CN114247461A - Hexagonal nanosheet composite membrane layer containing array macropores and preparation method thereof - Google Patents
Hexagonal nanosheet composite membrane layer containing array macropores and preparation method thereof Download PDFInfo
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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
- B01J27/24—Nitrogen compounds
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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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J35/64—Pore diameter
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Abstract
The invention belongs to the technical field of semiconductor composite photocatalytic materials, and relates to a hexagonal nanosheet composite membrane layer containing array macropores and a preparation method thereof, wherein the hexagonal nanosheet composite membrane layer containing the array macropores is formed by compounding hexagonal nanosheet carbon nitride and titanium dioxide nanoparticles, the thickness of the hexagonal nanosheet carbon nitride is 10-70 nm, the side length of the hexagonal nanosheet carbon nitride is 70-110 nm, and the composite membrane layer contains 0.8-2 nm micropores, 2-100nm mesopores and 400-1000 nm array macropores. The preparation method comprises the following steps: mixing tetrabutyl titanate, diethanol amine and absolute ethyl alcohol; dripping water; adding polyethylene glycol 400; coating on a ceramic sheet and drying; preparing scale-shaped carbon nitride precursor powder from urea; preparing a carbon nitride suspension aqueous solution; the carbon nitride suspension water solution and the substrate film are heated, washed and dried. The invention does not need complex equipment and has simple operation; the photocatalytic degradation performance of the composite film layer is improved; the environmental cost of the photocatalyst in the practical application process is reduced.
Description
Technical Field
The invention belongs to the technical field of semiconductor composite photocatalytic materials, and particularly relates to a hexagonal nanosheet composite membrane layer containing array macropores and a preparation method thereof.
Background
Due to the large population of China and the great demand of dyes and antibiotics in the textile, clothing and medical industries, the problem of water pollution caused by sewage discharge in the printing and dyeing industry and the medical industry becomes an environmental management problem to be solved urgently in China. The dye wastewater discharged by the printing and dyeing industry contains a large amount of pollutants with complex components, such as rhodamine B, bisphenol A and methylene blue, and the pollutants have great difficulty, long period and low degradation efficiency in the natural degradation process, thereby seriously affecting the quality of the water body of the nature. On the other hand, as the amount of antibiotics used in various industries, particularly in animal husbandry, is gradually increased, the amount of antibiotics discharged in the form of parent compounds is increased, and the storage and enrichment of the antibiotics in water bodies can significantly affect the ecological cycle of the nature and the physical health of human beings, and the harm is not inconsiderable. Therefore, there is a need for an efficient and feasible degradation method to treat water resources contaminated with dyes and antibiotics.
The photocatalyst can decompose pollutants into substances with no toxicity or less toxicity by means of sunlight, and the photocatalytic pollutant decomposition is considered to be one of the most economical and environment-friendly methods for treating environmental problems. As a new green catalyst, the graphite-like carbon nitride has excellent electronic structural characteristics and can effectively degrade various organic pollutants, such as phenols, printing and dyeing wastewater (terephthalic acid, methyl orange, methylene blue, rhodamine B and the like), antibiotics (levofloxacin, sulfamethazine, ciprofloxacin and the like) and the like. However, it has considerable problems, such as easy formation of compact lamellar structure, easy formation of photo-generated electron-hole pairs which are easy to recombine and annihilate, and the need of improving the photocatalytic activity. Semiconductor recombination is a method of combining a plurality of semiconductor materials with different energy levels by a certain means to form a heterojunction which is tightly connected with each other, and is one of the most common methods for realizing effective interface transfer and space separation of electron holes. G to C3N4With TiO2The photocatalysis performance and the degradation efficiency of harmful organic matters in the wastewater can be effectively improved by compounding. But now g-C3N4/TiO2The photocatalytic degradation process is mostly carried out in a suspension system by using composite photocatalytic powder, and the photocatalytic powder is difficult to recover and is easy to cause secondary pollution. Thus, an efficient and strongly loaded g-C is explored3N4/TiO2The composite photocatalytic porous membrane layer and the preparation method thereof have important practical application values for improving the oxidation-reduction capability of the existing photocatalyst and realizing green recycling of recovery and regeneration.
