CN113875775B - Preparation method of all-silicon molecular sieve encapsulated nano silver bactericide - Google Patents
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Abstract
The invention belongs to the technical field of bactericide preparation, and in particular relates to a preparation method of an all-silicon molecular sieve encapsulated nano silver bactericide. On one hand, the coordination effect of the (3-mercaptopropyl) trimethoxy silane and silver ions is utilized to prevent silver ions from precipitating, and the interaction between the (3-mercaptopropyl) trimethoxy silane and a molecular sieve precursor is utilized to enable the silver ions to be uniformly dispersed in the pore canal of the molecular sieve. On the other hand, the limited aperture of the molecular sieve can also effectively limit the release rate of silver ions, avoid the occurrence of the sudden release phenomenon, achieve the aim of slow release and control, and lead the molecular sieve to have wide application prospect as a broad-spectrum bactericide.
Description
Technical Field
The invention belongs to the technical field of nano silver bactericide preparation, and particularly relates to a preparation method of an all-silicon molecular sieve packaged nano silver bactericide.
Background
The silver ion has strong bactericidal effect, and researches show that the nano silver can be oxidized on the surface of the nano silver in water or water-containing air to release trace silver ions, and has good bactericidal effect when the concentration of the silver ions reaches 0.01ppm, and after bacteria die, the silver ions can be released again to continue to play a bactericidal function, so that the nano silver is a high-quality and long-acting bactericide. However, if nano silver is directly used for sterilization, the problems of high price, easy aggregation, unstable release and the like exist, and scientists have tried to uniformly load nano silver in various carriers for many years so as to obtain a better sterilization effect.
The molecular sieve is silicate or aluminosilicate in a crystalline state, has a regular structure and good thermal and hydrothermal stability, and meanwhile, the narrow pore canal of the molecular sieve can very effectively prevent aggregation of silver nano particles and control the release rate of the silver nano particles, so that the molecular sieve is a very ideal Ag bactericide slow-release carrier.
Currently, a certain research progress has been made by encapsulating nano silver with molecular sieves. For example, there are studies on the successful synthesis of Ag-TiO by a novel two-step hydrothermal method 2 Nanotube composite material consisting of nanotube TiO 2 Structural composition, ag nanoparticles are uniformly dispersed throughout the material, with a particle size of about 3nm, but scanning electron microscopy results show that there are silver nanoparticles of 32 to 103nm free outside the material. It has also been studied to pack Ag nanoparticles into hollow ZSM-5 molecular sieve crystals by conventional impregnation or to locate Ag clusters in the channels of molecular sieves using ion exchange. Although the molecular sieve encapsulated nano silver bactericide can be synthesized by the method, in the loading process, a part of metal precursor is inevitably adsorbed on the outer surface of a carrier or a framework, so that Ag is unevenly distributed, the release rate of the Ag bactericide is too high, and the sterilization performance is finally affected.
Therefore, a new preparation method of the molecular sieve encapsulated nano silver bactericide with strong universality is still required to be developed so as to improve the bactericidal activity and the controllable release rate of the nano silver bactericide.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of an all-silicon molecular sieve encapsulated nano silver bactericide, and the prepared bactericide consists of an all-silicon molecular sieve carrier and active components loaded on the carrier, wherein the active components are silver nano particles, and nano silver metal is uniformly dispersed in the carrier. The preparation method has the advantages of simple reaction system and mild reaction condition, and the obtained all-silicon molecular sieve encapsulated nano silver bactericide has novel structure, higher bactericidal activity and controllable release rate, and has wide application prospect as a broad-spectrum bactericide.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of an all-silicon molecular sieve encapsulated nano silver bactericide, which comprises the following steps:
s1, adding water into a tetrapropylammonium hydroxide solution to dilute, adding (3-mercaptopropyl) trimethoxysilane to prepare a mixed solution, and then adding a silver nitrate aqueous solution into the mixed solution, and continuously stirring for more than 30 minutes;
s2, adding tetraethyl silicate into the mixed system in the step S1 to obtain silver-silica sol, and aging the silver-silica sol to obtain silver-silica gel;
s3, carrying out static crystallization on the silver-silicon gel in the step S2, roasting at a high temperature in an air atmosphere, and then reducing at a high temperature in a hydrogen atmosphere to finally prepare the all-silicon molecular sieve packaged nano silver bactericide.
Preferably, the temperature of the static crystallization is 90-125 ℃ and the time is 48-144 hours. Specifically, the static crystallization is static crystallization at 95 ℃ for 4 days.
