CN113262785B - Photocatalytic film and preparation method and application thereof - Google Patents
Photocatalytic film and preparation method and application thereof Download PDFInfo
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- CN113262785B CN113262785B CN202110504557.9A CN202110504557A CN113262785B CN 113262785 B CN113262785 B CN 113262785B CN 202110504557 A CN202110504557 A CN 202110504557A CN 113262785 B CN113262785 B CN 113262785B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 27
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- 239000004332 silver Substances 0.000 claims abstract description 16
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 2
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
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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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
-
- 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
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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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Abstract
The invention belongs to the field of photocatalysis, and particularly relates to a photocatalysis film for improving self-cleaning and sterilizing properties of polyvinyl chloride and antifouling properties of various metal surfaces and taking epoxy resin as a transition layer, and a preparation method and application thereof. The bismuth oxide heterojunction photocatalytic film loaded with metallic silver is prepared on the surface of polyvinyl chloride or the surface of epoxy resin by a hydrothermal synthesis in-situ growth method and a soaking reduction method. Under the irradiation of visible light, the film generates free radicals such as superoxide, electrons, holes and the like to kill organic pollutants and microorganisms attached to the surface of the film, so that the self-cleaning and antibacterial properties of the polyvinyl chloride surface and the metal antifouling property with epoxy resin as a transition layer are respectively improved. The invention has simple process, easy control and low cost. For polyvinyl chloride, the preparation method of the polyvinyl chloride surface sterilization film is widened. In addition, the sterilizing performance of the polyvinyl chloride is ensured, and meanwhile, the self-cleaning efficiency is endowed.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a photocatalysis film for improving self-cleaning and sterilizing properties of polyvinyl chloride and antifouling properties of various metal surfaces and taking epoxy resin as a transition layer, and a preparation method and application thereof.
Background
The polyvinyl chloride material with strong sterilization performance by directly grafting quaternary ammonium salt base and indirectly embedding nano particles, antibacterial polymer and graphene-based material is applied to life due to excellent mechanical property, low cost and universality, and the films have a certain inhibition effect on microorganisms. However, the antimicrobial surface is not able to degrade organic contaminants and prevent dust from adhering due to its inherently low surface energy, and the increase and accumulation of contaminants can result in a decrease or loss of the antimicrobial properties of the antimicrobial surface. Similarly, dead bacteria attached to the antimicrobial surface can cause similar side effects. Therefore, an ideal antimicrobial polyvinyl chloride surface should have antimicrobial and self-cleaning properties. When the metal material is used in an environment such as the sea, the metal material is contaminated by microorganisms. The preparation of a layer of film on the surface of polyvinyl chloride and the surface of metal by a reasonable means has important significance for solving the problems.
In the past decades, photocatalysis has been widely used as a simple, green, non-specific means of air purification and antisepsis. At present, one kind of method for preparing a photocatalytic film on the surfaces of polyvinyl chloride and metal is to polymerize a photocatalyst into another polymer, and then prepare the photocatalyst on the surfaces of polyvinyl chloride and metal substrates by spraying, depositing or photocuring. However, this film preparation method has two drawbacks, on one hand, the embedding of the photocatalyst in the polymer affects the cross-linking of the polymer, thereby reducing the mechanical strength of the polymer composite; on the other hand, under light irradiation, the strong oxidative radicals generated by the embedded photocatalyst may cause photocatalytic degradation of the polymer. Therefore, the direct preparation of the photocatalytic material on the surfaces of polyvinyl chloride and metal substrates has important significance. The other method is to directly prepare the photocatalytic film on the surface of polyvinyl chloride and the surface of metal, and the adopted methods comprise chemical vapor deposition, physical vapor deposition, magnetron sputtering and the like, but a hydrothermal in-situ growth method with better grain size and shape controllability is not used. In addition, for the metal matrix, most of the current hydrothermal in-situ growth requires that the matrix and the photocatalytic film have the same elements, so that the use of the epoxy resin with excellent adhesive strength with the metal matrix as a transition layer has important significance.
Semiconductor Bi2O3Has many typical characteristics such as simple preparation, excellent photoconductivity and the like. And Bi2O3There are many crystalline phase structures including monoclinic alpha, tetragonal beta, body-centered cubic gamma and non-stoichiometric structures such as Bi2O2.7，Bi2O2.33And Bi2O2-xEtc., a heterostructure having a uniform interface can be formed under hydrothermal environment. In addition, Bi2O3Flower-like, true flowers formed in hydrothermal environmentsThe possibility of absorbing visible light can be enhanced by various morphological structures such as fungiform structures. And for the BiOI semiconductor, has excellent visible light absorption properties, BiOI and Bi2O3The two composite heterojunction structures can adjust the visible light absorption performance when adjusting the photon-generated carrier recombination efficiency, thereby having better performance. It is currently known that silver particles deposited on the surface of semiconductor nanocomposites can facilitate charge separation and that they can release silver ions to destroy cell membrane proteins of microorganisms as bio-antifouling materials. The silver modified heterojunction material can only be prepared into powder for use at present, and is prepared into a film on the surface of polyvinyl chloride or metal for the first time. The use of a film firstly reduces dust pollution from the powder and secondly facilitates recycling and further use. Therefore, the nano-silver particle modified photocatalytic film has a plurality of potential application prospects; however, there is a certain challenge to prepare a single pure photocatalytic semiconductor material on the surface of the above-mentioned substrate.
