CN113731451B - Ternary composite catalytic material for removing tetracycline in wastewater and preparation method thereof - Google Patents
Ternary composite catalytic material for removing tetracycline in wastewater and preparation method thereof Download PDFInfo
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- CN113731451B CN113731451B CN202111120755.1A CN202111120755A CN113731451B CN 113731451 B CN113731451 B CN 113731451B CN 202111120755 A CN202111120755 A CN 202111120755A CN 113731451 B CN113731451 B CN 113731451B
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- 239000011206 ternary composite Substances 0.000 title claims abstract description 44
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 36
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 34
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 33
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002351 wastewater Substances 0.000 title claims abstract description 18
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 48
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011218 binary composite Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims description 111
- 239000003054 catalyst Substances 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 230000001699 photocatalysis Effects 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000007146 photocatalysis Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 101710134784 Agnoprotein Proteins 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000002835 absorbance Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003517 fume Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 3
- 238000001354 calcination Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 10
- 238000005470 impregnation Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229940040944 tetracyclines Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a ternary composite catalytic material for removing tetracycline in wastewater and a preparation method thereof, comprising the following steps: (1) Preparation of g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the (2) Preparation of Bi 12 O 15 Cl 6 The method comprises the steps of carrying out a first treatment on the surface of the (3) Preparation of Bi 12 O 15 Cl 6 /g‑C 3 N 4 A binary composite material; (4) Preparation of AgCl/Bi 12 O 15 Cl 6 /g‑C 3 N 4 A ternary composite catalytic material. The prepared ternary composite catalytic material can be used for degrading tetracycline under the condition of visible light. The three-way photocatalyst is synthesized by the wet impregnation method, and has the characteristics of simple operation method and easy implementation. By combining AgCl and Bi 12 O 15 Cl 6 Doped to g-C 3 N 4 On the one hand, g-C is effectively improved 3 N 4 The utilization rate of visible light promotes the separation efficiency of the photo-generated carriers, thereby improving the visible light catalytic efficiency; the process flow is simple, is convenient to operate, and has a great application prospect in the aspect of sewage treatment.
Description
Technical Field
The invention relates to an AgCl/Bi for removing tetracycline in wastewater 12 O 15 Cl 6 /g-C 3 N 4 A ternary composite catalytic material and a preparation method thereof belong to the technical field of catalyst preparation and application.
Background
Technological advances and social developments have prompted rapid advances in the pharmaceutical industry, which is accompanied by, however, abuse of antibiotic drugs and rapid increases in the amount of medical wastewater discharge. In the face of increasingly serious medical wastewater pollution problems, the traditional treatment method is difficult to remove efficiently. In recent years, the photocatalysis technology is fast rising due to the characteristics of environmental protection, no secondary pollution and the like. Photocatalytic reactions are advanced oxidation techniques with a semiconductor photocatalyst as the core. In the course of the photocatalytic reaction, the photocatalyst plays an important role.
Graphite phase g-C 3 N 4 Is a medium band gap semiconductor (2.7 eV) with good visible light response. The graphite phase carbon nitride has the characteristics of excellent thermal stability and chemical stability, no toxicity, low raw material price, easy preparation, good biocompatibility and the like. These features indicate that g-C 3 N 4 Has great advantages in the field of environmental purification.
But in the photocatalytic process g-C 3 N 4 It is difficult to exhibit high photocatalytic activity due to its inherent drawbacks. First, g-C 3 N 4 The band gap of the light-emitting diode is wider (2.7 eV), so that the efficiency of utilizing sunlight is limited, and generated photo-generated carriers are fewer, and finally the photo-catalytic activity of the light-emitting diode is influenced. Second, due to the prepared g-C 3 N 4 The specific surface area is low, so that the photocatalyst has fewer active sites in the photoreaction process, and the photocatalytic efficiency is affected. Finally, due to the inherent defects of the structure, the recombination rate of the photo-induced electron holes is high, and finally, the photo-catalytic activity of the photo-induced electron holes is inhibited. Therefore, it is necessary to search for how to reduce the photoelectron-hole pair recombination rate and improve the photocatalytic efficiency. The semiconductor and semiconductor heterojunction structure can promote the separation of photo-generated electrons and holes, thereby improving the photocatalytic performance of the semiconductor photocatalyst.
