CN108187714B - Preparation method of separable flexible catalytic membrane - Google Patents
Preparation method of separable flexible catalytic membrane Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012528 membrane Substances 0.000 title claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 54
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 7
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
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- 239000011941 photocatalyst Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
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- 230000000593 degrading effect Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 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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Abstract
The invention belongs to the technical field of preparation of novel composite films, and particularly relates to a flexible separable photocatalytic composite film BiVO4/g‑C3N4The preparation method of (1). Ultra-thin g-C3N4Preparing a solution with the molar concentration of 5-10 mg/mL; BiVO (bismuth oxide) is added4The powder is prepared according to the ratio of g-C in the solution3N4The mass ratio of (1-5: 1) is added into the solution, and the solution is stirred for 3-8 hours. And (3) adding 0.1-0.5 g of PVA (polyvinyl alcohol) into 10mL of the obtained mixed solution, heating while stirring until the PVA is dissolved, wherein the heating temperature is 80-100 ℃, and the heating time is 0.5-1.5 h. Transferring the mixed solution to a glass vessel with the diameter of 3-8 cm, placing the glass vessel in an oven, curing the glass vessel at 50-80 ℃ for 3-6 h, and taking out the glass vessel to obtain a final product BiVO4/g‑C3N4The flexible catalytic membrane can be separated.
Description
Technical Field
The invention belongs to the technical field of preparation of novel composite films, and particularly relates to a flexible separable photocatalytic composite film BiVO4/g-C3N4The preparation method of (1).
Background
In recent years, environmental problems have emerged due to the rapid development of society and the accelerated urbanization process. Wastewater and waste gas discharged from industrial production of factories; people produce domestic sewage in daily life; in agriculture, the problem of water pollution is getting worse and worse due to the large use of chemical substances such as chemical fertilizers and pesticides. The shortage of available water resources on earth, combined with the increasing water pollution, has severely restricted the development of human society. Therefore, the treatment of water pollution is very important.
At present, there are many methods for solving water pollution, and the methods are roughly classified into physical methods, chemical methods and biological methods. The photocatalysis technology is a typical chemical method and has a series of advantages of high efficiency, low energy consumption, no secondary pollution, simple operation and the like. The principle of the photocatalysis technology is to degrade organic pollutants into inorganic micromolecules such as carbon dioxide, water and the like under the action of a catalyst by utilizing sunlight. Common photocatalysts are mainly metal oxides and sulfides, such as TiO2，ZnO，SnO2，ZrO2CdS, etc.
BiVO4The photocatalyst is a novel photocatalyst with strong visible light response and has good photocatalytic performance. g-C3N4The photocatalyst is a two-dimensional layered non-metal photocatalytic material, and has good stability and capability of degrading organic pollutants. Although a single powder material can also be used for degrading pollutants, a series of problems exist, such as secondary pollution caused by difficult recovery, small specific surface area, poor adsorption performance, easy agglomeration, necessity of a suspension system for catalyst powder and the like. However, the membrane has the advantages of large specific surface area, easy recovery and the like, and can well solve the problems. Most of the membranes currently studied have a substrate, which limits the reaction sites. The g-C3N4 material is non-toxic, and the precursor is cheap; the forbidden band width is 2.7eV, and the photocatalyst is suitable for being used as a photocatalyst; the relative position of the conduction band valence band is also suitable for photocatalysis; g-C3N4The lamellar structure of the nano-material makes the nano-material have larger specific surface area and is suitable for being used as a carrier of the nano-material.
The method enables BiVO4Particle loading g-C3N4The two precursors can generate a synergistic catalytic effect, so that the photocatalytic performance is effectively improved, and organic pollutants are better degraded.
Disclosure of Invention
The invention aims to provide a novel method for preparing a photocatalytic composite film BiVO4/g-C3N4The method of (1).
The method is adopted to prepare the photocatalytic complexBiVO (BiVO) of synthetic film material4/g-C3N4The raw material used is CH4N2O (analytically pure), NH4VO3(analytically pure) Bi (NO)3)3·5H2O (analytically pure), NaOH (analytically pure), HNO3(analytically pure), ammonia (analytically pure).
