CN113457710A - PDI/g-C3N4/Bi2WO6Composite photocatalyst and preparation method and application thereof - Google Patents

PDI/g-C3N4/Bi2WO6Composite photocatalyst and preparation method and application thereof Download PDF

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CN113457710A
CN113457710A CN202110751924.5A CN202110751924A CN113457710A CN 113457710 A CN113457710 A CN 113457710A CN 202110751924 A CN202110751924 A CN 202110751924A CN 113457710 A CN113457710 A CN 113457710A
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pdi
composite photocatalyst
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杨绍贵
许晨敏
杨冰
周文武
何欢
李时银
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Nanjing Normal University
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Abstract

The invention discloses a PDI/g-C3N4/Bi2WO6A composite photocatalyst, a preparation method and application thereof. The composite photocatalyst consists of PDI and g-C3N4And Bi2WO6Composition, PDI, g-C3N4And Bi2WO6The mass ratio of (1): 4-40: 6-60. The composite photocatalyst PDI/g-C of the invention3N4/Bi2WO6The preparation method is simple, the physicochemical property is stable, the visible light absorption capacity is strong, and pollutants such as sulfamethazine, tetracycline antibiotics and the like in water can be well degraded.

Description

PDI/g-C3N4/Bi2WO6Composite photocatalyst and preparation method and application thereof
Technical Field
The invention relates to a composite photocatalyst, a preparation method and application thereof, in particular to a PDI/g-C3N4/Bi2WO6A composite photocatalyst and a preparation method and application thereof.
Background
Photocatalytic technology can solve increasingly serious environmental problems, but a single photocatalytic material faces problems of insufficient light absorption capacity and low separation efficiency of photogenerated carriers, and thus many composite materials are emerging to solve the problems. In recent years, g-C3N4/Bi2WO6The composite material is rapidly developed due to the simple preparation method, stable physicochemical property, low price and excellent photoelectric property, but the problems of insufficient utilization of visible light, low separation efficiency of photon-generated carriers, insufficient stability and the like still exist.
The tetracycline antibiotic is a broad-spectrum antibacterial drug and is widely applied to livestock and poultry breeding, the half-life period of the tetracycline is 4.5-180 days, the tetracycline is stable under acidic conditions, the tetracycline drug resistance gene is also detected in water bodies and bottom mud of waste water plants, rivers, lakes and the like at present, and the highest detection concentration of the tetracycline is up to 249 ng/L. Long-term drinking of water containing tetracycline antibiotics can cause intestinal diseases or allergy, generate drug resistance to breed super bacteria, cause secondary infection, cause damage to teeth and bones, and interfere normal functions of human bodies. Therefore, how to effectively remove tetracycline from water bodies is one of the important challenges to ensure ecological environment, animal safety and human health.
The Perylene Diimide (PDI) is easy to synthesize and modify, has rich and easily-obtained raw materials, low cost, short average free path, strong visible light absorption capacity, excellent physical and chemical stability and strong electron affinity, and can be used as a cocatalyst with excellent performance.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides PDI/g-C which has the capability of degrading pollutants by utilizing visible light energy and photocatalysis, has high degradation efficiency and is environment-friendly3N4/Bi2WO6A composite photocatalyst is provided. The invention also provides a preparation method and application of the photocatalyst. A third object of the present invention is to provide a method for using the catalyst.
The technical scheme is as follows: the invention relates to a PDI/g-C3N4/Bi2WO6The composite photocatalyst consists of PDI and g-C3N4And Bi2WO6Composition, PDI, g-C3N4And Bi2WO6The mass ratio of (1): 4-40: 6-60.
The invention takes 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole as raw materials, adopts an organic synthesis method to obtain PDI, and then the PDI and the prepared ultrathin g-C3N4Nanosheet and sheet-like Bi2WO6Uniformly mixing to obtain the PDI/g-C3N4/Bi2WO6A composite photocatalyst is provided.
The preparation method of the composite catalyst comprises the following steps: preparing the PDI powder into a PDI solution, and sequentially adding triethylamine and HNO3、g-C3N4And Bi2WO6Stirring, filtering, washing to neutrality and drying to obtain PDI/g-C3N4/Bi2WO6A composite photocatalyst;
preferably PDI, triethylamine, 4mol/L HNO3、g-C3N4And Bi2WO6The addition amount is 1: 15-150: 700 + 7000: 4-40: 6-60.
Preferably, HNO is selected3The concentration of (2) is 4 mol/L.
