CN110841711A - Supermolecular heterojunction organic photocatalyst and preparation method and application method thereof - Google Patents
Supermolecular heterojunction organic photocatalyst and preparation method and application method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 20
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical group Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 117
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 230000000593 degrading effect Effects 0.000 claims abstract description 6
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 37
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- 238000005406 washing Methods 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 23
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- 239000011550 stock solution Substances 0.000 claims description 22
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- 238000003756 stirring Methods 0.000 claims description 17
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000002121 nanofiber Substances 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 229940000635 beta-alanine Drugs 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 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 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 abstract 8
- 239000002994 raw material Substances 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 101000734336 Arabidopsis thaliana Protein disulfide isomerase-like 1-2 Proteins 0.000 description 30
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- 101000609815 Caenorhabditis elegans Protein disulfide-isomerase 1 Proteins 0.000 description 22
- 101000609840 Caenorhabditis elegans Protein disulfide-isomerase 2 Proteins 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- ZOCMPVMKPVJTEP-UHFFFAOYSA-N diphepanol Chemical compound C=1C=CC=CC=1C(O)(C=1C=CC=CC=1)C(C)N1CCCCC1 ZOCMPVMKPVJTEP-UHFFFAOYSA-N 0.000 description 13
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- 239000000843 powder Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 101100135890 Caenorhabditis elegans pdi-6 gene Proteins 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000010170 biological method Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 206010007269 Carcinogenicity Diseases 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a supramolecular heterojunction organic photocatalyst, a preparation method and an application method thereof, wherein the photocatalyst is a BiOCl/PDI photocatalyst, a sheet BiOCl is prepared by adopting a hydrothermal method, Perylene Diimide (PDI) is synthesized by adopting an organic synthesis method, the BiOCl and the PDI are taken as raw materials to synthesize the BiOCl/PDI photocatalyst in a hydrothermal mode, or the BiOCl and acidified PDI are taken as raw materials to synthesize the BiOCl/PDI photocatalyst in a hydrothermal mode, and the application method of the photocatalyst for degrading organic micro-pollutant wastewater is provided. The BiOCl/PDI supermolecule photocatalyst prepared by the invention has the advantages of simple preparation process and high yield, can carry out high-efficiency photocatalytic degradation on organic micropollutants in water under the conditions of no additional addition of oxidant and neutrality, and has better photocatalytic effect on cationic pollutants.
Description
Technical Field
The invention relates to a photocatalyst, a preparation method and an application method thereof, in particular to a supermolecular heterojunction organic photocatalyst, a preparation method and an application method thereof, and belongs to the field of wastewater treatment.
Background
With the development of the dye chemical industry, dyes are widely applied to the industries of textile, leather, food, daily chemical industry and the like. China is a large dye production country at present, the dye yield reaches 99 million in 2017, and the dye yield shows a trend of rising year by year. The printing and dyeing wastewater has the characteristics of large water quantity, large chromaticity, high content of organic pollutants, stability, difficult degradation and the like, and belongs to one of the industrial wastewater difficult to treat. On the other hand, phenol and its derivatives are important toxic pollutants which are difficult to degrade and treat in the sewage generated in paper mills, dye manufacturing industries and oil refineries, can cause pollution to water bodies and atmosphere, and have corrosiveness, carcinogenicity and the like. The traditional treatment methods comprise a physical method, a chemical method and a biological method, but the physical method has high cost, organic pollutants cannot be completely removed, the chemical method can cause secondary pollution, and the biological method has long period and is greatly influenced by the surrounding environment.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a supramolecular heterojunction organic photocatalyst with high degradation efficiency, low cost and no secondary pollution, the second purpose of the invention is to provide a preparation method of the photocatalyst, and the third purpose of the invention is to provide an application method of the photocatalyst in degrading organic micropollutant wastewater.
The technical scheme is as follows: the supermolecular heterojunction organic photocatalyst is a BiOCl/PDI photocatalyst.
Further, the mass ratio of BiOCl to PDI is 0.25-1: 1.
Furthermore, BiOCl is a flaky BiOCl prepared by a hydrothermal method.