At present, few reports about the preparation method of the carbon nitride and titanium dioxide composite membrane are reported, and the existing literature reports also adopt the electrostatic spinning technology and the in-situ polymerization method to obtain the graphite phase g-C3N4@TiO2The nano-fiber membrane is formed by interweaving nano-fibers, is easy to generate fiber adhesion in the in-situ polymerization process to generate a bonding structure, does not contain micropores, cannot realize the formation of ordered array macropores, and has weaker bonding degree with a carrier. In the prior research, the hydrothermal method is used for preparing g-C containing array macropores3N4/TiO2The research of the composite film layer is not reported yet.
Disclosure of Invention
Object of the Invention
In order to solve the problems of secondary pollution and low degradation efficiency of a photocatalyst in the prior art, the invention aims to provide a hexagonal nanosheet composite membrane layer containing array macropores and a preparation method thereof3N4/TiO2And (5) compounding the film layer.
Technical scheme
The hexagonal nanosheet composite membrane layer containing the array macropores is formed by compounding hexagonal nanosheet composite membrane layers and titanium dioxide nanoparticles, wherein the thickness of the hexagonal nanosheet composite membrane layers is 10-70 nm, the side length of the hexagonal nanosheet composite membrane layers is 70-110 nm, and the composite membrane layers contain 0.8-2 nm micropores, 2-100nm mesopores and 400-1000 nm array macropores.
The preparation method of the hexagonal nanosheet composite membrane layer containing the array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanolamine and absolute ethyl alcohol, pouring into a mixing container, and uniformly stirring to obtain a mixed solution A;
continuously dripping a certain amount of water into the mixed solution A;
step three, adding a certain amount of polyethylene glycol 400 after water dripping is finished, uniformly stirring and standing to obtain sol;
coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film;
step five, weighing a certain amount of urea, putting the urea into a crucible with a cover, sealing, putting the crucible into a furnace, calcining and preserving heat to obtain scale-shaped carbon nitride precursor powder;
step six, weighing a certain amount of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution; and (4) transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying to obtain the hexagonal nanosheet composite film layer containing the array macropores.
Further, in the first step, the molar ratio of tetrabutyl titanate, diethanolamine and absolute ethyl alcohol is 1: 1: (24-40), the stirring speed is 400rad/min, and the stirring time is 10 min.
Further, in the second step, the molar ratio of water to tetrabutyl titanate used in the first step is 2.2: 1, the speed of dripping water into the mixed solution A is 15-20 s/drop, and the water is deionized water.
Further, in the third step, the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is (0.06-0.09): 1; the stirring time is 0.5-1 h, and the standing time is 0.5-1 h.
Further, in the fourth step, the drying temperature is 60 ℃, the drying time is 6-10 hours, the calcining temperature is 500 ℃, and the calcining time is 5 hours.
Further, in the fifth step, the loading amount of the urea in the crucible is 1/2-2/3 of the total capacity of the crucible, the crucible is placed into a muffle furnace after being sealed, the temperature is raised to 550 ℃ from the normal temperature at the speed of 8-10 ℃/min, and the temperature is maintained for 4 hours.
Further, in the sixth step, the concentration of the carbon nitride suspension aqueous solution is 0.4-0.7 g/L, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: (1-3), the heating temperature is 180 ℃, the heating time is 24 hours, the drying temperature is 60 ℃, and the drying time is 1-1.5 hours.
Further, the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining, and the filling ratio of the materials in the reaction kettle is 70-85%.
Advantages and effects
(1) Adopts titanium alkoxide and urea which are commonly used in industry as main raw materials, and realizes the hexagonal nanosheet g-C containing micropores, mesopores and array macropores only by a wet chemical method3N4/TiO2The preparation method of the composite film layer does not need complex equipment, is simple to operate, and can overcome the defect that the g-C is prepared by the existing electrostatic spinning method3N4/TiO2The nanofiber membrane has the defects of high requirement on equipment, high production cost, complex process and the like;
(2)g-C3N4/TiO2the composite film layer is formed by compounding hexagonal nano flaky carbon nitride and titanium dioxide nanoparticles, has developed pores and large loading capacity, is favorable for adsorption and transmission of degraded target molecules, can realize effective interface transfer and space separation of photoproduction electrons and holes, and improves the photocatalytic activity and widens the utilization range of visible light by utilizing an S-shaped heterojunction mechanism, thereby greatly improving the photocatalytic degradation performance of the material;
(3)g-C3N4/TiO2the preparation method of the composite film layer is suitable for various carriers, the film layer and the carriers are firmly combined, the cycle performance is good, the recovery, the regeneration and the cycle use are easy, the problem that the existing photocatalytic composite powder is easy to generate secondary pollution to water can be solved, and the photocatalytic composite powder can be obviously reducedEnvironmental cost of the agent in the practical application process.