Disclosure of Invention
The invention aims to provide a preparation method of a photocatalytic film for improving self-cleaning and sterilization performance of polyvinyl chloride and improving antifouling performance of various metal surfaces by taking epoxy resin as a transition layer.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing the photocatalytic film containing Bi on the surface of substrate by in-situ growing method2O3Soaking the composite photocatalytic film with different crystal phase heterostructure into silver-containing solution for reaction; obtaining Bi-containing silver modified2O3Composite photocatalytic films with different crystal phase heterostructures.
Soaking a substrate into the precursor solution, and growing Bi-containing on the surface of the substrate in situ homogeneous reaction by a hydrothermal method2O3Composite photocatalytic films with different crystal phase heterostructures; wherein the precursor solution is prepared by mixing solution A and solution B at a volume ratio of 7:1, and solution A is prepared by mixing Bi (NO)3)3·5H2Sequentially adding O and PVP into an ethylene glycol solution; the solution B is prepared by dissolving potassium iodideIn deionized water.
0.1-0.3 g of PVP and 0.05-0.3M Bi (NO) in 70 ml of ethylene glycol in the solution A3)3·5H2O; and (3) adding 0.05-0.2M KI into 10 ml of deionized water in the solution B.
The in-situ homogeneous reaction temperature of all the matrixes is controlled to be 120-160 ℃, and the reaction time is 1-4 h; and (3) after the reaction, the metal substrate is subjected to deionization washing, and is dried for 6-10 hours at the temperature of 60-80 ℃ after being washed.
The method specifically comprises the following steps:
the method comprises the following steps: weighing Bi (NO)3)3·5H2And O and PVP, and dissolving the mixed solution in an ethylene glycol solution to obtain a mixed solution A. Weighing potassium iodide, and dissolving the potassium iodide in deionized water to obtain a mixed solution B; and then mixing the solution A and the solution B for a period of time to obtain a precursor mixed solution C of the BiOI photocatalytic film.
Step two: transferring the mixed solution C into a homogeneous hydrothermal kettle containing a polyvinyl chloride hard plate and a metal matrix coated with epoxy resin, putting the homogeneous hydrothermal kettle into a homogeneous reactor for reaction, washing the mixed solution C for a plurality of times by using deionized water after the reaction is finished, and drying the washed mixed solution C on the surfaces of the polyvinyl chloride and the epoxy resin to obtain a composite photocatalytic film;
step three: immersing the film obtained in the second step into a silver nitrate solution for a period of time, and washing with deionized water to remove unadsorbed Ag+Then immersed in ascorbic acid solution for a period of time, Ag+Is reduced into nano silver particles.
Step four: and taking out the polyvinyl chloride and the metal matrix coated with the epoxy resin, washing with deionized water and drying to obtain the silver particle loaded photocatalytic film on the surfaces of the polyvinyl chloride and the metal matrix coated with the epoxy resin.
Further, the mixed solution A, B, C in the step (1) is obtained by continuously stirring for 15-30 min, wherein PVP and Bi (NO)3)3·5H2O is added according to a molar ratio of (0.005-0.4): (0.05-0.3) and Bi (NO)3)3·5H2O and KI are added according to the molar ratio of 1: 1-1: 4, and ethylene glycol and deionized water are added according to the volume ratio of 5: 1-8: 1.
Further, the step one, namely the uniform mixed solution of the A and the B, is obtained by pouring the solution B into the solution A and continuously stirring for 15-30 min.
Further, polishing the epoxy resin coating coated on the metal substrate in the second step or grinding the epoxy resin coating by using silicon carbide abrasive paper, wherein the mesh number of the abrasive paper is 80-2000.
Further, the temperature of the homogeneous reaction in the second step is controlled to be 120-160 ℃, and the reaction time is 1-4 h.
And further, washing the photocatalytic film obtained in the step two by using deionized water for 3-6 times, and drying the photocatalytic film in an air blast drying box at the temperature of 60 ℃ for 6-10 hours to obtain the heterojunction photocatalytic film.
Furthermore, the concentration of the silver nitrate solution is 5-20 g/L, the concentration of the ascorbic acid solution is 3-10 g/L, and the soaking time is 10-40 min.
Further, the photocatalytic film obtained in the fourth step is washed 3-6 times by using deionized water, and dried for 6-10 hours in an air blast drying oven with the drying condition of 60 ℃, so that the Bi loaded with the nano silver particles is respectively obtained on the surfaces of the polyvinyl chloride and the metal matrix coated with the epoxy resin2O3/Bi2O2.7And Bi2O3the/BiOI composite photocatalytic film.
