CN109134907B - Preparation method of cellulose acetate-based hybrid membrane - Google Patents
Preparation method of cellulose acetate-based hybrid membrane Download PDFInfo
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- CN109134907B CN109134907B CN201811050958.6A CN201811050958A CN109134907B CN 109134907 B CN109134907 B CN 109134907B CN 201811050958 A CN201811050958 A CN 201811050958A CN 109134907 B CN109134907 B CN 109134907B
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- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 196
- 239000012528 membrane Substances 0.000 title claims abstract description 163
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 108010022355 Fibroins Proteins 0.000 claims abstract description 96
- 239000000243 solution Substances 0.000 claims abstract description 76
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 60
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- 239000011259 mixed solution Substances 0.000 claims abstract description 43
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 12
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The preparation method of the cellulose acetate-based hybrid membrane comprises the following steps: preparing cellulose acetate solution from cellulose acetate particles and a solvent; adding fibroin powder into a cellulose acetate solution, uniformly stirring, and defoaming to obtain a mixed solution; uniformly coating the mixed solution on release paper, then soaking the release paper in the aqueous solution to form a film, taking out the film, drying the film, and then stripping the release paper to obtain a cellulose acetate/fibroin hybrid film; and immersing the cellulose acetate/fibroin hybrid membrane into a silver nitrate solution for light-resistant adsorption, then immersing the membrane into a glycol solution of sodium hydroxide, then immersing the membrane into a ferric chloride solution, taking out the membrane, washing and drying the membrane to obtain the cellulose acetate based hybrid membrane. The cellulose acetate based hybrid membrane prepared by the invention has the characteristics of biodegradability, firm immobilization and easy recovery, and can be used for purifying water resources and sterilizing.
Description
Technical Field
The invention belongs to the technical field of synthesis of nano materials, and particularly relates to a preparation method of a cellulose acetate-based hybrid membrane.
Background
Since the seventies of the last century, the continuous environmental pollution and energy shortage caused the concern of people about global crisis, especially the problem of water pollution, which has been increasingly prominent, seriously affected the sustainable development of human society and caused various health and safety problems, and the sewage treatment is imminent. At present, common methods for removing harmful substances from sewage comprise a coagulation method, an acid precipitation method, a biochemical method, a liquid membrane separation method, a granular activated carbon method and the like, but the effect is not ideal and the method is difficult to be applied independently. Therefore, development of new and practical environmental treatment technologies is necessary.
In recent years, the research on the photocatalytic properties of semiconductors with solar energy conversion and storage as the main background has been rapidly developed, and the research on the photocatalytic degradation of pollutants in water has also made many progress in the last decade. The main advantages of the technology are: various organic pollutants in water can be completely degraded into CO2、H2O, etc., the inorganic pollutants are oxidized or reduced into harmless substances; no additional electron acceptor is required; the photocatalyst has the advantages of low price, no toxicity, stability, reusability and the like; the photocatalyst may be activated using solar energy as a light source. Among them, silver chloride has a relatively narrow band gap and has been widely used in the fields of photocatalytic materials, solar cell materials, gas sensors, optoelectronic devices, and the like. Such as:
the Chinese invention patent application (application number: 201710336334. X) discloses an Ag @ AgCl-non-woven fabric nanocomposite and a preparation method thereof, and the Ag @ AgCl-non-woven fabric nanocomposite which is stable in structure and not easy to fall off is prepared by effectively grafting and loading the Ag @ AgCl-non-woven fabric nanocomposite on the surface of a non-woven fabric. However, nonwoven fabrics have the disadvantages of poor optical transparency, low specific surface area, insufficient utilization of light energy, and effective contact with target pollutants.
Cellulose is the main component of plant cell wall, widely distributed in nature, is a cheap and easily available natural high molecular compound, and is generated by photosynthesis every year up to 1 × 1012Ton. Among cellulose derivatives, cellulose acetate is a widely used cellulose organic acid ester, is the most popular film-making raw material in the market today, and has the advantages of low price, chemical stability, high mechanical strength, good thermal stability, simple film-making process, wide material source, easy obtainment and the like. However, cellulose acetate membranes also have the disadvantages of poor microbial corrosion resistance and easy useOxidized and easily polluted, etc. In order to expand the application range of the cellulose acetate film, modification research on the cellulose acetate film is required to improve the performance of the cellulose acetate film.
Silk fibroin is a natural protein composed of 18 amino acids connected by peptide bonds in a certain order. The silk fibroin film is a weak amino acid film, has good biocompatibility and biodegradability, and is wide in application range. However, the pure silk fibroin solution has poor mechanical properties after being prepared into a material, has high brittleness in a dry state, has poor mechanical properties and lacks practical value. Various performances of the fibroin hybrid membrane can be effectively improved through hybrid modification.
Therefore, aiming at the problems in the prior art, it is important to provide a photocatalytic material technology which is biodegradable, has high activity, firm immobilization and good recovery and adsorption performance, so as to solve the defects in the prior art.