Drawings
The invention is further described with reference to the following figures and detailed description. The scope of the invention is not limited to the following expressions.
Fig. 1 is an XRD pattern of the hexagonal nanosheet composite membrane layer containing arrayed macropores of example 1;
FIG. 2 is a scanning electron microscope image of a hexagonal nanosheet composite membrane layer containing arrayed macropores in example 1;
fig. 3 is a pore size distribution diagram of a hexagonal nanosheet composite membrane layer containing arrayed macropores in example 2;
FIG. 4 is a scanning electron microscope image of the hexagonal nanosheet composite membrane layer containing arrayed macropores in example 3;
FIG. 5 is a scanning electron microscope image of the hexagonal nanosheet composite membrane layer containing arrayed macropores in example 4;
fig. 6 is a scanning electron microscope image of the hexagonal nanosheet composite membrane layer containing arrayed macropores in example 5.
Detailed Description
The ethanol, tetrabutyl titanate, polyethylene glycol 400 and urea adopted in the embodiment of the invention are commercially available analytical pure reagents.
In the embodiment of the invention, the phase analysis test adopts an Shimadzu XRD-7000 type X-ray diffractometer.
In the embodiment of the invention, a Hitachi SU8010 field emission scanning electron microscope is adopted for micro-morphology detection.
The device adopted for detecting the pore structure in the embodiment of the invention is a V-Sorb 4800 specific surface area and pore diameter analyzer.
A preparation method of a hexagonal nanosheet composite membrane layer containing array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1: 1: (24-40), pouring the mixture into a mixing container (such as a beaker) for stirring, wherein the stirring speed is 400rad/min, the stirring time is 10min, and uniformly stirring to obtain a mixed solution A;
step two, continuously dripping a certain amount of water into the mixed solution A, wherein the molar ratio of the water to the tetrabutyl titanate used in the step one is 2.2: 1, dripping water into the mixed solution A at a speed of 15-20 s/drop, wherein the water is deionized water;
step three, adding polyethylene glycol 400 after water dripping is finished, wherein the molar ratio of the polyethylene glycol 400 to tetrabutyl titanate is (0.06-0.09): 1; stirring for 0.5-1 h to be uniform and standing for 0.5-1 h to obtain sol;
coating the obtained sol on a ceramic chip, drying, and calcining to obtain a substrate film, wherein the drying temperature is 60 ℃, the drying time is 6-10 h, the calcining temperature is 500 ℃, and the calcining time is 5h
Step five, weighing a certain amount of urea, putting the urea into a crucible with a cover, wherein the filling amount of the urea in the crucible is 1/2-2/3 of the total capacity of the crucible, putting the crucible into a muffle furnace after sealing, heating the crucible from normal temperature to 550 ℃ at the speed of 8-10 ℃/min, calcining and preserving heat for 4 hours to obtain scale-shaped carbon nitride precursor powder;
weighing a certain amount of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution, wherein the concentration of the carbon nitride suspension aqueous solution is 0.4-0.7 g/L; and C, transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying, wherein the reaction kettle is a reaction kettle lined with polytetrafluoroethylene, the filling ratio of the materials in the reaction kettle is 70-85%, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: (1-3), heating at 180 ℃ for 24h, drying at 60 ℃ for 1-1.5 h to obtain the hexagonal nanosheet composite membrane layer containing the array macropores.
The hexagonal nanosheet composite membrane layer containing the array macropores is formed by compounding hexagonal nanosheet-shaped carbon nitride and titanium dioxide nanoparticles, the thickness of the hexagonal nanosheet-shaped carbon nitride is 10-70 nm, the side length of the hexagonal nanosheet-shaped carbon nitride is 70-110 nm, and the composite membrane layer contains 0.8-2 nm micropores, 2-100nm mesopores and 400-1000 nm array macropores.
