CN112059200B - Silver nanoparticles and macro-controllable preparation method thereof - Google Patents
Silver nanoparticles and macro-controllable preparation method thereof Download PDFInfo
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Abstract
The invention discloses silver nanoparticles and a macro-controllable preparation method thereof. The agarose/carboxymethyl chitosan composite gel is prepared by preparing agarose/carboxymethyl chitosan mixed solution as gel precursor solution and utilizing the reversible temperature-sensitive property of agarose; soaking the composite gel in a solution containing silver ions to chelate and crosslink the silver ions and the gel, and reducing the silver ions in situ by using a reducing agent sodium borohydride to obtain the composite gel loaded with silver nanoparticles; after heating and dissolving, the silver nano particles can be obtained by separation. Through the mode, the silver nanoparticles with uniform size and good dispersibility can be prepared; the preparation method is simple, the application range is wide, the product performance is easy to regulate and control, the requirement of industrial scale production is met, the problems that silver nanoparticles are poor in dispersity and uneven in size and difficult to prepare massively and controllably in the prior art are solved, and the method has high practical application value.
Description
Technical Field
The invention relates to the technical field of silver nanoparticle preparation, in particular to silver nanoparticles and a macro-controllable preparation method thereof.
Background
The silver nanoparticles refer to silver particles with the characteristic dimension size of 1-100nm and between the bulk object and atoms and molecules. Compared with large-size silver materials, the nano-scale size of the silver nanoparticles enables the silver nanoparticles to have unique properties such as surface effect, small-size effect, quantum size effect, macroscopic quantum tunneling effect and the like, so that the silver nanoparticles have better optical, electrical, magnetic and chemical properties, and show wide application prospects in the fields of material science, information science, life science, catalysis and the like.
At present, the preparation methods of silver nanoparticles can be mainly divided into two main categories: the first kind is physical method, mainly including physical crushing method, mechanical ball milling method and magnetron sputtering method; the second kind is a chemical method, which mainly comprises a chemical reduction method, a photocatalysis method, an electro-reduction method, an ultrasonic reduction method, a gas-liquid two-phase method, a gel sol method, a micro-emulsion method and the like. Compared with a physical method, the chemical method has low requirements on equipment, is convenient to control and has high controllability, so that the chemical method can be widely applied. However, the existing chemical method still has the problems of high manufacturing cost and difficult control of reaction conditions; in addition, the silver nanoparticles are difficult to produce and apply on a large scale due to poor dispersion stability and easy agglomeration of the silver nanoparticles in a medium. Therefore, it is of great importance to develop a new technology capable of preparing stable silver nanoparticles.
Patent publication No. CN106180753A provides a method for preparing silver nanoparticles and silver nanoparticles prepared thereby. This patent prepares an agarose/nano-silver composite gel by mixing agarose and a silver salt, making the agarose serve as both a reducing agent and a stabilizing agent, and separates nano-silver particles from the composite gel. However, the single agarose has limited adsorption and reduction effects on silver ions, so that the method can only adsorb and treat trace silver ions, and the prepared nano silver particles have low content, and are difficult to meet the requirements of industrial large-scale mass production. How to ensure the stable dispersibility of the silver nanoparticles and enable the silver nanoparticles to be prepared in a macroscopic quantity is the focus of current research.
In view of the above, it is still necessary to provide silver nanoparticles and a macro-controllable preparation method thereof to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide silver nanoparticles and a macro-controllable preparation method thereof. Preparing agarose/carboxymethyl chitosan mixed solution as gel precursor solution, and preparing agarose/carboxymethyl chitosan composite gel by using the reversible temperature-sensitive property of agarose; and then soaking the silver nanoparticles in a solution containing silver ions to chelate and crosslink the silver ions and the gel, reducing the silver ions in situ by using a reducing agent sodium borohydride, and heating to dissolve the gel, thereby separating the silver nanoparticles with uniform and controllable size and better dispersibility.
In order to achieve the above object, the present invention provides a macro-controllable preparation method of silver nanoparticles, comprising the following steps:
s1, adding agarose and carboxymethyl chitosan into an alkali liquor, heating and stirring to fully dissolve the agarose and carboxymethyl chitosan to obtain a hot mixed solution; after the mixed solution is cooled, obtaining agarose/carboxymethyl chitosan composite gel;
s2, placing the composite gel obtained in the step S1 in a solution containing silver ions for fully soaking to obtain silver ion crosslinked double-network composite gel;
s3, placing the silver ion crosslinked double-network composite gel obtained in the step S2 in a sodium borohydride solution for reduction reaction to obtain a silver nanoparticle-loaded composite gel;
and S4, heating the silver nanoparticle-loaded composite gel obtained in the step S3, fully dissolving the gel to obtain an agarose/carboxymethyl chitosan/silver nanoparticle mixed solution, and centrifuging and washing to obtain the silver nanoparticles.
