CN112718000B - Organic-inorganic composite photocatalytic film and preparation method and application thereof - Google Patents
Organic-inorganic composite photocatalytic film and preparation method and application thereof Download PDFInfo
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- CN112718000B CN112718000B CN202011552730.4A CN202011552730A CN112718000B CN 112718000 B CN112718000 B CN 112718000B CN 202011552730 A CN202011552730 A CN 202011552730A CN 112718000 B CN112718000 B CN 112718000B
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- 239000002131 composite material Substances 0.000 title claims abstract description 174
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 102
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000243 solution Substances 0.000 claims abstract description 58
- 239000012528 membrane Substances 0.000 claims abstract description 49
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 22
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
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- 238000004108 freeze drying Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
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- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 abstract description 24
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
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- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention relates to the technical field of organic-inorganic hybrid materials, and discloses an organic-inorganic composite photocatalytic membrane and a preparation method and application thereof. The preparation method comprises the following steps: sequentially contacting the mixed solution I containing the poly-3-hexylthiophene with modified conductive carbon black and tungsten trioxide, uniformly coating the obtained coating solution, curing to form a film to obtain a composite film, sequentially contacting the composite film with a silver nitrate solution and a disodium hydrogen phosphate solution, and obtaining the organic-inorganic composite photocatalytic film fixedly loaded with silver/silver phosphate by a photo-reduction method. According to the invention, through the synergistic effect of the poly-3-hexylthiophene, the tungsten trioxide, the silver/silver phosphate and the silane coupling agent modified conductive carbon black, the utilization rate of visible light and the photocatalytic degradation efficiency can be obviously improved, so that the efficient adsorption of pollutants in a water body is realized.
Description
Technical Field
The invention relates to the technical field of organic-inorganic hybrid materials, in particular to an organic-inorganic composite photocatalytic film and a preparation method and application thereof.
Background
With the rapid development of modern industry, the global ecological pollution problem becomes more and more serious. Approximately 700000 to 1000000 tons of dyes are produced annually on average worldwide, of which about 280000 tons are discharged as industrial waste water. The industrial dye wastewater has the characteristics of high organic pollutant content, quick water quality change, deep chromaticity, large water quantity, difficult biodegradation and the like, so the treatment and purification process is also concerned by people.
Among them, the removal of organic dyes from industrial dye wastewater by photocatalytic degradation technology to reduce their influence on the environment has become an important research field.
As a photocatalytic material, a metal oxide semiconductor material has received attention from a large number of researchers because it exhibits excellent properties in the degradation of organic pollutants. Tungsten trioxide, a common metal oxide semiconductor, has the advantages of excellent photochemical stability, appropriate band gap width (2.5-3.5 eV), no toxicity, environmental friendliness and the like, and is widely used.
However, pure tungsten trioxide has the problems of low quantum yield, easy recombination of photo-generated electron-hole pairs and the like, so that the catalytic activity of the pure tungsten trioxide is very low, and the application of the pure tungsten trioxide is greatly limited.
Disclosure of Invention
The invention aims to overcome the defect of low catalytic activity of a tungsten trioxide photocatalytic material in the prior art, and provides an organic-inorganic composite photocatalytic film and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for producing an organic-inorganic composite photocatalytic film, comprising the steps of:
(1) Contacting and mixing the poly-3-hexylthiophene with a solvent to obtain a mixed solution I; the dosage mass ratio of the poly-3-hexylthiophene to the solvent is 1:6-12;
(2) Sequentially contacting the mixed solution I with modified conductive carbon black and tungsten trioxide to obtain a coating solution; the modified conductive carbon black is obtained by coupling reaction of a silane coupling agent and conductive carbon black, and the mass ratio of the silane coupling agent to the conductive carbon black is 1:20-50 parts of;
(3) Coating the film coating liquid on a substrate to obtain the substrate coated with the film coating liquid, and curing the substrate coated with the film coating liquid at an interval of 0-3 minutes to obtain a composite film;
(4) Sequentially contacting the composite membrane with a silver nitrate solution and a disodium hydrogen phosphate solution to obtain an organic-inorganic composite membrane;
(5) And (3) carrying out illumination treatment on the organic-inorganic composite membrane for 10-40min under an ultraviolet lamp to obtain the organic-inorganic composite photocatalytic membrane.
A second aspect of the present invention provides an organic-inorganic composite photocatalytic film produced by the method for producing an organic-inorganic composite photocatalytic film according to the first aspect.
The third aspect of the present invention provides the use of the organic-inorganic composite photocatalytic film according to the second aspect for degrading organic pollutants.
According to the invention, through the synergistic effect of the poly-3-hexylthiophene, the tungsten trioxide and the silane coupling agent modified conductive carbon black, the problems of low yield of tungsten trioxide quantum, easy recombination of electron-hole pairs and the like in the prior art can be effectively overcome, the photocatalytic quantum efficiency is remarkably improved, the spectral response range of a photocatalytic film can be expanded, the utilization rate of visible light is improved, and therefore, the efficient adsorption of pollutants in a water body is realized, and the photocatalytic degradation efficiency is improved.
