CN109174195B - A kind of preparation method of organic-inorganic blend membrane - Google Patents
A kind of preparation method of organic-inorganic blend membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Life Sciences & Earth Sciences (AREA)
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- Environmental & Geological Engineering (AREA)
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Abstract
本发明的一种有机‑无机共混膜的制备方法，将质量分数为10％~18％的聚氨酯高分子溶液中加入固含量为0.5%~1%的聚乙二醇溶液，得均匀分散的聚乙二醇‑聚氨酯溶液；加入固含量为12％~18％的负氧离子粉；涂敷于离型纸上后浸入水中，待有机‑无机混合液固化成膜后取出，清洗，干燥，将聚氨酯基薄膜浸泡在硝酸银溶液中避光吸附；依次在硝酸银溶液中加入磷酸氢二钠溶液、十六烷基三甲基溴化铵，避光反应，取出聚氨酯基薄膜，清洗，干燥，得有机‑无机共混膜。本发明具有以下特点：1.提高催化剂的催化性能，增加了反应的比表面积，增加反应活性位点，减小了光腐蚀，延长了催化剂的使用寿命；2.基底材料安全无毒，环境友好。
In the preparation method of an organic-inorganic blend film of the present invention, a polyethylene glycol solution with a solid content of 0.5% to 1% is added to a polyurethane polymer solution with a mass fraction of 10% to 18% to obtain a uniformly dispersed Polyethylene glycol-polyurethane solution; add negative oxygen ion powder with a solid content of 12% to 18%; apply it on a release paper and then immerse it in water, wait for the organic-inorganic mixed solution to solidify into a film, take it out, wash, dry, Soak the polyurethane-based film in the silver nitrate solution to avoid light absorption; add disodium hydrogen phosphate solution and cetyltrimethylammonium bromide to the silver nitrate solution in turn to avoid light-proof reaction, take out the polyurethane-based film, wash and dry , an organic-inorganic blend film was obtained. The invention has the following characteristics: 1. Improve the catalytic performance of the catalyst, increase the specific surface area of the reaction, increase the reaction active site, reduce the photocorrosion, and prolong the service life of the catalyst; 2. The base material is safe, non-toxic, and environmentally friendly .
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a preparation method of an organic-inorganic blend membrane.
Background
The control and treatment of environmental pollution are major issues facing human beings in the 21 st century. Among a plurality of environmental pollution treatment technologies, the photocatalysis technology is an attractive field in solar energy utilization at present and is mainly applied to environmental pollution treatment, water photolysis hydrogen production and CO catalysis2Reduction, and the like. Traditional photocatalyst main bodyThe photocatalyst is divided into a photocatalyst responding to ultraviolet light and a photocatalyst responding to visible light, wherein the ultraviolet light accounts for less than 5% of sunlight, and the visible light accounts for about 43% of the sunlight. Therefore, the development of a photocatalyst having a higher degree of visible light response has become an important research hotspot.
Ag3PO4Is a new visible light response type catalyst in recent years, has the quantum efficiency of 90 percent when absorbing visible light with the light wavelength less than 530nm, has strong capability of photo-catalytic oxidation and degradation of organic pollutants, and Ag3PO4The photocatalyst is a novel and efficient visible-light-driven photocatalyst with a good application prospect. Such as:
the Chinese invention patent application (application number: 201610334712.6) discloses' a GO/Ag3PO4The method takes graphene oxide as a matrix and deposits Ag on the surface of the graphene oxide3PO4Compared with AgBr particles, the ternary composite photocatalyst prepared by the invention is pure-phase Ag3PO4The photocatalytic performance of the photocatalyst is greatly improved, the specific surface area of the photocatalyst is increased by adding the flaky graphene oxide, photo-generated charges can be rapidly transferred, the recombination rate of electron-hole pairs is reduced, the three-way composite photocatalyst keeps high-efficiency oxidation capacity, and organic dyes in sewage are effectively degraded. But Ag3PO4Ag slightly soluble in water and partially soluble in water3PO4Will ionize to produce Ag+Become an electron capture agent, have serious photo-corrosion, greatly influence the stability and the photo-catalytic activity of the catalyst, and Ag generated by the reaction3PO4The Ag is often nano-sized or micro-sized particles, and the problems of difficult recovery, large loss amount and the like exist when the Ag is recovered and reused, which also becomes a restriction for Ag3PO4One important reason for the application.