Preferably, the high-temperature roasting temperature is 300-550 ℃, the time is 1-8 hours, and the heating rate is 0.5-5 ℃/min. Specifically, the high-temperature roasting temperature is 500 ℃, the time is 2 hours, and the heating rate is 0.5 ℃/min.
Preferably, the high-temperature reduction temperature is 250-500 ℃, the time is 2-4 hours, and the heating rate is 0.5-5 ℃/min. Specifically, the high-temperature reduction temperature is 300 ℃, the time is 2 hours, and the heating rate is 0.5 ℃/min.
Preferably, the aging is carried out at a temperature of 40 to 90 ℃ for a time of 1 to 2 hours. Specifically, the aging temperature was 80℃for 1 hour.
Preferably, in the step S1, the concentration of the tetrapropylammonium hydroxide solution is 25wt% to 40wt%, the concentration of the silver nitrate aqueous solution is 0.2wt% to 0.3wt%, and water is added for dilution so that the concentration of the tetrapropylammonium hydroxide in the silver-silica sol obtained in the step S2 is 9.0 wt% to 10.0wt% and the concentration of the silver nitrate is 0.06 wt% to 0.08wt%.
Preferably, the molar ratio of tetrapropylammonium hydroxide to tetraethyl silicate is 1:2-5.
Preferably, the molar ratio of silver nitrate to (3-mercaptopropyl) trimethoxysilane is 1:10 to 40 percent.
Preferably, the molar ratio of the tetrapropylammonium hydroxide to the (3-mercaptopropyl) trimethoxysilane is 1:0.15-0.25.
The invention also provides the all-silicon molecular sieve packaged nano silver bactericide prepared by the preparation method of the all-silicon molecular sieve packaged nano silver bactericide.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of an all-silicon molecular sieve encapsulated nano silver bactericide, which comprises the steps of introducing a nano silver precursor complex formed by (3-mercaptopropyl) trimethoxy silane and silver nitrate into a synthesis system of an all-silicon molecular sieve, encapsulating the nano silver precursor into the all-silicon molecular sieve through in-situ static crystallization, and finally preparing the all-silicon molecular sieve encapsulated nano silver bactericide through high-temperature roasting and hydrogen reduction. On one hand, the coordination effect of the (3-mercaptopropyl) trimethoxy silane and silver ions is utilized to protect the silver ions from precipitation in alkaline sol of the synthesized molecular sieve, and the interaction between the (3-mercaptopropyl) trimethoxy silane and a molecular sieve precursor is utilized to ensure that the silver ions are encapsulated into the molecular sieve pore canal in the synthesis process, so that aggregation of the silver ions on the outer surface of the molecular sieve is avoided to the greatest extent, and uniform dispersion of the silver ions in the molecular sieve pore canal is facilitated. On the other hand, the limited aperture of the molecular sieve can also effectively limit the release rate of silver ions, avoid the occurrence of the sudden release phenomenon, achieve the aim of slow release and control, can be used as a broad-spectrum bactericide, and has wide application prospect.
Drawings
FIG. 1 is an XRD pattern of an all-silicon molecular sieve encapsulated nano-silver biocide;
fig. 2 is a TEM image of an all-silicon molecular sieve encapsulated nano silver bactericide.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1 preparation method of an all-silicon molecular sieve-encapsulated nanosilver bactericide (Silicalite-1 molecular sieve is used as molecular sieve carrier)
(1) 7.32g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 40 wt%) was taken and added 5g H 2 Diluting with O, adding 0.507mL (3-mercaptopropyl) trimethoxysilane, and mixing uniformly to obtain a mixed solution; 0.022g of silver nitrate (AgNO) 3 ) 7.887gH is added 2 O is dissolved into a silver nitrate aqueous solution, and the obtained silver nitrate aqueous solution is dripped into the mixed solution and stirred for 30 minutes.
(2) And (3) dropwise adding 10g of tetraethyl silicate (TEOS) into the mixed system, uniformly mixing to obtain colorless and transparent silver-silica sol, heating the obtained silver-silica sol to 80 ℃, stirring and aging for 1h to obtain the silver-silica gel.
(3) And (3) placing the silver-silica gel into a crystallization kettle with a polytetrafluoroethylene lining, carrying out static crystallization for 4 days at 95 ℃, centrifuging, washing and drying after crystallization, transferring the obtained sample into a tube furnace, heating to 500 ℃ in an air atmosphere, roasting for 2 hours (heating rate of 0.5 ℃/min), cooling to room temperature after roasting, heating to 300 ℃ in a hydrogen atmosphere, and reducing for 2 hours (heating rate of 0.5 ℃/min), thus obtaining the all-silicon molecular sieve packaged nano silver bactericide (Ag@Silicalite-1).
