CN107376950B - Nano composite photocatalytic film material and preparation method thereof - Google Patents
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to the field of photocatalysis, and particularly relates to a photocatalytic film material and a preparation method thereof. The BiOI and the BiOBr with the molar ratio of 0.1-0.5 are formed into the BiOI/BiOBr nano composite photocatalytic film material with a sheet-shaped layered structure by an in-situ growth method and an ion exchange mode. The preparation process adopts in-situ growth combined with an ion exchange method to prepare the BiOI/BiOBr material which can be well attached to the surface of a stainless steel matrix to form a layer of film material with visible light catalytic activity. The preparation method provided by the invention is simple in process, easy to control and low in cost, constructs the BiOI/BiOBr nano composite sheet film structure with the visible light catalytic effect, and has potential application prospects in the fields of water body purification, marine antifouling and the like.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a photocatalytic film material and a preparation method thereof.
Background
With the overall progress of human society, human beings have greater and greater influence on the original natural ecology, and a series of environmental problems are caused when natural resources are over developed and utilized. Wherein the environmental problems of water resource shortage, water pollution and the like are increasingly prominent. Therefore, the treatment of sewage is very important. In a plurality of sewage treatment processes, the photocatalytic oxidation degradation technology has the outstanding advantages of high efficiency, no selectivity, high stability, greenness, no toxicity, no secondary pollution, low energy consumption, simple and convenient operation, low cost and the like. Especially with nano TiO in recent years2The semiconductor photocatalysis material is found to be an excellent water treatment photocatalyst, and can generate electron-hole under the condition of illuminationFor O, partial electrons and holes can be transferred to the semiconductor surface and the water environment2、OH-And the like to generate free radicals with strong chemical oxidation activity. The free radicals, the photo-generated electrons and the holes can directly react with the reactant to be degraded and oxidize and decompose the reactant to achieve the effect of degrading the organic pollutants by photocatalysis.
BiOX (X ═ Cl, Br, I) bismuth-based compound [ Bi2O2]2+And a strong built-in electric field exists between the material and a halogen layer, so that the material has high separation efficiency of electron-hole pairs and shows high visible light catalytic activity. However, due to the inherent energy band structure, the BiOX monomer material often has limited ability of visible light to catalytically degrade organic pollutants, which greatly limits the application of such photocatalytic materials in the field of water treatment.
In recent years, inorganic nanocomposite materials have been greatly developed. The nano-scale composite material can endow the material with more comprehensive performance, solve the application limitation of inorganic functional materials with single structures, and improve the material performance and the application range. For example, a heterojunction structure formed by effective recombination of two inorganic semiconductor nano materials can improve the photoproduction electron-hole separation efficiency and greatly improve the material photocatalysis efficiency. If the nano composite technology is adopted to carry out composite modification on the existing photocatalytic material to improve the material performance, the application of the material in the field of water treatment is inevitably greatly expanded. However, although the composite material with various morphologies is synthesized sequentially by different methods, such as a hydrothermal method, a solvothermal method, a sonochemical method, etc. are commonly used. Considering that the composite materials prepared by the methods are all powder-shaped nano materials, in a specific industrial application environment, the nano powder materials generally have the defects of difficult recovery and poor reutilization rate, so that the water treatment cost is greatly increased. Therefore, the effective immobilization of the photocatalyst, especially the nano composite photocatalyst, is a problem which is difficult to avoid in the practical application and popularization of the photocatalytic water treatment industry.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a nano composite photocatalytic film material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a BiOI/BiOBr nano composite photocatalytic film material with a sheet-shaped layered structure is formed by BiOI and BiOBr in a molar ratio of 0.1-0.5 through an in-situ growth method and an ion exchange mode.
The preparation method of the nano composite photocatalyst film material comprises the following steps:
1) adding Bi (NO)3)3·5H2O is dispersed in excess ethylene glycol and PVP surfactant is added followed by addition of Bi (NO)3)3·5H2O, uniformly mixing the two KI aqueous solutions, transferring the mixture into a lining of a reaction kettle, immersing the pretreated substrate to be protected into the mixed solution, reacting for 4-12 hours at 120-160 ℃, taking out, washing and drying for later use;
2) and dissolving tetrabutylammonium bromide in excessive water, transferring the solution to the inner liner of a reaction kettle after the tetrabutylammonium bromide is dissolved, immersing the dried substrate in the mixed solution in the reaction kettle, and reacting at 120-160 ℃ for 12-36 h to form the BiOI/BiOBr nano composite photocatalytic film with a sheet-shaped layered structure on the surface of the substrate.