Therefore, aiming at the problems in the prior art, it is important to develop a photocatalytic material technology for efficiently catalyzing and degrading organic pollutants, reducing light corrosion and increasing reaction active sites to solve the defects in the prior art.
Disclosure of Invention
The invention aims to avoid the defects in the prior art and provide a preparation method of an organic-inorganic blend membrane which can efficiently catalyze and degrade organic pollutants, reduce light corrosion and increase reaction active sites.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing an organic-inorganic blend membrane, all raw materials are calculated by weight,
step 1: fully dissolving polyurethane particles in a solvent to prepare a polyurethane polymer solution with the mass fraction of 10-18%;
step 2: completely dissolving polyethylene glycol with solid content of 0.5-1% in the polyurethane polymer solution to obtain uniformly dispersed polyethylene glycol-polyurethane solution;
and step 3: adding negative oxygen ion powder with the solid content of 12-18% into the polyethylene glycol-polyurethane solution, stirring for 20-30 minutes to obtain a uniform organic-inorganic mixed solution, and standing for defoaming.
And 4, step 4: coating the organic-inorganic mixed solution on release paper with a certain thickness, quickly immersing the coated release paper in water, taking out the release paper and the film after curing to form a film, repeatedly and alternately cleaning the film for three times by using absolute ethyl alcohol and deionized water, removing residual solvent on the surface of the film, cleaning the film, placing the film in an indoor ventilation drying place, drying the film at room temperature, and peeling the film from the release paper after the film on the release paper is completely dried to obtain the polyurethane-based film;
and 5: soaking the polyurethane-based film in a silver nitrate solution, and carrying out magnetic stirring and light-proof adsorption for a certain time to ensure that the silver nitrate is uniformly adsorbed on the surface of the film and in the internal hole structure;
step 6: dropwise adding a disodium hydrogen phosphate solution into the silver nitrate solution under the ultrasonic condition to react for 30 minutes in a dark place, and generating Ag in situ on the surface and the inner holes of the membrane3PO4Granulating to obtain the immobilized Ag3PO4A polyurethane-based film of particles; then Ag is carried in the solid3PO4Dropwise adding hexadecyl trimethyl ammonium bromide into the granular polyurethane-based film, and carrying out a dark reaction for 30 minutes by utilizing ultrasonic waves to ensure that the Ag on the upper part of the film3PO4The particles react to generate AgBr particles, the film is repeatedly washed by absolute ethyl alcohol and deionized water, impurities on the surface of the film are removed, the film is frozen in a refrigerator and then is dried in a freeze drying box, and the in-situ immobilized AgBr/Ag is obtained3PO4Nanoparticle polyurethane-based composite membranes, i.e., organic-inorganic blend membranes.
Preferably, the polyurethane in the step 1 is polyester type thermoplastic polyurethane particles, the Shore hardness is 55-65A, and the dissolving temperature is 30-45 ℃.
Preferably, the solvent in step 1 is at least one of N, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the polyethylene glycol in step 2 is polyethylene glycol 1000.
Preferably, the concentration of the silver nitrate solution in the step 5 is 0.015mol/L, and the light-shielding adsorption time is 5-7 hours. More preferably, the adsorption time is 6 hours in the absence of light.
Preferably, the ratio of the amount of silver nitrate to disodium hydrogen phosphate in step 6 is 3: 1.
preferably, the ratio of the amounts of the disodium hydrogen phosphate and the hexadecyl trimethyl ammonium bromide in the step 6 is 0.75-3.0: 1.
more preferably, the mass ratio of the disodium hydrogen phosphate to the cetyltrimethylammonium bromide is 1.5: 1.
preferably, the freeze-drying time in step 6 is preferably 1.5 hours.
