CN104607654A - Self-assembly material based on silver nanoparticles and preparation method thereof - Google Patents
Self-assembly material based on silver nanoparticles and preparation method thereof Download PDFInfo
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- CN104607654A CN104607654A CN201510068573.2A CN201510068573A CN104607654A CN 104607654 A CN104607654 A CN 104607654A CN 201510068573 A CN201510068573 A CN 201510068573A CN 104607654 A CN104607654 A CN 104607654A
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Abstract
The invention relates to a self-assembly material based on silver nanoparticles and a preparation method thereof. The constitution is characterized in that the center is a self-assembly body of Ag nanoparticles, the center is decorated with a layer of tannin, and an outermost layer is a sol gel SiO2 layer; the constitution is further characterized in that during a cladding process of silicon dioxide, by controlling the injection sequence of tetraethyl orthosilicate, a mononuclear composite structure or a multinuclear composite structure can be obtained, mononuclear silver nanoparticles or multinuclear silver nanoparticles are prepared, and the thichness of the SiO2 layer in outer layer is adjustable. The preparation method comprises the steps that first, the silver nanoparticles with tannin serving as a reducing agent and ligand are compounded, and then silicon dioxide cladding is conducted to the silver nanoparticles through a sol-gel method. The self-assembly material based on the silver nanoparticles and the preparation method thereof has the advantages that the method is simple, the mononuclear composite structure and the multinuclear composite structure are easy to achieve, and the composite structures are stable.
Description
Technical field
The present invention relates to a kind of self-assembled material based on silver nano-grain and preparation method thereof, belong to composite material of core-shell structure field.
Background technology
Owing to having the special character such as small-size effect, quantum tunneling effect, nano material receives to be paid close attention to more and more widely.Wherein, silver nano-grain, owing to having the special performance of noble metal nano particles, adds that again comparatively other Precious Metals-Gold, platinum etc. have price advantage, so be applied to the fields such as optical, electrical, catalysis, sensing and biology widely.
The prerequisite of silver nano-grain application to ensure the stability of nano particle and the possibility of surface chemical modification.Wherein coated with silica forms nucleocapsid structure is a kind of desirable stable further method using silver nano-grain, this is because: first the coated of nano SiO 2 particle effectively can stop silver nano-grain because surface-active or the reunion caused by environment change, secondly silica is coated with good optical transparency to silver nano-grain, silica again coated can improve the dispersiveness of silver nano-grain and water-soluble, and the oh group of last silica surface can further modification.
Wang Yan etc. (preparation of mesoporous silicon oxide coated with silver nano particle and anti-microbial property, natural science report) are with ethyl orthosilicate at Argent grain surface in situ growth silica shell, and method is complicated and preparation consumption raw material is large.Chinese invention patent (201210113128.X) discloses composite particles of a kind of coated with silica galactic nucleus and its preparation method and application, and the method prepares the composite particles of monokaryon, and structure is single, and synthetic method is loaded down with trivial details.At present, not yet there is the report about the composite construction distinguishing monokaryon and multinuclear, therefore, study the controlledly synthesis that a kind of simple method realizes composite construction, and realize the controlled synthesis of monokaryon or multinuclear, have great importance.
Summary of the invention
For prior art Problems existing, the invention provides a kind of self-assembled material based on silver nano-grain, this self-assembled material is a kind of nucleocapsid structure, kernel is made up of silver nano-grain, skin is silicon dioxide layer, intermediate layer is tannic acid ligand layer, and structure-controllable has wide market prospects.
Present invention also offers a kind of preparation method of the self-assembled material based on silver nano-grain, the method is simply controlled, by regulating different raw material addition sequences, prepares the self-assembled material of different structure.
The technical scheme that the present invention is adopted to achieve these goals is:
The invention provides a kind of self-assembled material based on silver nano-grain, described self-assembled material is nucleocapsid structure, and kernel is silver nano-grain, and intermediate layer is tannic acid part, and skin is formed by coated with silica.
Self-assembled material provided by the invention, kernel is more than one diameter is the silver nano-grain of 10-30nm, the intermediate layer thickness that tannic acid part is formed is 2-5nm, and the thickness of outer silicon dioxide layer can regulate and control, and thickness can be regulated and controled by the amount increasing or reduce ethyl orthosilicate.
Present invention also offers the preparation method of above-mentioned self-assembled material, comprise the following steps:
(1) PH regulate: by add in the tannic acid aqueous solution potash adjustment pH value be 6.5 or 7.5;
(2) prepare the solution of silver-containing nanoparticles: by the tannic acid aqueous solution heating water bath after adjustment to 30 DEG C, then add silver nitrate aqueous solution, stir, after centrifugation, the beds of precipitation add intermediate water, obtain the solution of silver-containing nanoparticles;
(3) self-assembled material of monokaryon silver nano-grain: mixing adding ethanol in the solution of silver-containing nanoparticles, adding ammoniacal liquor, then adding ethyl orthosilicate immediately, continue to stir.