Disclosure of Invention
The invention aims to avoid the defects in the prior art and provides a preparation method of a cellulose acetate based hybrid membrane which is biodegradable, good in mechanical property, easy to recover and reusable.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a cellulose acetate/fibroin hybrid membrane comprises the following steps of:
step 1, preparing cellulose acetate particles and a solvent into a cellulose acetate solution with the mass fraction of 9-15%, wherein the solvent can completely dissolve the cellulose acetate particles;
step 2, preparing a mixed solution: adding fibroin powder with solid content of 60-80% into the cellulose acetate solution, stirring for 20-30 minutes by using a high-speed stirrer to obtain a uniform mixed solution, and standing for defoaming to obtain a mixed solution;
step 3, preparing a cellulose acetate/fibroin hybrid membrane: uniformly coating the mixed solution on release paper, immersing the release paper in an aqueous solution, taking out the release paper after the mixed solution on the release paper is solidified into a thin film, and peeling the release paper after drying to obtain a cellulose acetate/fibroin hybrid film;
step 4, silver nanoparticle loading: immersing the cellulose acetate/fibroin hybrid membrane into silver nitrate solution to be adsorbed in a dark place, so that silver nitrate is adsorbed on the surface of the membrane and in an internal hole structure; then immersing the membrane into a glycol solution of sodium hydroxide for in-situ reduction reaction, and carrying out in-situ reduction on the surface and the inner holes of the membrane to generate Ag so as to obtain an Ag nanoparticle loaded cellulose acetate/fibroin hybrid membrane;
step 5, Ag/AgCl in-situ loading: and immersing the Ag nano-particle loaded cellulose acetate/fibroin hybrid membrane into ferric chloride solution for in-situ oxidation reaction, carrying out in-situ oxidation on the surface and the inner holes of the membrane to generate AgCl, taking out the AgCl, washing the membrane with deionized water for three times after taking out the membrane, and drying the membrane in a vacuum drying oven to obtain the Ag/AgCl loaded cellulose acetate/fibroin hybrid membrane, namely the cellulose acetate based hybrid membrane.
Therefore, the mechanical property of the fibroin film can be effectively improved by hybridizing the cellulose acetate and the fibroin. The obtained Ag/AgCl loaded cellulose acetate/fibroin miscellaneous cargo film organically combines the excellent stability of the cellulose acetate film with the outstanding biocompatibility of the fibroin film, realizes biodegradability, and does not cause secondary pollution to the environment after use.
The photocatalyst is loaded on the film carrier, so that the adsorption and degradation speed is effectively improved. Due to the existence of hydroxyl and carbonyl in the cellulose acetate and amino and carboxyl in amino acid in the fibroin, the cellulose acetate/fibroin hybrid membrane has strong affinity for noble metals, and can be used as an adsorbent for silver ions, so that Ag/AgCl particles are generated in situ on the cellulose acetate/fibroin hybrid membrane.
Preferably, the solvent in step 1 is N, N-dimethylformamide or N, N-dimethylacetamide; the dissolving temperature is 35-45 ℃.
Preferably, the particle size of the silk fibroin powder in the step 2 is 2-10 μm.
Preferably, in step 3, the thickness of the mixed solution coated on the release paper is 0.02-0.3 mm.
Preferably, the drying temperature in the step 3 is 35-45 ℃, and the drying time is 6-8 hours.
Preferably, the concentration of the silver nitrate solution in the step 4 is 0.05-0.25 mol/L, and the light-shielding adsorption time is 6-9 hours. The size, distribution and particle layer thickness of silver chloride particles generated in situ are controlled by controlling the concentration of silver nitrate, so that the performance of the cellulose acetate/fibroin hybrid membrane generated in situ by Ag/AgCl is adjusted.
More preferably, the concentration of the silver nitrate solution is 0.10mol/L, and the adsorption is carried out for 8 hours in a dark place. The size, distribution and thickness of the silver chloride particles generated under the condition have good appearance and optimal effect.
Preferably, the concentration of the ethylene glycol solution of sodium hydroxide in the step 4 is 0.05-0.25 mol/L.
More preferably, the concentration of the sodium hydroxide in the glycol solution is 0.10mol/L
Preferably, the concentration of the ferric chloride solution in the step 5 is 0.05-0.25 mol/L, the drying temperature is 40-50 ℃, and the drying time is 6-8 hours.
More preferably, the ferric chloride solution has a concentration of 0.10mol/L, a drying temperature of 40 ℃ and a drying time of 8 hours.
The reaction process of the cellulose acetate based hybrid membrane is controllable, the size, distribution and particle layer thickness of silver chloride particles produced in situ can be controlled by controlling the concentration of silver nitrate solution, so that the adjustment of the performance of the cellulose acetate based hybrid membrane is realized, when the concentration of silver nitrate solution is 0.10mol/L, the concentration of ethylene glycol solution of sodium hydroxide is 0.10mol/L and the concentration of ferric chloride solution is 0.10mol/L, Ag/AgCl on the surface of the hybrid membrane is tightly distributed, but no obvious agglomeration phenomenon exists, and the enhancement of photocatalytic activity and sterilization and disinfection effects is facilitated.
