CN113199034B - Ag-SiO2Composite microsphere and preparation method and application thereof - Google Patents
Ag-SiO2Composite microsphere and preparation method and application thereof Download PDFInfo
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- CN113199034B CN113199034B CN202110243634.XA CN202110243634A CN113199034B CN 113199034 B CN113199034 B CN 113199034B CN 202110243634 A CN202110243634 A CN 202110243634A CN 113199034 B CN113199034 B CN 113199034B
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- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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Abstract
The invention provides Ag-SiO2Composite microspheres and a preparation method and application thereof, belonging to the technical field of antibacterial materials. The invention provides Ag-SiO2The preparation method of the composite microsphere comprises the following steps: mixing ethyl orthosilicate, ethanol, ammonia water and water, adjusting the pH value to 9-11, adding silver nitrate aqueous solution into the obtained mixture, and compounding to obtain Ag-SiO2And (3) compounding the microspheres. The invention adopts a one-step method to prepare Ag-SiO2The silver particles can be uniformly dispersed in SiO by the composite microspheres2The surface of the microsphere is simple and convenient, and the prepared composite microsphere has excellent antibacterial performance.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to Ag-SiO2Composite microspheres and a preparation method and application thereof.
Background
At present, the research on antibacterial materials has become a hot topic. Bacteriostatic materials, which are effective in inhibiting and reducing the generation of bacteria, have been used in many fields, such as wall stickers, various sanitary appliances, and medical devices and other daily necessities. In ancient times, silver was considered to be one of the most important bacteriostatic agents, and nowadays, with the increasing knowledge of the antibacterial properties of silver particles, many theories about the silver bacteriostatic mechanism have been proposed. It is believed that silver, when in contact with the body, inactivates specific enzymes in pathogens, blocking cellular pathways of respiration, and thereby killing microorganisms. Cui L [ Cui L, chen P, chen S, et. In stability of the antibiotic activity and mechanism of action of silver nanoparticles enhanced Raman spectroscopy [ J].Anal Chem,2013,85 (11)；5436-5543.]Through SERS technology, it is studied that nano silver particles are used as bacteriostatic materials, and the protein components of bacteria are destroyed, so that the effect of inhibiting the growth of bacteria is achieved. Young Hwan Kim (Young H wan Kim, don Keun Lee, young Soo Kang, synthesis and catalysis o f Ag and Ag-SiO)2nanoparticles[J]Gels and Surfaces A. Physical and Engineering templates, 2004, 257.) and others synthesized nano Ag-SiO2The antibacterial performance of the microspheres is detected by using a Minimum Inhibitory Concentration (MIC) method, and the result shows that the silver nanoparticles are uniformly grown on the nano SiO2The microsphere surface shows good antibacterial performance. However, the method adopts two-step synthesis of nano-composite microspheres, silver in SiO2The surface of the microsphere is not uniformly dispersed and easily aggregated, and the antibacterial effect is not obvious.
Disclosure of Invention
The invention aims to provide Ag-SiO2Composite microsphere, preparation method and application thereof, and Ag-SiO prepared by adopting one-step method2Composite microsphere with silver particles uniformly dispersed in SiO2The surface of the microsphere has better antibacterial performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides Ag-SiO2The preparation method of the composite microsphere comprises the following steps:
mixing ethyl orthosilicate, ethanol, ammonia water and water, adjusting the pH value to 9-11, adding silver nitrate aqueous solution into the obtained mixture, and compounding to obtain Ag-SiO2And (3) compounding the microspheres.
Preferably, the volume ratio of the ethyl orthosilicate to the ethanol to the ammonia water to the water is (1-3) to (45-60) to (1-3) to (4-7).
Preferably, the mixing process of the tetraethoxysilane, the ethanol, the ammonia water and the water is as follows: and (3) carrying out first stirring and mixing on the ethanol, the ammonia water and the water, dropwise adding tetraethoxysilane into the obtained mixed material, and carrying out second stirring and mixing.