Disclosure of Invention
The invention aims to provide an AgCl/Bi for removing tetracycline in wastewater 12 O 15 Cl 6 /g-C 3 N 4 Ternary composite catalytic material and preparation method thereof, and Bi is utilized 12 O 15 Cl 6 Co-modification of g-C with AgCl 3 N 4 To improve its photocatalytic efficiency.
Bi is adopted in the invention 12 O 15 Cl 6 And g-C 3 N 4 In combination, g-C can be reduced by band matching 3 N 4 The forbidden bandwidth of (C) is increased 3 N 4 The response range to visible light further enhances g-C 3 N 4 Is a photocatalytic activity of (a); however Bi is 12 O 15 Cl 6 /g-C 3 N 4 The binary catalyst has longer period for degrading pollutants, and affects the large-scale application of the binary catalyst, so AgCl is doped in Bi 12 O 15 Cl 6 /g-C 3 N 4 In the above way, a double electron transfer mechanism is formed, and the recombination rate of photo-generated electrons and holes is further reduced, so that the catalytic activity of the catalyst is increased.
The invention provides an AgCl/Bi prepared by a wet impregnation method 12 O 15 Cl 6 /g-C 3 N 4 Composite material, bi 12 O 15 Cl 6 With g-C 3 N 4 The mass ratio of Bi is 1:2 12 O 15 Cl 6 /g-C 3 N 4 The mass ratio of the catalyst to AgCl is 20:1-10:3.
The invention provides the AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The preparation method of the ternary composite catalytic material comprises the following steps:
（1）g-C 3 N 4 is prepared from the following steps:
20 g urea was weighed and placed in a capped alumina crucible and heated to 550 c in an electric furnace at a rate of 5 c/min, maintaining 4 h. Cooling to room temperature after the reaction is finished, grinding and collecting the obtained light yellow powder to obtain g-C 3 N 4 A sample;
（2）Bi 12 O 15 Cl 6 is prepared from the following steps:
1 mmol of Bi (NO) was weighed out 3 ) 3 •5H 2 O was dissolved into 10 mL ethylene glycol with vigorous stirring to form a homogeneous solution a. Simultaneously weigh 0.33 mmol of NH 4 Cl was dissolved in distilled water of 35 mL to form solution B. Mix A with vigorous stirringThe solution was slowly added to the B solution and stirred at room temperature for 1 h. After stirring, it was transferred to an autoclave and heated at 160℃for 12 h. After the reaction was completed, the autoclave was cooled to room temperature and the resulting precipitate was washed three times with ethanol and distilled water and dried overnight at 60 ℃. Then, the obtained white solid powder was calcined at 400℃in an electric furnace at a rate of 2℃per minute for 5 h. Obtaining light yellow Bi after the reaction is finished 12 O 15 Cl 6 Powder, grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of binary composite material:
0.5g of g-C is weighed 3 N 4 In a 150 mL beaker, 30mL of methanol was measured and then sonicated for 30 min. 0.25g of Bi was weighed again 12 O 15 Cl 6 Dissolving it in g-C 3 N 4 And continuing to carry out ultrasonic treatment in the solution for 30 min. After which 24 h is continuously stirred in a fume hood. After methanol was volatilized, the resulting product was collected and dried at 60℃overnight to give Bi 12 O 15 Cl 6 /g-C 3 N 4 Binary composite material, labeled BOCl/CN;
（4）AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of a ternary composite catalytic material:
(1) weighing Bi prepared by the method of 0.5g 12 O 15 Cl 6 /g-C 3 N 4 Dissolving the binary composite material into 30mL of deionized water, and then performing ultrasonic dispersion for 30-60 min;
(2) placing 0.17-0.85 mmol of chlorine source into the solution (1), and stirring for 30-60 min at room temperature to obtain a suspension;
(3) AgNO is to be carried out 3 And (3) dropwise adding the solution into the suspension in the step (2), and continuously stirring for 4-8 hours at room temperature. AgNO addition 3 The same molar amount as the chlorine source in step (2);
(4) collecting precipitate, centrifugally washing with absolute ethanol and distilled water for 3-6 times, centrifuging at 8000-10000 r/min for 5-10 min, and collecting the productDispersing into a culture dish containing absolute ethanol, and then placing the culture dish into an oven to obtain AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 A ternary composite catalytic material is marked as A/BOCl/CN.
The AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The chlorine source in the step (4) and the step (2) is one of potassium chloride or sodium chloride.
The AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 In the preparation method of the ternary composite catalytic material, the time for ultrasonic dispersion of the chlorine source in the steps (4) and (2) in the ultrapure water is preferably 30 minutes.
The invention provides the AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 Application of ternary composite catalytic material in catalytic degradation of antibiotics in wastewater under visible light condition.
In the above application, the antibiotic is tetracycline; agCl/Bi in the photocatalytic degradation process 12 O 15 Cl 6 /g-C 3 N 4 The adding amount of the ternary composite catalytic material is 0.2-1.0 g/L of wastewater, and the concentration of tetracycline in the wastewater is 10-30 mg/L.
In the above application, 250 mL tetracycline solution was prepared at a concentration of 20 mg/L, and then 0.05g AgCl/Bi was weighed 12 O 15 Cl 6 /g-C 3 N 4 Adding the ternary composite catalytic material into a tetracycline solution, performing ultrasonic treatment for 15 min under a dark condition to uniformly disperse the catalyst, and performing magnetic stirring for 40 min under the dark condition to balance adsorption and desorption of the solution; then adopting a 300W xenon lamp with a 420 nm filter as a visible light source to carry out photocatalysis reaction, taking one sample every 20 min for the total time of the photocatalysis reaction to obtain a supernatant after centrifugal separation, and measuring the absorbance of the supernatant, wherein the maximum absorption wavelength of the tetracycline is 357 nm.
The invention has the beneficial effects that:
(1) The method prepares AgCl/Bi by the wet impregnation method for the first time 12 O 15 Cl 6 /g-C 3 N 4 The ternary catalyst has the advantages of simple preparation method, simple operation, low-cost and easily-obtained raw materials and the like
(2) AgCl/Bi prepared by the invention 12 O 15 Cl 6 /g-C 3 N 4 The three-way catalyst is a photocatalyst with high-efficiency photocatalytic performance under visible light. Bismuth oxyhalide Bi with oxygen enrichment 12 O 15 Cl 6 And AgCl pair g-C capable of generating surface plasma resonance effect 3 N 4 Modified to increase g-C 3 N 4 The adsorption capacity of the catalyst and the separation efficiency of photo-generated electron-hole pairs under the irradiation of visible light, thereby improving the photocatalysis performance of the catalyst.
(3) Novel AgCl/Bi prepared by the invention 12 O 15 Cl 6 /g-C 3 N 4 The three-way catalyst has higher photocatalytic performance and adsorption capacity than the g-C 3 N 4 The photocatalyst prepared by the method has higher stability.
(4) Using the prepared novel AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The ternary catalyst can degrade tetracycline under irradiation of light, and can reach degradation effect of more than 75.4% after 80min, and has excellent photocatalytic performance.