The second purpose of the invention is to provide an application of the cellulose acetate-based hybrid membrane in the catalytic degradation of organic pollutants in water under the irradiation of ultraviolet light or visible light.
The invention also aims to provide the application of the cellulose acetate-based hybrid membrane in sterilization and disinfection under ultraviolet light or visible light irradiation. The silver nanoparticles have strong antibacterial capacity, can resist bacteria under the condition of no need of illumination and oxygen, are a good antibacterial material, simultaneously play a role in inhibiting the recombination of electrons and holes, and can effectively improve the capacity of catalyzing and degrading pollutants of the cellulose acetate/fibroin hybrid membrane generated in situ.
The invention has the beneficial effects that:
according to the cellulose acetate-based hybrid membrane, cellulose acetate particles and a solvent are prepared into a cellulose acetate solution; adding fibroin powder into a cellulose acetate solution, uniformly stirring, and defoaming to obtain a mixed solution; uniformly coating the mixed solution on release paper, then soaking the release paper in the aqueous solution to form a film, taking out the film, drying the film, and then stripping the release paper to obtain a cellulose acetate/fibroin hybrid film; and immersing the cellulose acetate/fibroin hybrid membrane into a silver nitrate solution for light-resistant adsorption, then immersing the membrane into a glycol solution of sodium hydroxide, then immersing the membrane into a ferric chloride solution, taking out the membrane, washing and drying the membrane to obtain the cellulose acetate based hybrid membrane. Therefore, the substrate material is prepared by adopting a cellulose acetate/fibroin hybrid membrane and adopting wet phase inversion, and the Ag and AgCl modification is further carried out on the substrate material by utilizing a method of immersion-chemical reduction. Compared with the prior art, the invention has the following characteristics:
1. the biodegradable plastic has biodegradability, and can not cause secondary pollution to the environment after being used;
2. the performance of the cellulose acetate/fibroin hybrid membrane generated in situ by Ag/AgCl is adjusted, so that the method can adapt to different use environments;
3. Ag/AgCl is deposited on the substrate material, so that the immobilization is firm and the particle size is uniform;
4. the preparation method is carried out only at room temperature, is simple to operate, has strong response to ultraviolet light and visible light, does not need special conditions in the whole preparation process, has low requirements on equipment, and is suitable for large-scale production;
5. when used as an antibacterial film, the antibacterial film has excellent antibacterial effect; the catalyst can be repeatedly used, and has good stability without filtration and centrifugation after recovery;
6. the spectral response range is wide, and the photocatalytic activity for pollutant degradation is high.
Drawings
The invention is further illustrated by means of the attached drawings, the examples of which are not to be construed as limiting the invention in any way.
FIG. 1 is a scanning electron microscope image of the surface topography of one embodiment of a cellulose acetate-based hybrid membrane of the present invention;
FIG. 2 is a scanning electron microscope image of the cross-sectional morphology of one embodiment of a cellulose acetate-based hybrid membrane of the present invention.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
One embodiment of the preparation method of the cellulose acetate-based hybrid membrane comprises the following steps:
(1) preparing a cellulose acetate solution: respectively weighing 9g of cellulose acetate particles and 90g N g of N, N-dimethylformamide according to the proportion of 1:10, adding the N-dimethylformamide into a reaction vessel, stirring at the constant temperature of 25 ℃ for 8 hours, and completely dissolving the cellulose acetate particles to obtain a cellulose acetate solution with the mass fraction of 9.1%;
(2) preparing a mixed solution: adding fibroin powder with the particle size of 5 mu m and the solid content of 62% into the cellulose acetate solution, stirring for 30 minutes by using a high-speed stirrer, and then standing for defoaming for 30 minutes to obtain a mixed solution;
(3) preparing a cellulose acetate/fibroin hybrid membrane: coating the mixed solution on release paper with the thickness of 0.05 mm, quickly horizontally soaking the coated release paper into deionized water, taking out the release paper and the thin film after the mixed solution on the release paper is completely cured into a thin film, placing the thin film in a constant-temperature oven at 40 ℃ for drying for 8 hours, peeling the thin film from the release paper after the thin film on the release paper is completely dried to obtain a cellulose acetate/fibroin hybrid film, and cutting the obtained cellulose acetate/fibroin hybrid film into the size specification of length, width, and size of 10cm multiplied by 10 cm;
(4) silver nanoparticle loading: horizontally immersing the cut cellulose acetate/fibroin hybrid membrane into 50ml of silver nitrate solution with the concentration of 0.05mol/L for light-proof adsorption for 6 hours, so that silver nitrate is adsorbed on the surface and in the internal pore structure of the cellulose acetate/fibroin hybrid membrane; after light-resistant adsorption is finished, soaking the cellulose acetate/fibroin hybrid membrane after adsorbing the silver nitrate into 50ml of 0.05mol/L sodium hydroxide glycol solution for in-situ reduction reaction, and carrying out in-situ reduction on the surface and the inner holes of the hybrid membrane to generate simple substance Ag nano particles so as to obtain the silver-loaded cellulose acetate/fibroin hybrid membrane;
(5) Ag/AgCl in-situ load: horizontally immersing the silver-loaded cellulose acetate/fibroin hybrid membrane into 50ml of ferric chloride solution with the concentration of 0.05mol/L for in-situ oxidation reaction, carrying out in-situ oxidation reaction on the surface of the membrane and the inner holes after full reaction to generate AgCl, taking out the hybrid membrane after complete reaction, washing with deionized water for three times, and drying in a vacuum drying oven at 40 ℃ for 8 hours to obtain the cellulose acetate based hybrid membrane.