The base material is polyvinyl chloride or a metal base material coated with epoxy resin; wherein the metal substrate is 316 stainless steel, 304 stainless steel, copper sheet or aluminum sheet, and the epoxy resin coating is bisphenol A type epoxy resin.
When the base material is polyvinyl chloride, the in-situ homogeneous reaction temperature is controlled to be 120-160 ℃, and the reaction time is 1-4 h; after the reaction, the metal base material is deionized and washed, and then dried for 6-10 h at the temperature of 60-80 ℃, so that petal-like Bi is formed on the surface of the base material2O3/Bi2O2.7A heterojunction composite photocatalytic film;
when the substrate is a metal substrate coated with epoxy resin, the in-situ homogeneous reaction temperature is controlled to be 120-140 ℃, and the reaction time is 1-2 h; after the reaction, the metal substrate is deionized and washed, and then dried at 60-80 ℃ for 6-10h, namely forming flower-like Bi on the surface of the substrate2O3the/BiOI heterojunction composite photocatalytic film.
Immersing the substrate for forming the composite photocatalytic film in a silver nitrate solution with the concentration of 5-20 g/L for 10-40 min, taking out the substrate, immersing the substrate in an ascorbic acid solution with the concentration of 3-10 g/L for 10-40 min, and enabling the Ag to be in the solution+Is reduced into nano silver particles and is attached to the surface of the photocatalytic film, thus forming the Bi-containing material modified by silver2O3Composite photocatalytic films with different crystal phase heterostructures.
A photocatalytic film characterized by: the method forms Bi containing silver modified on the surface of a substrate2O3Composite photocatalytic films with different crystal phase heterostructures.
Use of a photocatalytic film for disinfecting, self-cleaning or anti-fouling applications.
The principle of the invention is as follows: the hydrothermal in-situ growth film has controllable crystal grains and appearance, and polymer materials such as polyvinyl chloride and epoxy resin respectively show different characteristics of each functional group under hydrothermal reaction. Firstly, obtaining a uniform yellow solution of a BiOI precursor through hydrolysis reaction of bismuth nitrate pentahydrate and potassium iodide, wherein the active dispersant PVP is mainly and uniformly coated on Bi3+And then respectively putting the polyvinyl chloride hard plate and the metal substrate coated with the epoxy resin into the solution, wherein the functional groups of the two polymer materials show different characteristics under the hydrothermal in-situ growth condition. For the polyvinyl chloride hard plate, the functional group chloride ions desorb and adsorb oxygen ions, and Bi is formed along with the prolonging of time2O3/Bi2O2.7A heterojunction photocatalytic film. The epoxy functional group of the epoxy resin reacts with PVP to further adsorb Bi3+Gradually form Bi with time2O3the/BiOI heterojunction photocatalytic film. Finally, the two films are further processed to obtain Ag+Adsorbing on the outer surfaces of the two films to make Ag+Reduction reaction with ascorbic acid, Ag+Reducing the silver particles into nano silver particles, and further respectively forming loads on the surface of polyvinyl chloride and the surface of epoxy resinPetal-like Bi of nano silver particles2O3/Bi2O2.7And flower-like Bi2O3the/BiOI heterojunction composite photocatalytic film. Finally, the polyvinyl chloride hard board has certain self-cleaning effect while having antibacterial property, and the antifouling property of the metal matrix taking the epoxy resin as the transition layer is improved.
The invention has the advantages of
The invention adopts a hydrothermal in-situ growth method to directly prepare the photocatalytic films on the surfaces of polyvinyl chloride and epoxy resin respectively, and overcomes the defect that the photocatalytic films are prepared by a method of using a photocatalyst as a filler, using a polymer as a binder and coating the photocatalyst by using high-molecular resin in the prior art. Free radicals generated by the photocatalytic film prepared by the prior art under the action of long-time illumination can damage a binder polymer, so that the coating fails. The ions selectively adsorb and grow on the surfaces of polyvinyl chloride and epoxy resin under the hydrothermal condition, and the pure inorganic phase photocatalytic heterojunction film is finally obtained by controlling the reaction temperature and time. In addition, the method has simple reaction steps, uniform heating and easy control, the product is always polar in the solvent, and the obtained photocatalytic composite film has fine crystal grains, good film appearance, tight connection of lamella and compact and uniform structure. The carried nano silver particles have low toxicity, and the photocatalytic performance can be further improved. Provides a new idea for further improving and widening the application value of the photocatalytic film.
Drawings
FIG. 1 is an XRD spectrum of a Bi-based semiconductor composite photocatalytic film prepared on the surfaces of polyvinyl chloride and epoxy resin respectively, wherein (A) is the surface of polyvinyl chloride, and R1 represents Bi2O3/Bi2O2.7Photocatalytic film, R2 represents Ag/Bi2O3/Bi2O2.7A photocatalytic film; (B) is an epoxy resin surface, S1 represents Bi2O3the/BiOI photocatalytic film, S2 represents Ag/Bi2O3a/BiOI photocatalytic film.