The invention has the beneficial effects that:
according to the preparation method of the organic-inorganic blend membrane, a polyethylene glycol solution with the solid content of 0.5-1% is added into a polyurethane polymer solution with the mass fraction of 10-18% to obtain a uniformly dispersed polyethylene glycol-polyurethane solution; adding negative oxygen ion powder with the solid content of 12-18% into a polyethylene glycol-polyurethane solution; applying organic-inorganic mixture to release paperSoaking the polyurethane-based film in water, taking out after the organic-inorganic mixed solution is solidified into a film, cleaning, drying, and stripping release paper to obtain a polyurethane-based film; soaking the polyurethane-based film in a silver nitrate solution to be adsorbed in a dark place; under the ultrasonic condition, sequentially adding a disodium hydrogen phosphate solution and hexadecyl trimethyl ammonium bromide into a silver nitrate solution, reacting in a dark place, taking out the polyurethane-based film, cleaning and drying to obtain the organic-inorganic blend film. Therefore, the polyurethane film substrate is prepared by wet phase inversion and inorganic filling modification technology, and Ag is simultaneously treated by the film+Adsorption and chemical ion exchange of Ag in situ on a polyurethane-based film substrate3PO4On the basis of nano particles, in-situ immobilization of AgBr/Ag with a heterostructure3PO4And (3) nanoparticles. Compared with the prior art, the invention has the following characteristics:
(1) with Ag alone3PO4Compared with the catalyst, the catalyst greatly improves the catalytic performance of the catalyst, increases the specific surface area of the reaction, thereby increasing the reaction active sites, greatly reducing the light corrosion and prolonging the service life of the catalyst;
(2) the polyurethane film substrate adopts degradable polyurethane as a framework supporting structure, adopts negative oxygen ion powder capable of releasing negative oxygen ions as filling modified inorganic filler, and is safe, non-toxic and environment-friendly;
(3) the negative oxygen ions released by the negative oxygen ion powder have higher activity and stronger redox effect, the degradation of pollutants in the water body can be accelerated, and the negative oxygen ion powder can effectively inhibit the recombination of electron hole pairs in the process of releasing the negative oxygen ions, thereby greatly enhancing the catalytic activity of the composite film;
(4) the preparation method of the material is simple, and AgBr/Ag3PO4The nano particles are firmly immobilized, the recovery is convenient, the reaction process is easy to control, and special equipment is not needed.
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 an organic-inorganic blend membrane of the present invention;
FIG. 2 is a scanning electron microscope image of the cross-sectional morphology of an embodiment of the organic-inorganic blend membrane of the present invention.
Detailed Description
The present invention will be described in further detail by the following specific examples, wherein the raw materials are all analytical industrial raw materials, and the equipment is common industrial production equipment.
Example 1
One embodiment of the method for preparing an organic-inorganic blend membrane of the present invention comprises the following steps:
accurately weighing 15g of polyester type thermoplastic polyurethane particles with Shore hardness of 55A and 100g of N, N-dimethylformamide solution, adding into a beaker, heating and stirring by using a magnetic stirrer at 40 ℃ to completely dissolve the polyurethane particles in the solvent to obtain a polyurethane polymer solution with mass fraction of 13%; accurately weighing 0.58g of polyethylene glycol 1000 and dissolving the polyethylene glycol 1000 in 5g of N, N-dimethylformamide solution to obtain a completely dissolved polyethylene glycol solution; adding the completely dissolved polyethylene glycol solution into a polyurethane polymer solution, and stirring for 10 minutes by using a magnetic stirrer to ensure that the polyethylene glycol solution is uniformly dispersed in the polyurethane polymer solution; adding 15.76g of negative oxygen ion powder into the obtained polyurethane polymer solution containing the polyethylene glycol, stirring for 20 minutes by using an electric high-speed stirrer to obtain uniform organic-inorganic mixed solution, and standing for defoaming; coating the obtained organic-inorganic mixed solution on release paper with a certain thickness, quickly immersing the coated release paper in water, taking out the release paper and the film after curing to form a film, repeatedly and alternately cleaning the film for three times by using absolute ethyl alcohol and deionized water, removing residual solvent on the surface of the film, cleaning the film, placing the film in an indoor ventilation drying place, drying the film at room temperature, peeling the film and the release paper after the film on the release paper is completely dried, and cutting the film into the size of 15cm multiplied by 15cm to obtain a substrate material-polyurethane-based film; immersing the above polyurethane-based filmSoaking in 100ml of 15mmol/L silver nitrate solution, and adsorbing for a certain time in a dark place by magnetic stirring to make the silver nitrate uniformly adsorbed on the surface of the membrane and in the internal pore structure; taking disodium hydrogen phosphate as a phosphorus source, dropwise adding 30ml of 16.67mmol/L disodium hydrogen phosphate solution into silver nitrate solution under the ultrasonic condition, carrying out ultrasonic photophobic reaction for 30 minutes, and then generating Ag in situ on the surface and inner holes of the membrane3PO4Granulating to obtain the immobilized Ag3PO4A polyurethane-based film of particles; under the ultrasonic condition, loading Ag to the solid3PO4Dropwise adding 30ml of 4.2mmol/L hexadecyl trimethyl ammonium bromide into the granular polyurethane-based film, and carrying out ultrasonic photophobic reaction for 30 minutes to ensure that the Ag on the upper part of the film3PO4The particles react to form AgBr particles, where n (AgBr): n (Ag)3PO4) = 1: 3, repeatedly washing the film for three times by using absolute ethyl alcohol and deionized water, removing impurities on the surface of the film, freezing the film in a refrigerator for 3 hours, and drying the film in a freeze drying oven for 1.5 hours to obtain the in-situ immobilized AgBr/Ag3PO4A nanoparticle polyurethane-based composite film.