Ag/AgCl particles loaded on the surface of the cellulose acetate-based hybrid membrane prepared by the embodiment are effectively immobilized on the surface and in the internal pore structure of the cellulose acetate/fibroin hybrid membrane, the particle size of crystals is 200-300 nm, the crystals are uniformly dispersed, and no obvious agglomeration phenomenon exists; further, as can be seen from the solid ultraviolet-visible absorption spectrum, the cellulose acetate based hybrid membrane prepared in this example has strong absorption in both ultraviolet and visible light ranges. Under the condition of ultraviolet light, 50ml of 10mg/L methyl orange solution is degraded by using 50mg of cellulose acetate-based hybrid membrane prepared by the embodiment, and the degradation rate can reach 90% within 60 minutes; under the condition of visible light, 50mg of the cellulose acetate-based hybrid membrane prepared in the embodiment degrades 50ml of 10mg/L methyl orange solution, and the degradation rate can reach 91% within 60 minutes. The cellulose acetate based hybrid membrane prepared by the embodiment has good antibacterial activity on staphylococcus aureus (gram positive bacteria), escherichia coli (gram negative bacteria) and the like.
Example 2
One embodiment of the preparation method of the cellulose acetate-based hybrid membrane comprises the following steps:
(1) preparing a cellulose acetate solution: respectively weighing 8g of cellulose acetate particles and 80g N of N, N-dimethylacetamide according to the ratio of 1:8, adding the N-dimethylacetamide into a reaction vessel, heating and stirring for 8 hours at 40 ℃, and completely dissolving the cellulose acetate particles to obtain a 11.1 mass percent cellulose acetate solution;
(2) preparing a mixed solution: adding fibroin powder with the particle size of 5 mu m and the solid content of 65 percent into the cellulose acetate solution, stirring for 30 minutes by using a high-speed stirrer to obtain an organic-inorganic mixed solution which is uniformly mixed, and standing and defoaming for 30 minutes to obtain a mixed solution;
(3) preparing a cellulose acetate/fibroin hybrid membrane: coating the mixed solution on release paper with the thickness of 0.10 mm, quickly horizontally soaking the coated release paper into deionized water, taking out the release paper and the thin film after the mixed solution on the release paper is completely cured into a thin film, placing the thin film in a constant-temperature oven at 45 ℃ for drying for 7 hours, peeling the thin film from the release paper after the thin film on the release paper is completely dried to obtain a cellulose acetate/fibroin hybrid film, and cutting the obtained cellulose acetate/fibroin hybrid film into the size specification of length, width, and thickness of 10cm multiplied by 10 cm;
(4) silver nanoparticle loading: horizontally immersing the cut cellulose acetate/fibroin hybrid membrane into 50ml of silver nitrate solution with the concentration of 0.10mol/L for light-proof adsorption for 6 hours, so that silver nitrate is adsorbed on the surface and in an internal hole structure of the cellulose acetate/fibroin hybrid membrane; after light-resistant adsorption is finished, soaking the cellulose acetate/fibroin hybrid membrane after adsorbing the silver nitrate into 50ml of 0.10mol/L sodium hydroxide glycol solution for in-situ reduction reaction, and carrying out in-situ reduction on the surface and the inner holes of the hybrid membrane to generate simple substance Ag nano particles so as to obtain the silver-loaded cellulose acetate/fibroin hybrid membrane;
(5) Ag/AgCl in-situ load: horizontally immersing the silver-loaded cellulose acetate/fibroin hybrid membrane into 50ml of ferric chloride solution with the concentration of 0.10mol/L for in-situ oxidation reaction, carrying out in-situ oxidation reaction on the surface of the membrane and the inner holes after full reaction to generate AgCl, taking out the hybrid membrane after complete reaction, washing with deionized water for three times, and drying in a vacuum drying oven at 45 ℃ for 7 hours to obtain the cellulose acetate based hybrid membrane.