X-ray diffraction (XRD) and Transmission Electron Microscope (TEM) analysis are carried out on the prepared all-silicon molecular sieve encapsulated nano silver bactericide, and the XRD data of figure 1 can show that the self structure of the encapsulated Silicalite-1 molecular sieve is not obviously affected. As can be seen from the transmission electron microscope data of FIG. 2, ag nanoparticles are uniformly dispersed in Silicalite-1 molecular sieve crystals, and the particle size is about 1-2nm.
Example 2 preparation method of all-silicon molecular sieve packaged nano silver bactericide
(1) 7.32g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 40 wt%) was taken and added 5g H 2 Diluting with O, adding 0.622mL (3-mercaptopropyl) trimethoxysilane, and mixing uniformly to obtain a mixed solution; 0.027g of silver nitrate (AgNO) 3 ) Add 7.887g H 2 O is dissolved into a silver nitrate aqueous solution, and the obtained silver nitrate aqueous solution is dripped into the mixed solution and stirred for 30 minutes.
(2) And (3) dropwise adding 10g of tetraethyl silicate (TEOS) into the mixed system, uniformly mixing to obtain colorless and transparent silver-silica sol, heating the obtained silver-silica sol to 80 ℃, stirring and aging for 1h to obtain the silver-silica gel.
(3) And (3) placing the silver-silicon gel into a crystallization kettle with a polytetrafluoroethylene lining, carrying out static crystallization for 4 days at 95 ℃, centrifuging, washing and drying after crystallization, transferring the obtained sample into a tube furnace, heating to 500 ℃ in an air atmosphere, roasting for 2 hours (the heating rate is 0.5 ℃/min), cooling to room temperature after roasting, heating to 300 ℃ in a hydrogen atmosphere, and reducing for 2 hours (the heating rate is 0.5 ℃/min), thus obtaining the all-silicon molecular sieve packaged nano silver bactericide.
XRD and TEM analysis results were consistent with example 1.
Example 3 preparation method of all-silicon molecular sieve packaged nano silver bactericide
(1) 7.32g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 40 wt%) was taken and added 5g H 2 Diluting with O, adding 0.761mL (3-mercaptopropyl) trimethoxysilane, and mixing uniformly to obtain a mixed solution; 0.033g of silver nitrate (AgNO) 3 ) Add 7.887g H 2 O is dissolved into a silver nitrate aqueous solution, and the obtained silver nitrate aqueous solution is dripped into the mixed solution and stirred for 30 minutes.
(2) And (3) dropwise adding 10g of tetraethyl silicate (TEOS) into the mixed system, uniformly mixing to obtain colorless and transparent silver-silica sol, heating the obtained silver-silica sol to 80 ℃, stirring and aging for 1h to obtain the silver-silica gel.
(3) And (3) placing the silver-silica gel into a crystallization kettle with a polytetrafluoroethylene lining, carrying out static crystallization for 4 days at 95 ℃, centrifuging, washing and drying after crystallization, transferring the obtained sample into a tube furnace, heating to 500 ℃ in an air atmosphere, roasting for 2 hours (heating rate of 0.5 ℃/min), cooling to room temperature after roasting, heating to 300 ℃ in a hydrogen atmosphere, and reducing for 2 hours (heating rate of 0.5 ℃/min), thus obtaining the all-silicon molecular sieve packaged nano silver bactericide.
XRD and TEM analysis results were consistent with example 1.
Example 4 preparation method of all-silicon molecular sieve packaged nano silver bactericide
(1) 7.32g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 40 wt%) was taken and added 5g H 2 Diluting with O, adding 1.153mL (3-mercaptopropyl) trimethoxysilane, and mixing uniformly to obtain a mixed solution; 0.05g of silver nitrate (AgNO) 3 ) 7.887gH is added 2 O is dissolved into a silver nitrate aqueous solution, and the obtained silver nitrate aqueous solution is dripped into the mixed solution and stirred for 30 minutes.
(2) And (3) dropwise adding 10g of tetraethyl silicate (TEOS) into the mixed system, uniformly mixing to obtain colorless and transparent silver-silica sol, heating the obtained silver-silica sol to 80 ℃, stirring and aging for 1h to obtain the silver-silica gel.