Preferably, the mass concentration of the ammonia water is 25 to 28%.
Preferably, the reagent for adjusting the pH value is ammonia water, and the mass concentration of the ammonia water is 25-28%.
Preferably, the concentration of the silver nitrate aqueous solution is 0.02-0.06 mol/L, and the volume ratio of the silver nitrate aqueous solution to the tetraethoxysilane is 10.
Preferably, the temperature of the compounding is 20-40 ℃, and the time is 6h.
The invention provides Ag-SiO prepared by the preparation method in the technical scheme2Composite microspheres of said Ag-SiO2The composite microspheres comprise silicon dioxide microspheres and silver particles, wherein the silver particles uniformly grow on the surfaces of the silicon dioxide microspheres.
Preferably, the Ag-SiO2The average grain diameter of the composite microspheres is 270nm.
The invention provides the Ag-SiO in the technical scheme2The application of the composite microspheres in antibacterial materials.
The invention provides Ag-SiO2The preparation method of the composite microsphere comprises the following steps: mixing ethyl orthosilicate, ethanol, ammonia water and water, adjusting the pH value to 9-11, adding silver nitrate aqueous solution into the obtained mixture, and compounding to obtain Ag-SiO2And (3) compounding the microspheres. The invention adds silver nitrate solution into solution containing tetraethoxysilane under alkaline condition, and then the silver nitrate solution is added into SiO2Uniformly dispersed SiO-groups can be generated in the nucleation process of the microspheres, electrophilic metal (Ag +) in silver nitrate solution is easy to combine with nucleophilic part (SiO-), and simultaneously, the Ag is reacted by ethanol+So that Ag particles are uniformly grown on SiO2The invention adopts a one-step method to prepare Ag-SiO on the surface of the nano microsphere2The composite microsphere is simple and convenient, and the prepared composite microsphere has excellent antibacterial performance.
Drawings
FIG. 1 is a diagram of Ag-SiO prepared in example 12TEM images of composite microspheres;
FIG. 2 is a schematic representation of Ag-SiO prepared in example 22TEM images of the composite microspheres;
FIG. 3 is Ag-SiO solid prepared in example 32TEM images of the composite microspheres;
FIG. 4 is an XPS survey of microspheres prepared in examples 1-3 and comparative example 1;
FIG. 5 is a partial enlarged view of the XPS survey spectrum of FIG. 4;
FIG. 6 is a graph showing the antibacterial effect of the microspheres prepared in examples 1 to 3 and comparative example 1 on Escherichia coli;
FIG. 7 is a graph showing the antibacterial effect against Staphylococcus aureus of the microspheres prepared in examples 1 to 3 and comparative example 1;
FIG. 8 is a schematic diagram of Ag-SiO prepared in comparative example 22SEM image of composite microspheres;
FIG. 9 is Ag-SiO solid prepared in comparative example 22The antibacterial effect of the composite microspheres is shown.
Detailed Description
The invention provides Ag-SiO2The preparation method of the composite microsphere comprises the following steps:
mixing ethyl orthosilicate, ethanol, ammonia water and water, adjusting the pH value to 9-11, adding silver nitrate aqueous solution into the obtained mixture, and compounding to obtain Ag-SiO2And (3) compounding the microspheres.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention mixes ethyl orthosilicate, ethanol, ammonia water and water. In the invention, the volume ratio of the ethyl orthosilicate to the ethanol to the ammonia water to the water is preferably (1-3) to (45-60) to (1-3) to (4-7), more preferably (1.5-2.5) to (50-55) to (1.5-2.5) to (5-6). In the present invention, the ethanol is preferably anhydrous ethanol; the process of mixing the ethyl orthosilicate, the ethanol, the ammonia water and the water is preferably as follows: and (3) carrying out first stirring and mixing on the ethanol, the ammonia water and the water, dropwise adding tetraethoxysilane into the obtained mixed material, and carrying out second stirring and mixing. The stirring and dropping rate is not particularly limited in the present invention and may be carried out according to a procedure well known in the art. In the invention, the time for the first stirring and mixing is preferably 5-10 min, and the temperature is preferably room temperature; the temperature of the second stirring and mixing is preferably room temperature, and the time is preferably 5-20 min.