Preferably, the PDI, triethylamine and 4mol/L HNO3、g-C3N4And Bi2WO6The addition amount is 2.125 mg-21.25 mg, 306.6mg, 14690mg, 87.5mg and 125 mg.
Preferably, PDI, g-C3N4And Bi2WO6The mass ratio of (A) to (B) is as follows: 1: 13-14: 19 to 20.
The PDI/g-C of the present invention3N4/Bi2WO6The preparation method of the composite photocatalyst comprises the following steps:
(1) weighing urea, heating a sample to 500-600 ℃ at a heating rate of 3-7 ℃/min, calcining for 2-4 h at the temperature to obtain a product, grinding and drying the obtained product, heating the sample to 500-600 ℃ at a heating rate of 3-7 ℃/min, keeping for 2-4 h at the temperature to obtain the flaky g-C3N4；
(2) Cetyl trimethyl ammonium bromide and Na2WO4·2H2O and Bi (NO)3)3·5H2Adding O into deionized water, fully stirring to obtain a mixture, pouring the mixture into an autoclave, sealing the autoclave, treating at 100-140 ℃ for 24-36 h, washing and drying the product to obtain flaky Bi2WO6；
(3) Organically synthesizing 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole, adding ethanol and HCl, stirring to prepare a stirring product, stirring, filtering, washing to be neutral and drying the obtained product to prepare PDI powder;
(4) preparing PDI powder into PDI solution, and sequentially adding triethylamine and HNO3、g-C3N4And Bi2WO6Stirring, filtering, washing to neutrality and drying to obtain PDI/g-C3N4/Bi2WO6A composite photocatalyst is provided.
Preferably, in the step (2), the hexadecyl trimethyl ammonium bromide and Na2WO4·2H2O and Bi (NO)3)3·5H2O is mixed according to the mass ratio of 1: 1.5E10：10～30。
Preferably, in the step (2), the hexadecyl trimethyl ammonium bromide and Na2WO4·2H2O and Bi (NO)3)3·5H2O is mixed according to the mass ratio of 1: 4-10: 12 to 30.
Preferably, in the step (2), the reaction temperature is 100-140 ℃ and the reaction time is 24-36 h.
Preferably, in the step (3), the mass ratio of the 3,4,9, 10-perylenetetracarboxylic dianhydride to the 3-aminopropionic acid to the imidazole is 1: 1.8: 10 to 20.
Preferably, in the step (3), the 3,4,9, 10-perylenetetracarboxylic dianhydride, the 3-aminopropionic acid and the imidazole are used for preparing the PDI powder under the argon atmosphere and at the temperature of 100-120 ℃.
In the step (3), ethanol is used as a dispersing solvent, HCl is used for adjusting pH, and preferably, the mass ratio of ethanol to hydrochloric acid is 8-10: 2-3.
Preferably, in step (4), PDI, g-C3N4And Bi2WO6The mass ratio of (1): 4-40: 6-60.
Preferably, in the step (4), the PDI, the triethylamine and the 4mol/L HNO3、g-C3N4And Bi2WO6The addition amount is 2.125 mg-21.25 mg, 306.6mg, 14690mg, 87.5mg and 125 mg.
Preferably, in the step (3), the drying temperature is 50-70 ℃.
The composite photocatalyst or the composite photocatalyst prepared by the preparation method is applied to hydrolysis of tetracycline hydrochloride and sulfamethazine.
The specific application method of the composite photocatalyst comprises the following steps: adding PDI/g-C into tetracycline hydrochloride or sulfamethazine solution3N4/Bi2WO6A composite photocatalyst; wherein the mass ratio of the photocatalyst to tetracycline hydrochloride or sulfamethazine is 10-100: 1.
has the advantages that: (1) the invention provides a PDI/g-C3N4/Bi2WO6Composite photocatalyst for degrading waterThe composite catalyst has broad degradation spectrum and can be used for treating tetracycline pollutants and other pollutants such as p-sulfamethazine, phenol and the like; (2) the composite catalyst can effectively solve the problems of insufficient utilization of visible light, low separation efficiency of photon-generated carriers, poor stability and the like of the traditional material; (3) in the preparation process, PDI is obtained through organic synthesis, and the PDI/g-C is constructed by using the PDI3N4/Bi2WO6The composite photocatalyst has the advantages of high light energy utilization rate, simple preparation process, mild preparation conditions, easiness in realizing large-scale production, low cost and easiness in mass preparation.