Fig. 2 is an SEM image of the nano silver particle-loaded photocatalytic thin film prepared on the surface of polyvinyl chloride and epoxy resin, respectively, according to the embodiment of the present invention, wherein (a) is the surface of polyvinyl chloride; (B) is an epoxy resin surface.
FIG. 3 is an SEM image of the preparation of photocatalytic films with different amounts of PVP added on the surface of PVC and epoxy resin, respectively, according to the embodiment of the present invention, wherein (A) is the surface of PVC; (B) is an epoxy resin surface.
FIG. 4 is an SEM image of a photocatalytic film prepared by hydrothermal in-situ growth on the surface of polyvinyl chloride and epoxy resin respectively for different periods of time according to an embodiment of the present invention, wherein (A) is the surface of polyvinyl chloride; (B) is an epoxy resin surface.
FIG. 5 is a UV-vis DRS spectrum of a nano-silver particle-loaded photocatalytic film prepared on the surface of polyvinyl chloride and epoxy resin, respectively, according to an embodiment of the present invention, wherein (A) is the surface of polyvinyl chloride, and R1 represents Bi2O3/Bi2O2.7Photocatalytic film, R2 represents Ag/Bi2O3/Bi2O2.7A photocatalytic film; (B) is an epoxy resin surface, S1 represents Bi2O3the/BiOI photocatalytic film, S2 represents Ag/Bi2O3a/BiOI photocatalytic film.
FIG. 6 shows the performance of preparing a photocatalytic composite film on a polyvinyl chloride surface according to an embodiment of the present invention, wherein (A) is a self-cleaning performance; (B) for sterilization, the (a1, d1, a2 and d2) are blank PVC, and the (b1, e1, b2 and e2) are Bi2O3/Bi2O2.7PVC, (c1, f1, c2, f2) is Ag/Bi2O3/Bi2O2.7The colony numbers of/PVC after (a1-c1, a2-c2)0h and (d1-f1, d2-f2)18h in (a1-f1) dark and (a2-f2) light.
FIG. 7 shows the antifouling property of the photocatalytic composite film prepared on the surface of epoxy resin according to the embodiment of the present invention, wherein (A) is a fluorescent photograph, wherein (a) is a blank epoxy resin, and (b) is Bi2O3a/BiOI, a (c) is Ag/Bi2O3A BiOI; (B) crystal Violet (CV) staining result, S1 represents Bi2O3the/BiOI photocatalytic film, S2 represents Ag/Bi2O3a/BiOI photocatalytic film.
Detailed Description
The present invention is further illustrated by the following specific examples, which are provided to assist those of ordinary skill in the art in more fully understanding the present invention, and are not intended to be limiting in any way. Other various changes and modifications can be made according to the technical scheme and the technical idea of the invention, and the invention still belongs to the protection scope covered by the invention.
The bismuth oxide heterojunction photocatalytic film loaded with metallic silver is prepared on the surface of polyvinyl chloride or the surface of epoxy resin by a hydrothermal synthesis in-situ growth method and a soaking reduction method. Particularly, a one-step hydrothermal in-situ growth method and a solution immersion reduction method are adopted to respectively form nano-silver particle modified petal-like Bi on the surfaces of polyvinyl chloride and metal taking epoxy resin as a transition layer2O3/Bi2O2.7And flower-like Bi2O3a/BiOI heterojunction film. Under the irradiation of visible light, the film generates free radicals of superoxide, electrons, holes and the like to kill organic pollutants and microorganisms attached to the surface of the film, so that the self-cleaning and antibacterial properties of the polyvinyl chloride surface and the metal antifouling property with epoxy resin as a transition layer are respectively improved. The invention has simple process, easy control and low cost. For polyvinyl chloride, the preparation method of the polyvinyl chloride surface sterilization film is widened. In addition, the sterilizing performance of the polyvinyl chloride is ensured, and meanwhile, the self-cleaning efficiency is endowed. For a metal matrix, a pure inorganic phase photocatalytic film is successfully prepared by taking epoxy resin as a transition layer, so that the antifouling property of the metal matrix is endowed. The method for preparing the photocatalytic film on the surface of the polymer material in a hydrothermal in-situ manner provides a new idea for the application of the photocatalytic film, and the prepared film has potential application prospects and reference significance in the aspects of buildings, medical treatment, marine engineering facilities, aquaculture, ship biological fouling prevention, water body purification, sterilization and disinfection and the like.
Example 1
(1) Weighing 0.1M Bi (NO)3)3·5H2Dissolving O and 0.1g PVP in the ethylene glycol solution, and continuously stirring for 20min to obtain a solution A; weighing 0Dissolve 1M KI in deionized water and continue stirring for 20min to obtain solution B. And mixing the solution A and the solution B for 20min to obtain a mixed solution C.