Drawings
FIG. 1 is a graph showing the production of g-C in example 1 of the present invention 3 N 4 、Bi 12 O 15 Cl 6 X-ray diffraction patterns of BOCl/CN and 15A/BOCl/CN ternary composite catalysts;
FIG. 2 is an SEM image of a 15A/BOCl/CN ternary composite catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph showing the production of g-C in example 1 of the present invention 3 N 4 、Bi 12 O 15 Cl 6 Ultraviolet-visible diffuse reflectance spectrograms of the ternary composite catalysts BOCl/CN and 15A/BOCl/CN;
FIG. 4 is a graph showing the production of g-C in example 1 of the present invention 3 N 4 、Bi 12 O 15 Cl 6 Band gap diagrams of BOCl/CN and 15A/BOCl/CN ternary composite catalysts;
FIG. 5 is a graph showing the production of g-C in example 1 of the present invention 3 N 4 、Bi 12 O 15 Cl 6 And the degradation effect of the ternary composite catalyst of BOCl/CN and 15A/BOCl/CN on 20 mg/L tetracycline is shown.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1:
the present embodiment provides an AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The preparation method and application of the ternary composite catalytic material are as follows:
（1）g-C 3 N 4 is prepared from the following steps:
20 g urea was weighed and placed in a capped alumina crucible and heated to 550 c in an electric furnace at a rate of 5 c/min, maintaining 4 h. Cooling to room temperature after the reaction is finished, grinding and collecting the obtained light yellow powder to obtain g-C 3 N 4 A sample;
（2）Bi 12 O 15 Cl 6 is prepared from the following steps:
1 mmol of Bi (NO) was weighed out 3 ) 3 •5H 2 O was dissolved into 10 mL ethylene glycol with vigorous stirring to form a homogeneous solution a. Simultaneously weigh 0.33 mmol of NH 4 Cl was dissolved in distilled water of 35 mL to form solution B. The a solution was slowly added to the B solution with vigorous stirring and stirred at room temperature for 1 h. After stirring, it was transferred to an autoclave and heated at 160℃for 12 h. After the reaction was completed, the autoclave was cooled to room temperature and the resulting precipitate was washed three times with ethanol and distilled water and dried overnight at 60 ℃. Then, the obtained white solid powder was calcined at 400℃in an electric furnace at a rate of 2℃per minute for 5 h. Obtaining light yellow Bi after the reaction is finished 12 O 15 Cl 6 Powder, grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of binary composite material:
weigh 0.5 g-C0.5 g 3 N 4 In a 150 mL beaker, 30mL of methanol was measured and then sonicated for 30 min. Re-weighing Bi of 0.25g 12 O 15 Cl 6 Dissolving it in g-C 3 N 4 And continuing to carry out ultrasonic treatment in the solution for 30 min. After which 24 h is continuously stirred in a fume hood. After methanol was volatilized, the resulting product was collected and dried at 60℃overnight to give Bi 12 O 15 Cl 6 /g-C 3 N 4 Binary composite material, labeled BOCl/CN;
（4）AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of a ternary composite catalytic material:
(1) weighing Bi prepared by the method of 0.5g 12 O 15 Cl 6 /g-C 3 N 4 Dissolving the binary composite material into deionized water of 30mL, and then performing ultrasonic dispersion for 30 min;
(2) placing 0.52 mmol of potassium chloride into the solution, and then continuously stirring for 30 min at room temperature to obtain suspension;
(3) AgNO is to be carried out 3 The solution was added drop wise to the suspension of step (2) and stirring was continued at room temperature 4 h. AgNO addition 3 The molar amount of (2) is the same as the molar amount of the chlorine source in step (2).
(4) Collecting precipitate, centrifuging with anhydrous ethanol and distilled water for 6 times at 8000 r/min for 5 min, collecting product, dispersing into culture dish containing anhydrous ethanol, and oven drying at 60deg.C for 12 h to obtain 15% AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The ternary composite catalytic material is marked as 15A/BOCl/CN.
Three tetracyclines were formulated at a concentration of 250 mL at 20 mg/L and then added at 0.05g g-C, respectively 3 N 4 BOCl/CN and 15A/BOCl/CN. The photocatalyst of (2) is subjected to ultrasonic treatment for 15 min under the dark condition to uniformly disperse the catalyst, and then the solution is subjected to magnetic stirring for 40 min under the dark condition to reach adsorption-desorption equilibrium; then a 300W xenon lamp with a 420 nm filter is adopted as a visible light source to carry out photocatalysis reactionThe total time of the photoreaction was 80min, one sample was taken every 20 min, and the absorbance of the supernatant was measured after centrifugation, and the maximum absorption wavelength of tetracycline was 357 nm. And then, drawing a curve by taking time (t) as an abscissa and the tetracycline concentration ratio at t as an ordinate, and testing the degradation performance of the ternary catalyst (see figure 5), wherein the degradation rate of the catalyst prepared by the method to the tetracycline can reach 75.4% within 80 min.