The preparation method comprises the following steps:
(1) mixing urea (CH)4N2O) is heated to 550 ℃ at the heating rate of 2 ℃/min and then calcined at the temperature of 550 ℃ for 4 hours to obtain g-C3N4(ii) a The g-C obtained3N4Calcining at the temperature rising rate of 5 ℃/min to 550 ℃ and then keeping the temperature at 550 ℃ for 1h to obtain the thin g-C3N4(ii) a Cutting the thin g-C3N4Calcining at the temperature rising rate of 2 ℃/min to 550 ℃ and then keeping the temperature at 550 ℃ for 1h to obtain ultrathin g-C3N4And (3) sampling.
(2) Reacting NH4VO3Dissolved in 2mol/L NaOH solution, Bi (NO)3)3·5H2HNO with O dissolved in 2mol/L3The solutions are prepared into solutions with the molar concentration of 0.5-2 mol/L. According to Bi3+And V5+Mixing the two solutions according to a molar ratio of 1:1, stirring the mixed solution on a magnetic stirrer for 0.5-1 h, and adjusting the pH value of the solution to 8 by using commercially available ammonia water and 1mol/L nitric acid solution. Continuously stirring for 0.5-2 h. And then transferring the mixed solution to a reaction kettle, and placing the reaction kettle in an oven for hydrothermal treatment for 15-24 hours at 160-200 ℃. Washing the obtained precipitate with water, and drying at 50-80 ℃ to obtain BiVO4And (3) sampling.
(3) g-C obtained in the preparation method (1)3N4Preparing the powder into a solution with the concentration of 5-10 mg/mL, preferably 10 mg/mL; BiVO in the preparation method (2)4The powder is prepared according to the ratio of g-C in the solution3N4Is added into the solution in a mass ratio of 1-5: 1, preferably 3:1, and is stirred for 3-8 hours.
(4) And (3) adding 0.1-0.5 g of PVA (polyvinyl alcohol) into 10mL of the mixed solution obtained in the preparation method (3), heating while stirring until the mixed solution is dissolved, wherein the heating temperature is 80-100 ℃, and the heating time is 0.5-1.5 h.
(5) Transferring the mixed solution to a glass vessel with the diameter of 3-8 cm, placing the glass vessel in an oven, curing the glass vessel at 50-80 ℃ for 3-6 h, and taking out the glass vessel to obtain a final product BiVO4/g-C3N4The flexible catalytic membrane can be separated.
The invention has the advantages of controlling g-C3N4Concentration of powder solution, BiVO4Powder and g-C3N4The mass ratio of (A) to (B), the BiVO prepared4/g-C3N4The separable photocatalytic composite film has good flexibility and high photocatalytic efficiency, can quickly degrade methylene blue and methyl orange, can be separated and recycled after the film is used, and cannot cause secondary pollution to water. The preparation process of the membrane is simple and easy to operate.
Drawings
BiVO prepared in figure 14/g-C3N4The macro topography of (a) can be seen, the film is flexible.
BiVO prepared in figure 24/g-C3N4The XRD pattern of the compound can show diffraction peaks and BiVO in the pattern4The standard cards of the monoclinic scheelite type structure are matched.
BiVO prepared in figure 34/g-C3N4The SEM image shows that there are a large number of BiVOs4The particles are loaded in g-C3N4On the sheet layer.
FIG. 4 is a graph showing the effect of degrading methylene blue by using the prepared membrane, and it can be seen from the graph that the sample in example 2 has the best photocatalytic effect.