Ag/AgCl particles loaded on the surface of the cellulose acetate-based hybrid membrane prepared by the embodiment are effectively immobilized on the surface and in the internal pore structure of the cellulose acetate/fibroin hybrid membrane, the particle size of the crystals is 400-500 nm, the crystals are uniformly dispersed, and no obvious agglomeration phenomenon exists; further, as can be seen from the solid ultraviolet-visible absorption spectrum, the cellulose acetate based hybrid membrane prepared in this example has strong absorption in both ultraviolet and visible light ranges. Under the condition of ultraviolet light, 50ml of 10mg/L methyl orange solution is degraded by using 50mg of cellulose acetate-based hybrid membrane prepared in the embodiment, and the degradation rate is close to 100% in 60 minutes; under visible light conditions, 50mg of the cellulose acetate-based hybrid membrane prepared in the embodiment degrades 50ml of 10mg/L methyl orange solution, and the degradation rate is close to 100% within 60 minutes. The cellulose acetate based hybrid membrane prepared by the embodiment has good antibacterial activity on staphylococcus aureus (gram positive bacteria), escherichia coli (gram negative bacteria) and the like.
Example 3
One embodiment of the preparation method of the cellulose acetate-based hybrid membrane comprises the following steps:
(1) preparing a cellulose acetate solution: respectively weighing 10g of cellulose acetate particles and 65g N g of N, N-dimethylformamide according to the proportion of 1:6.5, adding the N-dimethylformamide into a reaction vessel, heating and stirring at 45 ℃ for 8 hours, and completely dissolving the cellulose acetate particles to obtain a 13.3 mass percent cellulose acetate solution;
(2) preparing a mixed solution: adding fibroin powder with the particle size of 5 mu m and the solid content of 70 percent into the cellulose acetate solution, stirring for 30 minutes by using a high-speed stirrer to obtain an organic-inorganic mixed solution which is uniformly mixed, and standing and defoaming for 30 minutes to obtain a mixed solution;
(3) preparing a cellulose acetate/fibroin hybrid membrane: coating the mixed solution on release paper with the thickness of 0.05 mm, quickly horizontally soaking the coated release paper into deionized water, taking out the release paper and the thin film after the mixed solution on the release paper is completely cured into a thin film, placing the thin film in a constant-temperature oven at 45 ℃ for drying for 8 hours, peeling the thin film from the release paper after the thin film on the release paper is completely dried to obtain a cellulose acetate/fibroin hybrid film, and cutting the obtained cellulose acetate/fibroin hybrid film into the size specification of length, width, and size of 10cm multiplied by 10 cm;
(4) silver nanoparticle loading: horizontally immersing the cut cellulose acetate/fibroin hybrid membrane into 50ml of silver nitrate solution with the concentration of 0.15mol/L for light-proof adsorption for 6 hours, so that silver nitrate is adsorbed on the surface and in the internal pore structure of the cellulose acetate/fibroin hybrid membrane; after light-resistant adsorption is finished, soaking the cellulose acetate/fibroin hybrid membrane after adsorbing the silver nitrate into 50ml of 0.15mol/L sodium hydroxide glycol solution for in-situ reduction reaction, and carrying out in-situ reduction on the surface and the inner holes of the hybrid membrane to generate simple substance Ag nano particles so as to obtain the silver-loaded cellulose acetate/fibroin hybrid membrane;
(5) Ag/AgCl in-situ load: horizontally immersing the silver-loaded cellulose acetate/fibroin hybrid membrane into 50ml of ferric chloride solution with the concentration of 0.15mol/L for in-situ oxidation reaction, carrying out in-situ oxidation reaction on the surface of the membrane and the inner holes after full reaction to generate AgCl, taking out the hybrid membrane after complete reaction, washing with deionized water for three times, and drying in a vacuum drying oven at 45 ℃ for 8 hours to obtain the cellulose acetate based hybrid membrane.
Ag/AgCl particles loaded on the surface of the cellulose acetate-based hybrid membrane prepared by the embodiment are effectively immobilized on the surface and in the internal pore structure of the cellulose acetate/fibroin hybrid membrane, the particle size of the crystals is 700-800 nm, the crystals are uniformly dispersed, and no obvious agglomeration phenomenon exists; further, as can be seen from the solid ultraviolet-visible absorption spectrum, the cellulose acetate based hybrid membrane prepared in this example has strong absorption in both ultraviolet and visible light ranges. Under the condition of ultraviolet light, 50ml of 10mg/L methyl orange solution is degraded by using 50mg of cellulose acetate-based hybrid membrane prepared in the embodiment, and the degradation rate is close to 90% within 60 minutes; under visible light conditions, 50mg of the cellulose acetate-based hybrid membrane prepared in the embodiment degrades 50ml of 10mg/L methyl orange solution, and the degradation rate is close to 95% within 60 minutes. The cellulose acetate based hybrid membrane prepared by the embodiment has good antibacterial activity on staphylococcus aureus (gram positive bacteria), escherichia coli (gram negative bacteria) and the like.