(3) And (3) placing the silver-silica gel into a crystallization kettle with a polytetrafluoroethylene lining, carrying out static crystallization for 4 days at 95 ℃, centrifuging, washing and drying after crystallization, transferring the obtained sample into a tube furnace, heating to 500 ℃ in an air atmosphere, roasting for 2 hours (heating rate of 0.5 ℃/min), cooling to room temperature after roasting, heating to 300 ℃ in a hydrogen atmosphere, and reducing for 2 hours (heating rate of 0.5 ℃/min), thus obtaining the all-silicon molecular sieve packaged nano silver bactericide.
XRD and TEM analysis results were consistent with example 1.
Example 5 preparation method of all-silicon molecular sieve packaged nano silver bactericide
(1) 7.32g of tetrapropylammonium hydroxide aqueous solution (TPAOH, 40 wt%) was taken and added 5g H 2 Diluting with O, adding 0.577mL (3-mercaptopropyl) trimethoxysilane, and mixing uniformly to obtain a mixed solution; 0.25g of silver nitrate (AgNO) 3 ) 7.887gH is added 2 O is dissolved into silver nitrate aqueous solutionThe obtained silver nitrate aqueous solution was added dropwise to the above mixed solution, and stirring was continued for 30 minutes.
(2) And (3) dropwise adding 10g of tetraethyl silicate (TEOS) into the mixed system, uniformly mixing to obtain colorless and transparent silver-silica sol, heating the obtained silver-silica sol to 80 ℃, stirring and aging for 1h to obtain the silver-silica gel.
(3) And (3) placing the silver-silica gel into a crystallization kettle with a polytetrafluoroethylene lining, carrying out static crystallization for 4 days at 95 ℃, centrifuging, washing and drying after crystallization, transferring the obtained sample into a tube furnace, heating to 500 ℃ in an air atmosphere, roasting for 2 hours (heating rate of 0.5 ℃/min), cooling to room temperature after roasting, heating to 300 ℃ in a hydrogen atmosphere, and reducing for 2 hours (heating rate of 0.5 ℃/min), thus obtaining the all-silicon molecular sieve packaged nano silver bactericide.
XRD and TEM analysis results were consistent with example 1.
Comparative example 1 all-silicon molecular sieves loaded with nanosilver by impregnation
5g of all-silicon molecular sieve (Silicalite-1 molecular sieve) is immersed in 10mL of silver nitrate water solution (0.16 wt%) and then baked for 2 hours under the air atmosphere after the water is evaporated to dryness, the temperature is raised to 500 ℃ for 2 hours (the heating rate is 0.5 ℃/min), cooled to room temperature, and then reduced for 2 hours under the hydrogen atmosphere after the temperature is raised to 300 ℃ (the heating rate is 0.5 ℃/min), so that the all-silicon molecular sieve loaded with nano silver by the immersion method is obtained.
Experimental example 1 silver ion Release Rate test
The silver ion release rates of all-silicon molecular sieves of examples 1 and 2 were tested using the nano silver encapsulated nano silver bactericides as an example and using the nano silver loaded all-silicon molecular sieve samples by the immersion method as a control.
The whole silicon molecular sieve-encapsulated nano silver samples of examples 1 and 2 and the whole silicon molecular sieve sample loaded with nano silver by an immersion method (each sample contains about 0.4mg of nano silver calculated by silver content) are respectively weighed into a 50mL centrifuge tube, 20mL of absolute ethyl alcohol is added and shaking is continued for six days, centrifugation is carried out at 5000rpm for 10min during each sampling, 1mL of supernatant is taken as a sample by a pipette, and 1mL of absolute ethyl alcohol is supplemented. Performing ICP test on the obtained supernatant to measure the concentration of silver ions, and calculating to obtain the initial release rate of the all-silicon molecular sieve packaged nano silver sample in the example 1 to be about 3.38mg/L/d, and reducing to about 0.47mg/L/d after six days; the initial release rate of the all-silicon molecular sieve encapsulated nano-silver sample of example 2 was about 1.61mg/L/d, and after six days was reduced to about 0.225mg/L/d; the initial release rate of the all-silicon molecular sieve sample loaded with nano silver by the dipping method is about 13.33mg/L/d, and the initial release rate is reduced to about 2.50mg/L/d after six days. Therefore, the all-silicon molecular sieve packaged nano silver bactericide prepared by the method has controllable silver ion release rate.