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
(1) reacting NH4Cl solution to Bi (NO)3)3·5H2In O solution, hydrothermal reaction is carried out at the temperature of 140-160 ℃, and the BiOCl is obtained after washing, drying and calcining, wherein NH4Cl and Bi (NO)3)3·5H2The mass ratio of O is 1: 8-9;
(2) perylene-3, 4,9, 10-tetracarboxylic dianhydride, β -alanine and imidazole are organically synthesized at the mass ratio of 1:1.8:10-15 under the nitrogen atmosphere and at the temperature of 100-4The mass ratio of Cl is 1500-;
(3) filtering, washing and drying to obtain PDI;
(4) preparing a PDI stock solution with the concentration of 5-10mM, adding triethylamine and BiOCl, stirring and performing ultrasonic treatment;
(5) heating to 50-60 deg.C, adding HNO3Stirring the solution, filtering, washing and drying; wherein, the HNO3The mass ratio of the PDI to the PDI is 1-2: 1;
further, the mass ratio of triethylamine to PDI in step (4) is 1: 600-650.
Preferably, the calcination in step (1) is carried out in an air atmosphere at 400-450 ℃ for 5-6 hours.
Preferably, the filtering in step (3) is to suction-filter the product in step (2) using a 0.22-0.45 μm filter to obtain a glossy red solid, the washing in step (3) is to wash thoroughly with deionized water until the pH of the solution becomes 6.5-7.5, and the drying in step (3) is to dry the collected red solid in a vacuum oven.
Preferably, the heating mode in the step (5) is water bath.
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
(1) reacting NH4Cl solution to Bi (NO)3)3·5H2In O solution, hydrothermal reaction is carried out at the temperature of 140-160 ℃, and the BiOCl is obtained after washing, drying and calcining, wherein NH4Cl and Bi (NO)3)3·5H2The mass ratio of O is 1: 8-9;
(2) perylene-3, 4,9, 10-tetracarboxylic dianhydride, β -alanine and imidazole are organically synthesized at the mass ratio of 1:1.8:10-15 under the nitrogen atmosphere and at the temperature of 100-4The mass ratio of Cl is 1500-;
(3) filtering, washing and drying to obtain PDI;
(4) preparing a PDI stock solution with the concentration of 5-10mM, adding a triethylamine solution, and then adding HNO3Forming PDI nano fiber through solution, filtering, washing and drying; wherein, the HNO3The mass ratio of the PDI to the PDI is 1-2: 1;
(5) preparing a PDI nanofiber stock solution with the concentration of 5-10mM, adding triethylamine and BiOCl, stirring and performing ultrasonic treatment.
(6) Heating to 50-60 deg.C and adding HNO3Stirring the solution, filtering, washing and drying; wherein, HNO3The mass ratio of the PDI to the PDI is 1-2: 1.
Further, the mass ratio of triethylamine to PDI in the steps (4) and (5) is 1: 600-650.
Preferably, the calcination in step (1) is carried out in an air atmosphere at 400-450 ℃ for 5-6 hours.
Preferably, the filtering in step (3) is to suction-filter the product in step (2) using a 0.22-0.45 μm filter to obtain a glossy red solid, the washing in step (3) is to wash thoroughly with deionized water until the pH of the solution becomes 6.5-7.5, and the drying in step (3) is to dry the collected red solid in a vacuum oven.
Preferably, the heating mode in the step (6) is water bath.
Further, the application method of the supramolecular heterojunction organic photocatalyst in degradation of organic micropollutant wastewater comprises the following steps:
adding 25-50mg of photocatalyst into the organic micro-pollutant wastewater; carrying out visible light catalytic reaction.
Further, the organic micro-pollutant wastewater is one of phenol, methyl orange or rhodamine B wastewater.
Further, dark adsorption is carried out before visible light catalytic reaction, and visible light catalytic reaction is carried out after adsorption balance is achieved.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the material of the supermolecular heterojunction organic photocatalyst is electronegative, so that the supermolecular heterojunction organic photocatalyst has strong adsorption performance on cationic dye and high degradation efficiency; the cost is low and the mass preparation is easy; no secondary pollution is caused;
(2) compared with the traditional preparation method, the preparation method of the supermolecular heterojunction organic photocatalyst has the advantages that BiOCl is added in the PDI self-assembly process to form a BiOCl/PDI supermolecular heterojunction, the preparation process is simple, the preparation condition is mild, and the large-scale production is easy to realize;
(3) the application method of the supermolecule heterojunction organic photocatalyst disclosed by the invention can be used for rapidly degrading low-concentration printing and dyeing wastewater and phenol under a neutral condition without adding other oxidants; the device is practical, strong in operability, energy-saving and environment-friendly.