Example 4
One embodiment of the preparation method of the cellulose acetate-based hybrid membrane comprises the following steps:
(1) preparing a cellulose acetate solution: respectively weighing 10g of cellulose acetate particles and 55g N of N, N-dimethylacetamide according to the proportion of 1:5.5, adding the N-dimethylformamide into a reaction container, heating and stirring for 8 hours at 35 ℃, and completely dissolving the cellulose acetate particles to obtain a cellulose acetate solution with the mass fraction of 15.4%;
(2) preparing a mixed solution: adding fibroin powder with the particle size of 2 mu m and the solid content of 75% into the cellulose acetate solution, stirring for 30 minutes by using a high-speed stirrer to obtain an organic-inorganic mixed solution which is uniformly mixed, and standing and defoaming for 30 minutes to obtain a mixed solution;
(3) preparing a cellulose acetate/fibroin hybrid membrane: coating the mixed solution on release paper by 0.02mm, quickly horizontally immersing the coated release paper into deionized water, taking out the release paper and the thin film after the mixed solution on the release paper is completely cured into a thin film, placing the thin film in a constant-temperature oven at 40 ℃ for drying for 8 hours, peeling the thin film from the release paper after the thin film on the release paper is completely dried to obtain a cellulose acetate/fibroin hybrid film, and cutting the obtained cellulose acetate/fibroin hybrid film into the size specification of length, width, and the size specification of 10cm multiplied by 10 cm;
(4) silver nanoparticle loading: horizontally immersing the cut cellulose acetate/fibroin hybrid membrane into 50ml of silver nitrate solution with the concentration of 0.20mol/L for light-proof adsorption for 6 hours, so that silver nitrate is adsorbed on the surface and in an internal hole structure of the cellulose acetate/fibroin hybrid membrane; after light-resistant adsorption is finished, soaking the cellulose acetate/fibroin hybrid membrane after adsorbing the silver nitrate into 50ml of 0.20mol/L sodium hydroxide glycol solution for in-situ reduction reaction, and carrying out in-situ reduction on the surface and the inner holes of the hybrid membrane to generate simple substance Ag nano particles so as to obtain the silver-loaded cellulose acetate/fibroin hybrid membrane;
(5) Ag/AgCl in-situ load: horizontally immersing the silver-loaded cellulose acetate/fibroin hybrid membrane into 50ml of ferric chloride solution with the concentration of 0.20mol/L for in-situ oxidation reaction, carrying out in-situ oxidation reaction on the surface of the membrane and the inner holes after full reaction to generate AgCl, taking out the hybrid membrane after complete reaction, washing with deionized water for three times, and drying in a vacuum drying oven at 40 ℃ for 8 hours to obtain the cellulose acetate based hybrid membrane.
As shown in fig. 1 and 2, when the surface and cross-sectional morphology of the cellulose acetate-based hybrid membrane prepared in the embodiment are observed under a scanning electron microscope, it can be found that Ag/AgCl particles are effectively immobilized on the surface and internal pore structures of the cellulose acetate/fibroin hybrid membrane, the crystal particle size is 1-1.2 μm, the dispersion is uniform, and no obvious agglomeration phenomenon occurs; further, as can be seen from the solid ultraviolet-visible absorption spectrum, the cellulose acetate based hybrid membrane prepared in this example has strong absorption in both ultraviolet and visible light ranges. Under the condition of ultraviolet light, 50ml of 10mg/L methyl orange solution is degraded by using 50mg of cellulose acetate-based hybrid membrane prepared by the embodiment, and the degradation rate can reach 94% within 60 minutes; under the condition of visible light, 50mg of the cellulose acetate-based hybrid membrane prepared in the embodiment degrades 50ml of 10mg/L methyl orange solution, and the degradation rate can reach 94% within 60 minutes. The cellulose acetate based hybrid membrane prepared by the embodiment has good antibacterial activity on staphylococcus aureus (gram positive bacteria), escherichia coli (gram negative bacteria) and the like.