After the mixing is finished, the pH value of the obtained material is adjusted to 9-11, and a silver nitrate aqueous solution is added into the obtained mixture. In the present invention, the reagent for adjusting pH is preferably aqueous ammonia.
In the present invention, the mass concentration of the aqueous ammonia used in the above step is preferably 25 to 28%.
In the invention, the concentration of the silver nitrate aqueous solution is preferably 0.02-0.06 mol/L, and more preferably 0.03-0.05 mol/L; the volume ratio of the silver nitrate aqueous solution to the ethyl orthosilicate is preferably 10.
In the invention, the compounding is preferably carried out under the stirring condition, and the stirring speed is not specially limited, so that the smooth compounding can be ensured; the temperature of the compounding is preferably 20-40 ℃, more preferably 25-35 ℃, and the time is preferably 6h. In the compounding process, the solution is gradually changed into a semitransparent sol state from a transparent state, the pH value is adjusted, and after silver nitrate solution is added, siO is added2Uniformly dispersed SiO-groups can be generated in the nucleation process of the microspheres, electrophilic metal (Ag +) in silver nitrate solution is easy to combine with nucleophilic part (SiO-), and simultaneously, the Ag is reacted by ethanol+Reduction of Ag particles uniformly grown on SiO2Forming Ag-SiO on the surface of the nano microsphere2And (3) compounding the microspheres.
After the compounding is finished, the invention preferably carries out centrifugal washing and drying on the obtained material to obtain Ag-SiO2And (3) compounding the microspheres. The process of the centrifugal washing and drying is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The invention provides Ag-SiO prepared by the preparation method in the technical scheme2Composite microspheres of said Ag-SiO2The composite microspheres comprise silicon dioxide microspheres and silver particles, wherein the silver particles uniformly grow on the surfaces of the silicon dioxide microspheres.
In the present invention, the Ag-SiO2The average grain diameter of the composite microspheres is 270nm.
The invention provides the Ag-SiO in the technical scheme2The application of the composite microsphere in antibacterial materials. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Stirring and mixing 50mL of absolute ethyl alcohol, 1.5mL of ammonia water (with mass concentration of 28%) and 5mL of water at room temperature for 5min, then dropwise adding 3mL of tetraethoxysilane, stirring for 5min, then adjusting the pH value of the obtained material to 11 by using the ammonia water (with mass concentration of 28%), adding 10mL of silver nitrate aqueous solution with concentration of 0.02mol/L, stirring for 6h, centrifugally washing and drying the obtained material to obtain Ag-SiO2Composite microspheres, denoted SiO2-Ag-1。
Example 2
The only difference from example 1 is: the concentration of the silver nitrate aqueous solution is 0.04mol/L, and the prepared Ag-SiO2Composite microspheres, denoted SiO2-Ag-2。
Example 3
The only difference from example 1 is: the concentration of the silver nitrate aqueous solution is 0.06mol/L, and the prepared Ag-SiO2Composite microspheres, denoted SiO2-Ag-3。
Comparative example 1
Stirring and mixing 50mL of absolute ethyl alcohol, 1.5mL of ammonia water (with the mass concentration of 28%) and 5mL of water at room temperature for 20min, then dropwise adding 3mL of ethyl orthosilicate, stirring for 6h, and centrifugally washing and drying the obtained material to obtain SiO2And (4) microspheres.