Drawings
FIG. 1(a) is a scanning electron micrograph of BiOCl/PDI-2 prepared according to the present invention;
FIG. 1(b) is a transmission electron micrograph of a BiOCl/PDI-2 heterojunction prepared according to the present invention;
FIG. 2 is the X-ray diffraction pattern of BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 supermolecular heterojunction photocatalysts prepared by the present invention;
FIG. 3 is a graph of the quasi-first order kinetics and quasi-second order kinetics of adsorption of 10ppm RhB by BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 photocatalysts prepared according to the present invention;
FIG. 4 is a graph comparing the effect of BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 prepared according to the present invention on photo-degradation of 5ppm phenol, MO, RhB and 10ppm RhB;
FIG. 5 is a graph comparing the kinetics of photodegradation of 5ppm phenol, MO, RhB and 10ppm RhB by BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 prepared according to the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
according to NH4Cl and Bi (NO)3)3·5H2The mass ratio of O to NH is 1:84Cl solution was added rapidly to Bi (NO)3)3·5H2In the O solution and stirring is continued, the reaction system immediately becomes a white suspension. The suspension was poured into a 50mL polytetrafluoroethylene high-pressure hydrothermal kettle, and subjected to hydrothermal reaction at 140 ℃ for 12 hours. After the hydrothermal reaction is finished, washing the reaction product with deionized water and ethanol for three times, drying the powder at 80 ℃ in vacuum, and calcining the powder for 5 hours at 400 ℃ in an air atmosphere to obtain a BiOCl sample, wherein an XRD (X-ray diffraction) spectrum of the BiOCl sample is shown in figure 2.
Perylene-3, 4,9, 10-tetracarboxylic dianhydride, β -alanine and imidazole are placed in a four-neck flask according to the mass ratio of 1:1.8:10, heated for 4 hours at 110 ℃ under nitrogen atmosphere, reacted and cooled, and then added with ethanol, HCl and NH4Ethanol and HCl were added at a mass ratio of 1500:180:1 and stirred overnight. A glossy red solid was obtained by suction filtration using a 0.45 μm filter and washed thoroughly with distilled water until the pH of the solution became neutral. Finally, the collected red solid was dried in a vacuum oven to obtain a PDI sample, whose XRD pattern is shown in fig. 2.
A5 mM PDI stock solution was prepared and triethylamine was added in a mass ratio of 1:600 to PDI while maintaining stirring. BiOCl (250mg) was added to the stock solution containing 500mg PDI and stirred for 30 min, and sonicated for 30 min. Heating the solution to 60 ℃ and adding HNO3Adding HNO into PDI at the mass ratio of 1:13And stirred for 1 hour. The product is washed to be neutral by centrifugation and dried in a vacuum oven at 60 ℃ to obtain the BiOCl/PDI-1 supramolecular heterojunction photocatalyst, and the XRD pattern of the photocatalyst is shown in figure 2.
Example 2
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
a stock solution of 5mM PDI was prepared using the PDI prepared in example 1 and a triethylamine solution was continuously added at a triethylamine to PDI mass ratio of 1: 600. Then according to HNO3Adding HNO into PDI at the mass ratio of 1:13To form PDI nanofibers. It was washed to neutrality with distilled water and the collected solid was dried under vacuum at 60 ℃. Preparing a 5mM PDI nanofiber stock solution, adding triethylamine according to the mass ratio of the triethylamine to the PDI of 1:600, and keeping stirring. BiOCl (500mg) was added to the stock solution containing 500mg of nanofibers PDI and stirred for 30 minutes, followed by sonication for 30 minutes. The solution was heated to 60 ℃ by a water bath and treated with HNO3Adding HNO into PDI at the mass ratio of 1:13And stirred for 1 hour. Washing the red product to be neutral by centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the BiOCl/PDI-2 supramolecular heterojunction photocatalyst, wherein scanning electron micrographs and transmission electron micrographs of the catalyst are shown in figures 1(a) - (b), and an XRD (X-ray diffraction) spectrum is shown in figure 2.