(2) And transferring the mixed solution C into homogeneous hydrothermal kettles respectively containing polyvinyl chloride hard plates or 316 stainless steel sheets coated with epoxy resin polished by 80-mesh silicon carbide sand paper, filling the mixed solution into the homogeneous hydrothermal kettles by 80% of the volume of the reaction kettle, controlling the reaction temperature to be 140 ℃, reacting for 4 hours in the homogeneous hydrothermal kettles containing the polyvinyl chloride hard plates, reacting for 2 hours in the homogeneous hydrothermal kettles containing the 316 stainless steel sheets coated with the epoxy resin, taking out the sample after the reaction is finished, washing for 3 times with deionized water, drying for 8 hours at room temperature, and obtaining the composite photocatalytic film on the surface of the polymer (see figure 1).
(3) Soaking the base materials with the formed film in silver nitrate solution with the concentration of 8.5g/L for 30min, taking out the film, and washing with deionized water for 3 times. Then the reaction solution is subjected to reduction reaction in an ascorbic acid solution with the concentration of 17.6g/L for 20 min.
(4) And taking out the film, washing the film with deionized water for 3 times, and drying the film in an air blast drying oven at the temperature of 60 ℃ for 8 hours to obtain the photocatalytic film modified by the loaded nano silver particles on the surfaces of polyvinyl chloride and epoxy resin with different substrates. (see FIG. 2)
As can be seen from the XRD spectrum of the bismuth-based semiconductor composite photocatalytic film in figure 1, the surface of the polyvinyl chloride polymer corresponds to standard card PDF #27-0050 (Bi)2O3) And PDF #75-0993 (Bi)2O2.7) Illustrates that Bi is formed on the surface of polyvinyl chloride by hydrothermal in-situ growth2O3/Bi2O2.7A heterojunction photocatalytic film. On the surface of 316 stainless steel coated with epoxy resin, the standard card PDF #76-2478 (Bi) is correspondingly matched2O3) And PDF #10-0445 (BiOI). Illustrates that Bi is formed on the surface of the epoxy resin through hydrothermal in-situ growth2O3the/BiOI heterojunction photocatalytic film.
As can be seen from an SEM image of the photocatalytic heterojunction film with the polyvinyl chloride and epoxy resin surfaces loaded with the nano silver particles in the figure 2, a polyvinyl chloride spectrogram shows that petal-like sheets with the size of about 1-3 mu m are uniformly stacked on the surface of a polymer, and silver particles with the size of about 140nm are distributed on the surfaces of the petal-like sheets. An epoxy resin spectrogram shows that the film is formed by piling up flower-shaped microspheres with the diameter of about 3 mu m, is compact and uniform, shows a large specific surface area, and silver particles with the diameter of about 150-200 nm are uniformly distributed on the surfaces of the flower-shaped microspheres. The method proves that the nano silver particles are successfully loaded on the photocatalytic film on the surfaces of the polyvinyl chloride and the epoxy resin by a soaking reduction method.
Example 2
The amount of PVP added in example 1 was changed to 0.0 g. Other preparation conditions are not changed, namely the photocatalytic film modified by the loaded nano silver particles is obtained on the surfaces of polyvinyl chloride and epoxy resin of different substrates. (see FIG. 3)
As can be seen from SEM images of the photocatalytic heterojunction thin films without PVP on the surfaces of the two polymers in the figure 3, the results show that when PVP is not added on the surface of polyvinyl chloride, the uniform petal-like lamellar photocatalytic thin film with the thickness of about 1-3 mu m is also formed, which indicates that the PVP is irrelevant to the photocatalytic thin film. When no PVP is on the surface of the epoxy resin, the photocatalytic film is randomly stacked, which shows that PVP plays a certain role in the growth of the photocatalytic film on the surface of the epoxy resin.
Example 3
The hydrothermal in-situ growth time in example 1 was changed to 3 hours in a homogeneous hydrothermal kettle with a polyvinyl chloride hard plate and 1.5 hours in a homogeneous hydrothermal kettle with a 316 stainless steel sheet coated with epoxy resin. Other preparation conditions are not changed, namely the photocatalytic film modified by the loaded nano silver particles is obtained on the surfaces of polyvinyl chloride and epoxy resin of different substrates (see figure 4)
As can be seen from the SEM images of the photocatalytic heterojunction thin films grown in situ on the two polymers in a hydrothermal manner for different periods of time in fig. 4, the results show that when the surfaces of the two polymers are grown in a hydrothermal manner for 3 hours and 1.5 hours, the photocatalytic thin films with a petal-like shape and a flower-like microsphere uniform thickness can be formed, respectively, and thus the growth of the two thin films is promoted with the lapse of time.
Application example 1
The ultraviolet-visible diffuse reflection test is carried out by using the composite photocatalytic film formed on the surfaces of polyvinyl chloride and 316 stainless steel taking epoxy resin as a transition layer and the photocatalytic film modified by nano silver particles, which are obtained in the embodiment 1.
