CN111215139B - Floatable nano composite visible light catalytic film material and preparation method and application thereof - Google Patents

Floatable nano composite visible light catalytic film material and preparation method and application thereof Download PDF

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CN111215139B
CN111215139B CN201911180268.7A CN201911180268A CN111215139B CN 111215139 B CN111215139 B CN 111215139B CN 201911180268 A CN201911180268 A CN 201911180268A CN 111215139 B CN111215139 B CN 111215139B
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visible light
film material
floatable
light catalytic
nano composite
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CN111215139A (en
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蔡一啸
陈阳
王华平
陈仕艳
张婷婷
金梦甜
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Donghua University
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Abstract

The invention relates to a floatable nano composite visible light catalytic film material and a preparation method and application thereof, wherein wet bacterial cellulose after hydrophilic treatment is added into dispersion liquid of powder containing nano photocatalyst, and then the dispersion liquid is subjected to suction filtration, precooling and freeze drying to prepare the floatable nano composite visible light catalytic film material, wherein the particle size of the powder containing nano photocatalyst is not more than 100nm, and the mass ratio of the wet bacterial cellulose after hydrophilic treatment to the powder containing nano photocatalyst is not more than 50; the prepared photocatalytic film material has an equivalent circle diameter of 3.55-4.10 mm and a thickness of 0.05-0.06 mm, contains three-dimensional holes, and mainly comprises a bacterial cellulose matrix and nano-photocatalysts dispersed in the bacterial cellulose matrix and on the surface of the bacterial cellulose matrix; the method can be applied to the photocatalytic degradation of rhodamine b. The method is simple, and the prepared photocatalytic film has good floating property and wide application prospect.

Description

Floatable nano composite visible light catalytic film material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano composite materials and photocatalysis, and relates to a floatable nano composite visible light catalytic film material, a preparation method and application thereof.
Background
Conventional wastewater treatment processes typically employ biological methods to treat large amounts of organic compounds in water. The traditional method cannot achieve the expected target for trace organic pollutants in water with relatively low concentration, such as personal care products such as phenols and anilines, endocrine disruptors and the like. In addition, the existing physical methods represented by the adsorption method have strong limitations, and the adsorption/bearing capacity of the adsorption material needs to be frequently replaced, so that the treatment cost is directly influenced; on the other hand, the treatment generates 'pollution transfer', and is easy to cause secondary pollution to the atmosphere. In recent years, advanced oxidation processes based on semiconductor photocatalysis technology show the advantages of high efficiency in mineralizing pollutants, low cost and the like, and have good degradation effect on micropollutants which are easy to float on water. However, the main problem that the photocatalytic technology has not been applied on a large scale in wastewater treatment has been that the treatment process has two disadvantages: on one hand, a common photocatalyst is composed of a metal oxide semiconductor and a composite material thereof, and is generally prepared and utilized in the form of a powder material; the powder photocatalyst is easy to agglomerate and settle at the bottom of a water body, so that the photocatalytic effect is weakened, and the transmission of light in water is greatly weakened relative to the transmission of light in air; on the other hand, the powder photocatalyst is substantially powder with the size in the nanometer or micrometer range, is easy to cause secondary pollution of water after treatment, and is not beneficial to separation, recovery and reuse.
In order to overcome the defects of powder materials, a small number of researchers design a floating photocatalyst to carry out degradation research on micropollutants in recent years, but the methods all adopt a process path with complicated steps such as high-temperature calcination, vapor deposition and the like and high preparation cost in the preparation process.
Therefore, the photocatalytic film material which has better floating performance in water, keeps better photocatalytic performance, does not cause secondary pollution of water and can ensure that the active photocatalytic powder material is not easy to agglomerate, and the preparation method and the application thereof have very important significance.
Disclosure of Invention
The invention aims to solve the problems that photocatalytic materials are easy to settle in water when used in water to weaken photocatalytic performance and cause secondary pollution to water in the prior art, and provides a floatable nano composite visible light catalytic film material and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the floatable type nano composite visible light catalytic film material comprises the steps of adding wet bacterial cellulose subjected to hydrophilic treatment into dispersion liquid of powder containing nano photocatalyst, carrying out suction filtration, precooling and freeze drying, and obtaining the floatable type nano composite visible light catalytic film material, wherein the particle size of the powder containing nano photocatalyst is not more than 100nm, and the mass ratio of the wet bacterial cellulose subjected to hydrophilic treatment to the powder containing nano photocatalyst is not more than 50.