Example 3
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
according to NH4Cl and Bi (NO)3)3·5H2The mass ratio of O to NH is 1:94Cl solution was added rapidly to Bi (NO)3)3·5H2In the O solution and stirring is continued, the reaction system immediately becomes a white suspension. The suspension was poured into a 50mL polytetrafluoroethylene high-pressure hydrothermal kettle, and subjected to hydrothermal reaction at 160 ℃ for 12 hours. After the hydrothermal reaction is finished, washing the reaction product with deionized water and ethanol for three times, drying the powder at 80 ℃ in vacuum, and calcining the powder for 5 hours at 400 ℃ in an air atmosphere to obtain a BiOCl sample.
Perylene-3, 4,9, 10-tetracarboxylic dianhydride, β -alanine and imidazole are placed in a four-neck flask according to the mass ratio of 1:1.8:15, heated for 4 hours at 100 ℃ under nitrogen atmosphere, reacted and cooled, and then added with ethanol, HCl and NH4Ethanol and HCl were added at a Cl mass ratio of 1600:180:1 and stirred overnight. Using a 0.45 μm filter by suctionA glossy red solid was obtained by filtration and washed thoroughly with distilled water until the pH of the solution became neutral. Finally, the collected red solid was dried in a vacuum oven to obtain a PDI sample.
A10 mM PDI stock solution was prepared and triethylamine was added in a mass ratio of 1:650 while maintaining stirring. BiOCl (125mg) was added to the stock solution containing 500mg PDI and stirred for 30 min, and sonicated for 30 min. Heating the solution to 50 ℃ and adding HNO3Adding HNO into PDI in a mass ratio of 2:13And stirred for 1 hour. And washing the product to be neutral by centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the BiOCl/PDI-3 supramolecular heterojunction photocatalyst.
Example 4
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
according to NH4Cl and Bi (NO)3)3·5H2The mass ratio of O to NH is 1:8.54Cl solution was added rapidly to Bi (NO)3)3·5H2In the O solution and stirring is continued, the reaction system immediately becomes a white suspension. The suspension was poured into a 50mL polytetrafluoroethylene high-pressure hydrothermal kettle, and subjected to hydrothermal reaction at 150 ℃ for 12 hours. After the hydrothermal reaction is finished, washing the reaction product with deionized water and ethanol for three times, drying the powder at 80 ℃ in vacuum, and calcining the powder for 5 hours at 400 ℃ in an air atmosphere to obtain a BiOCl sample.
Perylene-3, 4,9, 10-tetracarboxylic dianhydride, β -alanine and imidazole are placed in a four-neck flask according to the mass ratio of 1:1.8:12, heated for 4 hours at 105 ℃ under nitrogen atmosphere, reacted and cooled, and then added with ethanol, HCl and NH4Ethanol and HCl were added at a Cl mass ratio of 1550:180:1 and stirred overnight. A glossy red solid was obtained by suction filtration using a 0.45 μm filter and washed thoroughly with distilled water until the pH of the solution became neutral. Finally, the collected red solid was dried in a vacuum oven to obtain a PDI sample.
A stock solution of 8mM PDI was prepared and triethylamine was added in a mass ratio of 1:630 triethylamine to PDI while maintaining stirring. BiOCl (250mg) was added to the stock solution containing 500mg PDI and stirred for 30 minAnd sonicated for 30 minutes. Heating the solution to 55 ℃ and adding HNO3Adding HNO with the mass ratio of 1.5:1 to PDI3And stirred for 1 hour. And washing the product to be neutral by centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the BiOCl/PDI-4 supramolecular heterojunction photocatalyst.