With BaSO4For a reference sample (U-4100, Hitachi, Japan), the visible light absorption characteristics thereof were analyzed using an ultraviolet-visible diffuse reflectance absorption apparatus (UV-vis DRS) equipped with an integrating sphere.
As can be seen from the UV-vis DRS spectrogram of the photocatalytic composite film shown in FIG. 5, the light absorption range of the photocatalytic film prepared on the surface of polyvinyl chloride is about 300-500 nm, and the visible light absorption range is widened to 800nm after the nano silver particles are loaded. The photocatalytic film prepared on the surface of the epoxy resin has stronger visible light absorption capacity relative to the surface of polyvinyl chloride, the light absorption range is about 300-650 nm, after the nano silver particles are loaded on the surface of the film, the light absorption range of the film is widened to 800nm, and the light absorption intensity is further improved. It is shown that after the surface of the photocatalytic film is loaded with the nano silver particles, the visible light absorption performance of the film is further improved.
Application example 2
The composite photocatalytic film prepared on the surface of polyvinyl chloride and the photocatalytic film modified by nano silver particles obtained in the above example 1 were used for film self-cleaning performance testing.
And (3) testing the self-cleaning performance of the film by adopting a method for circularly degrading the rhodamine B solution for 3 times. The concentration of the test solution was 12mg/L and the volume was 15 mL. The photocatalytic film is completely immersed in the RhB solution, perpendicular to the incident visible light. The dye absorbance decay measurement time for all tests was 2.5h, including additional control reference tests, such as the test for RhB solution (polyvinyl chloride material only) in the absence of the photocatalytic film. Further, before measuring the absorbance decay of the dye, all the photocatalytic films were immersed in a RhB solution (12mg/L) for 30 minutes in the dark to reach the adsorption-desorption equilibrium of the dye. (see FIG. 6(A))
From the self-cleaning property test of polyvinyl chloride shown in FIG. 6(A), it can be seen that in the blank control test of blank polyvinyl chloride, RhB exhibits a slow degradation process, and the degradation rate of blank RhB is about 75%, because the radical state and the excited state of RhB molecular structure are active in the visible light range of 400-600 nm. Compared with the blank polyvinyl chloride, the degradation rate of the polyvinyl chloride loaded with the composite photocatalytic film or the photocatalytic film plated with the nano silver particles is slightly different from that of the blank polyvinyl chloride RhB in the initial stage of illumination, and the degradation rate difference is gradually increased along with the gradual extension of the illumination time, so that the final degradation efficiency reaches 97 percent. This is because photooxidation active substances are gradually increased as the light irradiation time is prolonged. And the cycle test shows that the degradation efficiency of the rhodamine B solution is better in three times. The self-cleaning performance of the blank polyvinyl chloride hard board is effectively improved by the photocatalysis film loaded with the nano silver particles.
Application example 3
The photocatalytic film modified by the nano silver particles prepared on the surface of the polyvinyl chloride obtained in the above example 1 was used for the film sterilization performance test.
In normal times, E.coli was stored in glycerol at-20 ℃. For experimental work, 2mL of E.coli was taken out of the glycerol medium and cultured in 250mL of sterile LB medium under stirring (180rpm/min) at 37 ℃ for 20. + -.1 h. The bacteria were collected by centrifugation (4500rpm,15 minutes), then resuspended in sterile distilled water, and the absorbance value at 540nm (U2900, Hitachi, Japan) was 0.224. + -. 0.004(100mL), giving a "standard bacterial suspension" of 3.900. + -. 0.077X 107CFU/mL。
In a typical test procedure, all photocatalytic films and quartz tubes were irradiated with ultraviolet rays for 24 hours before the photocatalytic killing test of E.coli to avoid the influence of bacteria in the atmosphere. The photocatalytic membrane was soaked in a quartz tube after 13mL of standard bacterial suspension was added. The suspension was then exposed to visible light (PCX50C Discover, Beijing Pophyele technologies, Inc., China). 100 μ L of suspension was taken at both time points 0 and 18h and serially diluted 10-fold with sterile distilled water. mu.L of the diluted suspension was dropped on an LB agar plate, and incubated at 37 ℃ for 24 hours to observe the number of the cells. Wherein a blank polyvinyl chloride hard plate is placed in the bacterial liquid as a blank control. (see FIG. 6(B))
As can be seen from the polyvinyl chloride bactericidal performance test in FIG. 6(B), under the dark condition (a1-f1), the number of Escherichia coli on the surfaces of the three films is relatively increased, because neither the composite film nor the silver-plated composite film has bactericidal performance under the dark condition, and the nano silver particles loaded on the surface of the composite film are not enough to kill the Escherichia coli proliferated under the dark condition. After the film is irradiated by visible light (a2-f2), compared with blank polyvinyl chloride (a2, d2), the number of visible escherichia coli colonies on the LB plate corresponding to the composite film (b2, e2) is small, because the composite film generates oxidation active substances under the irradiation of the visible light, and the oxidation active substances destroy the structure of escherichia coli microorganisms, thereby preventing the growth of the microorganisms. Furthermore, almost no escherichia coli (c2, f2) exists on the LB plate corresponding to the nano-silver particle modified photocatalytic film, because besides the photogenerated oxidation active substances, the silver also generates a sterilization effect under the irradiation of light, and finally, the sterilization capacity of the nano-silver particle modified composite film is greater than 99.99%. The photocatalysis film loaded with the nano silver particles effectively improves the sterilization performance of the blank polyvinyl chloride hard board.