Drawings
FIG. 1 is a scanning electron microscope image of the surface morphology of the organic-inorganic composite photocatalytic film prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the surface morphology of the organic-inorganic composite photocatalytic film prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of the surface morphology of the organic-inorganic composite photocatalytic film prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of the surface morphology of the organic-inorganic composite photocatalytic film obtained in example 4 of the present invention;
FIG. 5 is a scanning electron microscope image of the surface morphology of the organic-inorganic composite photocatalytic film obtained in example 5 of the present invention;
FIG. 6 is a scanning electron microscope image of the surface morphology of the organic-inorganic composite photocatalytic film obtained in example 6 of the present invention;
fig. 7 is a scanning electron microscope image of the cross-sectional morphology of the organic-inorganic composite photocatalytic film prepared in example 3 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a method for producing an organic-inorganic composite photocatalytic film, comprising the steps of:
(1) Contacting and mixing the poly-3-hexylthiophene with a solvent to obtain a mixed solution I; the dosage mass ratio of the poly-3-hexylthiophene to the solvent is 1:6-12;
(2) Sequentially contacting the mixed solution I with modified conductive carbon black and tungsten trioxide to obtain a coating solution; the modified conductive carbon black is obtained by coupling reaction of a silane coupling agent and conductive carbon black, and the mass ratio of the silane coupling agent to the conductive carbon black is 1:20-50 parts of;
(3) Coating the film coating liquid on a substrate to obtain the substrate coated with the film coating liquid, and curing the substrate coated with the film coating liquid at an interval of 0-3 minutes to obtain a composite film;
(4) Sequentially contacting the composite membrane with a silver nitrate solution and a disodium hydrogen phosphate solution to obtain an organic-inorganic composite membrane;
(5) And (3) carrying out illumination treatment on the organic-inorganic composite membrane for 10-40min under an ultraviolet lamp to obtain the organic-inorganic composite photocatalytic membrane.
Preferably, in the step (1), the solvent is at least one selected from the group consisting of N, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, in the step (1), the mass ratio of the poly-3-hexylthiophene to the solvent is 1:6-8.
Preferably, in step (1), the contact mixing I is carried out under stirring conditions, wherein the stirring speed is 350-500rpm, and the stirring time is 8-10h.
Preferably, in step (1), the reaction temperature of the contact mixing I is 40-60 ℃.
According to a particularly preferred embodiment, the step of contacting the mixed liquid I with the modified conductive carbon black and the tungsten trioxide in this order in step (2) comprises: firstly, the mixed solution I is contacted with the modified conductive carbon black to be mixed, the mixture is stirred for 5-30min, then the obtained product is mixed with the tungsten trioxide, the stirring is carried out for 10-30min, and then the obtained mixed solution II is kept stand for 2-6h.
Preferably, in the step (2), the amount mass ratio of the modified conductive carbon black to the tungsten trioxide is 1:0.75-1.6.
Preferably, in the step (2), the tungsten trioxide is a tungsten trioxide powder having an average particle diameter of 3 to 8 μm.
Preferably, in the step (2), the conductive carbon black is conductive carbon black powder having an average particle diameter of 1 to 3 μm.
Preferably, in the step (2), the silane coupling agent is selected from at least one of KH540, KH550, KH560 and KH 570.
According to a particularly preferred embodiment, in step (2), the silane coupling agent is KH550. Under the optimal condition, the composite membrane obtained by the method has higher photocatalytic degradation efficiency, so that the high-efficiency adsorption of pollutants in the water body is realized.
According to another preferred embodiment, in the step (2), the method for preparing the modified conductive carbon black comprises the following steps: and (2) carrying out contact mixing II on the conductive carbon black and a first part of absolute ethyl alcohol to disperse to obtain a suspension, and then carrying out a first contact reaction on the suspension and a mixed solution of a silane coupling agent and a second part of absolute ethyl alcohol.
Preferably, the mass ratio of the silane coupling agent to the conductive carbon black is 1:30-35, wherein the mass ratio of the conductive carbon black to the first part of absolute ethyl alcohol is 1:2-5, wherein the mass ratio of the silane coupling agent to the second part of absolute ethyl alcohol is 1:0.5-2.
Preferably, the first contact reaction is carried out in the presence of stirring at a speed of 300 to 500rpm for a period of 2 to 5 hours.
Preferably, the temperature of the first contact reaction is 60 to 80 ℃.
According to a particularly preferred embodiment, the suspension is subjected to a thermostatic water bath at 60 to 70 ℃ before the first contact reaction is carried out, so as to obtain a thermostatic suspension.
Preferably, the method further comprises: and washing and vacuum-drying the product obtained by the first contact reaction, wherein the solvent for washing is water, the temperature for vacuum drying is 60-80 ℃, and the time for vacuum drying is 3-6h.
Preferably, in step (3), the substrate is a glass substrate.
Preferably, the amount of the coating solution is such that the thickness of the film on the substrate coated with the coating solution is 80-120 μm.
Preferably, in step (3), the conditions of the curing treatment at least satisfy: the temperature is 15-40 ℃ and the time is 5-8h.
Preferably, after the solidification treatment, the obtained composite membrane is sequentially subjected to cleaning I and freeze drying I, wherein the solvent of the cleaning I is water, the temperature of the freeze drying I is 55 ℃ below zero to 35 ℃ below zero, and the time of the freeze drying I is 1-4h.