Through the bacterial cellulose nanofiber subjected to hydrophilic treatment, the hydroxyl at the 6 th position of the bacterial cellulose nanofiber is oxidized into carboxyl, so that the hydrogen bonding effect among molecular chains is reduced, electrostatic repulsion is generated among negative charges on the surface of the nanofiber, the uniform dispersion of the nanofiber in water is promoted, the nano photocatalyst can be more uniformly and fully loaded on the surface of the bacterial cellulose, the combination is firmer, and a nano composite visible light catalytic film with better stability is formed;
according to the invention, a filtration mode is adopted to prepare a film material with a small size (the thickness is 0.05-0.06 mm, the equivalent circle diameter is 3.55-4.10 mm), a funnel is adopted for filtration, and bacterial cellulose and powder containing nano photocatalyst are accumulated to form a film at the orifice of a filter hole in the filtration process due to the fact that the funnel has a dispersed porous structure; a three-dimensional gradient hole structure is constructed in the nano composite visible light catalytic film material through precooling and freeze drying; meanwhile, the particle size of the powder containing the nano photocatalyst is controlled to be not more than 100nm, the mass ratio of the wet bacterial cellulose subjected to hydrophilic treatment to the powder containing the nano photocatalyst is not more than 50, the size and the structure of the nano composite visible light catalytic film and the size and the content of the loaded nano photocatalyst are matched with each other, so that the influence of the surface force on the nano composite visible light catalytic film in water is far larger than the volume force (such as gravity, electric field force and the like), and the surface tension has a leading effect on the prepared film to generate larger buoyancy, so that the nano composite visible light catalytic film has excellent floating property in water, and the problem that the catalytic performance is weakened due to sedimentation in water is solved.
As a preferred technical scheme:
the preparation method of the floatable nano composite visible light catalytic film material comprises the steps that the nano photocatalyst is BiOCl and g-C3N4Or TiO2。
The preparation method of the floatable nano composite visible light catalytic film material adopts TiO as the nano photocatalyst2Containing TiO2The powder is prepared from carbon-based material, urea and TiO2And nano Fe3O4Prepared by hydrothermal reaction; the titanium dioxide has photocatalytic performance, but can only react under ultraviolet light, so in order to improve the photoresponse range of the titanium dioxide, the invention modifies the titanium dioxide, and the iron and nitrogen doping introduces metal and non-metal ions into the TiO2Nanosystems, usually directly into TiO2Inside the crystal lattice of (1), the original Ti is replaced by metal ions4+Form O vacancy and finally form defect in the crystal lattice and even directly change the crystal lattice type, so that the original TiO2The wide band gap change of the photocatalyst is realized, so that the photocatalyst can react under visible light, the separation of photo-generated electrons and holes can be promoted, the photocurrent response is improved, and the photocatalytic activity of the photocatalyst is finally improved. The carbon-based material can also be replaced by Metal-Organic framework (Metal-Organic Frameworks) molecules, the Metal-Organic framework molecules are Organic-inorganic hybrid materials which are formed by self-assembling Organic ligands and Metal ions or clusters through coordination bonds and have intramolecular pores, and the Metal-Organic framework molecules have the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity and tailorability of topological structures and the like.
According to the preparation method of the floatable nano composite visible light catalytic film material, the carbon-based material is GO, carbon nano tubes or porous carbon.
The preparation method of the floatable nano composite visible light catalytic film material comprises the steps of preparing the carbon-based material, the urea and the TiO2And nano Fe3O4The mass ratio of (A) to (B) is 0.005-0.05: 5-10: 0.5-1: 0.2-1, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 6-24 h.
According to the preparation method of the floatable nano composite visible light catalytic film material, the wet bacterial cellulose subjected to hydrophilic treatment is wet bacterial cellulose subjected to Tempo reaction treatment; the concentration of the dispersion liquid of the powder containing the nano photocatalyst is 2-50 wt%.
According to the preparation method of the floatable nano composite visible light catalytic film material, the precooling temperature is-10 ℃ to-4 ℃, and the time is not less than 12 hours; the temperature of freeze drying is-60 ℃ to-50 ℃, the vacuum degree is 1Pa to 5Pa, and the time is 6h to 24 h.