Application example 4
The photocatalytic composite film prepared on the surface of the epoxy coating obtained in example 1 was used for antifouling performance test, and the antifouling performance of the photocatalytic film was evaluated by pseudo-alternating mode bacteria.
The bacteria were stored in glycerol at-20 ℃ in the usual pseudo-alternating mode. In the antifouling test of the test film, 2mL of pseudoalteromonas was taken out from the glycerol medium to 250mL of sterile 2216E medium, and cultured at 37 ℃ for 20. + -.1 h with stirring (180 rpm/min). The concentration of the re-cultured pseudoalteromonas as a "standard cell suspension" was about 5.6. + -. 0.08X 108CFU/mL. All used liquid solutions were sterile when the films were tested for soil resistance.
Three films for testing antifouling performance, namely a control group uncoated epoxy film, an experimental group composite photocatalytic film and a composite photocatalytic film plated with nano silver particles, 400mL of pseudo-alternate mode bacterial suspension is poured into a 500mL sterile bottle, the 400mL of pseudo-alternate mode bacterial suspension consists of 100 mu L of standard bacterial suspension and 399.9mL of 2216E sterile medium, the control group and the experimental group are hung in the sterile bottle, and then antifouling performance testing is carried out. The experiment is carried out in a closed cuboid device, a visible light source is a 10W Led lamp, in the test process, the pseudoalteromonas suspension is updated every four days, and the internal temperature of the device is kept at 22-23 ℃.
After 14 days of irradiation, the three membranes were removed from the pseudo-alternating pattern suspension and rinsed with Phosphate Buffered Saline (PBS) solution to remove all non-adherent microorganisms. Then, the number and the distribution of three pseudo-alternating mode bacteria suspensions with adhered membrane surfaces are observed by Crystal Violet (CV) dyeing and dead/live dye fluorescent dyeing respectively. Both staining methods generally follow the following steps.
CV dyeing is performed by first dyeing the washed film with 0.2% (by mass) CV distilled water for 30 minutes, and then removing the dyed film from the CV solution and washing it with distilled water to remove unabsorbed CV. Finally, the CV adsorbed on the membrane surface is decolorized with 1mL of 33% acetic acid solution (volume ratio) and mixed uniformly. The absorbance value of the homogeneous mixture indicates the amount of the pseudo-alternate mode bacteria adhered to the surface of the film as measured by a spectrophotometer (U2900, Hitachi, Japan). All tests were carried out in triplicate and the average values are given as experimental values.
The dead/live dye was subjected to fluorescent staining by immersing the washed membrane in a mixed solution of 2.5% (mass ratio) glutaraldehyde and PBS for 60 minutes, then in a mixed solution of PBS/DAPI (sterilized PBS: DAPI ═ 1ml: 1. mu.L) for 15 minutes, followed by observing the distribution of pseudoalteromonas adhered to the membrane surface with a fluorescence microscope (BX53M, OLYMPUS, Japan). (see FIG. 7)
In FIG. 7A, (a) is a blank epoxy resin and (b) is Bi2O3a/BiOI, (c) is Ag/Bi2O3The DAPI stained fluorescent photo of the bacteria on the surface can be seen after the/BiOI blank epoxy coating and the photocatalytic film are hung in the pseudo-alternating mode bacterial liquid for 14 days, and a large number of pseudo-alternating mode bacteria are attached to the surface of the blank epoxy coating (ER), because the blank epoxy coating cannot generate any substance for killing the pseudo-alternating mode bacteria under the illumination. After the composite film is grown in situ on the surface of the film (b), the number of pseudo-alternate microorganisms is reduced, because the composite film produces photogenerated oxidizing active substances to kill the microorganisms under illumination. And the bacteria are attached to the surface of the photocatalytic film loaded with the nano silver particles in a pseudo-alternating modeThe (c) is obviously reduced in one step because of the combined action of the nano silver particles and the photogenerated oxidation active substances. In addition, microorganisms mainly accumulate at the cracks of the film, where the film sterilization effect is relatively weak. The CV dyeing result of the blank epoxy coating and the photocatalytic film suspended in the pseudo-alternating mode bacterial liquid for 14 days in fig. 7(B) is visible, the CV dyeing absorption intensity on the surface of the blank epoxy coating is 2.02, and the CV dyeing absorption intensity on the surface of the photocatalytic film loaded with the nano silver particles is 0.35, which further shows that the film achieves better antifouling performance after the photocatalytic film loaded with the nano silver particles is prepared on the surface of the epoxy coating. Finally, the preparation method shows that after the epoxy resin is used as a transition layer to prepare the nano silver particle-loaded photocatalytic film through hydrothermal in-situ growth, the microbial contamination resistance of the metal surface can be reduced.