Experimental example 2 test of sterilizing Effect
Respectively weighing 0.2g of all-silicon molecular sieve packaging nano silver sample (taking example 1 as an example) and adopting an immersion method to load nano silver of all-silicon molecular sieve sample in a sterilized 50mL centrifuge tube, adding 20mL of deionized water, vibrating for 30 days, centrifugally separating the sample, washing to remove silver ions adsorbed on the surface, drying, weighing 0.05g as a sample, placing the sample in the sterilized 50mL centrifuge tube, adding 5mL of buffer solution, vibrating for 24 hours at 37 ℃ to fully release Ag ions, adding 0.1mL of escherichia coli bacterial solution into the sample as an experimental group, and carrying out the same operation with blank PBS buffer solution as a control group. Placing the sample added with the bacterial liquid into a constant temperature box at 37 ℃ for culturing for 2 hours, and adopting a ten-fold dilution method to prepare diluted 10 -2 Taking 0.1mL of diluted supernatant respectively from the multiplied samples, uniformly coating the diluted supernatant into a 9cm plastic culture dish filled with a solid culture medium, culturing the mixture at 37 ℃ for 18 hours, taking out the sample, and counting the sample, wherein the result shows that the sterilization rate of the all-silicon molecular sieve-packaged nano silver sample in the embodiment 1 can reach more than 99 percent; and the full-silicon molecular sieve sample loaded with nano silver by adopting the dipping method has lost the sterilization capability. Therefore, the all-silicon molecular sieve encapsulated nano silver bactericide prepared by the method has higher bactericidal activity.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (7)
1. The preparation method of the all-silicon molecular sieve encapsulated nano silver bactericide is characterized by comprising the following steps of:
s1, adding water into a tetrapropylammonium hydroxide solution to dilute, adding (3-mercaptopropyl) trimethoxysilane to prepare a mixed solution, then adding a silver nitrate aqueous solution into the mixed solution, and continuously stirring for more than 30 minutes, wherein the molar ratio of the tetrapropylammonium hydroxide to the (3-mercaptopropyl) trimethoxysilane is 1:0.15-0.25, and the molar ratio of the silver nitrate to the (3-mercaptopropyl) trimethoxysilane is 1:10-40;
s2, adding tetraethyl silicate into the mixed system in the step S1 to obtain silver-silica sol, aging the silver-silica sol to obtain silver-silica gel, wherein the molar ratio of the tetraethyl silicate to tetrapropylammonium hydroxide is 2-5: 1, a step of;
s3, carrying out static crystallization on the silver-silicon gel in the step S2, roasting at a high temperature in an air atmosphere, and then reducing at a high temperature in a hydrogen atmosphere to finally prepare the all-silicon molecular sieve packaged nano silver bactericide.
2. The method for preparing the all-silicon molecular sieve packaged nano silver bactericide according to claim 1, wherein the static crystallization temperature is 90-125 ℃ and the time is 48-144 hours.
3. The preparation method of the all-silicon molecular sieve packaged nano silver bactericide according to claim 1, wherein the high-temperature roasting temperature is 300-550 ℃, the time is 1-8 hours, and the heating rate is 0.5-5 ℃/min.
4. The preparation method of the all-silicon molecular sieve packaged nano silver bactericide according to claim 1, wherein the high-temperature reduction temperature is 250-500 ℃, the time is 2-4 hours, and the heating rate is 0.5-5 ℃/min.
5. The method for preparing the all-silicon molecular sieve packaged nano silver bactericide according to claim 1, wherein the aging temperature is 40-90 ℃ and the time is 1-2 hours.
6. The method for preparing the all-silicon molecular sieve packaged nano silver bactericide according to claim 1, wherein in the step S1, the concentration of the tetrapropylammonium hydroxide solution is 25-40 wt%, the concentration of the silver nitrate aqueous solution is 0.2-0.3 wt%, and the concentration of tetrapropylammonium hydroxide in the silver-silica sol obtained in the step S2 is 9.0-10.0wt% and the concentration of silver nitrate is 0.06-0.08wt%.
7. An all-silicon molecular sieve-encapsulated nano-silver bactericide prepared by the preparation method of the all-silicon molecular sieve-encapsulated nano-silver bactericide according to any one of claims 1 to 6.
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| CN112570015B (en) * | 2020-12-22 | 2022-08-26 | 天津大学 | Molecular sieve catalyst for packaging Pd-based alloy and preparation method and application thereof |
| CN113354973B (en) * | 2021-06-03 | 2022-06-03 | 中山大学 | Slow-release antifouling agent and preparation method and application thereof |
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| CN109999902A (en) * | 2019-04-11 | 2019-07-12 | 浙江工业大学 | The supported porous grade titanium-silicon molecular sieve catalyst of encapsulation type platinum family sub-nanometer metal and its preparation and application |
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