The invention also provides a floatable type nano composite visible light catalytic film material prepared by adopting the preparation method of the floatable type nano composite visible light catalytic film material, which contains three-dimensional holes (a cellulose film subjected to suction filtration contains a large amount of water molecules, ice is formed by precooling, the ice is directly sublimated into gaseous water vapor by a freeze dryer, and irregular holes are left on the cellulose), and the floatable type nano composite visible light catalytic film material mainly comprises a bacterial cellulose matrix and nano photocatalysts dispersed in the interior and on the surface of the bacterial cellulose matrix; the equivalent circle diameter of the floatable nano composite visible light catalytic film material is 3.55-4.10 mm, and the thickness is 0.05-0.06 mm.
The invention also provides the application of the floatable nano composite visible light catalytic film material, and the floatable nano composite visible light catalytic film material is used for photocatalytic degradation of rhodamine b.
As a preferred technical scheme:
the application comprises the following specific processes: adding the floatable nano composite visible light catalytic film material into a liquid containing rhodamine b, and irradiating for 30min by adopting visible light; the mass ratio of the floatable nano composite visible light catalytic film material to the liquid containing rhodamine b is 0.018-0.3: 100, the content of rhodamine b in the liquid containing rhodamine b is 1wt%, and the removal rate of rhodamine b is more than 95.8%.
Has the advantages that:
(1) the preparation method of the floatable nano composite visible light catalytic film material has relatively simple operation process and low cost;
(2) the floatable nano composite visible light catalytic film material keeps good floating property before and after reaction, and has good photodegradation effect on rhodamine b under the irradiation of visible light;
(3) after single photodegradation reaction, an operator can recover and recycle the film material;
(4) the floatable nano composite visible light catalytic film material has the adsorption and photocatalysis double functions, and in the treatment of surface water pollution, particularly in the treatment of novel pollutant water with small pollution concentration, pollutants can be firstly adsorbed on a film taking cellulose as a carrier, and then the pollutants can quickly move to the vicinity of a catalyst so as to be more efficiently utilized by a light source, the mass transfer rate is improved, and the floatable nano composite visible light catalytic film material has a wide application prospect.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps: adding wet bacterial cellulose (cellulose synthesized by acetobacter xylinum) subjected to the Tempo reaction treatment into dispersion liquid (the concentration of powder containing BiOCl in the dispersion liquid is 2 wt%) containing BiOCl powder with the particle size of 80nm, performing suction filtration, precooling and freeze drying, wherein the mass ratio of the wet bacterial cellulose subjected to the Tempo reaction treatment to the powder containing BiOCl is 45, the precooling temperature is-4 ℃, and the time is 12 hours; the temperature of freeze drying is-60 deg.C, vacuum degree is 5Pa, and time is 12 h.
The finally prepared floatable nano composite visible light catalytic film material has an equivalent circle diameter of 3.58mm and a thickness of 0.05mm, contains three-dimensional holes, and consists of a bacterial cellulose matrix and BiOCl dispersed in the bacterial cellulose matrix and on the surface of the bacterial cellulose matrix.
Adding the floatable type nano composite visible light catalytic film material into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.05:100, and the removal rate of the rhodamine b reaches 95.8% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.
Comparative example 1
A nanometer composite visible light catalytic film material, its preparation method is basically the same as example 1, the difference is only that the particle size of the powder containing BiOCl is 120nm, the nanometer composite visible light catalytic film material finally made, its equivalent circle diameter is 3.6mm, the thickness is 0.18mm, contain three-dimensional vug; the nano composite visible light catalytic film material is added into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.05:100, the nano composite visible light catalytic film material is irradiated for 30min by adopting visible light, and the removal rate of the rhodamine b is 82%.
Comparing comparative example 1 with example 1, it can be seen that the removal rate of rhodamine b by the floatable nano composite visible light catalytic film material prepared in example 1 under the same conditions is higher, because the particle size of the powder containing BiOCl in comparative example 1 is larger, and the particles loaded on cellulose are fewer, so that the nano photocatalyst directly participating in the reaction is fewer, and the degradation efficiency is reduced.
Comparative example 2
A nano composite visible light catalytic film material, the preparation method is basically the same as that in example 1, except that the mass ratio of wet bacterial cellulose after being treated by Tempo reaction to powder containing BiOCl is 60, and the finally prepared nano composite visible light catalytic film material has an equivalent circle diameter of 3.6mm, a thickness of 0.32mm and three-dimensional holes; the nano composite visible light catalytic film material is added into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.05:100, visible light is adopted for irradiation for 30min, and the removal rate of the rhodamine b is 50%.