Further, in step S1, the concentration of agarose in the mixed solution is 0.1w/v% -8 w/v%, and the concentration of carboxymethyl chitosan is 0.1w/v% -8 w/v%.
Further, in the step S1, the heating temperature in the heating and stirring process is 45-100 ℃, and the stirring time is 5-180 min.
Further, in step S2, the soaking time is 5 to 180min.
Further, in step S3, the reaction temperature of the reduction reaction is 0 to 60 ℃, and the reaction time is 5 to 180min.
Further, in step S4, the heating temperature is 45 to 100 ℃.
Further, in the step S1, the pH value of the alkali liquor is 8-10; the alkali liquor is sodium hydroxide aqueous solution or sodium bicarbonate aqueous solution.
Further, in step S2, the concentration of silver ions in the solution containing silver ions is 0.1 to 2mol/L.
Further, in the step S1, the degree of deacetylation of the carboxymethyl chitosan is 80% to 90%.
In order to achieve the purpose, the invention also provides silver nanoparticles, which are prepared according to any one of the technical schemes; the average particle diameter of the silver nanoparticles is 4-28 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the agarose/carboxymethyl chitosan mixed solution is prepared as the gel precursor solution, and the agarose/carboxymethyl chitosan composite gel can be prepared by utilizing the reversible temperature-sensitive property of agarose; soaking the composite gel in a solution containing silver ions to chelate and crosslink the silver ions and the gel, and further realizing the in-situ reduction of the silver ions under the action of a reducing agent sodium borohydride; and heating to dissolve the gel, and separating to obtain the silver nanoparticles. The average particle size of the silver nanoparticles is 4-28 nm, the size is uniform and controllable, the dispersibility is good, the preparation method is simple, the method is suitable for large-scale production, the problems that the silver nanoparticles are poor in dispersibility and uneven in size and difficult to prepare in a macroscopic quantity and controllable mode in the prior art are solved, and the requirements of practical application can be met.
2. The invention can utilize the reversible temperature-sensitive property of the agarose by preparing the hot agarose and carboxymethyl chitosan mixed solution and cooling, so that the carboxymethyl chitosan is embedded in the gel in the process of forming the agarose gel by reducing the temperature to form the agarose/carboxymethyl chitosan composite gel. Compared with single agarose gel, the carboxymethyl chitosan in the composite gel can be chelated and crosslinked with silver ions, so that the adsorption capacity of the composite gel to the silver ions can be greatly improved, and a network formed by crosslinking the carboxymethyl chitosan and the silver ions can be mutually interpenetrated with the original agar network to form the composite gel with a double-network structure. Meanwhile, the double-network structure can protect the microporous structure in the composite gel, promote the infiltration and adsorption of silver ions, further improve the adsorption capacity of the composite gel on the silver ions, and achieve the effect of macro-preparation of silver nanoparticles. In addition, the prepared agarose/carboxymethyl chitosan composite gel is used as a microreactor to prepare silver nanoparticles in situ, so that the traditional solution system can be replaced, negative effects caused by agglomeration of the nano material in the growth process are effectively inhibited, and the prepared silver nanoparticles are uniform in size and good in dispersibility.
3. The invention can realize the regulation and control of the silver ion adsorption capacity by regulating the concentration of the carboxymethyl chitosan; and the structure of the double-network composite gel is regulated and controlled by adjusting relevant process parameters in the preparation process, so that the pore structure, the crosslinking degree, the hydrophilicity and hydrophobicity, and the particle size and concentration of the silver nanoparticles of the gel are effectively controlled, and the controllable preparation of the silver nanoparticles is realized.
4. The agarose and carboxymethyl chitosan used in the invention are natural polymer materials, have good biodegradability, can ensure that the preparation process is safer and pollution-free, are convenient for re-dispersing and recovering silver nanoparticles, meet the requirements of industrial mass production, and have higher practical application value.
