CN113731451A - 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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- CN113731451A CN113731451A CN202111120755.1A CN202111120755A CN113731451A CN 113731451 A CN113731451 A CN 113731451A CN 202111120755 A CN202111120755 A CN 202111120755A CN 113731451 A CN113731451 A CN 113731451A
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- 239000011206 ternary composite Substances 0.000 title claims abstract description 40
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 37
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 37
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 37
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 37
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002351 wastewater Substances 0.000 title claims abstract description 18
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 50
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011218 binary composite Substances 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims description 108
- 238000003756 stirring Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 238000013032 photocatalytic reaction Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 238000010438 heat treatment Methods 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
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000003517 fume Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 5
- 239000006228 supernatant 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
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 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
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 10
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 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
- 230000007547 defect Effects 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
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement 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
- 238000001514 detection method Methods 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
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 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
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a ternary composite catalytic material for removing tetracycline in wastewater and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparation of g-C3N4(ii) a (2) Preparation of Bi12O15Cl6(ii) a (3) Preparation of Bi12O15Cl6/g‑C3N4A binary composite material; (4) preparation of AgCl/Bi12O15Cl6/g‑C3N4Ternary elementA composite catalytic material. The prepared ternary composite catalytic material can be used for degrading tetracycline under the condition of visible light. The invention synthesizes the ternary photocatalyst by a wet impregnation method, and has the characteristics of simple operation method and easy implementation. By mixing AgCl and Bi12O15Cl6Doping to g-C3N4Effectively increase g-C3N4The separation efficiency of photon-generated carriers of the visible light is promoted by the utilization rate of the visible light, so that the visible light catalysis efficiency is improved; the process is simple, convenient to operate and has a great application prospect in the aspect of sewage treatment.
Description
Technical Field
The invention relates to AgCl/Bi for removing tetracycline in wastewater12O15Cl6/g-C3N4A ternary composite catalytic material and a preparation method thereof belong to the technical field of catalyst preparation and application.
Background
Technological progress and social development have promoted the rapid development of the pharmaceutical industry, but accompanying the rapid development of the pharmaceutical industry are the abuse of antibiotic drugs and the rapid increase of the discharge amount of pharmaceutical wastewater. In the face of the increasingly serious problem of medical wastewater pollution, the traditional treatment method is difficult to remove efficiently. In recent years, the photocatalytic technology is rapidly started due to the characteristics of environmental protection, no secondary pollution and the like. The photocatalytic reaction is an advanced oxidation technology taking a semiconductor photocatalyst as a core. In the photocatalytic reaction process, a photocatalyst plays an important role.
Graphite phase g-C3N4Is a mid-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 characteristics indicate that g-C3N4Has great advantages in the field of environmental purification.
But in the photocatalytic process, g-C3N4It is difficult to exhibit high photocatalytic activity due to its inherent defects. First, g-C3N4The band gap is wider (2.7 eV), the sunlight utilization efficiency is limited, and the generated photon-generated carriers are generatedLess and ultimately has an effect on its photocatalytic activity. Second, due to the g-C prepared3N4The specific surface area is low, so the number of active sites of the photocatalyst in the photoreaction process is small, and the photocatalytic efficiency is influenced. Finally, due to the inherent defects of the structure, the recombination rate of photoinduced electron holes is high, and the inhibition effect is finally generated on the photocatalytic activity of the material. Therefore, it is necessary to search for how to reduce the recombination rate of photoelectron-hole pairs and improve the photocatalytic efficiency. The semiconductor and semiconductor heterojunction structure can promote the separation of photogenerated electrons and holes, thereby improving the photocatalytic performance of the semiconductor photocatalyst.
Disclosure of Invention
The invention aims to provide AgCl/Bi for removing tetracycline in wastewater12O15Cl6/g-C3N4Ternary composite catalytic material and preparation method thereof, and application of Bi12O15Cl6Co-modified with AgCl to form g-C3N4To improve its photocatalytic efficiency.
In the invention, Bi12O15Cl6And g-C3N4In combination, g-C can be reduced by band matching3N4The forbidden band width of the crystal is increased, and g-C is improved3N4The response range to visible light is further enhanced3N4Photocatalytic activity of (a); however, Bi12O15Cl6/g-C3N4The period of the binary catalyst for degrading pollutants is longer, which affects the large-scale application of the binary catalyst, so that AgCl is doped into Bi12O15Cl6/g-C3N4In 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 AgCl/Bi prepared by a wet impregnation method12O15Cl6/g-C3N4Composite material of Bi12O15Cl6And g-C3N4In a mass ratio of 1:2, Bi12O15Cl6/g-C3N4The mass ratio of the AgCl to the water is 20: 1-10: 3.