Through the observation of the lower surface and the cross section of the polyurethane-based composite film on an electron microscope, polyhedral silver phosphate and round-like silver bromide particles can be observed on the surface of the film and in the hole structures inside the film, the particle size of the silver phosphate is mainly about 1 mu m, each edge of the polyhedron is clear, each crystal face is smooth, the particle size of the silver bromide particles is mainly about 200-400 nm, and the particle sizes are different. As can be seen from the light absorption property curve of the hybrid material, the in-situ immobilized AgBr/Ag of the invention3PO4The nano-particle polyurethane-based composite film has strong absorption in a visible light range, red shift of an absorption edge occurs, and the forbidden bandwidth is about 1.96 eV. Under visible light conditions, 0.10g of the polyurethane-based composite film of this example degraded 100ml of methyl orange solution (25mg/L), and the degradation rate was 77% in 75 min.
Example 2:
one embodiment of the method for preparing an organic-inorganic blend membrane of the present invention comprises the following steps:
accurately weighing 12g of polyester type thermoplastic polyurethane particles with Shore hardness of 60A and 108g of N, N-dimethylacetamide solution, adding into a beaker, heating and stirring at 45 ℃ by using a magnetic stirrer, and completely dissolving the polyurethane particles in a solvent to obtain a polyurethane polymer solution with the mass fraction of 10%; accurately weighing 0.72g of polyethylene glycol 1000 and dissolving the polyethylene glycol 1000 in 5g of N, N-dimethylformamide solution to obtain a completely dissolved polyethylene glycol solution; adding the completely dissolved polyethylene glycol solution into a polyurethane polymer solution, and stirring for 15 minutes by using a magnetic stirrer to ensure that the polyethylene glycol solution is uniformly dispersed in the polyurethane polymer solution; adding 20.46g of negative oxygen ion powder into the obtained polyurethane polymer solution containing the polyethylene glycol, stirring for 25 minutes by using an electric high-speed stirrer to obtain uniform organic-inorganic mixed solution, and standing for defoaming; coating the obtained organic-inorganic mixed solution on release paper with a certain thickness, quickly immersing the coated release paper in water, taking out the release paper and the film after curing to form a film, repeatedly and alternately cleaning the film for three times by using absolute ethyl alcohol and deionized water, removing residual solvent on the surface of the film, cleaning the film, placing the film in an indoor ventilation drying place, drying the film at room temperature, peeling the film and the release paper after the film on the release paper is completely dried, and cutting the film into the size of 15cm multiplied by 15cm to obtain a substrate material-polyurethane-based film; soaking the polyurethane-based film in 100ml of 15mmol/L silver nitrate solution, and carrying out magnetic stirring and light-proof adsorption for a certain time to enable the silver nitrate to be uniformly adsorbed on the surface of the film and in the internal hole structure; taking disodium hydrogen phosphate as a phosphorus source, dropwise adding 30ml of 16.67mmol/L disodium hydrogen phosphate solution into silver nitrate solution under the ultrasonic condition, carrying out ultrasonic photophobic reaction for 30 minutes, and then generating Ag in situ on the surface and inner holes of the membrane3PO4Granulating to obtain the immobilized Ag3PO4A polyurethane-based film of particles; under the ultrasonic condition, loading Ag to the solid3PO4Dropwise adding 30ml of hexadecyl trimethyl ammonium bromide with the concentration of 6.67mmol/L into the granular polyurethane-based film, and carrying out ultrasonic photophobic reaction for 30 minutes to ensure that the Ag on the upper part of the film3PO4The particles react to form AgBr particles, wherein n（AgBr）：n（Ag3PO4) = 2: 3 repeatedly washing the film for three times by using absolute ethyl alcohol and deionized water, removing impurities on the surface of the film, freezing the film in a refrigerator for 3 hours, and drying the film in a freeze drying box for 1.5 hours to obtain the in-situ immobilized AgBr/Ag3PO4A nanoparticle polyurethane-based composite film.