Comparing the comparative example 2 with the example 1, it can be seen that the removal rate of rhodamine b by the floatable nano composite visible light catalytic film material prepared in the example 1 under the same conditions is higher, because the wet bacterial cellulose after the treatment of the Tempo reaction in the comparative example 1 has a larger mass ratio to the powder containing BiOCl, the cellulose is too much, the nano photocatalyst powder is covered or even wrapped, the separation of electron holes of the nano photocatalyst under the irradiation of light is influenced, and the degradation efficiency is greatly reduced; in addition, the increase of bacterial cellulose makes the dispersion viscous, which makes suction filtration difficult.
Comparative example 3
A nano composite visible light catalytic film material, its preparation method is basically the same as example 1, the difference lies in that the wet bacterial cellulose used is not processed by Tempo reaction, the nano composite visible light catalytic film material finally prepared, its equivalent circle diameter is 3.62mm, the thickness is 1.2mm, do not contain three-dimensional hole; the nano composite visible light catalytic film material is added into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.05:100, the nano composite visible light catalytic film material is irradiated for 30min by adopting visible light, and the removal rate of the rhodamine b is 73%.
Comparing the comparative example 3 with the example 1, it can be seen that the removal rate of rhodamine b by the floatable nano composite visible light catalytic film material prepared in the example 1 under the same conditions is higher, because the wet bacterial cellulose in the comparative example 1 is not subjected to Tempo reaction treatment, the hydrogen bonding action between molecular chains is strong, and the wet bacterial cellulose is aggregated due to the hydrogen bonding action, so that BiOCl cannot be uniformly dispersed on the surface of the wet bacterial cellulose and cannot enter the inside of the aggregated wet bacterial cellulose, therefore, compared with the example 1, the load of BiOCl on the wet bacterial cellulose is greatly reduced, and the BiOCl directly participating in the reaction is greatly reduced, thereby further weakening the performance of the catalyst.
Example 2
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps: adding wet bacterial cellulose (cellulose synthesized by Acetobacter xylinum) after Tempo reaction treatment into 100nm solution containing g-C3N4The dispersion of the powder of (g-C is contained in the dispersion)3N4The concentration of the powder is 25wt percent), then performing suction filtration, precooling and freeze drying, wherein the wet bacterial cellulose after the treatment of the Tempo reaction and the wet bacterial cellulose containing g-C3N4The mass ratio of the powder is 50, the precooling temperature is-6 ℃, and the time is 12 h; the temperature of freeze drying is-53 deg.C, vacuum degree is 3Pa, and time is 6 h.
The final product has equivalent circle diameter of 3.55mm and thickness of 0.06mm, contains three-dimensional pores, and is prepared from bacterial cellulose matrix and g-C dispersed in the interior and on the surface of the bacterial cellulose matrix3N4And (4) forming.
Adding the floatable type nano composite visible light catalytic film material into a liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.018:100, and the removal rate of the rhodamine b reaches 96% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.
Example 3
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps: adding wet bacterial cellulose (cellulose synthesized by acetobacter xylinum) after the Tempo reaction treatment into the mixture with the grain diameter of 96nm and containing g-C3N4The dispersion of the powder of (g-C is contained in the dispersion)3N4The concentration of the powder is 50 wt%), then performing suction filtration, precooling and freeze drying, wherein the wet bacterial cellulose after the Tempo reaction treatment and the wet bacterial cellulose containing g-C3N4The mass ratio of the powder is 49, the precooling temperature is-7 ℃, and the time is 18 h; the temperature of freeze drying is-55 deg.C, vacuum degree is 3Pa, and time is 24 h.
The final product has equivalent circle diameter of 4.03mm and thickness of 0.06mm, contains three-dimensional pores, and is prepared from bacterial cellulose matrix and g-C dispersed in the interior and on the surface of the matrix3N4And (4) forming.
Adding the floatable type nano composite visible light catalytic film material into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.3:100, and the removal rate of the rhodamine b reaches 96.5% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.
Example 4
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps: adding wet bacterial cellulose (cellulose synthesized by acetobacter xylinum) subjected to the Tempo reaction treatment into dispersion liquid (the concentration of powder containing BiOCl in the dispersion liquid is 30 wt%) containing BiOCl powder with the particle size of 90nm, performing suction filtration, precooling and freeze drying, wherein the mass ratio of the wet bacterial cellulose subjected to the Tempo reaction treatment to the powder containing BiOCl is 42, the precooling temperature is-5 ℃, and the time is 20 hours; the temperature of freeze drying is-52 deg.C, vacuum degree is 2Pa, and time is 10 h.