Preferably, the preparation method of the organic-inorganic composite photocatalytic film further comprises: and cutting the composite membrane subjected to the freeze drying I treatment.
Preferably, in the step (4), the step of contacting the composite membrane with the silver nitrate solution and the disodium hydrogen phosphate solution in sequence comprises: firstly, carrying out a second contact reaction on the composite membrane and the silver nitrate solution, and then carrying out a third contact reaction on a product obtained by the second contact reaction and the disodium hydrogen phosphate solution; the time of the second contact reaction is 5-12h, and the time of the third contact reaction is 1-3h.
Preferably, the third contact reaction is carried out in the presence of ultrasonic waves, and the frequency of the ultrasonic waves is 30-40KHz.
Preferably, in the step (4), the concentration of the silver nitrate solution is 0.03-0.18mol/L, and the concentration of the disodium hydrogen phosphate solution is 0.01-0.06mol/L.
More preferably, the concentration of the silver nitrate solution is 0.09-0.15mol/L, and the concentration of the disodium hydrogen phosphate solution is 0.03-0.05mol/L. In the preferable condition, the composite photocatalytic film obtained by the invention has better photocatalytic degradation efficiency.
According to a particularly preferred embodiment, the silver nitrate solution is prepared by: at 5-45 ℃, silver nitrate is contacted and mixed with deionized water to dissolve.
According to another preferred embodiment, the disodium hydrogen phosphate solution is prepared by the following method: disodium hydrogen phosphate is mixed with deionized water at 5-45 ℃ to dissolve.
Preferably, the third contact reaction is carried out in the presence of ultrasonic waves, and the frequency of the ultrasonic waves is 30-40KHz.
Preferably, in step (5), the method further comprises: and sequentially cleaning II and freeze-drying II the membrane obtained after the illumination treatment to obtain the organic-inorganic composite photocatalytic membrane, wherein the solvent for cleaning II is water, the temperature for freeze-drying II is 55 ℃ below zero to 35 ℃ below zero, and the time for freeze-drying II is 1-4h.
Preferably, the conditions of the light treatment of the present invention at least satisfy: the power is 10-30W, and the wavelength is 350-380nm.
As described above, the second aspect of the present invention provides an organic-inorganic composite photocatalytic film produced by the method for producing an organic-inorganic composite photocatalytic film according to the first aspect.
As described above, the third aspect of the present invention provides the use of the organic-inorganic composite photocatalytic film according to the foregoing second aspect for degrading organic pollutants.
In the present invention, "I" and "II" in washing I, washing II, and the like are used only to indicate that washing is performed twice, not the same washing, but this does not represent the order unless otherwise specified. In addition, the same matters as referred to in the characteristics of freeze-drying and the like have explanations similar thereto.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available unless otherwise specified.
Poly 3-hexylthiophene: the trade mark is H110541, purchased from Aladdin Biotechnology, inc.;
solvent: n, N-dimethylformamide, available from guangdong photowa science and technology ltd;
solvent: n, N-Dimethylacetamide, available from Guangdong Guanghua technologies, inc.;
conductive carbon black powder-1: purchased from Tianjin Yibo Rui chemical industry, with an average particle size of 3 μm;
conductive carbon black powder-2: purchased from Tianjin Yibo Rui chemical industry, with an average particle size of 1 μm;
silane coupling agent KH550: purchased from san Jose plastics chemical Co., ltd, foshan;
silane coupling agent KH560: purchased from san John's plastics chemical Co., ltd;
silane coupling agent KH570: purchased from san John's plastics chemical Co., ltd;
tungsten trioxide powder-1: purchased from national chemical group, chemical agents, ltd, and having an average particle size of 8 μm;
tungsten trioxide powder-2: purchased from national chemical group, chemical agents, ltd, and having an average particle size of 5 μm;
silver nitrate: purchased from tianjinke mimiou chemical reagents ltd;
disodium hydrogen phosphate: purchased from the national pharmaceutical group chemical agents limited.
In the following examples, the coating solution was used in such an amount that the thickness of the film on the glass substrate coated with the coating solution was 100 μm, unless otherwise specified.
The UV lamp was purchased from the Homepyr Lighting company with a power of 30W and a wavelength of 365nm.
Staphylococcus aureus was purchased from Ningbo Ming boat Biotechnology Inc. under the designation B66106.
Coli was purchased from Ningbo Ming boat Biotech, inc. under the designation B81158.
Biochemical incubator, LRH-250-A, purchased from medical instruments, inc. of Guangdong province.
Xenon lamp, PLS-SXE300, available from Peking Pofely technologies, inc.
Beef extract, 01-009-1, was purchased from Macbog biotech, inc., beijing.
Peptone, 01-001, available from MacoBoxing Biotechnology, inc., beijing.
Agar powder, 01-023, was purchased from Aobo Star Biotech, inc. of Beijing.
Sodium chloride, GR (Shanghai test) is not less than 99.8%, and is purchased from chemical reagents of national drug group, inc.
