fig. 1 and Fig. 2, and cobalt mesoporous SiO 2 silica TEM figure is shown in Fig. 3, and little angle XRD figure is shown in Fig. 4, and nitrogen adsorption curve map is shown in Fig. 5, and Dye Adsorption figure is shown in Fig. 6, and Magneto separate efficiency chart is shown in Fig. 7.
Can find out large-area CoSiO2 nucleocapsid structure from Fig. 1 and Fig. 2, granular size is homogeneous, and wherein the particle diameter of cobalt core is about 20nm, and the thickness of silica shells is about 15nm, illustrates that the experimental technique by designing successfully has prepared CoSiO
2core-shell structure material.And what show in Fig. 3 is the pattern of cobalt mesoporous SiO 2 silica, a) uniform cobalt mesoporous SiO 2 silicon dixoide nucleocapsid structure particle can be found out by Fig. 3, the size of its center is about 20nm, whole particle size is about 50nm, the b by amplifying further) figure can find out that silica shells defines obvious meso-hole structure.Fig. 4 is ConSiO
2mSiO
2, there is diffraction maximum when 2 θ angles are about 2.6 ° as seen from the figure, described the material synthesized and there is vermiform meso-hole structure in the little angle XRD diffracting spectrum of Core-shell structure material.By the ConSiO prepared
2mSiO
2material carries out nitrogen adsorption test by refluxing in 120 DEG C of ethanol after 20h removes unnecessary Surfactant CTAB, and as shown in Figure 5, what the curve that wherein square point is linked to be represented is adsorption curve to its result, and what the curve that circular point is linked to be represented is desorption curve.This figure is typical IV type adsorption curve, describes material and has meso-hole structure, and can see according to the pore-size distribution in b) figure, mesoporous pore size is 2.5nm.A) can see As time goes on by Fig. 6, the absorbance of rhdamine B presents downward trend, very fast at 1min inner dye adsorption rate, relatively slow within rear 5min, almost adsorbed completely to dyestuff during 6min, b) reflect the change of solution colour after sample adsorption dyestuff, in 6min, solution presents almost completely transparent state.ConSiO is demonstrated by Fig. 6
2mSiO
2material has excellent Dye Adsorption performance.Can find out that after silica is wrapped on cobalt nanometer particle surface, product still has stronger magnetic, as shown in figure a), and according to b) finding out the ConSiO wrapping mesoporous silicon oxide further according to Fig. 7
2mSiO
2the magnetic of material disappears not yet.This cobalt-based Core-shell structure material is faster to the response speed of magnet, has shown better magnetic characteristic.
It should be noted that, those of ordinary skill in the art should be appreciated that and can modify to technical scheme of the present invention or equivalent replacement, and does not depart from aim and the scope of technical solution of the present invention, and it all should be encompassed in the middle of right of the present invention.
Claims (4)
1. a preparation method for the efficient organic dyestuff sorbing material easily reclaimed, it is characterized in that, it comprises the following steps:
1) solution of preparation containing transition metal nanoparticles, described transition metal nanoparticles is cobalt nanometer particle, Fe nanometer particles or nickel nano particle;
2) by step 1) solution that obtains pours in the mixed liquor of ethanol, silane coupler and tetraethyl orthosilicate, stir, the product obtained is collected with magnet, be the nano particle of transition metal nanoparticles core/silica shell structure, described silane coupler is 3-aminopropyl triethoxysilane;
3) by step 2) again disperse to obtain in ethanol the alcohol dispersion liquid of product after the product cleaning that obtains, wherein the mass ratio of product and ethanol is 1:150-1:200;
4) surfactant is added in the mixed liquor of second alcohol and water, the described surfactant of 0.002-0.0025g is added in the mixed liquor of the described second alcohol and water of every milliliter, then adding ammoniacal liquor regulates pH within the scope of 10-11, by step 3) alcohol dispersion liquid of product that obtains adds in described mixed liquor, stir, add tetraethyl orthosilicate again, stir 5-7h, wash products is also dry, obtain described organic dyestuff sorbing material, the wherein alcohol dispersion liquid of product: ethanol: water: the volume ratio of tetraethyl orthosilicate is 2:30:40:0.5, described surfactant is softex kw.
2. preparation method as claimed in claim 1, it is characterized in that, the preparation method of described cobalt nanometer particle is: by raw material cobalt chloride hexahydrate, and monohydrate potassium and sodium borohydride mix under nitrogen protection condition, obtain cobalt nanometer particle after stirring.
3. the organic dyestuff sorbing material that obtains of preparation method as claimed in claim 1, is characterized in that, described organic dyestuff sorbing material is take transition metal nanoparticles as the double-shell structure of core, and the outer shell in described double shells is mesoporous silicon oxide.
4. organic dyestuff sorbing material as claimed in claim 3, it is characterized in that, described mesoporous pore size is 2.5nm, and the particle diameter of nanoparticle core is 15nm, and the gross thickness of double shells is 20nm.
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| CN104741140B (en) * | 2015-02-17 | 2017-03-01 | 浙江工业大学 | A kind of functional amido mesoporous silicon dioxide micro-sphere heterogeneous catalyst and preparation method and application |
| CN104826388A (en) * | 2015-04-21 | 2015-08-12 | 安徽凤凰滤清器股份有限公司 | Adsorption filtering agent for nano strontium titanate modified montmorilonite clay and preparation method therefor |
| CN105964216B (en) * | 2016-05-12 | 2019-03-19 | 西安建筑科技大学 | The amido modified Fe with meso-hole structure3O4@SiO2@mSiO2The preparation and application of composite particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110311635A1 (en) * | 2009-02-12 | 2011-12-22 | The Regents Of The University Of California | Hollow metal oxide spheres and nanoparticles encapsulated therein |
| CN102836710A (en) * | 2012-09-28 | 2012-12-26 | 黑龙江大学 | Preparation method of silica core/mesoporous silica shell-supported gold nano-particle microspheres |
| CN103242802A (en) * | 2013-05-16 | 2013-08-14 | 南京航空航天大学 | Preparation method of hollow Fe/Fe3O4@SiO2 nanostructure with adjustable wave-absorbing property |
| CN103447028A (en) * | 2013-08-30 | 2013-12-18 | 武汉理工大学 | Preparation method of shape-controllable nano silver core/mesoporous silicon dioxide shell structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110311635A1 (en) * | 2009-02-12 | 2011-12-22 | The Regents Of The University Of California | Hollow metal oxide spheres and nanoparticles encapsulated therein |
| CN102836710A (en) * | 2012-09-28 | 2012-12-26 | 黑龙江大学 | Preparation method of silica core/mesoporous silica shell-supported gold nano-particle microspheres |
| CN103242802A (en) * | 2013-05-16 | 2013-08-14 | 南京航空航天大学 | Preparation method of hollow Fe/Fe3O4@SiO2 nanostructure with adjustable wave-absorbing property |
| CN103447028A (en) * | 2013-08-30 | 2013-12-18 | 武汉理工大学 | Preparation method of shape-controllable nano silver core/mesoporous silicon dioxide shell structure |
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