CN111922357A - Nano silver cage and preparation method and application thereof - Google Patents
Nano silver cage and preparation method and application thereof Download PDFInfo
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- CN111922357A CN111922357A CN202010895475.7A CN202010895475A CN111922357A CN 111922357 A CN111922357 A CN 111922357A CN 202010895475 A CN202010895475 A CN 202010895475A CN 111922357 A CN111922357 A CN 111922357A
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a nano silver cage and a preparation method and application thereof. The invention adopts AgNO3、Na2CO3And carrying out normal-temperature light-resistant reaction with gallic acid to obtain the nano silver cage, wherein the obtained nano silver cage has a hollow and open structure. The method is simple to prepare, can synthesize the silver nano material with the hollow superstructure by template-free self-assembly of the silver nano particles, has good preparation effect, is non-toxic and pollution-free, and accords with the green chemical concept. According to the invention, by regulating and controlling the space and the opening size of the silver cage, different target substances can be matched and effectively contacted, spatially limited and enriched, so that the application range of the material in the fields of catalysis, antibiosis, detection and the like is better widened.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a nano silver cage and a preparation method and application thereof.
Background
The silver nanoparticles have a plasma resonance effect and can be widely applied to the fields of catalysis, Raman spectroscopy, biological imaging, antibiosis and the like. The hollow structure (called superstructure or multilevel structure) assembled by the silver nano particles has unique physical and chemical characteristics, for example, the hollow structure material has large surface area and can provide abundant electrochemical active sites; the large cavity can carry medicine; the space density of the hollow structure material is low; the hollow structure material can reduce the consumption of materials, so that the materials can be used more economically and effectively. This makes it a wide range of potential applications in catalysts, sensors, absorbents, drug delivery vehicles, biomedical diagnostics, lightweight fillers, sound insulation, and chemical reactors.
Research has been conducted to date to prepare various types of hollow structures, such as closed single/multi-shell hollow structures, single-hole hollow structures, medium-hole hollow structures, and yolk shell hollow structures. The preparation method comprises template-assisted (soft template, hard template and self-template) assembly and template-free assembly methods. Template-directed synthesis using hard templates (e.g., polymer latex particles, silica spheres, metal nanoparticles, and carbon spheres) or soft templates (e.g., emulsion droplets, micelles, and bubbles) has proven to be an effective method for inorganic hollow structure synthesis, and the structure and morphology of the final hollow particles can be precisely controlled by controlling the reaction conditions. However, both methods require the use of templates, and the morphology and stability of hollow superstructures produced by soft template methods is often poor due to the deformability of the soft template. Direct self-assembly of primary particles without an external template has also been used to create hollow structures, but generally requires the use of solid reactants as self-sacrificial templates, based on ostwald ripening, current displacement or the kirkendall effect, using surfactants or polymers as structure directing agents. Since the properties of inorganic hollow nanostructures can be well adjusted by adjusting their morphology and crystallinity, some recent studies have been directed to synthesizing inorganic hollow nanostructures in non-spherical morphology, such as cubic morphology.
The hollow silver nano cubic structure is paid attention to due to low cost, a multi-level structure and strong catalytic activity. However, the preparation of silver hollow nanocubes still requires the use of templates, or the use of complex instrumentation, at present. For example, document MorphosyntheIn sis of cubic silver capsules on monolithic activated carbon, the total time consumption of the experiment was about 5 hours and the activated carbon was modified first. The synthesized silver cubes are all closed and have no opening. In the document "Template-associated synthesis of uniform nano-sheet-associated silver hold microorganisms", the total time consumption of the experiment is about 3 hours, and Cu is prepared first2O microcubes as templates in Cu2Reacting the surface of the O microcubes to obtain a silver layer, and finally adding dilute HNO3Etching of Cu2And (4) an O core. The obtained hollow silver nanocubes were free of openings. The aim of people to pursue is to explore a simple, quick, green and efficient synthesis method to realize the controllable preparation of the silver hollow nanocube.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a nano silver cage, and solves the problems of multiple and complicated preparation steps, harsh preparation conditions and long preparation time of a silver hollow nanocube in the prior art.
The invention also aims to provide the nano silver cage prepared by the method.
The invention further aims to provide application of the nano silver cage.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nano silver cage comprises the following steps:
under the condition of oscillation, AgNO is added into water in sequence3、Na2CO3And reacting with gallic acid at normal temperature in a dark place for 0.5-2.5 hours by oscillation, centrifuging to remove supernatant fluid to obtain the nano silver cage, and dispersing and storing the nano silver cage by using water again.
Preferably, the AgNO3、Na2CO3The ratio of gallic acid to gallic acid is (0.4-0.65) g: (2.5-7.5) mmol: (2-4) mmol.
Preferably, the AgNO3The mass concentration of the water in the water is 0.005-0.013%.
Preferably, the AgNO3With AgNO3Adding the mixture in the form of aqueous solution, wherein the mass concentration of the aqueous solution is 0.5-2%.
Preferably, the Na is2CO3With Na2CO3Adding the mixture in the form of aqueous solution, wherein the concentration of the aqueous solution is 0.1-1 mol/L.