FIG. 1 is an XRD pattern (a: g-C) of a sample prepared in example 1 3 N 4 , b: Bi 12 O 15 Cl 6 BOCl/CN and 15A/BOCl/CN). From the figure, it is clear that the sample has good crystal phase growth and strong and sharp diffraction peaks. Monomers g-C 3 N 4 Diffraction peaks at 13.04 ° and 27.40 ° correspond to (001) and (002) crystal planes, respectively, corresponding to standard card JCPDS No. 87-1526. In ternary complex 15A/BOCl/CN, it can be seen that the ascribed g-C 3 N 4 、Bi 12 O 15 Cl 6 And characteristic peaks of AgCl, corresponding to the cards JCPDS No. 87-1526, JCPDS No.70-0249 and JCPDS No.85-1355, respectively, illustrate Bi 12 O 15 Cl 6 And AgCl was successfully loaded into g-C 3 N 4 And (3) upper part.
FIG. 2 is an SEM image of a 15A/BOCl/CN ternary composite catalyst prepared in example 1, and it can be seen that Bi is present in the form of needle-like particles 12 O 15 Cl 6 And AgCl in the form of particles loaded onto g-C 3 N 4 On the nanoplatelets.
FIG. 3 is a graph of g-C prepared in example 1 3 N 4 、Bi 12 O 15 Cl 6 The ultraviolet-visible diffuse reflection spectrograms of the ternary composite catalyst of BOCl/CN and 15A/BOCl/CN show that g-C 3 N 4 470 nm, and light absorption edges 500 nm and 510 nm for BOCl/CN and 15A/BOCl/CN, respectively, compared to the monomer g-C 3 N 4 All have red shift, which indicates Bi 12 O 15 Cl 6 And AgCl incorporation improves g-C 3 N 4 The utilization rate of visible light.
FIG. 4 is a graph of g-C prepared in example 1 3 N 4 、Bi 12 O 15 Cl 6 Band gap diagrams of the ternary composite catalysts of BOCl/CN and 15A/BOCl/CN show that g-C 3 N 4 、Bi 12 O 15 Cl 6 The bandgap values of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts were 2.74 eV, 2.36 eV, 2.67 eV and 2.63 eV, respectively, indicating Bi 12 O 15 Cl 6 And AgCl loading g-C 3 N 4 The band gap is narrowed, the separation of photo-generated electron-hole pairs is promoted, and the utilization rate of visible light is improved.
FIG. 5 is a graph of g-C prepared in example 1 3 N 4 、Bi 12 O 15 Cl 6 And the degradation effect of the ternary composite catalyst of BOCl/CN and 15A/BOCl/CN on 20 mg/L tetracycline is shown. g-C after 80min of visible light irradiation 3 N 4 、Bi 12 O 15 Cl 6 、Bi 12 O 15 Cl 6 /g-C 3 N 4 And AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The degradation rates of the ternary composite material to 20 mg/L tetracycline are 30.7%, 63% and 75.4%, respectively, which shows that Bi 12 O 15 Cl 6 And AgCl incorporation improves g-C 3 N 4 Is used for the photocatalytic activity of the catalyst.
Example 2:
the present embodiment provides an AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The preparation method and application of the ternary composite catalytic material are as follows:
（1）g-C 3 N 4 is prepared from the following steps:
20 g urea was weighed and placed in a capped alumina crucible and heated to 550 c in an electric furnace at a rate of 5 c/min, maintaining 4 h. Cooling to room temperature after the reaction is finished, grinding and collecting the obtained light yellow powder to obtain g-C 3 N 4 A sample;
（2）Bi 12 O 15 Cl 6 is prepared from the following steps:
1 mmol of Bi (NO) was weighed out 3 ) 3 •5H 2 O, dissolving it in 10 mL glycol under vigorous stirring to formThe solution A was homogenized. Simultaneously weigh 0.33 mmol of NH 4 Cl was dissolved in distilled water of 35 mL to form solution B. The a solution was slowly added to the B solution with vigorous stirring and stirred at room temperature for 1 h. After stirring, it was transferred to an autoclave and heated at 160℃for 12 h. After the reaction was completed, the autoclave was cooled to room temperature and the resulting precipitate was washed three times with ethanol and distilled water and dried overnight at 60 ℃. Then, the obtained white solid powder was calcined at 400℃in an electric furnace at a rate of 2℃per minute for 5 h. Obtaining light yellow Bi after the reaction is finished 12 O 15 Cl 6 Powder, grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of binary composite material:
weigh 0.5 g-C0.5 g 3 N 4 In a 150 mL beaker, 30mL of methanol was measured and then sonicated for 30 min. 0.25g of Bi was weighed again 12 O 15 Cl 6 Dissolving it in g-C 3 N 4 And continuing to carry out ultrasonic treatment in the solution for 30 min. After which 24 h is continuously stirred in a fume hood. After methanol was volatilized, the resulting product was collected and dried at 60℃overnight to give Bi 12 O 15 Cl 6 /g-C 3 N 4 Binary composite material, labeled BOCl/CN;
（4）AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of a ternary composite catalytic material:
(1) weighing Bi prepared by the method of 0.5g 12 O 15 Cl 6 /g-C 3 N 4 Dissolving the binary composite material into 30mL deionized water, and then performing ultrasonic dispersion for 40 min;