Drawings
FIG. 1 is g-C prepared for comparative sample 23N4/Bi2WO6Transmission electron micrograph of (1), g-C3N4/Bi2WO6Is in a sheet structure;
FIG. 2 is a transmission electron micrograph of the PDI prepared in step (3) of example 2, which shows a one-dimensional irregular microfilament morphology;
FIG. 3 shows PDI/g-C prepared in example 23N4/Bi2WO6The transmission electron microscope picture of the composite photocatalyst shows that g-C modified by PDI is successfully synthesized3N4/Bi2WO6；
FIG. 4 shows the results of steady state fluorescence spectroscopy;
FIG. 5 is a graph of photocurrent density of a catalyst;
FIG. 6 shows PDI/g-C prepared in example 2 of the present invention3N4/Bi2WO6A degradation effect diagram of the composite photocatalyst for degrading tetracycline hydrochloride with different concentrations;
FIG. 7 is a graph showing the degradation effect of different materials prepared according to the present invention on 10ppm sulfamethazine under simulated sunlight irradiation;
FIG. 8 is a comparison of the degradation effect of different samples according to the invention on iohexol 10 ppm;
FIG. 9 is a graph showing the degradation effect of different materials prepared by the present invention on 10ppm tetracycline hydrochloride under simulated sunlight irradiation.
Detailed Description
First, sample preparation
Example 1: PDI/g-C3N4/Bi2WO6Preparation of composite photocatalyst
(1) Preparation of flake g-C3N4: weighing 10g of urea, heating the sample to 500 ℃ at the heating rate of 3 ℃/min, calcining for 2h at the temperature, grinding and drying the prepared product, heating the sample to 500 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2h to prepare the flaky g-C3N4。
(2) Preparation of Bi flakes2WO6: 0.05g of cetyltrimethylammonium bromide and 0.2g of Na were added2WO4·2H2O and 0.5g Bi (NO)3)3·5H2Adding O into 80mL of deionized water, fully stirring, pouring the obtained mixture into an autoclave, sealing the autoclave, treating at 100 ℃ for 24 hours, washing and drying the product to obtain flaky Bi2WO6。
(3) Preparing PDI: (3-1) mixing the following components in a mass ratio of 1.376 g: 2.5 g:12 g of 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole are placed in a four-neck flask under the nitrogen atmosphere and at the temperature of 100 ℃ for organic synthesis, ethanol (with the mass concentration of 99 percent and the volume of 100mL) and HCl (with the mass concentration of 2mol/L and the volume of 300 mL) are added and stirred to prepare a stirring product; (3-2) filtering, washing to neutrality and drying the stirred product to prepare PDI powder, wherein the aperture of a filtering membrane of the filtering membrane is 0.22 mu m, and the drying temperature is 50 ℃;
(4)PDI/g-C3N4/Bi2WO6preparing a composite photocatalyst: preparing 50mL PDI stock solution, and sequentially adding triethylamine and HNO3(4mol/L)、g-C3N4And Bi2WO6Stirring, filtering, washing to neutrality and drying to obtain PDI/g-C3N4/Bi2WO6Composite photocatalyst (0.01 PCB). PDI, triethylamine and 4mol/L HNO3、g-C3N4And Bi2WO6The addition amount is 2.125mg, 306.6mg, 14690mg, 87.5mg and 125 mg.
Example 2: PDI-g-C3N4/Bi2WO6Preparation of composite photocatalyst
(1) Preparation of flake g-C3N4: weighing 10g of urea, heating the sample to 550 ℃ at the heating rate of 5 ℃/min, calcining for 2h at the temperature, grinding and drying the prepared product, heating the sample to 550 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2h to prepare the flaky g-C3N4。
(2) Preparation of Bi flakes2WO6: 0.05g of cetyltrimethylammonium bromide and 0.33g of Na were added2WO4·2H2O and 0.97g Bi (NO)3)3·5H2Adding O into 80mL of deionized water, fully stirring, pouring the obtained mixture into an autoclave, sealing the autoclave, treating at 120 ℃ for 24 hours, washing and drying the product to obtain flaky Bi2WO6。
(3) Preparing PDI: (3-1) mixing the following components in a mass ratio of 1.376 g: 2.5 g: 18g of 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole are placed in a four-neck flask under the nitrogen atmosphere and at the temperature of 110 ℃ for organic synthesis, ethanol (with the mass concentration of 99 percent and 100mL) and HCl (2mol/L and 300mL of hydrochloric acid) are added and stirred to prepare a stirring product; (3-2) filtering, washing to neutrality and drying the stirred product to prepare PDI powder, wherein the aperture of a filtering membrane of the filtering membrane is 0.22 mu m, and the drying temperature is 60 ℃; the prepared PDI transmission electron micrograph is shown in FIG. 2.