Comparative example 2
Is prepared by the prior art bin2Ag nano composite microsphere [ Wangbin, zhang Li, zhuo Xin, guo Shi Hua, liu xi Hui, yang Fu Gen, siO2Synthesis of/Ag nano composite microsphere and research on antibacterial and catalytic properties of/Ag nano composite microsphere [ J]The university of combined fertilizer industry journal (Nature science edition), 2014,37 (06), 720-724.]As comparative example 2: adopts sol-gel method to synthesize uniform nano SiO2Weighing 30mg of SiO2Adding the powder into a three-neck flask filled with 30mL of ultrapure water, and carrying out ultrasonic treatment for 10min; then 30mg of PVP is added, and ultrasonic treatment is carried out for 10min; then adding 10mL of silver ammonia solution (0.01 mol/L) and stirring for 10min, stirring in a 70 ℃ water bath, and adding 10mL of ascorbic acid solution (1 g/L); color of solution is composed ofGradually changing milk white into black, reacting for 30min, centrifuging the obtained product, washing with ultrapure water and anhydrous ethanol, repeating the above operation, and drying in a vacuum constant temperature oven at 50 deg.C for 24 hr to obtain SiO2The Ag nano composite microsphere.
Characterization and testing
1) For Ag-SiO prepared in examples 1 to 32TEM representation is carried out on the composite microspheres, and the results are respectively shown in figures 1-3; as can be seen from FIGS. 1 to 3, under the conditions of different silver contents, silver particles grow on the surface of the silica microspheres, and the particle sizes of the prepared composite microspheres are all about 270nm.
2) For the composite microspheres prepared in examples 1-3 and the SiO prepared in comparative example 12The XPS test of the microspheres shows that the results are shown in FIG. 4 and FIG. 5, wherein FIG. 4 is a full spectrum and FIG. 5 is a detail spectrum;
from FIG. 4, it can be observed that the peak positions of O2s, si2p, si2s, C1s, and O1s give a peak of Si2p at a binding energy of 103.2 eV, which is in turn combined with SiO2The binding energy values are consistent; meanwhile, characteristic peaks of Ag3d and Ag3p can be clearly observed, which indicates the existence of silver element. It can be observed from FIG. 5 that the peaks at binding energies of about 368.2eV and 374.2eV are assigned to Ag, respectively3d5/2And Ag3d3/2This proves that silver element exists in zero valence state, further proving that nano SiO is explained2The silver ions on the microspheres are all reduced.
Application example
SiO prepared in comparative example 12Microspheres and Ag-SiO prepared in examples 1 to 32The composite microspheres are respectively subjected to antibacterial performance tests, and are detected by taking escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538) as test strains, and the specific method comprises the following steps: respectively putting 1mL of bacterial suspension (escherichia coli and staphylococcus aureus) into a sterilization plate, adding 15mL of sterilization solid culture medium with the temperature of 46 ℃ and the temperature of 2 ℃ and uniformly mixing to uniformly disperse the strains in the culture medium, and standing to solidify the strains; after the fungus-containing culture medium is solidified, punching the culture medium by using a puncher (taking out the culture medium in the hole), and putting the sample into the hole by using a spoon; siO prepared as in comparative example 12Microsphere samples as controls, and controls and testsSample (Ag-SiO prepared in example 1)2Composite microspheres) on the same plate; after the sample is filled, the plate is covered, the plate is placed in a 37 ℃ incubator, and the result is observed after the plate is cultured for 18 hours; the diameter of the antibacterial ring (including the hole) was measured with a vernier caliper and recorded. The results of the measurement are shown in FIGS. 6 and 7, in which FIG. 6 shows the results of the test for antibacterial activity against Escherichia coli, and FIG. 7 shows the results of the test for antibacterial activity against Staphylococcus aureus (in which reference numeral 1 is SiO prepared in comparative example 1)2Microspheres; no. 2 is Ag/SiO solid prepared in example 12Compounding the microspheres; code 3 Ag/SiO prepared in example 22Compounding the microspheres; no. 4 Ag/SiO solid prepared in example 32Composite microspheres).