(2) placing 0.17 mmol of sodium chloride into the solution, and then continuously stirring for 40 min at room temperature to obtain a suspension;
(3) AgNO is to be carried out 3 The solution was added drop wise to the suspension of step (2) and stirring was continued at room temperature for 5 h. AgNO addition 3 The molar amount of (2) is the same as the molar amount of the chlorine source in step (2).
(4) Collecting the sedimentCentrifuging and washing the precipitate with absolute ethanol and distilled water for 5 times at 9000 r/min and 7 min, collecting the product, dispersing into culture dish containing absolute ethanol, and oven drying at 60deg.C for 12 h to obtain 5% AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 A ternary composite catalytic material.
Three tetracyclines were formulated at a concentration of 250 mL at 20 mg/L and then added at 0.05g g-C, respectively 3 N 4 、Bi 12 O 15 Cl 6 /g-C 3 N 4 And 5% AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The photocatalyst of (2) is subjected to ultrasonic treatment for 15 min under the dark condition to uniformly disperse the catalyst, and then the solution is subjected to magnetic stirring for 40 min under the dark condition to reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp with a 420 nm filter as a visible light source to carry out photocatalysis reaction, taking one sample every 20 min for the total time of the photocatalysis reaction to obtain a supernatant after centrifugal separation, and measuring the absorbance of the supernatant, wherein the maximum absorption wavelength of the tetracycline is 357 nm. And then, drawing a curve by taking time (t) as an abscissa and the tetracycline concentration ratio at t as an ordinate, and testing the degradation performance of the three-way catalyst. Tested, this example 5% AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The degradation rate of the tetracycline is 73%, which shows that Bi 12 O 15 Cl 6 And AgCl incorporation improves g-C 3 N 4 Is used for the photocatalytic activity of the catalyst.
Example 3:
the present embodiment provides an AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The preparation method and application of the ternary composite catalytic material are as follows:
（1）g-C 3 N 4 is prepared from the following steps:
20 g urea was weighed and placed in a capped alumina crucible and heated to 550 c in an electric furnace at a rate of 5 c/min, maintaining 4 h. Cooling to room temperature after the reaction is finished, grinding and collecting the obtained light yellow powder to obtain g-C 3 N 4 A sample;
（2）Bi 12 O 15 Cl 6 is prepared from the following steps:
1 mmol of Bi (NO) was weighed out 3 ) 3 •5H 2 O was dissolved into 10 mL ethylene glycol with vigorous stirring to form a homogeneous solution a. Simultaneously weigh 0.33 mmol of NH 4 Cl was dissolved in distilled water of 35 mL to form solution B. The a solution was slowly added to the B solution with vigorous stirring and stirred at room temperature for 1 h. After stirring, it was transferred to an autoclave and heated at 160℃for 12 h. After the reaction was completed, the autoclave was cooled to room temperature and the resulting precipitate was washed three times with ethanol and distilled water and dried overnight at 60 ℃. Then, the obtained white solid powder was calcined at 400℃in an electric furnace at a rate of 2℃per minute for 5 h. Obtaining light yellow Bi after the reaction is finished 12 O 15 Cl 6 Powder, grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of binary composite material:
weigh 0.5 g-C0.5 g 3 N 4 In a 150 mL beaker, 30mL of methanol was measured and then sonicated for 30 min. Re-weighing Bi of 0.25g 12 O 15 Cl 6 Dissolving it in g-C 3 N 4 And continuing to carry out ultrasonic treatment in the solution for 30 min. After which 24 h is continuously stirred in a fume hood. After methanol was volatilized, the resulting product was collected and dried at 60℃overnight to give Bi 12 O 15 Cl 6 /g-C 3 N 4 Binary composite material, labeled BOCl/CN;
（4）AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of a ternary composite catalytic material:
(1) weighing Bi prepared by the method of 0.5g 12 O 15 Cl 6 /g-C 3 N 4 Dissolving the binary composite material into 30mL deionized water, and then performing ultrasonic dispersion for 60min;
(2) placing 0.34 mmol of sodium chloride into the solution, and then continuously stirring for 50 min at room temperature to obtain suspension;
(3) AgNO is to be carried out 3 The solution was added drop wise to the suspension of step (2) and stirring was continued at room temperature for 6 h. AgNO addition 3 The molar amount of (2) is the same as the molar amount of the chlorine source in step (2).