The comprehensive concentration range of PVP in the step 1) is 0.05-2 g/L.
The reactant Bi (NO) used in step 1)3)3·5H2The concentration of O and KI is 0.05-0.15 mol/L.
The concentration of tetrabutylammonium bromide in the step 2) is 1-12 mmol/L.
The thin film material is applied to being used as a photocatalyst.
The film material is applied to sewage treatment or biofouling prevention.
The invention has the beneficial effects that:
the invention adopts an in-situ growth method and an ion exchange method to prepare the BiOI/BiOBr nano composite photocatalytic film material with a sheet-shaped layered structure on the surface of an iron substrate. It solves the problem of immobilization of the nano composite photocatalytic material. Compared with the commonly adopted sol-gel method for preparing the nano composite photocatalytic film material, the method has the technical advantages of one-step forming and simple operation. The BiOI/BiOBr nano composite photocatalytic curing membrane material with the specific structure has high-efficiency photocatalytic performance, the degradation rate of rhodamine B can reach 91% in 60min of visible light, and the killing rate of Escherichia coli is more than 99.9% in 2h of visible light; specifically, the method comprises the following steps:
(1) the preparation method adopted by the invention has the advantages of simple process, easy control and low cost.
(2) The prepared BiOI/BiOBr nano composite photocatalytic film material with the sheet-shaped layered structure has wide application prospect in sewage treatment and biological fouling prevention.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a BiOI/BiOBr film prepared in accordance with the present invention (with the abscissa being 2 θ (angle) and the unit being degree (degrees) and the ordinate being Intensity and the unit being a.u (absolute units)).
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a BiOI/BiOBr film prepared according to the present invention.
FIG. 3 is an ultraviolet-visible diffuse reflectance absorption (UV-DRS) spectrum of a BiOI/BiOBr film prepared in accordance with the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to provide a more complete understanding of the invention by one of ordinary skill in the art, and are not intended to be limiting in any way.
The invention prepares the BiOI/BiOBr nano composite photocatalytic film material with a sheet-shaped layered structure on the surface of a stainless steel substrate by combining in-situ growth with an ion exchange method. The BiOI/BiOBr nano composite material is directly prepared on the surface of the stainless steel matrix in situ, so that the binding force between the BiOI/BiOBr nano composite film material and the surface of the stainless steel matrix is stronger, and the structural stability of the film is ensured. The photocatalytic film material has good visible light absorption performance, the flaky structure accelerates the separation of photon-generated carriers, reduces the recombination probability of photon-generated electron-hole pairs, shows efficient photocatalytic effect under visible light, and has good practical value and potential application prospect in the fields of water body purification, marine antifouling and the like. Meanwhile, the nano composite photocatalyst film material has the characteristics of uniform film formation, low price, good repeatability and the like.
Example 1: preparation method of BiOI/BiOBr nano composite photocatalytic film material with sheet-shaped layered structure
Firstly, preparing a BiOI precursor film material with a sheet-shaped layered structure on the surface of a stainless steel substrate by an in-situ growth method under a hydrothermal condition. Weighing 8mmol of Bi (NO)3)3·5H2O and 0.1g PVP are added to 70mL of ethylene glycol, dispersed by sonication for 30min, 8mmol of KI is weighed and dissolved in 10mL of water, and then the two solutions are mixed well and transferred to a 100mL reaction kettle. And immersing the pretreated stainless steel net in the mixed solution. The reactor was then heated to 140 ℃ for 4 h. After the reaction is finished, the stainless steel net is taken out, washed clean by absolute ethyl alcohol and distilled water in sequence, and finally dried for 6 hours in a drying oven at 60 ℃. 0.48mmol of tetrabutylammonium bromide was weighed into 80mL of water, dissolved by magnetic stirring, and transferred to a 100mL reaction vessel. The stainless steel net was immersed in the mixed solution again. The reactor was then heated to 140 ℃ for 24 h. After the reaction is finished, the stainless steel net is taken out, washed clean by absolute ethyl alcohol and distilled water in sequence, and finally dried for 6 hours in a drying oven at 60 ℃.