Modified conductive carbon black powder-1: under an ultrasonic environment, 13g of conductive carbon black powder-1 and 52g of first part of absolute ethyl alcohol are contacted and mixed II to disperse, ultrasonic treatment (ultrasonic frequency is 30 KHz) is carried out for 1 hour to obtain suspension, then the suspension is placed in a constant-temperature water bath kettle, the water bath temperature is kept at 70 ℃ to obtain constant-temperature suspension, then 0.40g of silane coupling agent KH570 and 0.40g of second part of absolute ethyl alcohol are mixed, the obtained mixed solution is dropwise added into the constant-temperature suspension at the speed of 1 drop/second to carry out first contact reaction, the mixture is stirred in the constant-temperature water bath for 3 hours at the stirring speed of 350rpm and the temperature of 70 ℃ and then is filtered, then the mixture is washed by deionized water, and the mixture is dried in vacuum for 5 hours at the temperature of 60 ℃ to obtain the modified conductive carbon black powder-1.
Modified conductive carbon black powder-2: similar to the preparation process of the modified conductive carbon black powder-1, except that: carrying out contact mixing II on 14g of conductive carbon black powder-1 and 54g of first part of absolute ethyl alcohol to disperse; mixing 0.45g of the silane coupling agent KH560 with 0.45g of a second portion of anhydrous ethanol; vacuum drying at 80 deg.c for 4 hr to obtain modified conductive carbon black powder-2.
Modified conductive carbon black powder-3: similar to the preparation process of the modified conductive carbon black powder-1, except that: 12g of conductive carbon black powder-2 and 48g of first part of absolute ethyl alcohol are contacted and mixed II to be dispersed; mixing 0.35g of silane coupling agent KH550 with 0.35g of a second portion of anhydrous ethanol; vacuum drying is carried out at the temperature of 80 ℃ to obtain the modified conductive carbon black powder-3.
Example 1
This example is intended to illustrate a method for producing an organic-inorganic composite photocatalytic film according to the present invention.
The preparation method of the organic-inorganic composite photocatalytic film comprises the following steps:
(1) Adding 8g of poly-3-hexylthiophene into 55g of N, N-dimethylacetamide solution at 60 ℃, and completely dissolving under magnetic stirring at the stirring speed of 450rpm for 9 hours to obtain a mixed solution I;
(2) Adding 8g of modified conductive carbon black powder-1 into the mixed solution I, stirring for 15min by using an electric high-speed stirrer (the rotating speed is 650 rpm), adding 6g of tungsten trioxide powder-1, continuing stirring for 30min, and standing and defoaming the obtained mixed solution II for 4h to obtain a coating solution;
(3) Coating the film coating liquid on a glass substrate to obtain the glass substrate coated with the film coating liquid, horizontally immersing the glass substrate coated with the film coating liquid into an aqueous solution immediately, curing at the temperature of 20 ℃ for 8 hours, taking out after the film coating liquid on the glass substrate is completely cured, washing the taken-out film with deionized water for three times, then placing the film in a freeze dryer at the temperature of-35 ℃ for drying for 3 hours, and cutting the film into the size of 8cm multiplied by 8cm to obtain a composite film;
(4) Placing the composite membrane in 100mL of silver nitrate solution with the concentration of 0.12mol/L for light-proof adsorption for 10 hours, then dropwise adding 100mL of disodium hydrogen phosphate solution with the concentration of 0.04mol/L into the obtained composite membrane for adsorbing silver nitrate at the speed of 1 drop/s under the condition of ultrasonic wave (the ultrasonic frequency is 35 KHz) in the light-proof condition, reacting for 1 hour (timing from the beginning of dropwise adding the disodium hydrogen phosphate solution), and obtaining the organic-inorganic composite membrane;
(5) And (3) placing the organic-inorganic composite membrane under an ultraviolet lamp, irradiating the front side and the back side of the organic-inorganic composite membrane for 20min respectively, washing the irradiated organic-inorganic composite membrane with deionized water for three times, and then placing the organic-inorganic composite membrane in a freeze dryer at the temperature of-55 ℃ for drying for 3h to obtain the organic-inorganic composite photocatalytic membrane.
As shown in fig. 1, by observing the surface morphology of the organic-inorganic composite photocatalytic film prepared in this example under an electron microscope, it is found that the conductive carbon black and tungsten trioxide are agglomerated on the organic-inorganic composite photocatalytic film, the continuity of the organic-inorganic composite photocatalytic film is enhanced, silver/silver phosphate particles firmly grow in situ on the surface and the internal pore structure of the organic-inorganic composite photocatalytic film, the particle size is increased, the agglomeration phenomenon occurs, and the silver/silver phosphate/tungsten trioxide jointly construct a Z-type heterostructure on the surface of the organic-inorganic composite photocatalytic film.
Example 2
This example is intended to illustrate a method for producing an organic-inorganic composite photocatalytic film according to the present invention.