(4)PDI/g-C3N4/Bi2WO6Preparing a composite photocatalyst: preparing 50mL PDI stock solution, and sequentially adding triethylamine and HNO3、g-C3N4And Bi2WO6Stirring, filtering, washing to neutrality and drying to obtain PDI/g-C3N4/Bi2WO6Composite photocatalyst (0.03 PCB). PDI, triethylamine and 4mol/L HNO3、g-C3N4And Bi2WO6The addition amount is 6.375mg:306.6mg:14690 mg:87.5mg to 125 mg. Prepared PDI/g-C3N4/Bi2WO6The transmission electron micrograph of the composite photocatalyst is shown in FIG. 3.
Example 3: according to the preparation method of example 2, PDI, triethylamine and 4mol/L HNO3、g-C3N4And Bi2WO6The addition amount is 12.75mg:306.6mg:14690 mg:87.5mg, 125mg dosage preparation PDI/g-C3N4/Bi2WO6Composite catalyst (0.06 PCB).
Example 4: PDI/g-C3N4/Bi2WO6Preparation of composite photocatalyst
(1) Preparation of flake g-C3N4: weighing 10g of urea, heating the sample to 600 ℃ at the heating rate of 7 ℃/min, calcining for 2h at the temperature, grinding and drying the prepared product, heating the sample to 600 ℃ at the heating rate of 7 ℃/min, and keeping the temperature for 2h to prepare the flaky g-C3N4。
(2) Preparation of Bi flakes2WO6: 0.05g of cetyltrimethylammonium bromide and 0.5g of Na were added2WO4·2H2O and 1.5g Bi (NO)3)3·5H2Adding O into 80mL of deionized water, fully stirring, pouring the obtained mixture into an autoclave, sealing the autoclave, treating at 140 ℃ for 24 hours, washing and drying the product to obtain flaky Bi2WO6。
(3) Preparing PDI: (3-1) mixing the following components in a mass ratio of 1.376 g: 2.5 g: 24g of 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole are placed in a four-neck flask under the nitrogen atmosphere and at the temperature of 120 ℃ for organic synthesis, ethanol (with the mass concentration of 99 percent and 100mL) and HCl (2mol/L and 300mL of hydrochloric acid) are added and stirred to prepare a stirring product; (3-2) filtering, washing to neutrality and drying the stirred product to prepare PDI powder, wherein the aperture of a filtering membrane of the filtering membrane is 0.45 mu m, and the drying temperature is 70 ℃;
(4)PDI/g-C3N4/Bi2WO6preparing a composite photocatalyst: preparing 50mL PDI stock solution, and sequentially adding triethylamine and HNO3、g-C3N4And Bi2WO6Stirring, filtering, washing to neutrality and drying to obtain PDI/g-C3N4/Bi2WO6Composite photocatalyst (0.1 PCB). PDI, triethylamine and 4mol/L HNO3、g-C3N4And Bi2WO6The amount added was 21.25mg, 306.6mg, 14690mg, 87.5mg, 125 mg.
Preparation of a comparative sample:
comparative 1 (PDI): the PDI prepared in step (3) of example 2 was used as a photocatalyst.
Comparative 2(0.03CB or CB): preparation of g-C using the preparation method of example 23N4/Bi2WO6As the photocatalyst, PDI was not added in the step (4), other raw materials, compounding ratio, preparation method and detection method were the same as those of example 2, and triethylamine and 4mol/L HNO were used as raw materials3、g-C3N4And Bi2WO6The addition amount is 306.6mg:14690mg: 3.75mg to 125 mg.
Comparative 3(0.03 PB): the preparation of example 2 was carried out without addition of g-C3N4Preparation of PDI and Bi2WO6Catalyst of (D), PDI to Bi2WO6And (3) adjusting the dosage of the step (4) to be 0.03 of the mass: PDI, triethylamine and 4mol/L HNO3、Bi2WO6The addition amount is 6.375mg:306.6mg:14690 mg: 212.5 mg.
Control 4(0.03 PC): the preparation method of example 2 was adopted, without adding Bi2WO6Preparation of PDI and g-C3N4Catalyst of (PDI) in g-C3N4And (3) adjusting the dosage of the step (4) to be 0.03 of the mass: PDI, triethylamine, 4mol/LHNO3、g-C3N4The addition amount is 6.375mg:306.6mg:14690 mg: 212.5 mg.