(4) Collecting precipitate, centrifuging with anhydrous ethanol and distilled water for 4 times at 10000 r/min for 5 min, collecting product, dispersing into culture dish containing anhydrous ethanol, and oven drying at 60deg.C for 12 h to obtain 10% AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 A ternary composite catalytic material.
Three tetracyclines were formulated at a concentration of 250 mL at 20 mg/L and then added at 0.05g g-C, respectively 3 N 4 、Bi 12 O 15 Cl 6 /g-C 3 N 4 And 10% AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 The photocatalyst of (2) is subjected to ultrasonic treatment for 15 min under the dark condition to uniformly disperse the catalyst, and then the solution is subjected to magnetic stirring for 40 min under the dark condition to reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp with a 420 nm filter as a visible light source to carry out photocatalysis reaction, taking one sample every 20 min for the total time of the photocatalysis reaction to obtain a supernatant after centrifugal separation, and measuring the absorbance of the supernatant, wherein the maximum absorption wavelength of the tetracycline is 357 nm. And then, drawing a curve by taking time (t) as an abscissa and the tetracycline concentration ratio at t as an ordinate, and testing the degradation performance of the three-way catalyst. As a result of detection, 10% AgCl/Bi of this example 12 O 15 Cl 6 /g-C 3 N 4 The degradation rate of the tetracycline is 72.5%, which shows that Bi 12 O 15 Cl 6 And AgCl incorporation improves g-C 3 N 4 Is used for the photocatalytic activity of the catalyst.
Claims (8)
1. A ternary composite catalytic material for removing tetracycline in wastewater is characterized in that the composite material is AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 Bi in composite material 12 O 15 Cl 6 /g-C 3 N 4 The mass ratio of the catalyst to AgCl is 20:1-10:3; bi in the composite material 12 O 15 Cl 6 And g-C 3 N 4 The mass ratio of (2) is 1:2.
2. The ternary composite catalytic material for removing tetracycline from wastewater of claim 1, wherein Bi 12 O 15 Cl 6 /g-C 3 N 4 The mass ratio of the catalyst to AgCl is 20:3.