The preparation method of the organic-inorganic composite photocatalytic film comprises the following steps:
(1) Adding 8g of poly-3-hexylthiophene into 60g of N, N-dimethylacetamide solution at 60 ℃, and completely dissolving under magnetic stirring at the stirring speed of 500rpm for 8 hours to obtain a mixed solution I;
(2) Adding 9g of modified conductive carbon black powder-2 into the mixed solution I, stirring for 15min by using an electric high-speed stirrer (the rotating speed is 650 rpm), adding 8g of tungsten trioxide powder-2, continuing to stir for 30min, and then standing and defoaming the obtained mixed solution II for 4h to obtain a coating solution;
(3) Coating the film coating liquid on a glass substrate to obtain the glass substrate coated with the film coating liquid, immediately horizontally immersing the glass substrate coated with the film coating liquid in an aqueous solution, curing at the temperature of 30 ℃ for 7 hours, taking out after the film coating liquid on the glass substrate is completely cured, washing the taken-out film with deionized water for three times, then placing the film in a freeze dryer at the temperature of-40 ℃ for drying for 3 hours, and cutting the film into the size of 8cm multiplied by 8cm to obtain a composite film;
(4) Placing the composite membrane in 100mL of silver nitrate solution with the concentration of 0.15mol/L for light-proof adsorption for 7 hours, then dropwise adding 100mL of disodium hydrogen phosphate solution with the concentration of 0.05mol/L into the obtained composite membrane for adsorbing the silver nitrate at the speed of 1 drop/s under the condition of ultrasonic waves (the ultrasonic frequency is 30 KHz) for light-proof, and reacting for 1 hour (starting to time from the beginning of dropwise adding the disodium hydrogen phosphate solution) to obtain an organic-inorganic composite membrane;
(5) And (3) placing the organic-inorganic composite membrane under an ultraviolet lamp, irradiating the front side and the back side of the organic-inorganic composite membrane for 18min respectively, washing the irradiated organic-inorganic composite membrane with deionized water for three times, and then placing the organic-inorganic composite membrane in a freeze dryer at the temperature of-40 ℃ for drying for 3h to obtain the organic-inorganic composite photocatalytic membrane.
As shown in fig. 2, by observing the surface morphology of the organic-inorganic composite photocatalytic film prepared in this embodiment under an electron microscope, it is found that the conductive carbon black and tungsten trioxide are agglomerated on the organic-inorganic composite photocatalytic film, silver/silver phosphate particles are firmly grown in situ on the surface and the internal pore structure of the organic-inorganic composite photocatalytic film, the particle size is increased, the agglomeration occurs, and silver/silver phosphate/tungsten trioxide jointly construct a Z-type heterostructure on the surface of the organic-inorganic composite photocatalytic film.
Example 3
This example is intended to illustrate a method for producing an organic-inorganic composite photocatalytic film according to the present invention.
The preparation method of the organic-inorganic composite photocatalytic film comprises the following steps:
(1) Adding 7g of poly-3-hexylthiophene into 50g of N, N-dimethylformamide solution at 50 ℃, and completely dissolving under magnetic stirring at the stirring speed of 400rpm for 10 hours to obtain a mixed solution I;
(2) Adding 5g of modified conductive carbon black powder-3 into the mixed solution I, stirring for 15min by using an electric high-speed stirrer (the rotating speed is 600 rpm), adding 8g of tungsten trioxide powder-2, continuing stirring for 30min, and standing and defoaming the obtained mixed solution II for 4h to obtain a coating solution;
(3) Coating the film coating liquid on a glass substrate to obtain the glass substrate coated with the film coating liquid, horizontally immersing the glass substrate coated with the film coating liquid into an aqueous solution immediately, curing at 35 ℃ for 5 hours, taking out after the film coating liquid on the glass substrate is completely cured, washing the taken-out film with deionized water for three times, then placing the film in a freeze dryer at-55 ℃ for drying for 3 hours, and cutting the film into the size of 8cm multiplied by 8cm to obtain a composite film;
(4) Placing the composite membrane in 100mL of silver nitrate solution with the concentration of 0.09mol/L for dark adsorption for 8 hours, then dropwise adding 100mL of disodium hydrogen phosphate solution with the concentration of 0.03mol/L at the speed of 1 drop/s into the obtained composite membrane for adsorbing the silver nitrate under the condition of ultrasonic waves (the ultrasonic frequency is 40 KHz) for dark adsorption, and reacting for 1 hour (starting to time from the beginning of dropwise adding the disodium hydrogen phosphate solution) to obtain an organic-inorganic composite membrane;
(5) And placing the organic-inorganic composite membrane under an ultraviolet lamp, irradiating the front side and the back side of the organic-inorganic composite membrane for 20min respectively, washing the irradiated organic-inorganic composite membrane with deionized water for three times, and then placing the organic-inorganic composite membrane in a freeze dryer at the temperature of-35 ℃ for drying for 3h to obtain the organic-inorganic composite photocatalytic membrane.
As shown in fig. 3, it was found that the conductive carbon black and the tungsten trioxide are uniformly distributed on the organic-inorganic composite photocatalytic film, the continuity of the organic-inorganic composite photocatalytic film is enhanced, the silver/silver phosphate particles firmly grow in situ on the surface and in the internal pore structure of the organic-inorganic composite photocatalytic film, the silver/silver phosphate/tungsten trioxide are uniformly dispersed, no obvious agglomeration phenomenon occurs, and the silver/silver phosphate/tungsten trioxide jointly construct a Z-type heterostructure on the surface of the organic-inorganic composite photocatalytic film.
Example 4
This example is provided to illustrate the preparation method of the organic-inorganic composite photocatalytic film provided by the present invention.
This example prepared an organic-inorganic composite photocatalytic film in a similar manner to example 3, except that: in the step (4), the concentration of the disodium hydrogen phosphate is 0.06mol/L.