Through the observation of the lower surface (shown in figure 1) and the cross section appearance (shown in figure 2) of the polyurethane-based composite film on an electron microscope, polyhedral silver phosphate and round-like silver bromide particles can be observed in a hole structure on the surface and inside of the film, the particle size of the silver phosphate is mainly about 1 mu m, each edge of the polyhedron is clear, each crystal face is smooth, the particle size of the silver bromide particles is mainly about 200-400 nm, and the particle sizes are different. As can be seen from the light absorption property curve of the hybrid material, the in-situ immobilized AgBr/Ag of the invention3PO4The nano-particle polyurethane-based composite film has strong absorption in a visible light range, red shift of an absorption edge occurs, and the forbidden bandwidth is about 1.70 eV. Under visible light conditions, 0.10g of the polyurethane-based composite film of this example degraded 100ml of methyl orange solution (25mg/L), and the degradation rate was 98% within 75 min.
The photocatalysis experiment of the hybrid material prepared by the embodiment shows that the in-situ immobilized AgBr/Ag prepared by the method3PO4The nano-particle polyurethane-based composite membrane has a good photocatalytic effect.
Example 3:
one embodiment of the method for preparing an organic-inorganic blend membrane of the present invention comprises the following steps:
accurately weighing 13g of polyester type thermoplastic polyurethane particles with Shore hardness of 65A and 74g of N, N-dimethylacetamide solution, adding into a beaker, heating and stirring by using a magnetic stirrer at 40 ℃ to completely dissolve the polyurethane particles in the solvent to obtain a polyurethane polymer solution with mass fraction of 15%; accurately weighing 0.84g of polyethylene glycol 1000 and dissolving the polyethylene glycol 1000 in 5g of N, N-dimethylformamide solution to obtain a completely dissolved polyethylene glycol solution; adding the completely dissolved polyethylene glycol solution into polyurethaneStirring the molecular solution for 15 minutes by using a magnetic stirrer to ensure that the polyethylene glycol solution is uniformly dispersed in the polyurethane polymer solution; adding 16.38g of negative oxygen ion powder into the obtained polyurethane polymer solution containing the polyethylene glycol, stirring for 20 minutes by using an electric high-speed stirrer to obtain uniform organic-inorganic mixed solution, and standing for defoaming; coating the obtained organic-inorganic mixed solution on release paper with a certain thickness, quickly immersing the coated release paper in water, taking out the release paper and the film after curing to form a film, repeatedly and alternately cleaning the film for three times by using absolute ethyl alcohol and deionized water, removing residual solvent on the surface of the film, cleaning the film, placing the film in an indoor ventilation drying place, drying the film at room temperature, peeling the film and the release paper after the film on the release paper is completely dried, and cutting the film into the size of 15cm multiplied by 15cm to obtain a substrate material-polyurethane-based film; soaking the polyurethane-based film in 100ml of 15mmol/L silver nitrate solution, and carrying out magnetic stirring and light-proof adsorption for a certain time to enable the silver nitrate to be uniformly adsorbed on the surface of the film and in the internal hole structure; taking disodium hydrogen phosphate as a phosphorus source, dropwise adding 30ml of 16.67mmol/L disodium hydrogen phosphate solution into silver nitrate solution under the ultrasonic condition, carrying out ultrasonic photophobic reaction for 30 minutes, and then generating Ag in situ on the surface and inner holes of the membrane3PO4Granulating to obtain the immobilized Ag3PO4A polyurethane-based film of particles; under the ultrasonic condition, loading Ag to the solid3PO4Dropwise adding 30ml of hexadecyl trimethyl ammonium bromide with the concentration of 8.33mmol/L into the granular polyurethane-based film, and carrying out ultrasonic photophobic reaction for 30 minutes to ensure that the Ag on the upper part of the film3PO4The particles react to form AgBr particles, where n (AgBr): n (Ag)3PO4) = 3: 3 repeatedly washing the film for three times by using absolute ethyl alcohol and deionized water, removing impurities on the surface of the film, freezing the film in a refrigerator for 3 hours, and drying the film in a freeze drying box for 1.5 hours to obtain the in-situ immobilized AgBr/Ag3PO4A nanoparticle polyurethane-based composite film.