Drawings
Fig. 1 is a schematic diagram of a process for the macro-controlled preparation of silver nanoparticles provided in example 1;
fig. 2 is a performance test chart of the gel and silver nanoparticles prepared in example 1: (a) is an optical photograph of the gel after adsorbing silver ions; (b) Scanning electron microscope images and contact angle test results of the composite gel loaded with the silver nanoparticles after freeze-drying are shown; (c) Is a transmission electron microscope picture and a particle size distribution picture of the silver nanoparticle aqueous solution;
fig. 3 is a performance test chart of the gel and silver nanoparticles prepared in example 2: (a) is an optical photograph of the gel after adsorbing silver ions; (b) Scanning electron microscope images and contact angle test results of the composite gel loaded with the silver nanoparticles after freeze-drying are shown; (c) Is a transmission electron microscope picture and a particle size distribution picture of the silver nanoparticle aqueous solution;
fig. 4 is a performance test chart of the gel and silver nanoparticles prepared in example 3: (a) is an optical photograph of the gel after adsorbing silver ions; (b) Scanning electron microscope images and contact angle test results of the composite gel loaded with the silver nanoparticles after freeze-drying are shown; (c) Is a transmission electron microscope picture and a particle size distribution chart of the silver nanoparticle aqueous solution;
fig. 5 is a performance test chart of the gel and the silver nanoparticles prepared in comparative example 1: (a) is an optical photograph of the gel after adsorbing silver ions; (b) Scanning electron microscope images and contact angle test results of the composite gel loaded with the silver nanoparticles after freeze-drying are shown; (c) Is a transmission electron microscope picture and a particle size distribution chart of the silver nanoparticle aqueous solution;
fig. 6 is a graph of the change in properties of gel and silver nanoparticles at different carboxymethyl chitosan concentrations: (a) The gel optical photo prepared under different carboxymethyl chitosan concentrations and the change chart of the adsorption quantity of the gel optical photo to silver ions are shown; (b) Is an ultraviolet absorbance test chart of the silver nanoparticle aqueous solution prepared under different carboxymethyl chitosan concentrations.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The invention provides a macroscopic quantity controllable preparation method of silver nanoparticles, which comprises the following steps:
s1, adding agarose and carboxymethyl chitosan into an alkali liquor, heating and stirring to fully dissolve the agarose and carboxymethyl chitosan to obtain a hot mixed solution; after the mixed solution is cooled, obtaining agarose/carboxymethyl chitosan composite gel;
s2, placing the composite gel obtained in the step S1 in a solution containing silver ions for fully soaking to obtain silver ion crosslinked double-network composite gel;
s3, placing the silver ion crosslinked double-network composite gel obtained in the step S2 in a sodium borohydride solution for reduction reaction to obtain a silver nanoparticle-loaded composite gel;
and S4, heating the silver nanoparticle-loaded composite gel obtained in the step S3, fully dissolving the gel to obtain an agarose/carboxymethyl chitosan/silver nanoparticle mixed solution, and centrifuging and washing to obtain the silver nanoparticles.
In step S1, the concentration of agarose in the mixed solution is 0.1w/v% -8 w/v%, and the concentration of carboxymethyl chitosan is 0.1w/v% -8 w/v%.
In the step S1, the heating temperature in the heating and stirring process is 45-100 ℃, and the stirring time is 5-180 min.
In step S2, the soaking time is 5-180 min.
In step S3, the reaction temperature of the reduction reaction is 0-60 ℃, and the reaction time is 5-180 min.
In step S4, the heating temperature is 45-100 ℃.
In the step S1, the pH value of the alkali liquor is 8-10; the alkali liquor is sodium hydroxide aqueous solution or sodium bicarbonate aqueous solution.
In step S2, the concentration of silver ions in the solution containing silver ions is 0.1 to 2mol/L.
In step S1, the degree of deacetylation of the carboxymethyl chitosan is 80% to 90%.
The invention also provides a silver nanoparticle, which is prepared according to any one of the technical schemes; the average particle diameter of the silver nanoparticles is 4-28 nm.
The silver nanoparticles and the macro-controllable preparation method thereof provided by the invention are described below with reference to the examples, comparative examples and drawings.
Example 1
The embodiment provides a macroscopic quantity controllable preparation method of silver nanoparticles, a schematic diagram of a preparation process of the macroscopic quantity controllable preparation method is shown in fig. 1, and the macroscopic quantity controllable preparation method specifically comprises the following steps:
s1, adding agarose and carboxymethyl chitosan with deacetylation degree of 85% into a sodium hydroxide solution with pH of 10, heating and stirring at 85 ℃ for 10min to fully dissolve the agarose and the carboxymethyl chitosan to obtain a hot mixed solution; the concentration of agarose in the mixed solution is 1w/v%, and the concentration of carboxymethyl chitosan is 0.5w/v%; and cooling the mixed solution to room temperature to obtain the agarose/carboxymethyl chitosan composite gel.