(4) self-assembled material of multinuclear silver nano-grain: mixing adding ethanol in the solution of silver-containing nanoparticles, adding ethyl orthosilicate, stirs, adds ammoniacal liquor, continue to stir.
Further, described tannic acid is 2:1 with the mass ratio of silver nitrate.
Further, the mol ratio of described ammoniacal liquor, ethyl orthosilicate, silver nitrate is 1.1:0.01-0.1:0.1.
Further, when the tannic acid aqueous ph value of optimization is 6.5, in step (2), mixing time is more than 100min; When pH value is 7.5, mixing time is more than 40min.
Further, in described step (3), the solution of silver-containing nanoparticles and the volume ratio of ethanol are 1:8.Add ammoniacal liquor again after stirring 15-30min after adding ethyl orthosilicate in described step (4), continue to stir 200-400min.
First the present invention is utilize tannic acid to do controlledly synthesis that part and reducing agent carry out silver nano-grain, multiple ortho positions phenolic hydroxyl structure of tannic acid, as multidentate ligand with Nano silver grain generation complex reaction, thus form the intermediate layer of nucleocapsid structure, then the method for sol-gel is utilized to carry out the coated of silica, in coated process, by controlling addition sequence and the mixing time of various raw material accurately, thus realize the preparation of monokaryon and multinuclear composite construction.The present invention is by controlling the addition of ethyl orthosilicate, and the thickness that can realize silicon dioxide layer is accurately controlled.Method provided by the invention is simple, and with low cost, coated process is carried out at ambient temperature, and composite construction controllable precise is reproducible, is applicable to suitability for industrialized production.
Advantage of the present invention is:
1. the present invention utilizes tannic acid to do the silver nano-grain of part for core, then by the hydrolysis-condensation reaction of ethyl orthosilicate, achieves coated to silver nano-grain of silica.The present invention, by controlling addition sequence and the mixing time of ammoniacal liquor and ethyl orthosilicate, prepares monokaryon or multinuclear silver nano-grain self-assembled material.
2. preparation method of the present invention is simple, controllable precise, and coated process can be carried out under being room temperature condition, energy-conserving and environment-protective.
Accompanying drawing explanation
Fig. 1 is transmission (TEM) figure of the silver nano-grain that embodiment 1 is synthesized.
Fig. 2 is transmission (TEM) figure of the monokaryon silver nano-grain self-assembled material of the coated with silica that embodiment 1 is synthesized.
Fig. 3 is transmission (TEM) figure of the multinuclear silver nano-grain self-assembled material of the coated with silica of the 2-in-1 one-tenth of embodiment.
Fig. 4 is transmission (TEM) figure of the monokaryon silver nano-grain self-assembled material of the coated with silica that embodiment 3 is synthesized.
Detailed description of the invention
Below by embodiment, the present invention will be further elaborated, it is to be understood that following explanation is only to explain the present invention, do not limit its content.
In the present invention use the mass fraction of ammoniacal liquor to be 25%.
Embodiment 1
1.1 by 0.0170g tannic acid, joins in 20 milliliters of intermediate waters, obtains the tannic acid aqueous solution for subsequent use after dissolving completely;
1.2 drip solution of potassium carbonate (0.1M) in above-mentioned 20 milliliters of tannic acid aqueous solution, and the pH regulating solution is 7.5;
1.3 by 1.2 gained pH be 7.5 the tannic acid aqueous solution fixed in 30 DEG C of water-soluble pots, make its temperature stabilization be 30 DEG C, then drip silver nitrate aqueous solution 0.5 milliliter (0.1M), to stir after 60 minutes centrifugation in the intermediate water of 10 milliliters, the solution of silver nano-grain must be contained, the results are shown in Figure 1;
The aqueous solution 0.5 milliliter containing silver nano-grain obtained in 1.3 mixes with ethanolic solution 4 milliliters by 1.4, add ammonia spirit 0.1 milliliter again, then ethyl orthosilicate 2 microlitre is added, stir 300min, the centrifugal self-assembled material (composite construction of monokaryon silver nano-grain and silica) that can obtain based on silver nano-grain, is shown in Fig. 2.
The size of silver nano-grain can be observed at 10 ran from Fig. 1.Can observe the silver nano-grain surface that silica is coated on individual particle uniformly in Fig. 2, thickness is 10-20 nanometer, and centre is tannic acid part.