Example 5
One embodiment of the preparation method of the cellulose acetate-based hybrid membrane comprises the following steps:
(1) preparing a cellulose acetate solution: weighing 9g of cellulose acetate particles and 85g N, adding N-dimethylformamide into a reaction container, heating and stirring for 8 hours at 35 ℃, and completely dissolving the cellulose acetate particles to obtain a cellulose acetate solution with the mass fraction of 9.57%;
(2) preparing a mixed solution: adding fibroin powder with the particle size of 10 mu m and the solid content of 60% into the cellulose acetate solution, stirring for 30 minutes by using a high-speed stirrer to obtain an organic-inorganic mixed solution which is uniformly mixed, and standing and defoaming for 30 minutes to obtain a mixed solution;
(3) preparing a cellulose acetate/fibroin hybrid membrane: coating the mixed solution on release paper with the thickness of 0.2mm, quickly horizontally soaking the coated release paper into deionized water, taking out the release paper and the thin film after the mixed solution on the release paper is completely cured into a thin film, placing the thin film in a constant-temperature oven at 40 ℃ for drying for 8 hours, peeling the thin film from the release paper after the thin film on the release paper is completely dried to obtain a cellulose acetate/fibroin hybrid film, and cutting the obtained cellulose acetate/fibroin hybrid film into the size specification of length, width, and the size specification of 10cm multiplied by 10 cm;
(4) silver nanoparticle loading: horizontally immersing the cut cellulose acetate/fibroin hybrid membrane into 50ml of silver nitrate solution with the concentration of 0.25mol/L for light-proof adsorption for 9 hours, so that silver nitrate is adsorbed on the surface and in the internal pore structure of the cellulose acetate/fibroin hybrid membrane; after light-resistant adsorption is finished, soaking the cellulose acetate/fibroin hybrid membrane after adsorbing the silver nitrate into 50ml of 0.25mol/L sodium hydroxide glycol solution for in-situ reduction reaction, and carrying out in-situ reduction on the surface and the inner holes of the hybrid membrane to generate simple substance Ag nano particles so as to obtain the silver-loaded cellulose acetate/fibroin hybrid membrane;
(5) Ag/AgCl in-situ load: horizontally immersing the silver-loaded cellulose acetate/fibroin hybrid membrane into 50ml of ferric chloride solution with the concentration of 0.25mol/L for in-situ oxidation reaction, carrying out in-situ oxidation reaction on the surface of the membrane and the inner holes after full reaction to generate AgCl, taking out the hybrid membrane after complete reaction, washing with deionized water for three times, and drying in a vacuum drying oven at 50 ℃ for 8 hours to obtain the cellulose acetate based hybrid membrane.
The cellulose acetate based hybrid membrane prepared in this example has strong absorption in both ultraviolet and visible light ranges. Under the condition of ultraviolet light, 50ml of 10mg/L methyl orange solution is degraded by using 50mg of cellulose acetate-based hybrid membrane prepared by the embodiment, and the degradation rate can reach 91% in 60 minutes; under the condition of visible light, 50mg of the cellulose acetate-based hybrid membrane prepared in the embodiment degrades 50ml of 10mg/L methyl orange solution, and the degradation rate can reach 91% within 60 minutes. The cellulose acetate based hybrid membrane prepared by the embodiment has good antibacterial activity on staphylococcus aureus (gram positive bacteria), escherichia coli (gram negative bacteria) and the like.
Example 6
One embodiment of the preparation method of the cellulose acetate-based hybrid membrane comprises the following steps:
(1) preparing a cellulose acetate solution: weighing 15g of cellulose acetate particles and 95g N, adding N-dimethylformamide into a reaction container, heating and stirring for 8 hours at 35 ℃, and completely dissolving the cellulose acetate particles to obtain a 13.63 mass percent cellulose acetate solution;
(2) preparing a mixed solution: adding fibroin powder with the particle size of 5 mu m and the solid content of 80% into the cellulose acetate solution, stirring for 30 minutes by using a high-speed stirrer to obtain an organic-inorganic mixed solution which is uniformly mixed, and standing and defoaming for 30 minutes to obtain a mixed solution;
(3) preparing a cellulose acetate/fibroin hybrid membrane: coating the mixed solution on release paper with the thickness of 0.3 mm, quickly horizontally soaking the coated release paper into deionized water, taking out the release paper and the thin film after the mixed solution on the release paper is completely cured into a thin film, placing the thin film in a constant-temperature oven at 40 ℃ for drying for 8 hours, peeling the thin film from the release paper after the thin film on the release paper is completely dried to obtain a cellulose acetate/fibroin hybrid film, and cutting the obtained cellulose acetate/fibroin hybrid film into the size specification of length, width, and the size specification of 10cm multiplied by 10 cm;
(4) silver nanoparticle loading: horizontally immersing the cut cellulose acetate/fibroin hybrid membrane into 50ml of silver nitrate solution with the concentration of 0.25mol/L for light-proof adsorption for 9 hours, so that silver nitrate is adsorbed on the surface and in the internal pore structure of the cellulose acetate/fibroin hybrid membrane; after light-resistant adsorption is finished, soaking the cellulose acetate/fibroin hybrid membrane after adsorbing the silver nitrate into 50ml of 0.25mol/L sodium hydroxide glycol solution for in-situ reduction reaction, and carrying out in-situ reduction on the surface and the inner holes of the hybrid membrane to generate simple substance Ag nano particles so as to obtain the silver-loaded cellulose acetate/fibroin hybrid membrane;
(5) Ag/AgCl in-situ load: horizontally immersing the silver-loaded cellulose acetate/fibroin hybrid membrane into 50ml of ferric chloride solution with the concentration of 0.25mol/L for in-situ oxidation reaction, carrying out in-situ oxidation reaction on the surface of the membrane and the inner holes after full reaction to generate AgCl, taking out the hybrid membrane after complete reaction, washing with deionized water for three times, and drying in a vacuum drying oven at 50 ℃ for 8 hours to obtain the cellulose acetate based hybrid membrane.