Preferably, the gallic acid is added in the form of gallic acid aqueous solution, and the concentration of the aqueous solution is 0.05-0.5 mol/L.
More preferably, 40-65 uL of AgNO with the mass concentration of 1% is sequentially added into 5-8 mL of water3Aqueous solution, 5-15 uL of Na with the concentration of 0.5mol/L2CO3An aqueous solution and 20-40 uL of gallic acid aqueous solution with the concentration of 0.1 mol/L.
Preferably, the oscillation frequency is 600-800 rpm; the rotating speed of the centrifugation is 4000-6000 rpm, and the centrifugation time is 3-8 min.
Preferably, the AgNO3、Na2CO3The time interval between the addition of the gallic acid and the addition of the gallic acid is 3-8 seconds.
Preferably, the nano silver cage is stored below 4 ℃.
The nano silver cage prepared by the method.
The nano silver cage is provided with an opening and a hollow superstructure.
The application of the nano silver cage is provided.
Preferably in the fields of catalysis, antibiosis and detection.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method and the steps are simple, the template-free self-assembly of the silver nanoparticles is not needed, the silver nano material with the hollow superstructure can be synthesized, the preparation effect is good, the obtained nano silver cages are uniform in shape, the preparation method is simple and has high cost benefit, and the requirements of high-throughput and rapid preparation can be met.
(2) The invention only needs to add AgNO3Solution, Na2CO3The solution and the gallic acid solution are 3 reagents, and the hollow reaction can be completed by one step reaction at normal temperature and normal pressureThe preparation of the nano silver cage metamaterial does not need to use organic reagents and expensive and complicated instruments and equipment. The used reagents are easy to obtain, are non-toxic and pollution-free, and accord with the green chemical concept.
(3) The hollow silver nanocubes synthesized by the prior art are basically closed without an opening, and substances cannot or are difficult to enter the cavity. The nano silver cage synthesized by the method is hollow and provided with an opening, and is more beneficial to functional design. By regulating the size of the silver cage and the size of the opening, different target substances can be matched through the size of the space, effective contact, space limitation and enrichment are carried out, and the application range of the nano silver cage in the fields of catalysis, antibiosis, detection and the like is widened better.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a nanosilver cage at 2000 x magnification in an example of the invention.
FIG. 2 is a Transmission Electron Microscope (TEM) image of Ag Silver cages in the document "High-Yield Synthesis of Hollow Octahedral Silver Nanocages with Controllable Pack sensitivity and the same High-Performance sensors Application".
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
Example 1
Taking a 10mL centrifuge tube with a clean inner wall, and adding 6mL deionized water; placing the centrifugal tube on an oscillator, and setting the oscillation frequency to 700 rpm; sequentially adding 55uL of AgNO with the mass fraction of 1 w%3Solution, 10uL of Na with a molar concentration of 0.5mol/L2CO3The time interval between the solution and 30uL of gallic acid solution with the concentration of 0.1mol/L and the reagent is 5 seconds; after all the reagents are added, the reaction is carried out for 1 hour at normal temperature in a dark place under the oscillation condition of 700 rpm; the reaction is completed, and the reaction solution is subjected to reaction,taking down the centrifugal tube, centrifuging at the rotating speed of 5000rpm for 6min, removing supernatant, adding 5.5mL of deionized water, and re-dispersing to obtain a nano silver cage; the prepared substrate was stored in a refrigerator at 4 ℃.
According to the example 1, the experiment takes about 1 hour and 10 minutes, and the used Gallic acid (Gallic acid) is from plants, has wide sources, is non-toxic and harmless, has no pollution to the environment, and accords with the green chemical concept. Fig. 1 is an SEM image of the nano-silver cage obtained in this example at 2000 x magnification. As can be seen from figure 1, the prepared nano silver cage is uniform in size and good in dispersity, and the shape of the cage is a hollow cuboid with an opening on one surface. In the preparation process, a template is not needed, the silver nanoparticles are self-assembled to form a nano silver cage multilevel structure, and the inner surface and the outer surface of the nano silver cage are rough. One side of the synthesized nano silver cage is provided with an opening, the opening is large, the edge of the opening is uneven, and the prepared nano silver cage is in a hollow structure when being observed from the opening.
Example 2
Taking a 10mL centrifuge tube with a clean inner wall, and adding 5mL deionized water; placing the centrifugal tube on an oscillator, and setting the oscillation frequency to be 800 rpm; sequentially adding 40uL of AgNO with the mass fraction of 1 w%3Solution, 5uL of Na with a molar concentration of 0.5mol/L2CO3The time interval between the solution and the 20uL gallic acid solution with the concentration of 0.1mol/L and the reagent is 3 seconds; after all the reagents are added, the reaction is carried out for 0.5 hour at normal temperature in a dark place under the oscillation condition of 800 rpm; after the reaction is finished, taking down the centrifugal tube, centrifuging for 8min at the rotating speed of 4000rpm, removing supernatant, adding 5mL of deionized water, and re-dispersing to obtain a nano silver cage; the prepared substrate was stored in a refrigerator at 4 ℃.