Characterization of the BiOI/BiOBr nano composite photocatalytic film material:
the X-ray diffraction analysis results of fig. 1 show that the composite material contains only two phases, the BiOI and the BiOBr; the X-ray energy spectrum analysis result shows that the molar ratio of BiOI/BiOBr in the nano composite photocatalytic material is 0.27; as can be seen from the scanning electron micrograph of fig. 2, the BiOI and BiOBr materials are in a sheet shape, and a larger part of the sheet material is vertical to the surface of the stainless steel mesh substrate, the crystallinity is higher, and the sheet thin-film layered structure has a larger specific surface area and good visible light absorption performance (see the UV-DRS spectrum of fig. 3).
Example 2: preparation method of BiOI/BiOBr nano composite photocatalytic film material with sheet-shaped layered structure
Firstly, preparing a BiOI precursor film material with a sheet-shaped layered structure on the surface of a stainless steel substrate by an in-situ growth method under a hydrothermal condition. Weighing 4mmol of Bi (NO)3)3·5H2O and 0.2g PVP were added to 70mL of ethylene glycol, dispersed by sonication for 30min, 4mmol of KI was weighed and dissolved in 10mL of water, and then the two solutions were mixed well and transferred to a 100mL reaction kettle. And immersing the pretreated stainless steel net in the mixed solution. The reaction vessel was subsequently heated to 160 ℃ for 8 h. After the reaction is finished, the stainless steel net is taken out, washed clean by absolute ethyl alcohol and distilled water in sequence, and finally dried for 6 hours in a drying oven at 60 ℃. 0.80mmol of tetrabutylammonium bromide was weighed into 80mL of water, dissolved by magnetic stirring, and transferred to a 100mL reaction vessel. The stainless steel net was immersed in the mixed solution again. The autoclave was subsequently heated to 160 ℃ for 36 h. After the reaction is finished, the stainless steel net is taken out, washed clean by absolute ethyl alcohol and distilled water in sequence, and finally dried for 6 hours in a drying oven at 60 ℃.
Example 3: preparation method of BiOI/BiOBr nano composite photocatalytic film material with sheet-shaped layered structure
Firstly, preparing a BiOI precursor film material with a sheet-shaped layered structure on the surface of a stainless steel substrate by an in-situ growth method under a hydrothermal condition. Weighing 12mmol of Bi (NO)3)3·5H2O and 0.05g PVP were added to 70mL of ethylene glycol, dispersed by sonication for 30min, 12mmol of KI was weighed and dissolved in 10mL of water, and then the two solutions were mixed well and transferred to a 100mL reaction kettle. And immersing the pretreated stainless steel net in the mixed solution. The reactor was then heated to 120 ℃ for 12 h. After the reaction is finished, the stainless steel net is taken out, washed clean by absolute ethyl alcohol and distilled water in sequence, and finally dried for 6 hours in a drying oven at 60 ℃. 0.16mmol of tetrabutylammonium bromide was weighed into 80mL of water, dissolved by magnetic stirring, and transferred to a 100mL reaction vessel. The stainless steel net was immersed in the mixed solution again. The reactor was then heated to 120 ℃ for 12 h. After the reaction is finished, the stainless steel mesh is taken out and sequentially usedWashing with ethanol and distilled water, and drying at 60 deg.C for 6 hr.
Example 4
A certain area (generally 15X 40 mm)2) The BiOI/BiOBr nano composite photocatalytic film material with the sheet-shaped layered structure prepared by the embodiment is spread and then placed into a quartz test tube, and then a certain amount of rhodamine B with proper concentration is added and placed into a light reaction instrument for photocatalytic reaction for a certain time. The organic matter in the quartz tube was sucked out and the concentration C was measuredtAnd press
And calculating the photocatalytic degradation rate eta of the current time. The degradation rate of rhodamine B can reach 91% after 60min of visible light illumination.