Example 1
A preparation method of a hexagonal nanosheet composite membrane layer containing array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1: 1: 24, respectively adding 17ml of tetrabutyl titanate, 4.8ml of diethanolamine and 70ml of absolute ethyl alcohol into a mixing container, stirring at the stirring speed of 400rad/min for 10min, and uniformly stirring to obtain a mixed solution A;
step two, continuously dripping 2ml of water into the mixed solution A, wherein the mol ratio of the water to the tetrabutyl titanate used in the step one is 2.2: 1, dripping water into the mixed solution A at the speed of 15 s/drop, wherein the water is deionized water;
step three, adding 1.2g of polyethylene glycol 400 after the water dropping is finished, wherein the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is 0.06: 1; stirring for 0.5h to be uniform and standing for 1h to obtain sol;
step four, coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film, wherein the drying temperature is 60 ℃, the drying time is 6 hours, the calcining temperature is 500 ℃, and the calcining time is 5 hours
Step five, weighing 6g of urea, putting the urea into a crucible with a cover, wherein the filling amount of the urea in the crucible is 1/2 of the total capacity of the crucible, putting the crucible into a muffle furnace after sealing, heating the crucible to 550 ℃ from normal temperature at the speed of 8 ℃/min, calcining, and keeping the temperature for 4 hours to obtain scale-shaped carbon nitride precursor powder;
sixthly, weighing 0.03g of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution, wherein the concentration of the carbon nitride suspension aqueous solution is 0.4 g/L; and C, transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying, wherein the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining, the filling ratio of the materials in the reaction kettle is 70%, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: 1, heating at 180 ℃ for 24h, drying at 60 ℃ for 1h to obtain the hexagonal nanosheet composite membrane layer containing array macropores.
The XRD spectrum of the obtained composite film is shown in fig. 1, and it can be seen from fig. 1 that distinct graphite-phase carbon nitride diffraction peaks appear in the vicinity of 2 θ of 12.8 ° and 27.4 °, and the rest XRD diffraction peaks correspond well to the characteristic peaks of anatase titanium dioxide. Shows that under the conditions of example 1, ag-C3N4/TiO2And (5) compounding the film layer.
The scanning electron microscope picture of the obtained composite film layer is shown in figure 2, and g-C prepared by the invention can be seen from figure 23N4/TiO2The composite film layer is formed by compounding hexagonal nano flaky carbon nitride and titanium dioxide nano particles, and the carbon nitride nano sheets are in a regular hexagon; the developed pores in the film layer contain array macropores of 400-1000 nm and mesopores of 2-100nm overlapped by the nanosheets.
Example 2
A preparation method of a hexagonal nanosheet composite membrane layer containing array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1: 1: 30, respectively adding 17ml of tetrabutyl titanate, 4.8ml of diethanolamine and 88ml of absolute ethyl alcohol into a mixing container, stirring at the stirring speed of 400rad/min for 10min, and uniformly stirring to obtain a mixed solution A;
step two, continuously dripping 2ml of water into the mixed solution A, wherein the mol ratio of the water to the tetrabutyl titanate used in the step one is 2.2: 1, dripping water into the mixed solution A at a speed of 20 s/drop, wherein the water is deionized water;
step three, adding 1.4g of polyethylene glycol 400 after the water dropping is finished, wherein the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is 0.07: 1; stirring for 0.6h to be uniform and standing for 0.9h to obtain sol;
step four, coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film, wherein the drying temperature is 60 ℃, the drying time is 7 hours, the calcining temperature is 500 ℃, and the calcining time is 5 hours
Step five, weighing 10g of urea, putting the urea into a crucible with a cover, wherein the filling amount of the urea in the crucible is 2/3 of the total capacity of the crucible, putting the crucible into a muffle furnace after sealing, heating the crucible to 550 ℃ from normal temperature at the speed of 8 ℃/min, calcining, and keeping the temperature for 4 hours to obtain scale-shaped carbon nitride precursor powder;
sixthly, weighing 0.0375g of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution, wherein the concentration of the carbon nitride suspension aqueous solution is 0.5 g/L; and C, transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying, wherein the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining, the filling ratio of the materials in the reaction kettle is 74%, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: and 2, heating at 180 ℃ for 24h, drying at 60 ℃ for 1.1h to obtain the hexagonal nanosheet composite membrane layer containing the array macropores.
The BJH adsorption pore size distribution curve of the obtained composite membrane layer is shown in FIG. 3, and the specific surface area of the composite membrane layer obtained by BET calculation is 98.1m2(ii) in terms of/g. As can be seen from FIG. 3, the BJH adsorption pore size distribution curve has a plurality of most probable pore sizes, which are respectively near 1.8nm, 3nm, 60nm and 110nm, and the composite membrane layer prepared by the invention contains micropores and mesopores besides the array macropores.