Example 3
Taking a 10mL centrifuge tube with a clean inner wall, and adding 8mL deionized water; placing the centrifugal tube on an oscillator, and setting the oscillation frequency to be 600 rpm; adding 1 w% of AgNO with 65uL mass fraction in sequence3Solution, 15uL of Na with a molar concentration of 0.5mol/L2CO3The time interval between the solution and 40uL of gallic acid solution with the concentration of 0.1mol/L and the reagent is 7 seconds; after all reagents are addedReacting for 2 hours at normal temperature in a dark place under the oscillation condition of 600 rpm; after the reaction is finished, taking down the centrifugal tube, centrifuging at the rotating speed of 6000rpm for 3min, removing supernatant, and adding 8mL of deionized water for re-dispersing to obtain a nano silver cage; the prepared substrate was stored in a refrigerator at 4 ℃.
Comparative example 1
In the method of the reference "Template-assisted synthesis of inorganic nano-particles-assisted silver nanoparticles", Cu is used in the synthesis of typical hollow Ag particles2And O is a template. The method comprises the following steps:
1)Cu2and (3) synthesizing an O template: 4.5g of polyvinylpyrrolidone was dissolved in 100mL of 0.01mol/L CuCl2·2H2To the O aqueous solution, 10.0mL of a 2.0mol/L NaOH aqueous solution was added dropwise, the mixture was stirred for 0.5 hour, 10.0mL of a 0.6mol/L ascorbic acid aqueous solution was further added dropwise, and the mixture was incubated for 3 hours. All steps were performed under constant stirring and heated in a water bath at 55 ℃. The resulting precipitate was collected by centrifugation and washed repeatedly with deionized water and ethanol to remove residual inorganic ions and polymer, and finally dried in vacuum at 60 ℃ for 5 hours.
2) Synthesis of silver nanocages: 4.29mg Cu by sonication for 10min2O template was dispersed in 100mL deionized water, then 1.0mL of 30mmol/L aqueous sodium citrate and 1.05mL of 100mmol/L NaBH4The aqueous solution is sequentially dropped with Cu2O template solution. After stirring for 5 minutes, 1.05mL of 10mmol/L AgNO was added dropwise3In aqueous solution, the color of the solution changed from orange to light yellow, indicating the formation of small Ag nanoparticles. As the reaction proceeded for 1 hour, the solution gradually became dark yellow indicating the formation of Cu2O @ Ag nanostructures. Subsequently, 1.7mL of 1% volume fraction CH was added3Aqueous COOH, for 2 hours to completely dissolve Cu2And (4) forming an O template. The precipitate was collected by centrifugation and decantation, washed several times with distilled water and absolute ethanol, and then dispersed in absolute ethanol for further characterization.
The experiment took about 13-14 hours, which is a standard template preparation. Subjecting the obtained Ag hollow particles to TEMScanning by electron microscope, it can be observed from FIG. 2 that Cu is removed by acetic acid2The silver cage obtained after the O template is in an octahedral shape with clear outline and has no opening. The hollow interior structure can be confirmed by the strong color contrast between the edge (dark color) and the center (gray color) in fig. 2.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the nano silver cage is characterized by comprising the following steps of:
under the condition of oscillation, AgNO is added into water in sequence3、Na2CO3And reacting with gallic acid at normal temperature in a dark place for 0.5-2.5 hours by oscillation, and centrifuging to remove supernatant fluid to obtain the nano silver cage.
2. The method for preparing nano-silver cage according to claim 1, wherein the AgNO is3、Na2CO3The ratio of gallic acid to gallic acid is (0.4-0.65) g: (2.5-7.5) mmol: (2-4) mmol.
3. The method for preparing nano-silver cage according to claim 1, wherein the AgNO is3The mass concentration of the water in the water is 0.005-0.013%.
4. The method for preparing nano-silver cage according to claim 1, wherein the AgNO is3、Na2CO3The time interval between the addition of the gallic acid and the addition of the gallic acid is 3-8 seconds.
5. The method for preparing nano-silver cage according to claim 1, wherein the AgNO is3With AgNO3Adding in the form of an aqueous solution, the mass of whichThe concentration is 0.5-2%.
6. The method for preparing nano-silver cage according to claim 1, wherein Na is added2CO3With Na2CO3Adding the mixture in the form of aqueous solution, wherein the concentration of the aqueous solution is 0.1-1 mol/L.
7. The method for preparing the nano-silver cage according to claim 1, wherein the gallic acid is added in the form of an aqueous solution of gallic acid, and the concentration of the aqueous solution is 0.05-0.5 mol/L.
8. The method for preparing the nano-silver cage according to claim 1, wherein 40-65 uL of AgNO with the mass concentration of 1% is sequentially added into 5-8 mL of water3Aqueous solution, 5-15 uL of Na with the concentration of 0.5mol/L2CO3An aqueous solution and 20-40 uL of gallic acid aqueous solution with the concentration of 0.1 mol/L.
9. A nanosilver cage produced by the method of any one of claims 1 to 8.
10. The use of a nanosilver cage according to claim 9.
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