As can be seen from FIGS. 6 and 7, for Escherichia coli and Staphylococcus aureus, sample No. 1 has no zone of inhibition, samples No. 2, 3 and 4 have zones of inhibition that are all very obvious (greater than 7 mm), and the diameters of the zones of inhibition increase in sequence and diffusion zones appear to different degrees, which illustrates that SiO in comparative example 1 has a diffusion zone2The microspheres had no bacteriostatic effect, ag/SiO prepared in examples 1-32The composite microspheres have excellent antibacterial performance on escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC 6538), and the antibacterial performance is enhanced in sequence.
In addition, siO prepared in comparative example 22The SEM image and the antibacterial performance of the/Ag nano composite microsphere are respectively shown in the figure 8 and the figure 9; as can be seen from FIGS. 8 and 9, the method is well suited for SiO2Silver is attached to the surface of the microsphere, but as can be seen from the SEM image, the silver is on the SiO2The microspheres are not uniformly dispersed on the surface, are easy to aggregate and have no obvious antibacterial effect. The invention adopts a one-step method to prepare SiO2/Ag composite microspheres, siO2The silver particles can be uniformly dispersed on the surface of the microsphere, and the antibacterial property is better.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. Ag-SiO2Of composite microspheresThe preparation method is characterized by comprising the following steps:
mixing ethyl orthosilicate, ethanol, ammonia water and water, adjusting the pH value to 9-11, adding silver nitrate aqueous solution into the obtained mixture, and compounding to obtain Ag-SiO2Compounding the microspheres;
the temperature of the compounding is 20-40 ℃, and the time is 6h.
2. The preparation method of claim 1, wherein the volume ratio of the ethyl orthosilicate, the ethanol, the ammonia water and the water is (1-3) to (45-60) to (1-3) to (4-7).
3. The preparation method according to claim 1, wherein the mixing of the tetraethoxysilane, the ethanol, the ammonia water and the water comprises: and (3) carrying out first stirring and mixing on the ethanol, the ammonia water and the water, dropwise adding tetraethoxysilane into the obtained mixed material, and carrying out second stirring and mixing.
4. The process according to any one of claims 1 to 3, wherein the ammonia water has a mass concentration of 25 to 28%.
5. The method according to claim 1, wherein the reagent for adjusting the pH value is ammonia water, and the mass concentration of the ammonia water is 25-28%.
6. The preparation method according to claim 1, wherein the concentration of the silver nitrate aqueous solution is 0.02 to 0.06mol/L, and the volume ratio of the silver nitrate aqueous solution to the ethyl orthosilicate is 10.
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| CN101049631A (en) * | 2007-05-16 | 2007-10-10 | 华东师范大学 | Composition of silicon dioxide - metal hud particles, and preparation method |
| CN102660160B (en) * | 2012-04-18 | 2013-12-11 | 浙江理工大学 | Silica-coated silver core composite particles and their preparation method and use |
| CN102632247B (en) * | 2012-04-20 | 2013-12-04 | 武汉大学 | Preparation method of load-type silver nano-composite material |
| CN103143721B (en) * | 2013-03-14 | 2014-08-06 | 山东大学 | Preparation method of Ag@SiO2 core-shell structure nano composite |
| CN103231072B (en) * | 2013-04-09 | 2015-06-03 | 昆明理工大学 | Preparation method of silicon dioxide/silver core-shell composite powder for high temperature electronic paste |
| CN103223488B (en) * | 2013-05-08 | 2015-07-22 | 宁波大学 | Preparation method for silver-coated silicon dioxide composite microsphere particles |
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| CN104858413B (en) * | 2014-02-21 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of preparation method of silicon dioxide carried noble metal nano particles |
| CN105561988A (en) * | 2014-10-16 | 2016-05-11 | 西安艾菲尔德复合材料科技有限公司 | Synthesizing method for silicon dioxide-silver nano-composite microspheres |
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