Example 3
A preparation method of a hexagonal nanosheet composite membrane layer containing array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1: 1: 32, pouring 17ml of tetrabutyl titanate, 4.8ml of diethanolamine and 93ml of absolute ethyl alcohol into a mixing container, stirring at the stirring speed of 400rad/min for 10min, and uniformly stirring to obtain a mixed solution A;
step two, continuously dripping 2ml of water into the mixed solution A, wherein the mol ratio of the water to the tetrabutyl titanate used in the step one is 2.2: 1, dripping water into the mixed solution A at a speed of 16 s/drop, wherein the water is deionized water;
step three, adding 1.6g of polyethylene glycol 400 after the water dropping is finished, wherein the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is 0.08: 1; stirring for 0.7h to be uniform and standing for 0.8h to obtain sol;
step four, coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film, wherein the drying temperature is 60 ℃, the drying time is 9 hours, the calcining temperature is 500 ℃, and the calcining time is 5 hours
Step five, weighing 12g of urea, putting the urea into a crucible with a cover, wherein the filling amount of the urea in the crucible is 2/3 of the total capacity of the crucible, putting the crucible into a muffle furnace after sealing, heating the crucible to 550 ℃ from normal temperature at a speed of 9 ℃/min, calcining, and keeping the temperature for 4 hours to obtain scale-shaped carbon nitride precursor powder;
sixthly, weighing 0.045g of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution, wherein the concentration of the carbon nitride suspension aqueous solution is 0.7 g/L; and C, transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying, wherein the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining, the filling ratio of the materials in the reaction kettle is 81%, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: and 3, heating at 180 ℃ for 24h, drying at 60 ℃ for 1.2h to obtain the hexagonal nanosheet composite membrane layer containing the array macropores.
The scanning electron microscope picture of the obtained composite film layer is shown in FIG. 4, and it can be seen from FIG. 4 that g-C prepared by the invention3N4/TiO2The composite film layer is formed by compounding hexagonal nano flaky carbon nitride and titanium dioxide nano particles, and the shape of the carbon nitride nano sheet is regular; the developed pores in the film layer contain 400-1000 nm array macropores, 2-100nm mesopores lapped by nano sheets and 100-200nm mesopores.
Example 4
A preparation method of a hexagonal nanosheet composite membrane layer containing array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1: 1: 35, pouring 17ml of tetrabutyl titanate, 4.8ml of diethanolamine and 102ml of absolute ethyl alcohol into a mixing container, stirring at the stirring speed of 400rad/min for 10min, and uniformly stirring to obtain a mixed solution A;
step two, continuously dripping 2ml of water into the mixed solution A, wherein the mol ratio of the water to the tetrabutyl titanate used in the step one is 2.2: 1, dripping water into the mixed solution A at a speed of 16 s/drop, wherein the water is deionized water;
step three, adding 1.8g of polyethylene glycol 400 after the water dropping is finished, wherein the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is 0.09: 1; stirring for 0.8h to be uniform and standing for 0.7h to obtain sol;
step four, coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film, wherein the drying temperature is 60 ℃, the drying time is 9 hours, the calcining temperature is 500 ℃, and the calcining time is 5 hours
Step five, weighing 15g of urea, putting the urea into a crucible with a cover, wherein the filling amount of the urea in the crucible is 2/3 of the total capacity of the crucible, putting the crucible into a muffle furnace after sealing, heating the crucible to 550 ℃ from normal temperature at a speed of 9 ℃/min, calcining, and keeping the temperature for 4 hours to obtain scale-shaped carbon nitride precursor powder;
sixthly, weighing 0.0525g of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution, wherein the concentration of the carbon nitride suspension aqueous solution is 0.7 g/L; and C, transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying, wherein the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining, the filling ratio of the materials in the reaction kettle is 81%, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: and 3, heating at 180 ℃ for 24h, drying at 60 ℃ for 1.3h to obtain the hexagonal nanosheet composite membrane layer containing the array macropores.
The scanning electron microscope picture of the obtained composite film layer is shown in FIG. 5, and it can be seen from FIG. 5 that g-C prepared by the invention3N4/TiO2The composite film layer is formed by compounding hexagonal nano flaky carbon nitride and titanium dioxide nano particles, and the shape of the carbon nitride nano sheet is regular; the developed pores in the film layer contain 400-1000 nm array macropores, 2-100nm mesopores lapped by nano sheets and 100-200nm mesopores.