A certain area (generally 15X 40 mm)2) The BiOI/BiOBr nano composite photocatalytic film material with the sheet-shaped layered structure prepared by the embodiment is spread in a quartz test tube after being subjected to ultraviolet sterilization, and 4mL of bacteria with the concentration of about 10 are added6PBS bacterial solution of the order of cfu/mL. The subsequent experiment processes are consistent, the reaction system is sampled after being illuminated for a certain time (30min) under a dark condition, and the survival rate and the sterilization rate of bacteria are determined by a plate counting method. The killing rate of the escherichia coli by visible light for 2 hours is more than 99.9%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (7)
1. A nano composite photocatalyst film material is characterized in that BiOI and BiOBr with the molar ratio of 0.1 ~ 0.5.5 are formed into a BiOI/BiOBr nano composite photocatalyst film material with a sheet-shaped layered structure by an in-situ growth method and an ion exchange mode;
the above-mentionedThe preparation method of the nano composite photocatalyst film material comprises the following steps: 1) adding Bi (NO)3)3·5H2O is dispersed in excess ethylene glycol and PVP surfactant is added followed by addition of Bi (NO)3)3·5H2O, uniformly mixing the two KI aqueous solutions, transferring the mixture into a liner of a reaction kettle, immersing the pretreated substrate to be protected into the mixed solution, reacting at 120 ~ 160 ℃ for 4 ~ 12h, taking out, washing and drying for later use;
2) and dissolving tetrabutylammonium bromide in excessive water, transferring the solution to the inner liner of a reaction kettle after the tetrabutylammonium bromide is dissolved, and then immersing the dried substrate in the mixed solution in the reaction kettle to react for 12 ~ 36h at 120 ~ 160 ℃ to obtain the BiOI/BiOBr nano composite photocatalytic film with the sheet-shaped layered structure on the surface of the substrate.
2. The method for preparing the nano composite photocatalyst film material as claimed in claim 1, which is characterized in that:
1) adding Bi (NO)3)3·5H2O is dispersed in excess ethylene glycol and PVP surfactant is added followed by addition of Bi (NO)3)3·5H2O, uniformly mixing the two KI aqueous solutions, transferring the mixture into a liner of a reaction kettle, immersing the pretreated substrate to be protected into the mixed solution, reacting at 120 ~ 160 ℃ for 4 ~ 12h, taking out, washing and drying for later use;
2) and dissolving tetrabutylammonium bromide in excessive water, transferring the solution to the inner liner of a reaction kettle after the tetrabutylammonium bromide is dissolved, and then immersing the dried substrate in the mixed solution in the reaction kettle to react for 12 ~ 36h at 120 ~ 160 ℃ to obtain the BiOI/BiOBr nano composite photocatalytic film with the sheet-shaped layered structure on the surface of the substrate.
3. The method for preparing the nano composite photocatalyst film material as claimed in claim 2, wherein the concentration of PVP in the step 1) is 0.05 ~ 2 g/L.
4. The nanocomposite photocatalyst of claim 2The preparation method of the oxidant film material is characterized by comprising the following steps: the reactant Bi (NO) used in step 1)3)3·5H2The concentration of O and KI was 0.05 ~ 0.15.15 mol/L.
5. The method for preparing the nano composite photocatalyst film material as claimed in claim 2, wherein the concentration of tetrabutylammonium bromide in the step 2) is 1 ~ 12 mmol/L.
6. The use of the nanocomposite photocatalyst film material as claimed in claim 1, wherein: the thin film material is applied to being used as a photocatalyst.
7. The use of the nanocomposite photocatalyst film material as claimed in claim 1, wherein: the film material is applied to sewage treatment or biofouling prevention.
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| CN108178192A (en) * | 2018-01-17 | 2018-06-19 | 南京信息工程大学 | BiOF electrode materials of a kind of nanometer of chip architecture and preparation method thereof and electrochemical energy storage application |
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| CN103055901A (en) * | 2012-12-15 | 2013-04-24 | 新昌县冠阳技术开发有限公司 | Development and application method of bismuth oxyhalide system material for processing organic pollutant efficiently |
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| CN102671679A (en) * | 2012-06-08 | 2012-09-19 | 上海师范大学 | BiOI/BiOBr multilevel structure composite visible light catalyst, and preparation method and application thereof |
| CN103055901A (en) * | 2012-12-15 | 2013-04-24 | 新昌县冠阳技术开发有限公司 | Development and application method of bismuth oxyhalide system material for processing organic pollutant efficiently |
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