Example 5
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
a10 mM PDI stock solution was prepared using the PDI prepared in example 1 and a triethylamine solution was prepared at a weight ratio of triethylamine to PDI of 1: 650. Then according to HNO3Adding HNO into PDI in a mass ratio of 2:13To form PDI nanofibers. It was washed to neutrality with distilled water and the collected solid was dried under vacuum at 60 ℃. Preparing a 10mM PDI nanofiber stock solution, adding triethylamine according to the mass ratio of the triethylamine to the PDI of 1:650, and keeping stirring. BiOCl (250mg) was added to the stock solution containing 500mg of nanofibers PDI and stirred for 30 minutes, followed by sonication for 30 minutes. The solution was heated to 50 ℃ by a water bath and treated with HNO3Adding HNO into PDI in a mass ratio of 2:13And stirred for 1 hour. And washing the red product to be neutral by centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the BiOCl/PDI-5 supramolecular heterojunction photocatalyst.
Example 6
The preparation method of the supramolecular heterojunction organic photocatalyst comprises the following steps:
an 8mM PDI stock solution was prepared using the PDI prepared in example 1 and a triethylamine solution was continuously added at a triethylamine to PDI mass ratio of 1: 630. Then according to HNO3Adding HNO with the mass ratio of 1.5:1 to PDI3To form PDI nanofibers. It was washed to neutrality with distilled water and the collected solid was dried under vacuum at 60 ℃. Preparing 8mM PDI nanofiber stock solution, adding triethylamine according to the mass ratio of the triethylamine to the PDI being 1:630, and keeping stirring. BiOCl (250mg) was added to the stock solution containing 500mg of nanofibers PDI and stirred for 30 minutes, followed by sonication for 30 minutes. The solution was heated to 55 ℃ by a water bath and treated with HNO3And the quality of PDIHNO is added in the ratio of 1.5:13And stirred for 1 hour. And washing the red product to be neutral by centrifugation, and drying in a vacuum oven at 60 ℃ to obtain the BiOCl/PDI-6 supramolecular heterojunction photocatalyst.
Example 7
50mg of the prepared BiOCl/PDI-3 photocatalyst is weighed into a colorimetric tube, 50mL of RhB with the concentration of 10ppm is respectively added to react for 180 minutes under dark reaction, and the residual concentration of the RhB is measured by using an ultraviolet-visible spectrophotometer. BiOCl/PDI-3 has stronger adsorption performance on RhB, and the saturated adsorption capacity is 7.74mg/g (R)2＝0.996)。
Example 8
35mg of the prepared BiOCl/PDI-4 photocatalyst is weighed into a colorimetric tube, 50mL of RhB with the concentration of 10ppm is respectively added to the colorimetric tube, the RhB is firstly reacted for 180 minutes under dark reaction, and the residual concentration of the RhB is measured by using an ultraviolet-visible spectrophotometer. BiOCl/PDI-4 has stronger adsorption performance on RhB, and the saturated adsorption capacity is 8.16mg/g (R)2＝0.992)。
Example 9
Weighing 25mg of prepared BiOCl/PDI-5 photocatalyst into a colorimetric tube, respectively adding 50mL of RhB with the concentration of 10ppm, reacting for 180 minutes under a dark reaction, and measuring the residual concentration of the RhB by using an ultraviolet-visible spectrophotometer. BiOCl/PDI-5 has stronger adsorption performance on RhB, and the saturated adsorption capacity is 11.28mg/g (R)2＝0.999)。
Example 10
Weighing 25mg of prepared BiOCl/PDI-6 photocatalyst into a colorimetric tube, respectively adding 50mL of RhB with the concentration of 10ppm, reacting for 180 minutes under a dark reaction, and measuring the residual concentration of the RhB by using an ultraviolet-visible spectrophotometer. BiOCl/PDI-6 has stronger adsorption performance on RhB, and the saturated adsorption capacity is 9.30mg/g (R)2＝0.993)。
Comparative example 1
Weighing 25mg of prepared BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 photocatalyst in a colorimetric tube, respectively adding 50mL of RhB with the concentration of 10ppm, reacting for 180 minutes under a dark reaction, and measuring the residual concentration of the RhB by using an ultraviolet visible spectrophotometer. As shown in FIG. 3, BiOCl/PDI-1 and BiOCl/PDI-2 both have strong adsorption to RhBThe performance and the saturated adsorption capacity are respectively 8.84mg/g (R)20.997) and 10.00mg/g (R)2＝0.999)。
Comparative example 2
Weighing 25mg of prepared BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 photocatalyst into a colorimetric tube, respectively adding 50mL of phenol with the concentration of 5ppm, reacting for 30 minutes under a dark reaction, after reaching adsorption equilibrium, reacting for 4 hours under a xenon lamp (420nm filter) with the power of 800W, and measuring the residual concentration of the phenol by using High Performance Liquid Chromatography (HPLC), as shown in fig. 4 and 5, the PDI, the BiOCl/PDI-1 and the BiOCl/PDI-2 can degrade the phenol under visible light, the degradation efficiency of the BiOCl/PDI-2 is relatively higher, the degradation rate is faster, and the degradation rate of the phenol can reach 60.4%.