And S2, soaking the composite gel obtained in the step S1 in a silver nitrate solution with the concentration of 0.1mol/L for 120min to enable silver ions to be fully adsorbed by the composite gel, and carrying out chelation crosslinking to obtain the silver ion crosslinked double-network composite gel.
And S3, placing the silver ion crosslinked double-network composite gel obtained in the step S2 in 0.1mol/L sodium borohydride aqueous solution for reduction reaction, and after the reaction is carried out for 60min at 25 ℃, reducing the silver ions into silver nanoparticles in situ to obtain the silver nanoparticle loaded composite gel.
S4, putting the silver nanoparticle-loaded composite gel obtained in the step S3 into hot water at 60 ℃, and mechanically stirring until the gel is completely dissolved to obtain an agarose/carboxymethyl chitosan/silver nanoparticle mixed solution; centrifuging and washing the mixed solution to obtain silver nanoparticles; and dispersing the silver nanoparticles in water to obtain a silver nanoparticle aqueous solution.
In order to determine the adsorption effect of the agarose/carboxymethyl chitosan composite gel on silver ions, the concentration of the silver ions in the silver nitrate solution before and after the gel is soaked in the step S2 is determined, and the reduction amount of the silver ions in the silver nitrate solution is calculated, so that the adsorption amount of the composite gel on the silver ions in the embodiment is calculated to be 21.67mg/g.
The performance of the gel and the silver nanoparticles prepared in this example were further tested and analyzed, and the results are shown in fig. 2. Wherein (a) is the silver ion crosslinked double-network composite gel (shown as DNG) obtained in step S2 0.5 ) The gel is relatively transparent as can be seen from the figure. (b) The contact angle test chart of the silver nanoparticle-loaded composite gel obtained in the step S3 and the scanning electron microscope chart of the composite gel after freeze drying show that a large amount of silver is uniformly loaded on the surface of the gelNanoparticles having a surface contact angle of 95 °. (c) The transmission electron microscope image and the particle size distribution image of the silver nanoparticle aqueous solution obtained in step S4 show that the silver nanoparticles in the silver nanoparticle aqueous solution are uniformly distributed, and the average particle size of the silver nanoparticles is 7.1 ± 0.4nm.
And further performing an ultraviolet absorbance test on the silver nanoparticle aqueous solution obtained in the step S4 by using an ultraviolet spectrophotometer to obtain a relative ultraviolet absorbance of 0.304.
According to the test results, the agarose/carboxymethyl chitosan composite gel prepared by the method provided by the embodiment can adsorb a large amount of silver ions, so that the effect of preparing silver nanoparticles on a large scale is achieved; the silver nanoparticles prepared by the embodiment have uniform size and good dispersibility.
Examples 2 to 3 and comparative example 1
Examples 2 to 3 respectively provide a method for preparing silver nanoparticles, which is different from example 1 in that the concentration of carboxymethyl chitosan in the mixed solution in step S1 is changed. The concentration of carboxymethyl chitosan in example 2 and example 3 was 1w/v% and 2w/v%, respectively, and the rest of the steps and process parameters were the same as those in example 1, and will not be described herein again.
Comparative example 1 provides a method for preparing silver nanoparticles, which is different from example 1 in that carboxymethyl chitosan is not added in step S1, the prepared gel is only agarose gel, and the rest steps and process parameters are consistent with those of example 1, and are not described herein again.
The performance tests of the gels and silver nanoparticles prepared in examples 2 to 3 and comparative example 1 are shown in fig. 3 to 5, respectively; the property profile between the gels prepared in examples 1 to 3 and comparative example 1 and the silver nanoparticles is shown in fig. 6. The silver ion-adsorbed gels obtained in step S2 in examples 2 to 3 and comparative example 1 are respectively denoted as DNG 1 、DNG 2 And DNG 0 。
As can be seen from fig. 3 to 6, the results of the performance test of the gels and silver nanoparticles prepared in examples 2 to 3 and comparative example 1 are shown in table 1.