Detailed Description
Example 1
Mixing urea (CH)4N2O) is heated to 550 ℃ at the heating rate of 2 ℃/min and then calcined at the temperature of 550 ℃ for 4 hours to obtain g-C3N4(ii) a The g-C obtained3N4Calcining at the temperature rising rate of 5 ℃/min to 550 ℃ and then keeping the temperature at 550 ℃ for 1h to obtain the thin g-C3N4(ii) a Cutting the thin g-C3N4Calcining at the temperature rising rate of 2 ℃/min to 550 ℃ and then keeping the temperature at 550 ℃ for 1h to obtain ultrathin g-C3N4And (3) sampling. Reacting NH4VO3Dissolved in 2mol/L NaOH solution, Bi (NO)3)3·5H2HNO with O dissolved in 2mol/L3The solutions were all prepared to a molar concentration of 0.5 mol/L. Separately, 10mL of NH were dispensed4VO3Solution and 10mL of Bi (NO)3)3·5H2And mixing the O solution, stirring the mixture on a magnetic stirrer for 0.5h, and adjusting the pH to 8 by using ammonia water and 1mol/L nitric acid solution. Stirring was continued for 1 h. Then the mixed solution is moved to a reaction kettle and is placed in an oven for hydrothermal treatment at 160 ℃ for 18 hours. Washing the obtained precipitate with water, and drying at 50 ℃ to obtain BiVO4And (3) sampling. G to C3N4Preparing solution with the molar concentration of 5mg/mL and 50mg of BiVO4Dispersed in 10mL of g-C3N4And stirring the lamellar solution in a magnetic stirrer until the solution is uniform, wherein the heating temperature is 80 ℃, and the heating time is 0.5 h. To 10mL of the solution obtained above, 0.3g of PVA (polyvinyl alcohol) was added and the mixture was stirred while heating until dissolved. Transferring the obtained mixed solution to a glass vessel, placing the glass vessel in an oven, curing the mixed solution for 3 hours at the temperature of 50 ℃, and taking out the glass vessel to obtain the BiVO4/g-C3N4A photocatalytic composite film.
Example 2
Examples g to C3N4The preparation process of (a) was substantially the same as in example 1. Reacting NH4VO3Dissolved in 2mol/L NaOH solution, Bi (NO)3)3·5H2HNO with O dissolved in 2mol/L3The solutions are prepared into a solution with the molar concentration of 1 mol/L. Separately, 10mL of NH were dispensed4VO3Solution and 10mL of Bi (NO)3)3·5H2And mixing the O solution, stirring the mixture on a magnetic stirrer for 0.5h, and adjusting the pH to 8 by using ammonia water and 1mol/L nitric acid solution. Stirring was continued for 1.5 h. Then the mixed solution is transferred to a reaction kettle and is put in an oven for hydrothermal treatment for 20 hours at 180 ℃. Washing the obtained precipitate with water, and drying to obtain BiVO4And (3) sampling. G to C3N4Preparing a solution with the molar concentration of 10mg/mL,300mg of BiVO4g-C dissolved in 10mL3N4And stirring the lamellar solution in a magnetic stirrer until the solution is uniform. To 10mL of the solution obtained above, 0.1g of PVA (polyvinyl alcohol) was added and the mixture was dissolved by stirring with heating at 100 ℃ for 1.5 hours. Transferring the obtained mixed solution to a glass vessel, placing the glass vessel in an oven, curing the mixed solution for 3 hours at the temperature of 55 ℃, and taking out the glass vessel to obtain the photocatalytic composite film BiVO4/g-C3N4。
Example 3
Examples g to C3N4The preparation process of (a) was substantially the same as in example 1. Reacting NH4VO3Dissolved in 2mol/L NaOH solution, Bi (NO)3)3·5H2HNO with O dissolved in 2mol/L3The solutions are prepared into a solution with the molar concentration of 1 mol/L. Separately, 10mL of NH were dispensed4VO3Solution and 10mL of Bi (NO)3)3·5H2And mixing the O solution, stirring the mixture on a magnetic stirrer for 1 hour, and adjusting the pH to 8 by using ammonia water and 1mol/L nitric acid solution. Stirring was continued for 2 h. Then the mixed solution is transferred to a reaction kettle and is put in an oven for hydrothermal treatment at 200 ℃ for 24 hours. Washing the obtained precipitate with water, and drying to obtain BiVO4And (3) sampling. G to C3N4Preparing solution with the molar concentration of 7mg/mL and 350mg of BiVO4Disperse 10mL of g-C3N4And stirring the lamellar solution in a magnetic stirrer until the solution is uniform. To 10mL of the solution obtained above, 0.5g of PVA (polyvinyl alcohol) was added and the mixture was dissolved by stirring with heating at 90 ℃ for 1 hour. Transferring the obtained mixed solution to a glass vessel, placing the glass vessel in an oven, curing the mixed solution for 6 hours at the temperature of 60 ℃, and taking out the glass vessel to obtain the photocatalytic composite film BiVO4/g-C3N4。
The films prepared in the above three examples are shown in fig. 1, and the films have very good flexibility in combination with video. FIG. 3 is an SEM photograph of the film prepared in example 2, and it can be seen that a large amount of BiVO is present4The particles are loaded in g-C3N4On the sheet layer. As can be seen from the degradation effect diagram in fig. 4, the composite membrane prepared by the method 2 has the optimal photocatalytic performance.