Claims (4)
1. A preparation method of a photocatalytic film is characterized by comprising the following steps: obtaining Bi-containing on the surface of a substrate by in-situ growth2O3Soaking the composite photocatalytic film with different crystal phase heterostructure into silver-containing solution for reaction; thus obtaining the Bi-containing silver-modified2O3Composite photocatalytic films with different crystal phase heterostructures;
soaking a substrate into the precursor solution, and growing Bi-containing on the surface of the substrate in situ homogeneous reaction by a hydrothermal method2O3Composite photocatalytic films with different crystal phase heterostructures; wherein the precursor solution is prepared by mixing solution A and solution B at a volume ratio of 7:1, and solution A is prepared by mixing Bi (NO)3)3·5H2Sequentially adding O and PVP into an ethylene glycol solution; the solution B is prepared by dissolving potassium iodide in deionized water;
0.1 g-0.3 g PVP and 0.05-0.3M Bi (NO) in 70 ml of ethylene glycol in the solution A3)3·5H2O; 0.05-0.2M KI in 10 ml of deionized water in the solution B;
the temperature of the in-situ homogeneous reaction is controlled to be 120-160 ℃, and the reaction time is 1-4 h; after reaction, the substrate is deionized and washed, and then dried for 6-10 h at the temperature of 60-80 ℃;
the base material is polyvinyl chloride or a metal base material coated with epoxy resin; wherein the metal substrate is 316 stainless steel, 304 stainless steel, copper sheet or aluminum sheet, and the epoxy resin coating is bisphenol A type epoxy resin;
immersing the substrate for forming the composite photocatalytic film in a silver nitrate solution with the concentration of 5-20 g/L for 10-40 min, taking out the substrate, immersing the substrate in an ascorbic acid solution with the concentration of 3-10 g/L for 10-40 min, and enabling the Ag to be in the solution+Is reduced into nano silver particles and is attached to the surface of the photocatalytic film, thus forming the Bi-containing material modified by silver2O3Composite photocatalytic films with different crystal phase heterostructures.
2. The method of preparing a photocatalytic film according to claim 1, characterized in that: when the base material is polyvinyl chloride, the in-situ homogeneous reaction temperature is controlled to be 120-160 ℃, and the reaction time is 1-4 h; washing the reacted substrate by deionized water, and drying the washed substrate for 6 to 10 hours at the temperature of between 60 and 80 ℃ to form petal-like Bi on the surface of the substrate2O3/Bi2O2.7A heterojunction composite photocatalytic film;
when the substrate is a metal substrate coated with epoxy resin, the in-situ homogeneous reaction temperature is controlled to be 120-140 ℃, and the reaction time is 1-2 h; washing the reacted metal substrate by deionized water, and drying the washed metal substrate for 6 to 10 hours at the temperature of between 60 and 80 ℃ to form flower-like Bi on the surface of the substrate2O3the/BiOI heterojunction composite photocatalytic film.
3. A photocatalytic film prepared by the method of claim 1, wherein: the method of claim 1 forming a silver-modified Bi-containing layer on a substrate surface2O3Composite photocatalytic films with different crystal phase heterostructures.
4. Use of a photocatalytic film according to claim 3, characterized in that: the use of said film for disinfecting or preventing fouling.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009116181A1 (en) * | 2008-03-21 | 2009-09-24 | 住友金属工業株式会社 | Visible light-responsive photocatalyst and method for producing the same |
| CN106179425A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院海洋研究所 | A kind of photocatalysis film material and preparation method thereof |
| CN108786808A (en) * | 2018-06-26 | 2018-11-13 | 陕西科技大学 | A kind of Ag/BiO2-x/Bi2O3/Bi2O2.75Composite photo-catalyst and preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009116181A1 (en) * | 2008-03-21 | 2009-09-24 | 住友金属工業株式会社 | Visible light-responsive photocatalyst and method for producing the same |
| CN106179425A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院海洋研究所 | A kind of photocatalysis film material and preparation method thereof |
| CN108786808A (en) * | 2018-06-26 | 2018-11-13 | 陕西科技大学 | A kind of Ag/BiO2-x/Bi2O3/Bi2O2.75Composite photo-catalyst and preparation method and application |
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| Title |
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| Ag-decorated Bi2O3 nanospheres with enhanced visible-light-driven photocatalytic activities for water treatment;Xin Zhong等;《RSC Advances》;20151231;第69312-69318页 * |
| The synthesis, characterization and photocatalytic activity of V(V), Pb(II), Ag(I) and Co(II)-doped Bi2O3;Jimin Xie等;《Dyes and Pigments》;20070312;第43-47页 * |
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