Embodiment 2
2.1 by 0.0170 gram of tannic acid, is dissolved in 20 milliliters of intermediate waters, obtains the tannic acid aqueous solution for subsequent use after dissolving completely;
2.2 drip solution of potassium carbonate (0.1M) in above-mentioned 20 milliliters of tannic acid aqueous solution, and the pH regulating solution is 7.5;
2.3 by embodiment 1.2 gained pH be 7.5 the tannic acid aqueous solution fixed in 30 DEG C of water-soluble pots, make its temperature stabilization be the temperature of water-bath, then drip silver nitrate aqueous solution 0.5 milliliter (0.1M), to stir after 60 minutes centrifugation in the intermediate water of 10 milliliters;
The silver-colored aqueous solution 0.5 milliliter obtained in 2.3 mixes with ethanolic solution 4 milliliters by 2.4, add ethyl orthosilicate 2 microlitre again, stir 20 minutes, color becomes orange red from yellow, add ammonia spirit 0.1 milliliter again, stir 5 hours centrifugal self-assembled materials (composite construction of multinuclear silver nano-grain and silica) that can obtain based on silver nano-grain, see Fig. 3.
Can observe silica and be coated on granose silver nano-grain surface uniformly from Fig. 3, thickness is 10 ran, and centre is tannic acid part.
Embodiment 3
3.1 by 0.0170 gram of tannic acid, is dissolved in 20 milliliters of intermediate waters, obtains the tannic acid aqueous solution for subsequent use after dissolving completely;
3.2 drip solution of potassium carbonate (0.1M) in above-mentioned 20 milliliters of tannic acid aqueous solution, and the pH regulating solution is 6.5;
3.3 by 3.2 gained pH be 6.5 the tannic acid aqueous solution fixed in 30 DEG C of water-soluble pots, its temperature stabilization is made to be the temperature of water-bath, then silver nitrate aqueous solution 0.5 milliliter (0.1M) is dripped, stir centrifugation after 400 minutes and, in the intermediate water of 10 milliliters, the aqueous solution of silver nano-grain must be contained;
The aqueous solution 0.5 milliliter containing silver nano-grain obtained in 3.3 mixes with ethanolic solution 4 milliliters by 3.4, add ammonia spirit 0.1 milliliter again, then ethyl orthosilicate 2 microlitre is added, stir the centrifugal self-assembled material (composite construction of monokaryon silver nano-grain and silica) that can obtain based on silver nano-grain of 300min, see Fig. 4.
Can observe the silver nano-grain surface that silica is coated on individual particle uniformly in Fig. 4, silver nano-grain size is 30 ran, and silicon dioxide thickness is 10 ran, and centre is tannic acid part.
Embodiment 4
4.1 by 0.0170g tannic acid, joins in 20 milliliters of intermediate waters, obtains the tannic acid aqueous solution for subsequent use after dissolving completely;
4.2 drip solution of potassium carbonate (0.1M) in above-mentioned 20 milliliters of tannic acid aqueous solution, and the pH regulating solution is 7.5;
4.3 by 4.2 gained pH be 7.5 the tannic acid aqueous solution fixed in 30 DEG C of water-soluble pots, its temperature stabilization is made to be 30 DEG C, then drip silver nitrate aqueous solution 0.5 milliliter (0.1M), stir centrifugation after 60 minutes and, in the intermediate water of 10 milliliters, the solution of silver nano-grain must be contained;
The aqueous solution 0.5 milliliter containing silver nano-grain obtained in 4.3 mixes with ethanolic solution 4 milliliters by 4.4, add ammonia spirit 0.1 milliliter again, then ethyl orthosilicate 15 microlitre is added, stir 300min, the centrifugal self-assembled material (composite construction of monokaryon silver nano-grain and silica) that can obtain based on silver nano-grain.
In the self-assembled material of the silver nano-grain of preparation, the size of silver nano-grain is at 10 ran.Silica is coated on the silver nano-grain surface of individual particle uniformly, and thickness is 50-80nm, and centre is tannic acid part.
Claims (8)
1. based on a self-assembled material for silver nano-grain, it is characterized in that: described self-assembled material is nucleocapsid structure, kernel is silver nano-grain, and intermediate layer is tannic acid part, and skin is formed by coated with silica.
2. self-assembled material according to claim 1, is characterized in that: described kernel is more than one diameter is the silver nano-grain of 10-30nm, and the intermediate layer thickness that tannic acid part is formed is 2-5nm, and the thickness of outer silicon dioxide layer can regulate and control.