The finally prepared floatable nano composite visible light catalytic film material has an equivalent circle diameter of 3.55mm and a thickness of 0.05mm, contains three-dimensional holes, and consists of a bacterial cellulose matrix and BiOCl dispersed in the bacterial cellulose matrix and on the surface of the bacterial cellulose matrix.
Adding the floatable type nano composite visible light catalytic film material into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.12:100, and the removal rate of the rhodamine b reaches 96.8% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.
Example 5
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps:
(1) comprises GO, urea and TiO with the mass ratio of 0.005:5:0.5:0.22And nano Fe3O4Carrying out hydrothermal reaction for 24 hours at the temperature of 120 ℃ to obtain the TiO-containing material2The powder of (4);
(2) adding wet bacterial cellulose (cellulose synthesized by acetobacter xylinum) after Tempo reaction treatment into TiO-containing material with particle size of 97nm2Dispersion of the powder of (TiO-containing dispersion)2The concentration of the powder is 15wt percent), then performing suction filtration, precooling and freeze drying, wherein the wet bacterial cellulose after the Tempo reaction treatment and the TiO-containing bacteria cellulose2The mass ratio of the powder is 47, the precooling temperature is-8 ℃, and the time is 16 h; the temperature of freeze drying is-50 deg.C, vacuum degree is 4Pa, and time is 6 h.
The final product has equivalent circle diameter of 4.10mm and thickness of 0.06mm, contains three-dimensional pores, and is prepared from bacterial cellulose matrix and TiO dispersed in the interior and on the surface of the matrix2And (4) forming.
Adding the floatable type nano composite visible light catalytic film material into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.15:100, and the removal rate of the rhodamine b reaches 95.9% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.
Example 6
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps:
(1) comprises carbon nano-tubes, urea and TiO with the mass ratio of 0.005:7:0.8:0.52And nano Fe3O4Carrying out hydrothermal reaction for 16h at the temperature of 150 ℃ to obtain the TiO-containing material2The powder of (4);
(2) adding wet bacterial cellulose (cellulose synthesized by Acetobacter xylinum) after Tempo reaction treatment into TiO-containing material with particle size of 100nm2Dispersion of the powder of (TiO-containing dispersion)2The concentration of the powder is 50wt percent), then performing suction filtration, precooling and freeze drying, wherein the wet bacterial cellulose after the treatment of the Tempo reactionWith TiO containing2The mass ratio of the powder is 50, the precooling temperature is-10 ℃, and the time is 14 h; the temperature of freeze drying is-50 deg.C, vacuum degree is 1Pa, and time is 10 h.
The final product has equivalent circle diameter of 4.10mm and thickness of 0.06mm, contains three-dimensional pores, and is prepared from bacterial cellulose matrix and TiO dispersed in the interior and on the surface of the matrix2And (4) forming.
Adding the floatable type nano composite visible light catalytic film material into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.3:100, and the removal rate of the rhodamine b reaches 96.5% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.
Example 7
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps:
(1) consists of porous carbon, urea and TiO with the mass ratio of 0.05:10:1:12And nano Fe3O4Carrying out hydrothermal reaction for 6h at the temperature of 200 ℃ to obtain the TiO-containing material2The powder of (4);
(2) adding wet bacterial cellulose (cellulose synthesized by acetobacter xylinum) after the Tempo reaction treatment into TiO-containing material with the particle size of 88nm2Dispersion of the powder of (TiO-containing dispersion)2The concentration of the powder is 32wt percent), then performing suction filtration, precooling and freeze drying, wherein the wet bacterial cellulose after the Tempo reaction treatment and the TiO-containing bacteria cellulose2The mass ratio of the powder is 48, the precooling temperature is-5 ℃, and the time is 14 h; the temperature of freeze drying is-55 deg.C, vacuum degree is 4Pa, and time is 20 h.
The final product has equivalent circle diameter of 4.02mm and thickness of 0.06mm, contains three-dimensional pores, and is prepared from bacterial cellulose matrix and TiO dispersed in the interior and on the surface of the matrix2And (4) forming.
Adding the floatable type nano composite visible light catalytic film material into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.15:100, and the removal rate of the rhodamine b reaches 96.2% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.