Comparative sample 5: the preparation method of example 2 was followed, and the prepared PDI and g-C were3N4、Bi2WO6Mixing the components according to the dosage of 6.375mg:87.5mg:125mg, and grinding to obtain the physically mixed PDI/g-C3N4/Bi2WO6A catalyst.
Second, performance test
1. Fluorescence spectroscopy and photocurrent density measurements of different catalysts
PDI/g-C prepared in example 23N4/Bi2WO6Composite Photocatalyst (PCB), PDI catalyst prepared by reference sample 1 and g-C prepared by reference sample 23N4/Bi2WO6The photocatalyst (CB) was subjected to performance measurement, and the measurement results are shown in fig. 4 and 5. Fig. 4 is a test result of a steady-state fluorescence spectrum, and it can be seen from fig. 4 that the fluorescence intensity of the composite 0.03PCB photocatalyst is far lower than that of CB, indicating that the separation of carriers of the composite photocatalyst prepared by the present invention is greatly improved. Fig. 5 is a photo current density diagram of the catalyst, and it can be seen from fig. 5 that the photo current density of the 0.03PCB composite catalyst prepared by the present invention is greatly improved, which indicates that the composite photocatalyst prepared by the present invention has more carriers to participate in the reaction on the surface.
2. Test of degradation effect of composite catalyst on tetracycline hydrochloride with different concentrations
In order to verify the degradation effect of the composite photocatalyst prepared in example 2 on tetracycline hydrochloride with different concentrations, 25mg of the composite photocatalyst was added to solutions with tetracycline hydrochloride concentrations of 5, 20, and 40mg/L, and the degradation results are shown in fig. 6.
3. Degradation performance test of different catalysts on different pollutants
3.1 degradation method
Degradation of tetracycline hydrochloride: before the photodegradation reaction, 25mg of the catalytic material powder and 50mL of tetracycline hydrochloride solution (10ppm) were added to the quartz tube reactor, and a simulated solar light source was provided by an 800W xenon lamp. First, magnetic stirring was carried out for half an hour in the dark to reach adsorption-desorption equilibrium. Then, approximately 2mL of the solution was collected at intervals and centrifuged to remove the photocatalyst. Next, the suspension was filtered through a 0.22 μm microporous membrane.
Degradation of sulfamethazine: prior to the photodegradation reaction, 25mg of catalytic material powder and 50mL of sulfamethazine solution (10ppm) were added to a quartz tube reactor, and a simulated solar light source was provided by an 800W xenon lamp. First, magnetic stirring was carried out for half an hour in the dark to reach adsorption-desorption equilibrium. Then, approximately 2mL of the solution was collected at intervals and centrifuged to remove the photocatalyst. Next, the suspension was filtered through a 0.22 μm microporous membrane.
3.2 degradation results
The degradation effect of different catalysts on sulfadiazine is shown in fig. 7, specifically, fig. 7 is a graph of the degradation effect of different materials prepared by the invention on 10ppm sulfadiazine under the irradiation of simulated sunlight, and fig. 7 shows the result of direct illumination of the pholysis without any catalyst; PDI is the degradation effect of PDI prepared in step (3) of example 2; CB is the degradation effect of the catalyst prepared in comparative example 2; 0.1PCB is the degradation effect of the composite catalyst prepared in example 3; 0.01PCB is the degradation effect of the composite catalyst prepared in example 1; 0.03PCB is the degradation effect of the composite catalyst prepared in example 2.
FIG. 8 shows the degradation effect of different materials prepared according to the present invention on iohexol 10ppm (tetracycline hydrochloride was replaced with iohexol according to the degradation method of tetracycline hydrochloride), and in FIG. 8, 0.01PCB is the degradation effect of the composite catalyst prepared in example 1; 0.03PCB is the degradation effect of the composite catalyst prepared in example 2; 0.1PCB is the degradation effect of the composite catalyst prepared in example 3; 0.03PB is the degradation effect of the catalyst of comparative example 3; 0.03CB is the degradation effect of the catalyst prepared in comparative example 2; 0.03PC is the degradation effect of the catalyst prepared in comparative example 4; PDI is the degradation effect of PDI prepared in step (3) of example 2; BWO is Bi prepared in step (2) of example 22WO6The degradation effect of (2); g-C3N4Is g-C prepared in step (1) of example 23N4The degradation effect of (2); from FIG. 8, it can be found that when PDI is associated with g-C3N4/Bi2WO6When the mass ratio is 0.03, the degradation effect is optimal. PDI and g-C3N4/Bi2WO6The degradation effect of (a) is also much lower than that of the material of the invention.