3. a preparation method for the self-assembled material as described in any one of claim 1-2, is characterized in that, comprises the following steps:
(1) PH regulate: by add in the tannic acid aqueous solution potash adjustment pH value be 6.5 or 7.5;
(2) prepare the solution of silver-containing nanoparticles: by the tannic acid aqueous solution heating water bath after adjustment to 30 DEG C, then add silver nitrate aqueous solution, stir, after centrifugation, the beds of precipitation add intermediate water, obtain the solution of silver-containing nanoparticles;
(3) self-assembled material of monokaryon silver nano-grain: mixing adding ethanol in the solution of silver-containing nanoparticles, adding ammoniacal liquor, then adding ethyl orthosilicate immediately, continue to stir;
(4) self-assembled material of multinuclear silver nano-grain: mixing adding ethanol in the solution of silver-containing nanoparticles, adding ethyl orthosilicate, stirs, adds ammoniacal liquor, continue to stir.
4. preparation method according to claim 3, is characterized in that: described tannic acid is 2:1 with the mass ratio of silver nitrate.
5. preparation method according to claim 3, is characterized in that: the mol ratio of described ammoniacal liquor, ethyl orthosilicate, silver nitrate is 1.1:0.01-0.1:0.1.
6. preparation method according to claim 3, is characterized in that: when described tannic acid aqueous ph value is 6.5, and in step (2), mixing time is more than 100min; When pH value is 7.5, mixing time is more than 40min.
7. preparation method according to claim 3, is characterized in that: in described step (3), the solution of silver-containing nanoparticles and the volume ratio of ethanol are 1:8.
8. preparation method according to claim 3, is characterized in that: add ammoniacal liquor again after stirring 15-30min after adding ethyl orthosilicate in described step (4), continues to stir 200-400min.
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Cited By (9)
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| CN106366769A (en) * | 2016-09-13 | 2017-02-01 | 江南大学 | Anti-oxidative nano-copper conductive ink, and preparation method and printing application |
| CN107282918A (en) * | 2017-05-17 | 2017-10-24 | 宁波大学 | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application |
| CN108707248A (en) * | 2018-04-24 | 2018-10-26 | 天津大学 | A kind of preparation method of fire-retardant super-hydrophobic melamine sponge |
| CN108822332A (en) * | 2018-04-24 | 2018-11-16 | 天津大学 | The preparation method of super-hydrophobic sponge for absorbing organic solvent |
| CN110591159A (en) * | 2019-10-11 | 2019-12-20 | 厦门大学 | Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof |
| CN110883340A (en) * | 2018-09-10 | 2020-03-17 | 河南金渠银通金属材料有限公司 | Electronegative superfine silver powder and preparation method thereof |
| CN111068609A (en) * | 2019-12-13 | 2020-04-28 | 武汉工程大学 | SERS active material for detecting chromate ions and preparation method thereof |
| CN111202091A (en) * | 2020-01-08 | 2020-05-29 | 华南理工大学 | Nano-silver loaded mesoporous silica antibacterial material and preparation method and application thereof |
| CN111349247A (en) * | 2020-02-25 | 2020-06-30 | 深圳大学 | Self-assembly material and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106366769A (en) * | 2016-09-13 | 2017-02-01 | 江南大学 | Anti-oxidative nano-copper conductive ink, and preparation method and printing application |
| CN107282918A (en) * | 2017-05-17 | 2017-10-24 | 宁波大学 | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application |
| CN108707248A (en) * | 2018-04-24 | 2018-10-26 | 天津大学 | A kind of preparation method of fire-retardant super-hydrophobic melamine sponge |
| CN108822332A (en) * | 2018-04-24 | 2018-11-16 | 天津大学 | The preparation method of super-hydrophobic sponge for absorbing organic solvent |
| CN108822332B (en) * | 2018-04-24 | 2020-12-11 | 天津大学 | Preparation method of super-hydrophobic sponge for adsorbing organic solvent |
| CN108707248B (en) * | 2018-04-24 | 2021-02-26 | 天津大学 | Preparation method of flame-retardant super-hydrophobic melamine sponge |
| CN110883340A (en) * | 2018-09-10 | 2020-03-17 | 河南金渠银通金属材料有限公司 | Electronegative superfine silver powder and preparation method thereof |
| CN110591159A (en) * | 2019-10-11 | 2019-12-20 | 厦门大学 | Modified nano silver particles and preparation method thereof, silane compound and preparation method thereof, antifouling paint and preparation method thereof |
| CN111068609A (en) * | 2019-12-13 | 2020-04-28 | 武汉工程大学 | SERS active material for detecting chromate ions and preparation method thereof |
| CN111202091A (en) * | 2020-01-08 | 2020-05-29 | 华南理工大学 | Nano-silver loaded mesoporous silica antibacterial material and preparation method and application thereof |
| CN111349247A (en) * | 2020-02-25 | 2020-06-30 | 深圳大学 | Self-assembly material and preparation method thereof |
| CN111349247B (en) * | 2020-02-25 | 2022-04-12 | 深圳大学 | Self-assembly material and preparation method thereof |
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