As shown in fig. 4, by observing the surface morphology of the organic-inorganic composite photocatalytic film prepared in this example under an electron microscope, it is found that the conductive carbon black and the tungsten trioxide are uniformly distributed on the organic-inorganic composite photocatalytic film, the silver/silver phosphate particles firmly grow in situ on the surface of the organic-inorganic composite photocatalytic film and in the internal pore structure, the dispersion is uniform, a very small amount of agglomeration occurs, and the silver/silver phosphate/tungsten trioxide jointly construct a Z-type heterostructure on the surface of the organic-inorganic composite photocatalytic film.
Example 5
This example is intended to illustrate a method for producing an organic-inorganic composite photocatalytic film according to the present invention.
This example prepared an organic-inorganic composite photocatalytic film in a similar manner to example 3, except that: in the step (4), the concentration of the silver nitrate solution is 0.18mol/L.
As shown in fig. 5, by observing the surface morphology of the organic-inorganic composite photocatalytic film prepared in this embodiment under an electron microscope, it is found that the conductive carbon black and the tungsten trioxide are uniformly distributed on the organic-inorganic composite photocatalytic film, the silver/silver phosphate particles firmly grow in situ on the surface and in the internal pore structure of the organic-inorganic composite photocatalytic film, the silver/silver phosphate/tungsten trioxide are uniformly dispersed, and a small amount of aggregation phenomenon occurs, and the silver/silver phosphate/tungsten trioxide jointly construct a Z-type heterostructure on the surface of the organic-inorganic composite photocatalytic film.
Example 6
This example is intended to illustrate a method for producing an organic-inorganic composite photocatalytic film according to the present invention.
This example prepared an organic-inorganic composite photocatalytic film in a similar manner to example 3, except that: in the step (2), the amount of the modified conductive carbon black powder-3 is 6g, and the amount of the tungsten trioxide powder-2 is 12g.
As shown in fig. 6, by observing the surface and cross-sectional morphology of the organic-inorganic composite photocatalytic film prepared in this example under an electron microscope, it is found that the conductive carbon black and tungsten trioxide slightly agglomerate on the organic-inorganic composite photocatalytic film, silver/silver phosphate particles firmly grow in situ on the surface and internal pore structure of the organic-inorganic composite photocatalytic film, the particle size increases, no significant agglomeration occurs, and silver/silver phosphate/tungsten trioxide jointly construct a Z-type heterostructure on the surface of the organic-inorganic composite photocatalytic film.
Example 7
This example is intended to illustrate a method for producing an organic-inorganic composite photocatalytic film according to the present invention.
This example prepared an organic-inorganic composite photocatalytic film in a similar manner to example 3, except that: the model of the silane coupling agent is KH151.
Compared with the organic-inorganic composite photocatalytic film prepared in example 3, the organic-inorganic composite photocatalytic film obtained in this example has the advantages that a large number of pore structures exist on the surface of the organic-inorganic composite photocatalytic film, the cross section of the organic-inorganic composite photocatalytic film has an asymmetric pore structure, the aggregation ratio of the conductive carbon black and the tungsten trioxide on the organic-inorganic composite photocatalytic film is larger, the continuity of the organic-inorganic composite photocatalytic film is weakened, silver/silver phosphate particles firmly grow in situ on the surface of the organic-inorganic composite photocatalytic film and in the internal pore structures, the silver/silver phosphate particles are uniformly dispersed, no obvious aggregation phenomenon occurs, and the silver/silver phosphate/tungsten trioxide jointly construct a Z-type heterostructure on the surface of the organic-inorganic composite photocatalytic film.
Example 8
This example is intended to illustrate a method for producing an organic-inorganic composite photocatalytic film according to the present invention.
This example prepared an organic-inorganic composite photocatalytic film in a similar manner to example 3, except that: in the step (2), the amount of the silane coupling agent KH550 was 0.35g, and the amount of the conductive carbon black powder-2 was 7g.
Compared with the organic-inorganic composite photocatalytic film prepared in example 3, the organic-inorganic composite photocatalytic film obtained in this example has the advantages that a large number of pore structures exist on the surface of the organic-inorganic composite photocatalytic film, the cross section of the organic-inorganic composite photocatalytic film has an asymmetric pore structure, more aggregates of conductive carbon black and tungsten trioxide appear on the organic-inorganic composite photocatalytic film, silver/silver phosphate particles firmly grow in situ on the surface of the organic-inorganic composite photocatalytic film and in the internal pore structures, the silver/silver phosphate/tungsten trioxide are uniformly dispersed, and no obvious aggregation phenomenon occurs, so that a Z-type heterostructure is jointly constructed on the surface of the organic-inorganic composite photocatalytic film by silver/silver phosphate/tungsten trioxide.
Comparative example 1
In the comparative example, tungsten trioxide powder-2 is directly used as a photocatalytic material for comparison with the organic-inorganic composite photocatalytic film prepared by the method provided by the invention.
Test example 1
The cross-sectional morphology of the organic-inorganic composite photocatalytic film prepared in example 3 was observed under an electron microscope, and the observation result is shown in fig. 7.
As shown in fig. 7, by observing the cross-sectional morphology of the organic-inorganic composite photocatalytic film prepared in this embodiment under an electron microscope, it is found that a large number of pore structures exist on the surface of the organic-inorganic composite photocatalytic film, and the cross section of the organic-inorganic composite photocatalytic film has an asymmetric pore structure.