TABLE 1 results of Performance test of examples 2 to 3 and comparative example 1
As can be seen from fig. 2 to 6 and table 1, the transparency of the agarose/carboxymethyl chitosan composite gel gradually decreases and the adsorption amount of silver ions gradually increases with the increase of the concentration of carboxymethyl chitosan. Compared with the gel prepared in the comparative example 1 without adding carboxymethyl chitosan, the adsorption capacity of the examples 1 to 3 to silver ions is obviously higher, mainly because the carboxymethyl chitosan can be chelated and crosslinked with the silver ions, so that the adsorption capacity of the composite gel to the silver ions is greatly improved, and the method provided by the invention can realize the macroscopic preparation of the silver nanoparticles.
Meanwhile, with the increase of the concentration of the carboxymethyl chitosan, the contact angle of the surface of the gel loaded with the nano silver is gradually increased, which shows that the hydrophobicity of the gel is gradually enhanced. Therefore, the hydrophilicity and the hydrophobicity of the gel can be regulated and controlled by adjusting the concentration of the carboxymethyl chitosan so as to be suitable for different requirements, and the overall controllability is strong.
In addition, the increase of the concentration of carboxymethyl chitosan in examples 1 to 3 gradually increases the average particle size of the silver nanoparticles prepared therefrom and the relative ultraviolet absorbance thereof, indicating that the particle size of the silver nanoparticles and the relative concentration thereof can be controlled by adjusting the concentration of carboxymethyl chitosan. Compared with the comparative example 1, the average particle size of the silver nanoparticles prepared in the example 1 is smaller, which shows that the addition of carboxymethyl chitosan in a proper amount can not only improve the adsorption amount of silver ions, but also promote the dispersion of the silver nanoparticles, avoid the agglomeration of the silver nanoparticles and ensure that the silver nanoparticles have smaller particle sizes.
Therefore, compared with the single agarose gel adopted in the prior art, the composite gel prepared by mixing carboxymethyl chitosan and agarose can utilize the carboxymethyl chitosan to generate chelation crosslinking with silver ions, greatly improves the adsorption amount of the composite gel to the silver ions, and achieves the effect of preparing silver nanoparticles in a macroscopic quantity. And a network formed by crosslinking carboxymethyl chitosan and silver ions can be mutually interpenetrated with the original agar network to form the composite gel with a double-network structure. Under the action of the double-network structure, the gel pore structure, the crosslinking degree, the hydrophilicity and hydrophobicity, and the particle size and the concentration of the silver nanoparticles can be effectively controlled by adjusting the concentration of the carboxymethyl chitosan, so that the controllable preparation of the silver nanoparticles is realized.
In order to prepare the silver nanoparticles in a macroscopic quantity and have smaller average particle size and better dispersibility, the concentration range of the carboxymethyl chitosan is preferably 0.1w/v% -8 w/v%. When the concentration of the carboxymethyl chitosan is 0.1w/v%, the adsorption capacity of the prepared gel to silver ions is 8.2mg/g, the contact angle of the surface of the gel loaded with the nano silver is 88 degrees, the average particle size of the dispersed silver nanoparticles is 6.8 +/-0.8 nm, and the relative ultraviolet absorbance is 0.189; when the concentration of the carboxymethyl chitosan is 8w/v%, the adsorption capacity of the prepared gel to silver ions is 38.6mg/g, the contact angle of the surface of the gel loaded with the nano silver is 125 degrees, the average particle size of the silver nanoparticles after dispersion is 25.3 +/-2.8 nm, and the relative ultraviolet absorbance is 0.862.
Examples 4 to 9
Examples 4 to 9 respectively provide a method for preparing silver nanoparticles, which is different from example 1 in that some process parameters in steps S1 to S3 are changed, and specific parameters and raw materials corresponding to each example are shown in table 2. The rest steps and parameters are the same as those in embodiment 1, and are not described herein again.
TABLE 2 Process parameters for examples 4 to 9
The gels and silver nanoparticles prepared in examples 4 to 9 were tested for their properties, and the results are shown in table 3.
Table 3 results of performance test of the gels and silver nanoparticles prepared in examples 4 to 9
As can be seen from table 3, the change of the agarose gel concentration has a small influence on the silver ion adsorption capacity, and the main effect is that the agarose gel is cured at room temperature to form hydrogel with a three-dimensional network structure, so that carboxymethyl chitosan molecules are embedded inside, and adsorption sites are provided for the attachment of silver ions; the adsorption amount of silver ions is gradually increased along with the increase of the concentration of the carboxymethyl chitosan and reaches a saturated state. Meanwhile, the adsorption amount of silver ions can be increased by increasing the soaking time of the composite gel in the silver nitrate solution within a certain range, so that the silver ions are gradually increased to reach a saturated state. In addition, the temperature of the reduction reaction can also regulate and control the particle size of the silver nanoparticles, the silver nanoparticles can quickly nucleate or grow under the high-temperature condition, and the formed nanoparticles have relatively large particle size.