Example 8
The preparation method of the floatable nano composite visible light catalytic film material comprises the following steps:
(1) consists of metal-organic framework molecules (UiO-66), urea and TiO with the mass ratio of 0.05:8:0.5:0.82And nano Fe3O4Carrying out hydrothermal reaction for 15h at the temperature of 180 ℃ to obtain the TiO-containing material2The powder of (4);
(2) adding wet bacterial cellulose (cellulose synthesized by acetobacter xylinum) after Tempo reaction treatment into TiO-containing material with particle size of 90nm2Dispersion of the powder of (TiO-containing dispersion)2The concentration of the powder is 45wt percent), then performing suction filtration, precooling and freeze drying, wherein the wet bacterial cellulose after the Tempo reaction treatment and the TiO-containing bacteria cellulose2The mass ratio of the powder is 49, the precooling temperature is-7 ℃, and the time is 9 h; the temperature of freeze drying is-55 deg.C, vacuum degree is 3Pa, and time is 10 h.
The final product has equivalent circle diameter of 4.10mm and thickness of 0.06mm, contains three-dimensional pores, and is prepared from bacterial cellulose matrix and TiO dispersed in the interior and on the surface of the matrix2And (4) forming.
Adding the floatable type nano composite visible light catalytic film material into liquid containing rhodamine b (the content of the rhodamine b is 1 wt%), wherein the mass ratio of the floatable type nano composite visible light catalytic film material to the liquid containing the rhodamine b is 0.25:100, and the removal rate of the rhodamine b reaches 96.3% after the floatable type nano composite visible light catalytic film material is irradiated for 30min by adopting visible light.

Claims (6)

1. The preparation method of the floatable nano composite visible light catalytic film material is characterized by comprising the following steps: adding the wet bacterial cellulose after hydrophilic treatment into dispersion liquid of powder containing nano photocatalyst, then carrying out suction filtration, precooling and freeze drying to obtain the floatable nano composite visible light catalytic film material, wherein the powder containing nano photocatalystThe particle size of the powder is not more than 100nm, and the mass ratio of the wet bacterial cellulose subjected to hydrophilic treatment to the powder containing the nano photocatalyst is not more than 50; adding the floatable nano composite visible light catalytic film material into a liquid containing rhodamine b, and irradiating for 30min by adopting visible light; the mass ratio of the floatable nano composite visible light catalytic film material to the liquid containing rhodamine b is 0.018-0.3: 100, the content of rhodamine b in the liquid containing rhodamine b is 1wt%, and the removal rate of rhodamine b is more than 95.8%; the nano photocatalyst is BiOCl, g-C3N4Or TiO2(ii) a The wet bacterial cellulose after hydrophilic treatment is wet bacterial cellulose after Tempo reaction treatment; the concentration of the dispersion liquid of the powder containing the nano photocatalyst is 2-50 wt%; precooling at-10 to-4 ℃ for not less than 12 h; the temperature of freeze drying is-60 ℃ to-50 ℃, the vacuum degree is 1Pa to 5Pa, and the time is 6h to 24 h.
2. The method for preparing a floatable nano composite visible light catalytic film material according to claim 1, wherein the nano photocatalyst is TiO2Containing TiO2The powder is prepared from carbon-based material, urea and TiO2And nano Fe3O4Prepared by hydrothermal reaction.
3. The method for preparing the floatable nano composite visible light catalytic thin film material according to claim 2, wherein the carbon-based material is GO, carbon nano tubes or porous carbon.
4. The method for preparing a floatable nano composite visible light catalytic film material according to claim 2, characterized in that the carbon-based material, urea, TiO2And nano Fe3O4The mass ratio of (A) to (B) is 0.005-0.05: 5-10: 0.5-1: 0.2-1, the temperature of the hydrothermal reaction is 120-200 ℃, and the time is 6-24 h.
5. The floatable type nano composite visible light catalytic film material prepared by the preparation method of the floatable type nano composite visible light catalytic film material as claimed in any one of claims 1 to 4, which is characterized in that: the nano photocatalyst contains three-dimensional holes and mainly consists of a bacterial cellulose matrix and nano photocatalysts dispersed in the bacterial cellulose matrix and on the surface of the bacterial cellulose matrix; the equivalent circle diameter of the floatable nano composite visible light catalytic film material is 3.55-4.10 mm, and the thickness is 0.05-0.06 mm.
6. The use of the floatable nanocomposite visible light catalytic film material of claim 5, wherein: the floatable nano composite visible light catalytic film material is used for photocatalytic degradation of rhodamine b.
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