3. A method of preparing a ternary composite catalytic material for removing tetracycline from wastewater as claimed in claim 1 or 2, characterized by comprising the steps of:
（1）g-C 3 N 4 is prepared from the following steps:
weighing 10-30 g of urea, placing the urea in an alumina crucible with a cover, heating the urea to 550 ℃ in an electric furnace at a speed of 5 ℃/min, and keeping the temperature at 4 h; cooling to room temperature after the reaction is finished, grinding and collecting the obtained light yellow powder to obtain g-C 3 N 4 A sample;
（2）Bi 12 O 15 Cl 6 is prepared from the following steps:
1 mmol of Bi (NO) was weighed out 3 ) 3 •5H 2 O, dissolving the O into ethylene glycol of 10 mL under intense stirring to form a uniform solution A; simultaneously weigh 0.33 mmol of NH 4 Cl, dissolved in distilled water of 35 mL to form solution B; slowly adding the solution A to the solution B under vigorous stirring, and stirring at room temperature for 1 h; after stirring, transferring the mixture into an autoclave, and heating the autoclave at 160 ℃ for 12 h; after the reaction, the autoclave was cooled to room temperature and the obtained precipitate was washed three times with ethanol and distilled water, and dried overnight at 60 ℃; then, calcining the obtained white solid powder in an electric furnace at 400 ℃ for 5 h, wherein the heating rate is 2 ℃/min; obtaining light yellow Bi after the reaction is finished 12 O 15 Cl 6 Powder, grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi 12 O 15 Cl 6 /g-C 3 N 4 binary compositePreparation of materials:
0.5g of g-C is weighed 3 N 4 In a 150 mL beaker, 30mL of methanol is measured and then ultrasonic treatment is carried out for 30 min; bi having a mass of 0.25g was reweighed 12 O 15 Cl 6 Dissolving it in g-C 3 N 4 Continuing to carry out ultrasonic treatment in the solution for 30 min; then stirring continuously in a fume hood for 24 h; after methanol was volatilized, the resulting product was collected and dried at 60℃overnight to give Bi 12 O 15 Cl 6 /g-C 3 N 4 Binary composite material, labeled BOCl/CN;
（4）AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 preparation of a ternary composite catalytic material:
(1) weighing Bi prepared by the method of 0.5g 12 O 15 Cl 6 /g-C 3 N 4 The binary composite material is dissolved in deionized water of 30mL and then dispersed by ultrasonic;
(2) placing 0.17-0.85 mmol of chlorine source into the solution (1), and stirring at room temperature to obtain a suspension;
(3) AgNO is to be carried out 3 Dropwise adding the solution into the suspension in the step (2), and continuously stirring for 4-8 hours at room temperature; agNO addition 3 The same molar amount as the chlorine source in step (2);
(4) collecting precipitate, centrifugally washing the precipitate with absolute ethyl alcohol and distilled water for 3-6 times, wherein the centrifugal speed is 8000-10000 r/min, the centrifugal time is 5-10 min, collecting a product, dispersing the product into a culture dish containing absolute ethyl alcohol, and then placing the culture dish into an oven for drying to obtain AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 A ternary composite catalytic material is marked as A/BOCl/CN.
4. The method for preparing ternary composite catalytic material for removing tetracycline from wastewater as defined in claim 3, wherein Bi in steps (4) and (1) is 12 O 15 Cl 6 /g-C 3 N 4 The ultrasonic time of the binary composite material at room temperature is 30-60 min.
5. The method for preparing ternary composite catalytic material for removing tetracycline from wastewater according to claim 3, wherein the chlorine source in steps (4) and (2) is one of potassium chloride and sodium chloride; stirring for 30-60 min at room temperature.
6. Use of the ternary composite catalytic material of claim 1 or 2 for removing tetracycline from wastewater under visible light conditions.
7. The use according to claim 6, characterized in that: agCl/Bi in the photocatalytic degradation process 12 O 15 Cl 6 /g-C 3 N 4 The adding amount of the ternary composite catalytic material is 0.2-1.0 g/L of wastewater, and the concentration of tetracycline in the wastewater is 10-30 mg/L.
8. The use according to claim 7, characterized in that: preparing 250-mL tetracycline solution with concentration of 20 mg/L, and weighing 0.05g AgCl/Bi 12 O 15 Cl 6 /g-C 3 N 4 Adding the ternary composite catalytic material into a tetracycline solution, performing ultrasonic treatment for 15 min under a dark condition to uniformly disperse the catalyst, and then performing magnetic stirring for 40 min to balance adsorption and desorption of the solution; then adopting a 300W xenon lamp with a 420 nm filter as a visible light source to carry out photocatalysis reaction, taking one sample every 20 min for the total time of the photocatalysis reaction, carrying out secondary centrifugal separation on the obtained solution at 10000 rpm for 5 min each time, and then taking supernatant fluid and filtering with a filter membrane of 0.45 mu m; finally, testing absorbance of the filtered clear liquid on an ultraviolet-visible spectrophotometer; the absorbance of the filtrate was measured at 357 nm wavelength.
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