Therefore, the adsorption quantity of silver ions and the particle size of the prepared silver nanoparticles can be regulated and controlled by adjusting relevant process parameters in the preparation process of the silver nanoparticles, the controllability of the whole preparation process is high, and the requirement of actual industrial mass production can be met.
It should be noted that, as will be understood by those skilled in the art, the alkali solution used in step S1 may be an aqueous solution of sodium hydroxide or sodium bicarbonate, and the pH of the solution is adjusted to 8 to 10; the deacetylation degree of the used carboxymethyl chitosan can be 80-90%; the heating temperature in the heating and stirring process can be adjusted between 45 ℃ and 100 ℃, and the stirring time can be adjusted between 5 min and 180min. The concentration of silver ions in the solution containing silver ions used in step S2 may be adjusted to be between 0.1 and 2mol/L. The heating temperature in step S4 can be adjusted between 45 ℃ and 100 ℃, and the invention belongs to the protection scope.
In conclusion, the invention discloses silver nanoparticles and a macro-controllable preparation method thereof. The agarose/carboxymethyl chitosan composite gel is prepared by preparing an agarose/carboxymethyl chitosan mixed solution as a gel precursor solution and utilizing the reversible temperature-sensitive property of agarose; soaking the composite gel in a solution containing silver ions to chelate and crosslink the silver ions and the gel, and reducing the silver ions in situ by using a reducing agent sodium borohydride to obtain the composite gel loaded with silver nanoparticles; after being heated and dissolved, the silver nano particles can be separated. Through the mode, the silver nanoparticles with uniform size and good dispersibility can be prepared; the preparation method is simple, the application range is wide, the product performance is easy to regulate and control, the requirement of industrial scale production is met, the problems of poor dispersibility, uneven size and difficulty in macroscopic quantity controllable preparation of silver nanoparticles in the prior art are solved, and the method has high practical application value.
The above description is only for the purpose of illustrating the technical solutions of the present invention and is not intended to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; all the equivalent structures or equivalent processes performed by using the contents of the specification and the drawings of the invention, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (5)
1. A macro-controllable preparation method of silver nanoparticles is characterized by comprising the following steps:
s1, adding agarose and carboxymethyl chitosan into an alkali liquor, heating and stirring to fully dissolve the agarose and carboxymethyl chitosan to obtain a hot mixed solution; after the mixed solution is cooled, obtaining agarose/carboxymethyl chitosan composite gel; the concentration of agarose in the mixed solution is 0.1w/v% -8 w/v%, and the concentration of carboxymethyl chitosan is 0.1w/v% -8 w/v%;
s2, placing the composite gel obtained in the step S1 in a solution containing silver ions for full soaking to obtain silver ion crosslinked double-network composite gel; the concentration of silver ions in the solution containing the silver ions is 0.1 to 2mol/L, and the soaking time is 5 to 180 min;
s3, placing the silver ion crosslinked double-network composite gel obtained in the step S2 in a sodium borohydride solution for reduction reaction to obtain a silver nanoparticle-loaded composite gel;
s4, heating the silver nanoparticle-loaded composite gel obtained in the step S3, wherein the heating temperature is 45-100 ℃, fully dissolving the gel to obtain an agarose/carboxymethyl chitosan/silver nanoparticle mixed solution, and centrifuging and washing to obtain silver nanoparticles; the average particle size of the silver nanoparticles is 4-28 nm.
2. The macro-controllable preparation method of silver nanoparticles according to claim 1, characterized in that: in the step S1, the heating temperature in the heating and stirring process is 45 to 100 ℃, and the stirring time is 5 to 180min.
3. The macro-controllable preparation method of silver nanoparticles according to claim 1, characterized in that: in step S3, the reaction temperature of the reduction reaction is 0 to 60 ℃, and the reaction time is 5 to 180min.
4. The macro-controllable preparation method of silver nanoparticles according to claim 1, characterized in that: in the step S1, the pH value of the alkali liquor is 8 to 10; the alkali liquor is sodium hydroxide aqueous solution or sodium bicarbonate aqueous solution.
5. The macro-controllable preparation method of the silver nanoparticles as claimed in any one of claims 1 to 4, which is characterized in that: in the step S1, the deacetylation degree of the carboxymethyl chitosan is 80% -90%.
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