FIG. 9 is a graph showing the degradation effect of various materials prepared according to the present invention on tetracycline hydrochloride of 10ppm under simulated solar irradiation, wherein in FIG. 9, photolysis is the result without any catalyst, and PDI is the degradation effect of PDI prepared in step (3) of example 2; CB is the degradation effect of the catalyst prepared in comparative example 2; physical mixing is the degradation effect of the catalyst prepared in comparative example 5, and 0.01PCB is the degradation effect of the composite catalyst prepared in example 1; 0.03PCB is the degradation effect of the composite catalyst prepared in example 2; 0.06PCB is the degradation effect of the composite catalyst prepared in example 3; 0.1PCB is the degradation effect of the composite catalyst prepared in example 4.

Claims (10)

1. PDI/g-C3N4/Bi2WO6The composite photocatalyst is characterized by consisting of PDI and g-C3N4And Bi2WO6Composition, PDI, g-C3N4And Bi2WO6The mass ratio of (1): 4-40: 6-60.
2. The PDI/g-C of claim 13N4/Bi2WO6The composite photocatalyst is characterized in that PDI and g-C3N4And Bi2WO6The mass ratio of (A) to (B) is as follows: 1: 13-14: 19 to 20.
3. The PDI/g-C of claim 13N4/Bi2WO6The preparation method of the composite photocatalyst is characterized by comprising the following steps:
(1) weighing urea, heating a sample to 500-600 ℃ at a heating rate of 3-7 ℃/min, calcining for 2-4 h at the temperature to obtain a product, grinding and drying the obtained product, heating the sample to 500-600 ℃ at a heating rate of 3-7 ℃/min, keeping for 2-4 h at the temperature to obtain the flaky g-C3N4；
(2) Cetyl trimethyl ammonium bromide and Na2WO4·2H2O and Bi (NO)3)3·5H2Adding O into deionized water, fully stirring to obtain a mixture, pouring the obtained mixture into an autoclave, sealing the autoclave, treating at 100-140 ℃ for 24-36 h,washing and drying the product to obtain the flaky Bi2WO6；
(3) Organically synthesizing 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole, adding ethanol and HCl, stirring to prepare a stirring product, stirring, filtering, washing to be neutral and drying the obtained product to prepare PDI powder;
(4) preparing PDI powder into PDI solution, and sequentially adding triethylamine and HNO3、g-C3N4And Bi2WO6Stirring, filtering, washing to neutrality and drying to obtain PDI/g-C3N4/Bi2WO6A composite photocatalyst is provided.
4. The method according to claim 3, wherein in the step (2), cetyltrimethylammonium bromide and Na are added2WO4·2H2O and Bi (NO)3)3·5H2O is mixed according to the mass ratio of 1: 1.5-10: 10 to 30.
5. The preparation method according to claim 3, wherein in the step (3), the mass ratio of the 3,4,9, 10-perylenetetracarboxylic dianhydride to the 3-aminopropionic acid to the imidazole is 1: 1.8: 10 to 20.
6. The method according to claim 3, wherein in the step (3), the 3,4,9, 10-perylenetetracarboxylic dianhydride, the 3-aminopropionic acid and the imidazole are used to prepare the PDI powder under an argon atmosphere at a temperature of 100 ℃ and 120 ℃.
7. The production method according to claim 3, wherein in the step (4), PDI, g-C3N4And Bi2WO6The mass ratio of (1): 4-40: 6-60.
8. The method according to claim 3, wherein the drying temperature in the step (3) is 50 to 70 ℃.
9. Use of the composite photocatalyst according to any one of claims 1 to 2 or the composite photocatalyst prepared by the preparation method according to any one of claims 3 to 8 in hydrolysis of tetracycline hydrochloride and sulfadiazine.
10. The use of claim 9, wherein PDI/g-C is added to the tetracycline hydrochloride or sulfamethazine solution3N4/Bi2WO6A composite photocatalyst; wherein the mass ratio of the photocatalyst to tetracycline hydrochloride or sulfamethazine is 10-100: 1.
CN202110751924.5A 2021-07-02 2021-07-02 PDI/g-C3N4/Bi2WO6Composite photocatalyst and preparation method and application thereof Pending CN113457710A (en)

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