Test example 2
In this test example, staphylococcus aureus (gram-positive bacteria) and escherichia coli (gram-negative bacteria) were typically used as representatives, and the antibacterial activities of the organic-inorganic composite photocatalytic film prepared according to the present invention and the photocatalytic material of the comparative example were evaluated by a disk diffusion method.
All glassware and medium solutions were sterilized in a vertical automated electric pressure steam autoclave at 120 ℃ for 21 minutes prior to testing. The entire testing process was performed under sterile conditions.
A beef extract peptone medium (formulation: 3g beef extract, 10g peptone, 5g sodium chloride, 15g agar powder and 1000ml deionized water) was prepared in advance.
The specific method comprises the following steps:
(1) Pouring 30ml of beef extract peptone culture medium into a culture dish, and standing to solidify;
(2) Respectively and uniformly inoculating 1mL of staphylococcus aureus culture solution and 1mL of escherichia coli culture solution on two different culture media through an inoculating loop;
(3) Respectively cutting the organic-inorganic composite photocatalytic membrane subjected to sterile treatment into circular sheets with the diameter of 10mm, and slightly pressing the circular sheets by using sterile forceps to enable the circular sheets to be adhered to a culture medium;
(4) The culture dish is placed in a biochemical incubator and cultured for 24 hours at 37 ℃, the antibacterial performance of the organic-inorganic composite photocatalytic membrane is evaluated according to the diameter of the inhibition ring, 5 groups of parallel experiments are carried out, and the specific results are shown in table 1.
TABLE 1
| Diameter/mm of inhibition ring of staphylococcus aureus | Inhibition circle diameter/mm of Escherichia coli | |
| Example 1 | 11.52 | 12.64 |
| Example 2 | 11.90 | 13.16 |
| Example 3 | 11.24 | 12.10 |
| Example 4 | 11.35 | 12.27 |
| Example 5 | 11.38 | 12.32 |
| Example 6 | 11.12 | 12.24 |
| Example 7 | 11.07 | 12.17 |
| Example 8 | 11.21 | 12.12 |
| Comparative example 1 | 10.41 | 10.92 |
The results in table 1 show that the organic-inorganic composite photocatalytic film prepared by the embodiment of the present invention has an obvious inhibition zone around the film, which indicates that the organic-inorganic composite photocatalytic film prepared by the present invention has good antibacterial activity against staphylococcus aureus (gram-positive bacteria) and escherichia coli (gram-negative bacteria).
Test example 3
The photocatalytic materials of the examples and the comparative examples were subjected to degradation rate detection, and the photocatalytic activity of the organic-inorganic composite photocatalytic film was evaluated by photocatalytic degradation of rhodamine B solution under irradiation of a 300w xenon lamp (λ >420 nm).
Before the examination, the organic-inorganic composite photocatalytic film obtained in example and the photocatalytic material of comparative example were cut into a size of 4cm × 4 cm.
The specific detection method comprises the following steps: under the condition of visible light, respectively immersing the cut organic-inorganic composite photocatalytic film and the photocatalytic material into rhodamine B solution (50ml, 10mg/L), wherein the distance between a xenon lamp light source and the organic-inorganic composite photocatalytic film is 15cm, testing the degradation rate of the organic-inorganic composite photocatalytic film and the photocatalytic material within 60min, wherein the calculation formula of the degradation rate is as follows: [ (initial concentration-concentration after degradation)/initial concentration ] × 100%, wherein the units of the initial concentration and the concentration after degradation are both mg/L, the specific test results are shown in Table 2.
TABLE 2
| Degradation Rate/% within 60min | |
| Example 1 | 88.02 |
| Example 2 | 98.24 |
| Example 3 | 83.13 |
| Example 4 | 88.31 |
| Example 5 | 90.19 |
| Example 6 | 85.35 |
| Example 7 | 89.62 |
| Example 8 | 85.48 |
| Comparative example 1 | 71.32 |
The results in table 2 show that the problems of low quantum yield of tungsten trioxide, easy recombination of electron-hole pairs and the like can be solved by the compounding synergy of the poly-3-hexylthiophene, the modified conductive carbon black, the silver phosphate and the tungsten trioxide, so that the photocatalytic degradation rate of the photocatalytic film is remarkably improved.
Compared with the comparative examples, the organic-inorganic composite photocatalytic film obtained by adopting the poly-3-hexylthiophene with a specific ratio as the main film forming raw material, modifying the conductive carbon black through the preferable silane coupling agent, combining the tungsten trioxide, the silver phosphate and the optimized process steps and process parameters has better photocatalytic degradation rate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (24)
1. A preparation method of an organic-inorganic composite photocatalytic film for degrading organic pollutants is characterized by comprising the following steps:
(1) The poly-3-hexylthiophene is contacted with a solvent to be mixed with the solvent I to be dissolved, so that a mixed solution I is obtained; the mass ratio of the poly-3-hexylthiophene to the solvent is 1:6-12;
(2) Sequentially contacting the mixed solution I with modified conductive carbon black and tungsten trioxide to obtain a coating solution; the modified conductive carbon black is obtained by coupling reaction of a silane coupling agent and conductive carbon black, and the mass ratio of the silane coupling agent to the conductive carbon black is 1:20-50 parts of; the conductive carbon black is conductive carbon black powder with the average particle size of 1-3 mu m;
(3) Coating the coating liquid on a substrate to obtain the substrate coated with the coating liquid, and curing the substrate coated with the coating liquid at intervals of 0-3 minutes to obtain a composite film;
(4) Sequentially contacting the composite membrane with a silver nitrate solution and a disodium hydrogen phosphate solution to obtain an organic-inorganic composite membrane;
(5) And (3) carrying out illumination treatment on the organic-inorganic composite membrane for 10-40min under an ultraviolet lamp to obtain the organic-inorganic composite photocatalytic membrane.