The cellulose acetate based hybrid membrane prepared in this example has strong absorption in both ultraviolet and visible light ranges. Under the condition of ultraviolet light, 50ml of 10mg/L methyl orange solution is degraded by using 50mg of cellulose acetate-based hybrid membrane prepared by the embodiment, and the degradation rate can reach 90% within 60 minutes; under the condition of visible light, 50mg of the cellulose acetate based hybrid membrane prepared in the embodiment degrades 50ml of 10mg/L methyl orange solution, and the degradation rate can reach 87% within 60 minutes. The cellulose acetate based hybrid membrane prepared by the embodiment has good antibacterial activity on staphylococcus aureus (gram positive bacteria), escherichia coli (gram negative bacteria) and the like.
Finally, it should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that any modification or equivalent replacement can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A cellulose acetate-based hybrid membrane comprising the steps of:
step 1, preparing a cellulose acetate solution: preparing cellulose acetate particles and a solvent into a cellulose acetate solution with the mass fraction of 9-15%, wherein the solvent can completely dissolve the cellulose acetate particles;
step 2, preparing a mixed solution: adding fibroin powder into the cellulose acetate solution, uniformly stirring, and defoaming to obtain a mixed solution with the solid content of 60-80%;
step 3, preparing a cellulose acetate/fibroin hybrid membrane: uniformly coating the mixed solution on release paper, immersing the release paper in an aqueous solution, taking out the release paper after the mixed solution on the release paper is solidified into a thin film, and peeling the release paper after drying to obtain a cellulose acetate/fibroin hybrid film;
step 4, Ag nano-particle loading: immersing the cellulose acetate/silk fibroin hybrid membrane into a silver nitrate solution for light-shielding adsorption, and then immersing the cellulose acetate/silk fibroin hybrid membrane into a glycol solution of sodium hydroxide to obtain an Ag nano-particle loaded cellulose acetate/silk fibroin hybrid membrane;
step 5, Ag/AgCl in-situ loading: and immersing the Ag nano-particle loaded cellulose acetate/fibroin hybrid membrane into a ferric chloride solution, taking out, washing and drying to obtain the cellulose acetate based hybrid membrane.
2. The method for preparing a cellulose acetate-based hybrid membrane according to claim 1, wherein: the solvent in the step 1 is N, N-dimethylformamide or N, N-dimethylacetamide.
3. The method for preparing a cellulose acetate-based hybrid membrane according to claim 1, wherein: and 2, the particle size of the silk fibroin powder in the step 2 is 2-10 mu m.
4. The cellulose acetate-based hybrid membrane according to claim 1, wherein: in the step 3, the thickness of the mixed liquid coated on the release paper is 0.02-0.3 mm.
5. The cellulose acetate-based hybrid membrane according to claim 1, wherein: and 4, the concentration of the silver nitrate solution is 0.05-0.25 mol/L, and the light-proof adsorption time is 6-9 hours.
6. The cellulose acetate-based hybrid membrane according to claim 5, wherein: and 4, the concentration of the silver nitrate solution is 0.10mol/L, and the adsorption time in the dark is 8 hours.
7. The cellulose acetate-based hybrid membrane according to claim 1, wherein: and 4, the concentration of the glycol solution of the sodium hydroxide is 0.05-0.25 mol/L.
8. The cellulose acetate-based hybrid membrane according to claim 1, wherein: and 4, the concentration of the ethylene glycol solution of the sodium hydroxide is 0.10 mol/L.
9. The cellulose acetate-based hybrid membrane according to claim 1, wherein: and 5, the concentration of the ferric chloride solution is 0.05-0.25 mol/L.
10. Use of a cellulose acetate based hybrid membrane according to any one of claims 1 to 9 for disinfecting and/or catalytically degrading organic contaminants in water under irradiation of ultraviolet and/or visible light.
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| CN108165962A (en) * | 2018-01-15 | 2018-06-15 | 陕西师范大学 | A kind of preparation method of porous silver membrane |
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| CN106944105A (en) * | 2017-05-13 | 2017-07-14 | 上海大学 | A kind of Ag@AgCl non-woven fabrics nano composite materials and preparation method thereof |
| CN108165962A (en) * | 2018-01-15 | 2018-06-15 | 陕西师范大学 | A kind of preparation method of porous silver membrane |
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| Title |
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| "Nanofibrous Membrane of Silk Fibroin/Cellulose Acetate Blend for Heavy Metal Ion Adsorption";Weitao Zhou et al.;《Advanced Materials Research》;20111231;第148-149卷;第1431-1435页 * |
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