Example 5
A preparation method of a hexagonal nanosheet composite membrane layer containing array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1: 1: 37, pouring 17ml of tetrabutyl titanate, 4.8ml of diethanolamine and 108ml of absolute ethyl alcohol into a mixing container, stirring at the stirring speed of 400rad/min for 10min, and uniformly stirring to obtain a mixed solution A;
step two, continuously dripping 2ml of water into the mixed solution A, wherein the mol ratio of the water to the tetrabutyl titanate used in the step one is 2.2: 1, dripping water into the mixed solution A at the speed of 18 s/drop, wherein the water is deionized water;
step three, adding 1.8g of polyethylene glycol 400 after the water dropping is finished, wherein the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is 0.09: 1; stirring for 0.9h to be uniform and standing for 0.6h to obtain sol;
step four, coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film, wherein the drying temperature is 60 ℃, the drying time is 10 hours, the calcining temperature is 500 ℃, and the calcining time is 5 hours
Step five, weighing 15g of urea, putting the urea into a crucible with a cover, wherein the filling amount of the urea in the crucible is 2/3 of the total capacity of the crucible, putting the crucible into a muffle furnace after sealing, heating the crucible from normal temperature to 550 ℃ at a speed of 10 ℃/min, calcining and preserving heat for 4 hours to obtain scaly carbon nitride precursor powder;
sixthly, weighing 0.05g of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution, wherein the concentration of the carbon nitride suspension aqueous solution is 0.6 g/L; and C, transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying, wherein the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining, the filling ratio of the materials in the reaction kettle is 83%, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: and 2.5, heating at 180 ℃ for 24h, drying at 60 ℃ for 1.4h to obtain the hexagonal nanosheet composite membrane layer containing the array macropores.
The scanning electron microscope picture of the obtained composite film layer is shown in FIG. 6, and it can be seen from FIG. 6 that g-C prepared by the invention3N4/TiO2The composite film layer is formed by compounding hexagonal nano flaky carbon nitride and titanium dioxide nano particles, and the shape of the carbon nitride nano sheet is regular; the developed pores in the film layer contain 400-1000 nm array macropores, 2-100nm mesopores lapped by nano sheets and 100-200nm mesopores.
Example 6
A preparation method of a hexagonal nanosheet composite membrane layer containing array macropores comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1: 1: 40, pouring 17ml of tetrabutyl titanate, 4.8ml of diethanolamine and 117ml of absolute ethyl alcohol into a mixing container, stirring at the stirring speed of 400rad/min for 10min, and uniformly stirring to obtain a mixed solution A;
step two, continuously dripping 2ml of water into the mixed solution A, wherein the mol ratio of the water to the tetrabutyl titanate used in the step one is 2.2: 1, dripping water into the mixed solution A at a speed of 20 s/drop, wherein the water is deionized water;
step three, adding 1.5g of polyethylene glycol 400 after the water dropping is finished, wherein the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is 0.075: 1; stirring for 1h to be uniform and standing for 0.5h to obtain sol;
step four, coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film, wherein the drying temperature is 60 ℃, the drying time is 10 hours, the calcining temperature is 500 ℃, and the calcining time is 5 hours
Step five, weighing 10g of urea, putting the urea into a crucible with a cover, wherein the filling amount of the urea in the crucible is 1/2 of the total capacity of the crucible, putting the crucible into a muffle furnace after sealing, heating the crucible from normal temperature to 550 ℃ at a speed of 10 ℃/min, calcining and preserving heat for 4 hours to obtain scaly carbon nitride precursor powder;
sixthly, weighing 0.042g of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution, wherein the concentration of the carbon nitride suspension aqueous solution is 0.5 g/L; and C, transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying, wherein the reaction kettle is a reaction kettle lined with polytetrafluoroethylene, the filling ratio of the materials in the reaction kettle is 85%, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: 1, heating at 180 ℃ for 24h, drying at 60 ℃ for 1.5h to obtain the hexagonal nanosheet composite membrane layer containing array macropores.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that various changes and modifications can be made on the basis of the above description, and all embodiments cannot be exhaustive, and obvious changes and modifications included in the technical solutions of the present invention are within the scope of the present invention.