2. The method for producing an organic-inorganic composite photocatalytic film according to claim 1, wherein in step (1), the solvent is at least one selected from the group consisting of N, N-dimethylformamide and N, N-dimethylacetamide.
3. The method for producing an organic-inorganic composite photocatalytic film according to claim 1, wherein in step (1), the amount by mass ratio of the poly-3-hexylthiophene to the solvent is 1:6-8.
4. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (1), the contact mixing I is carried out under stirring conditions, wherein the stirring speed is 350 to 500rpm, and the stirring time is 8 to 10 hours.
5. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (1), the reaction temperature of the contact mixing I is 40 to 60 ℃.
6. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in the step (2), the step of bringing the mixed solution I into contact with the modified conductive carbon black and the tungsten trioxide in this order comprises: firstly, the mixed solution I is contacted with the modified conductive carbon black to be mixed, the mixture is stirred for 5-30min, then the obtained product is mixed with the tungsten trioxide, the stirring is carried out for 10-30min, and then the obtained mixed solution II is kept stand for 2-6h.
7. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (2), the amount by mass ratio of the modified conductive carbon black and the tungsten trioxide is 1:0.75-1.6.
8. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (2), the tungsten trioxide is a tungsten trioxide powder having an average particle diameter of 3 to 8 μm.
9. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (2), the silane coupling agent is at least one selected from the group consisting of KH540, KH550, KH560, and KH 570.
10. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein, in step (2), the silane coupling agent is KH550.
11. The method for producing an organic-inorganic composite photocatalytic film according to claim 1, wherein in step (2), the method for producing the modified conductive carbon black comprises the steps of: and (2) carrying out contact mixing II on the conductive carbon black and a first part of absolute ethyl alcohol to disperse to obtain a suspension, and then carrying out a first contact reaction on the suspension and a mixed solution of a silane coupling agent and a second part of absolute ethyl alcohol.
12. The method for producing an organic-inorganic composite photocatalytic film according to claim 11, wherein the silane coupling agent and the conductive carbon black are used in a mass ratio of 1:30-35, wherein the mass ratio of the conductive carbon black to the first part of absolute ethyl alcohol is 1:2-5, wherein the mass ratio of the silane coupling agent to the second part of absolute ethyl alcohol is 1:0.5-2.
13. The method for producing an organic-inorganic composite photocatalytic film according to claim 11 or 12, wherein the first contact reaction is carried out in the presence of stirring at a speed of 300 to 500rpm for 2 to 5 hours.
14. The method for producing an organic-inorganic composite photocatalytic film according to claim 11 or 12, wherein the temperature of the first contact reaction is 60 to 80 ℃.
15. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (3), the substrate is a glass substrate.
16. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein the amount of the coating solution is such that the thickness of the film on the substrate coated with the coating solution is 80 to 120 μm.
17. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (3), the conditions of the curing treatment at least satisfy: the temperature is 15-40 ℃, and the time is 5-8h.
18. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein after the curing treatment, the composite film obtained is sequentially subjected to a cleaning I and a freeze-drying I, wherein the solvent of the cleaning I is water, the temperature of the freeze-drying I is from-55 ℃ to-35 ℃, and the time of the freeze-drying I is 1 to 4 hours.
19. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in the step (4), the step of sequentially contacting the composite film with a silver nitrate solution and a disodium hydrogen phosphate solution comprises: firstly, carrying out a second contact reaction on the composite membrane and the silver nitrate solution, and then carrying out a third contact reaction on a product obtained by the second contact reaction and the disodium hydrogen phosphate solution; the time of the second contact reaction is 5-12h, and the time of the third contact reaction is 1-3h.
20. The method for producing an organic-inorganic composite photocatalytic film according to claim 19, wherein the third contact reaction is performed in the presence of ultrasonic waves having a frequency of 30 to 40KHz.
21. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein the concentration of the silver nitrate solution is 0.03 to 0.18mol/L, and the concentration of the disodium hydrogen phosphate solution is 0.01 to 0.06mol/L.
22. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein the silver nitrate solution has a concentration of 0.09 to 0.15mol/L and the disodium hydrogen phosphate solution has a concentration of 0.03 to 0.05mol/L.
23. The method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 3, wherein in step (5), the method further comprises: and sequentially cleaning II and freeze-drying II the membrane obtained after the illumination treatment to obtain the organic-inorganic composite photocatalytic membrane, wherein the solvent for cleaning II is water, the temperature for freeze-drying II is 55 ℃ below zero to 35 ℃ below zero, and the time for freeze-drying II is 1-4h.
24. An organic-inorganic composite photocatalytic film produced by the method for producing an organic-inorganic composite photocatalytic film according to any one of claims 1 to 23.
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