Claims (5)
1. A preparation method of a separable flexible catalytic membrane is characterized by comprising the following specific steps:
(1) ultra-thin g-C3N4Preparing a powder sample into a solution;
(2) BiVO (bismuth oxide) is added4The powder is prepared according to the ratio of g-C in the solution3N4Adding the mixed solution into the solution in a mass ratio of 1-5: 1, and stirring to obtain a mixed solution 1;
(3) adding polyvinyl alcohol into the mixed solution 1, and stirring while heating until the polyvinyl alcohol is dissolved to obtain a mixed solution 2;
(4) transferring the mixed solution 2 to a glass vessel, placing the glass vessel in an oven for curing, and taking out the glass vessel to obtain a final product BiVO4/g-C3N4A separable flexible catalytic membrane;
in the step (3), 0.1-0.5 g of polyvinyl alcohol is added into each 10mL of the mixed solution 1; the heating temperature is 80-100 ℃, and the heating time is 0.5-1.5 h;
in the step (4), the diameter of the glass vessel is 3-8 cm; the curing refers to curing for 3-6 h at 50-80 ℃;
said ultra-thin g-C3N4The preparation method of the powder sample comprises the following steps: mixing urea (CH)4N2O) is heated to 550 ℃ at the heating rate of 2 ℃/min and then calcined at the temperature of 550 ℃ for 4 hours to obtain g-C3N4(ii) a The g-C obtained3N4Calcining at the temperature rising rate of 5 ℃/min to 550 ℃ and then keeping the temperature at 550 ℃ for 1h to obtain the thin g-C3N4(ii) a Cutting the thin g-C3N4Calcining at the temperature rising rate of 2 ℃/min to 550 ℃ and then keeping the temperature at 550 ℃ for 1h to obtain ultrathin g-C3N4A sample;
the BiVO4The preparation method of the powder comprises the following steps: reacting NH4VO3Dissolved in 2mol/L NaOH solution, Bi (NO)3)3·5H2HNO with O dissolved in 2mol/L3The solutions are prepared into solutions with the molar concentration of 0.5-2 mol/L according to Bi3+And V5+Mixing two in a molar ratio of 1:1And (2) inoculating the solution, stirring the mixed solution on a magnetic stirrer for 0.5-1 h, adjusting the pH value of the solution to 8 by using commercially available ammonia water and 1mol/L nitric acid solution, continuously stirring for 0.5-2 h, transferring the mixed solution to a reaction kettle, placing the reaction kettle in a drying oven for hydrothermal treatment at 160-200 ℃ for 15-24 h, washing the obtained precipitate with water, and drying at 50-80 ℃ to obtain BiVO4And (3) sampling.
2. The method for preparing a separable flexible catalytic membrane according to claim 1, wherein in the step (1), the concentration of the solution is 5 to 10 mg/mL.
3. The method for preparing a separable flexible catalytic membrane according to claim 1, wherein in the step (2), the stirring time is 3 to 8 hours.
4. The method for preparing a detachable flexible catalytic membrane according to claim 2, wherein in the step (1), the concentration of the solution is 10 mg/mL.
5. The method for preparing a separable flexible catalytic membrane according to claim 1, wherein in the step (2), BiVO is used4Powder and g-C3N4In a mass ratio of 3: 1.
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