Claims (9)
1. A hexagonal nanosheet composite membrane layer containing array macropores is characterized in that: the hexagonal nanosheet composite membrane layer containing the array macropores is formed by compounding hexagonal nanosheet-shaped carbon nitride and titanium dioxide nanoparticles, the thickness of the hexagonal nanosheet-shaped carbon nitride is 10-70 nm, the side length of the hexagonal nanosheet-shaped carbon nitride is 70-110 nm, and the composite membrane layer contains 0.8-2 nm micropores, 2-100nm mesopores and 400-1000 nm array macropores.
2. The preparation method of the hexagonal nanosheet composite membrane layer containing arrayed macropores according to claim 1, wherein the preparation method comprises the following steps:
step one, respectively measuring tetrabutyl titanate, diethanolamine and absolute ethyl alcohol, pouring into a mixing container, and uniformly stirring to obtain a mixed solution A;
continuously dripping a certain amount of water into the mixed solution A;
step three, adding a certain amount of polyethylene glycol 400 after water dripping is finished, uniformly stirring and standing to obtain sol;
coating the obtained sol on a ceramic chip, drying and calcining to obtain a substrate film;
step five, weighing a certain amount of urea, putting the urea into a crucible with a cover, sealing, putting the crucible into a furnace, calcining and preserving heat to obtain scale-shaped carbon nitride precursor powder;
step six, weighing a certain amount of the scale-shaped carbon nitride precursor powder, and ultrasonically dispersing the scale-shaped carbon nitride precursor powder in distilled water to prepare a carbon nitride suspension aqueous solution; and (4) transferring the carbon nitride suspension aqueous solution and the substrate film obtained in the fourth step into a reaction kettle simultaneously for heating, washing and drying to obtain the hexagonal nanosheet composite film layer containing the array macropores.
3. The preparation method of the hexagonal nanosheet composite membrane layer containing the arrayed macropores according to claim 2, wherein the preparation method comprises the following steps: in the first step, the molar ratio of tetrabutyl titanate, diethanolamine to absolute ethyl alcohol is 1: 1: (24-40), the stirring speed is 400rad/min, and the stirring time is 10 min.
4. The preparation method of the hexagonal nanosheet composite membrane layer containing the arrayed macropores according to claim 2, wherein the preparation method comprises the following steps: in the second step, the molar ratio of water to tetrabutyl titanate used in the first step is 2.2: 1, the speed of dripping water into the mixed solution A is 15-20 s/drop, and the water is deionized water.
5. The preparation method of the hexagonal nanosheet composite membrane layer containing the arrayed macropores according to claim 2, wherein the preparation method comprises the following steps: in the third step, the molar ratio of the polyethylene glycol 400 to the tetrabutyl titanate is (0.06-0.09): 1; the stirring time is 0.5-1 h, and the standing time is 0.5-1 h.
6. The preparation method of the hexagonal nanosheet composite membrane layer containing the arrayed macropores according to claim 2, wherein the preparation method comprises the following steps: in the fourth step, the drying temperature is 60 ℃, the drying time is 6-10 h, the calcining temperature is 500 ℃, and the calcining time is 5 h.
7. The preparation method of the hexagonal nanosheet composite membrane layer containing the arrayed macropores according to claim 2, wherein the preparation method comprises the following steps: and in the fifth step, the filling amount of the urea in the crucible is 1/2-2/3 of the total capacity of the crucible, the crucible is placed into a muffle furnace after being sealed, the temperature is raised to 550 ℃ from the normal temperature at the speed of 8-10 ℃/min, and the temperature is maintained for 4 hours.
8. The preparation method of the hexagonal nanosheet composite membrane layer containing the arrayed macropores according to claim 2, wherein the preparation method comprises the following steps: in the sixth step, the concentration of the carbon nitride suspension aqueous solution is 0.4-0.7 g/L, and the molar ratio of the carbon nitride to the titanium dioxide on the substrate film is 1: (1-3), the heating temperature is 180 ℃, the heating time is 24 hours, the drying temperature is 60 ℃, and the drying time is 1-1.5 hours.
9. The preparation method of the hexagonal nanosheet composite membrane layer containing the arrayed macropores according to claim 2 or 8, wherein: the reaction kettle is a reaction kettle lined with polytetrafluoroethylene, and the filling ratio of the materials in the reaction kettle is 70-85%.
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