Comparative example 3
Weighing 25mg of prepared BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 photocatalyst into a colorimetric tube, respectively adding 50mL of anionic dye MO with the concentration of 5ppm, reacting for 30 minutes under a dark reaction, after reaching adsorption equilibrium, reacting for 3 hours under a 800W xenon lamp (420nm filter), and measuring the residual concentration of the MO by using an ultraviolet visible spectrophotometer, wherein the PDI, the BiOCl/PDI-1 and the BiOCl/PDI-2 shown in figures 4 and 5 can degrade the MO under visible light, the degradation efficiency of the BiOCl/PDI-1 and the degradation efficiency of the BiOCl/PDI-2 are similar, and the degradation rate of the MO can reach 70.7% and 73.4%.
Comparative example 4
Weighing 25mg of prepared BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 photocatalyst into a colorimetric tube, respectively adding 50mL of cationic dye RhB with the concentration of 5ppm, reacting for 30 minutes under dark reaction, after reaching adsorption equilibrium, reacting for 3 hours under a 800W xenon lamp (420nm filter), and measuring the residual concentration of RhB by using ultraviolet visible spectrophotometry, as shown in FIG. 4 and FIG. 5, wherein BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 can degrade RhB under visible light, and the degradation efficiency of BiOCl/PDI-2 is higher and the degradation rate is faster and can reach 100%.
Comparative example 5
Weighing 25mg of prepared BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 photocatalyst into a colorimetric tube, respectively adding 50mL of cationic dye RhB with the concentration of 10ppm, reacting for 30 minutes under dark reaction, after reaching adsorption equilibrium, reacting for 3 hours under a 800W xenon lamp (420nm filter), and measuring the residual concentration of RhB by using ultraviolet visible spectrophotometry, as shown in FIG. 4 and FIG. 5, wherein BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 can degrade RhB under visible light, and the degradation efficiency of BiOCl/PDI-2 is higher, the degradation rate is faster and can reach 99.5%.
Examples 1 to 10 BiOCl sheets were prepared by hydrothermal method, PDI supramolecular photocatalyst was synthesized by organic synthesis method, BiOCl/PDI-1 and BiOCl/PDI-2 were obtained by water bath heating method by changing stock solution concentration, triethylamine to PDI mass ratio, BiOCl mass, PDI mass, water bath heating temperature and HNO3BiOCl/PDI-3, BiOCl/PDI-4, BiOCl/PDI-5 and BiOCl/PDI-6 obtained by mass ratio of the molecular sieve to PDI have stronger adsorption capacity on RhB.
Comparative examples 1 to 5, BiOCl/PDI-1 and BiOCl/PDI-2 both had strong adsorption performance for RhB, and the saturated adsorption amounts were 8.84mg/g (R)20.997) and 10.00mg/g (R)20.999), the BiOCl/PDI-2 has relatively higher degradation efficiency and higher degradation rate, and the degradation rate of phenol can reach 60.4%. PDI, BiOCl/PDI-1 and BiOCl/PDI-2 can degrade MO under visible light, the degradation efficiency of BiOCl/PDI-1 and BiOCl/PDI-2 is similar, and the degradation rate of MO can reach 70.7% and 73.4%. BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 can degrade 5ppm RhB under visible light, the degradation efficiency of BiOCl/PDI-2 to 5ppm RhB is higher, the degradation rate is faster and can reach 100%. BiOCl, PDI, BiOCl/PDI-1 and BiOCl/PDI-2 can degrade 10ppm RhB under visible light, the degradation efficiency of BiOCl/PDI-2 is higher, the degradation rate is faster and can reach 99.5%.