By observing the surface and cross-sectional appearance of the polyurethane-based composite film under an electron microscope, polyhedral structures can be observed on the surface and in the hole structures of the filmThe silver phosphate particle size is mainly about 1 mu m, each edge of a polyhedron is clear, each crystal face is smooth, the silver bromide particle size is mainly about 200-400 nm, and the particle sizes are different. As can be seen from the light absorption property curve of the hybrid material, the in-situ immobilized AgBr/Ag of the invention3PO4The nano-particle polyurethane-based composite film has strong absorption in a visible light range, red shift of an absorption edge occurs, and the forbidden bandwidth is about 1.71 eV. Under visible light conditions, 0.10g of the polyurethane-based composite film of this example degraded 100ml of methyl orange solution (25mg/L), and the degradation rate was 95% within 75 min.
Example 4:
one embodiment of the method for preparing an organic-inorganic blend membrane of the present invention comprises the following steps:
accurately weighing 14g of polyester type thermoplastic polyurethane particles with Shore hardness of 55A and 64g of N, N-dimethylacetamide solution, adding into a beaker, heating and stirring by using a magnetic stirrer at 35 ℃ to completely dissolve the polyurethane particles in the solvent to obtain 18 mass percent of polyurethane polymer solution; accurately weighing 0.42g of polyethylene glycol 1000 and dissolving the polyethylene glycol 1000 in 5g of N, N-dimethylformamide solution to obtain a completely dissolved polyethylene glycol solution; adding the completely dissolved polyethylene glycol solution into a polyurethane polymer solution, and stirring for 10 minutes by using a magnetic stirrer to ensure that the polyethylene glycol solution is uniformly dispersed in the polyurethane polymer solution; adding 11.38g of negative oxygen ion powder into the obtained polyurethane polymer solution containing the polyethylene glycol, stirring for 20 minutes by using an electric high-speed stirrer to obtain uniform organic-inorganic mixed solution, and standing for defoaming; coating the obtained organic-inorganic mixed solution on release paper with a certain thickness, quickly immersing the coated release paper in water, taking out the release paper and the film after curing to form a film, repeatedly and alternately cleaning with absolute ethyl alcohol and deionized water for three times to remove residual solvent on the surface of the film, cleaning, placing in an indoor ventilation drying place, drying at room temperature, peeling the film from the release paper after the film on the release paper is completely dried, cutting to 15cm multiplied by 15cm to obtain a base materialPolyurethane-based films; soaking the polyurethane-based film in 100ml of 15mmol/L silver nitrate solution, and carrying out magnetic stirring and light-proof adsorption for a certain time to enable the silver nitrate to be uniformly adsorbed on the surface of the film and in the internal hole structure; taking disodium hydrogen phosphate as a phosphorus source, dropwise adding 30ml of 16.67mmol/L disodium hydrogen phosphate solution into silver nitrate solution under the ultrasonic condition, carrying out ultrasonic photophobic reaction for 30 minutes, and then generating Ag in situ on the surface and inner holes of the membrane3PO4Granulating to obtain the immobilized Ag3PO4A polyurethane-based film of particles; under the ultrasonic condition, loading Ag to the solid3PO4Dropwise adding 30ml of 9.52mmol/L hexadecyl trimethyl ammonium bromide into the granular polyurethane-based film, and carrying out ultrasonic photophobic reaction for 30 minutes to ensure that the Ag on the upper part of the film3PO4The particles react to form AgBr particles, where n (AgBr): n (Ag)3PO4) = 4: 3 repeatedly washing the film for three times by using absolute ethyl alcohol and deionized water, removing impurities on the surface of the film, freezing the film in a refrigerator for 3 hours, and drying the film in a freeze drying box for 1.5 hours to obtain the in-situ immobilized AgBr/Ag3PO4A nanoparticle polyurethane-based composite film.
Through the observation of the lower surface and the cross section of the polyurethane-based composite film on an electron microscope, polyhedral silver phosphate and round-like silver bromide particles can be observed on the surface of the film and in the hole structures inside the film, the particle size of the silver phosphate is mainly about 1 mu m, each edge of the polyhedron is clear, each crystal face is smooth, the particle size of the silver bromide particles is mainly about 200-400 nm, and the particle sizes are different. As can be seen from the light absorption property curve of the hybrid material, the in-situ immobilized AgBr/Ag of the invention3PO4The nano-particle polyurethane-based composite film has strong absorption in a visible light range, red shift of an absorption edge occurs, and the forbidden bandwidth is about 1.87 eV. Under visible light conditions, 0.10g of the polyurethane-based composite film of this example degraded 100ml of methyl orange solution (25mg/L), and the degradation rate was 90% within 75 min.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
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