Claims (10)
1. A supramolecular heterojunction organic photocatalyst is characterized in that: the supramolecular heterojunction organic photocatalyst is a BiOCl/PDI photocatalyst.
2. The supramolecular heterojunction organic photocatalyst as claimed in claim 1, wherein: the mass ratio of BiOCl to PDI is 0.25-1: 1.
3. The supramolecular heterojunction organic photocatalyst as claimed in claim 1, wherein: the BiOCl is sheet BiOCl prepared by a hydrothermal method.
4. A method for preparing the supramolecular heterojunction organic photocatalyst as claimed in claim 1, comprising the steps of:
(1) reacting NH4Cl solution to Bi (NO)3)3·5H2In O solution, hydrothermal reaction is carried out at the temperature of 140-160 ℃, and the BiOCl is obtained after washing, drying and calcining, wherein NH4Cl and Bi (NO)3)3·5H2The mass ratio of O is 1: 8-9;
(2) perylene-3, 4,9, 10-tetracarboxylic dianhydride, β -alanine and imidazole are organically synthesized at the mass ratio of 1:1.8:10-15 under the nitrogen atmosphere and at the temperature of 100-4The mass ratio of Cl is 1500-;
(3) filtering, washing and drying to obtain PDI;
(4) preparing a PDI stock solution with the concentration of 5-10mM, adding triethylamine and BiOCl, stirring and performing ultrasonic treatment;
(5) heating to 50-60 deg.C, adding HNO3Stirring the solution, filtering, washing and drying; wherein, the HNO3The mass ratio of the PDI to the PDI is 1-2: 1.
5. The method of preparing a supramolecular heterojunction organic photocatalyst as claimed in claim 4, characterized in that: the mass ratio of triethylamine to PDI in the step (4) is 1: 600-650.
6. A method for preparing the supramolecular heterojunction organic photocatalyst as claimed in claim 1, comprising the steps of:
(1) reacting NH4Cl solution to Bi (NO)3)3·5H2In O solution, hydrothermal reaction is carried out at the temperature of 140-160 ℃, and the BiOCl is obtained after washing, drying and calcining, wherein NH4Cl and Bi (NO)3)3·5H2The mass ratio of O is 1: 8-9;
(2) perylene-3, 4,9, 10-tetracarboxylic dianhydride, β -alanine and imidazole are organically synthesized at the mass ratio of 1:1.8:10-15 under the nitrogen atmosphere and at the temperature of 100-4The mass ratio of Cl is 1500-;
(3) filtering, washing and drying to obtain PDI;
(4) preparing a PDI stock solution with the concentration of 5-10mM, adding a triethylamine solution, and then adding HNO3Forming PDI nano fiber through solution, filtering, washing and drying; wherein, the HNO3The mass ratio of the PDI to the PDI is 1-2: 1;
(5) preparing a PDI nanofiber stock solution with the concentration of 5-10mM, adding triethylamine and BiOCl, stirring and performing ultrasonic treatment;
(6) heating to 50-60 deg.C and adding HNO3Stirring the solution, filtering, washing and drying; wherein, HNO3The mass ratio of the PDI to the PDI is 1-2: 1.
7. The method of preparing a supramolecular heterojunction organic photocatalyst as claimed in claim 6, characterized in that: the mass ratio of the triethylamine to the PDI in the steps (4) and (5) is 1: 600-650.
8. The application method of the supramolecular heterojunction organic photocatalyst in degrading organic micropollutant wastewater in claim 1 is characterized by comprising the following steps:
adding 25-50mg of photocatalyst into the organic micro-pollutant wastewater; carrying out visible light catalytic reaction.
9. The application method of the supramolecular heterojunction organic photocatalyst in degrading organic micropollutant wastewater according to claim 8, characterized in that: the organic micro-pollutant wastewater is one of phenol, methyl orange or rhodamine B wastewater.
10. The application method of the supramolecular heterojunction organic photocatalyst in degrading organic micropollutant wastewater according to claim 8, characterized in that: dark adsorption is carried out before the visible light catalytic reaction, and the visible light catalytic reaction is carried out after adsorption balance is achieved.
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