The invention provides the AgCl/Bi12O15Cl6/g-C3N4The preparation method of the ternary composite catalytic material comprises the following steps:
（1）g-C3N4the preparation of (1):
20 g of urea were weighed, placed in a covered alumina crucible, heated to 550 ℃ in an electric furnace at a rate of 5 ℃/min, and held for 4 h. Cooling to room temperature after the reaction is finished, grinding the obtained light yellow powder and collecting to obtain g-C3N4A sample;
（2）Bi12O15Cl6the preparation of (1):
weigh 1 mmol of Bi (NO)3)3•5H2O, which was dissolved in 10 mL of ethylene glycol with vigorous stirring to form a homogeneous solution A. Simultaneously weigh 0.33 mmol of NH4Cl, dissolved in 35 mL of distilled water to form solution B. The solution A was slowly added to the solution B with vigorous stirring and stirred at room temperature for 1 h. After the stirring was completed, it was transferred to an autoclave and heated at 160 ℃ for 12 hours. 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 at 60 ℃ overnight. Then, the obtained white solid powder was calcined in an electric furnace at 400 ℃ for 5 hours at a heating rate of 2 ℃/min. After the reaction is finished, light yellow Bi is obtained12O15Cl6Grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi12O15Cl6/g-C3N4preparing a binary composite material:
weigh 0.5g of g-C3N4In a 150 mL beaker, 30mL of methanol was measured and sonicated for 30 min. Further weigh 0.25g of Bi12O15Cl6Dissolving it in g-C3N4Continuing to perform ultrasonic treatment for 30 min. After which stirring was continued in a fume hood for 24 h. After evaporation of the methanol, the resulting product was collected and dried at 60 ℃ overnight to obtain Bi12O15Cl6/g-C3N4Binary composite materialMaterial, marked as BOCl/CN;
（4）AgCl/Bi12O15Cl6/g-C3N4preparing a ternary composite catalytic material:
weighing 0.5g of Bi prepared by the method12O15Cl6/g-C3N4Dissolving the binary composite material into 30mL of deionized water, and then carrying out ultrasonic dispersion for 30-60 min;
secondly, placing 0.17-0.85 mmol of chlorine source in the solution, and then stirring for 30-60 min at room temperature to obtain suspension;
③ AgNO3And (4) dropwise adding the solution into the suspension obtained in the step (II), and continuously stirring at room temperature for 4-8 hours. Adding AgNO3The molar quantity of the chlorine source is the same as that of the chlorine source in the step II;
collecting the precipitate, centrifugally washing the precipitate for 3-6 times by using absolute ethyl alcohol and distilled water, wherein the centrifugal rotating speed is 8000-10000 r/min, the centrifugal time is 5-10 min, collecting the product, dispersing the product into a culture dish containing the absolute ethyl alcohol, and then placing the culture dish into an oven to obtain AgCl/Bi12O15Cl6/g-C3N4The ternary composite catalytic material is marked as A/BOCl/CN.
The AgCl/Bi12O15Cl6/g-C3N4The preparation method of the ternary composite catalytic material comprises the step (4) and the chlorine source is one of potassium chloride or sodium chloride.
The AgCl/Bi12O15Cl6/g-C3N4The preparation method of the ternary composite catalytic material comprises the step (4) and the step (II), wherein the ultrasonic dispersion time of the chlorine source in the ultrapure water is preferably 30 min.
The invention provides the AgCl/Bi12O15Cl6/g-C3N4The application of the ternary composite catalytic material in catalytic degradation of antibiotics in wastewater under the condition of visible light.
In the above application, the antibiotic is tetracycline; AgCl/Bi in photocatalytic degradation process12O15Cl6/g-C3N4Adding of ternary composite catalytic materialThe amount of the tetracycline in the wastewater is 0.2-1.0 g/L, and the concentration of the tetracycline in the wastewater is 10-30 mg/L.
In the above application, 250 mL of tetracycline solution with a concentration of 20 mg/L was prepared, and then 0.05g of AgCl/Bi was weighed12O15Cl6/g-C3N4Adding 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 under the dark condition to ensure that the solution achieves adsorption-desorption balance; then, a 300W xenon lamp with a 420 nm optical filter is used as a visible light source for carrying out photocatalytic reaction, the total time of the photocatalytic reaction is 80min, samples are taken every 20 min, supernatant liquid is taken after centrifugal separation to measure the absorbance, and the maximum absorption wavelength of tetracycline is 357 nm.
The invention has the beneficial effects that:
(1) the invention firstly utilizes a wet impregnation method to prepare AgCl/Bi12O15Cl6/g-C3N4The three-way catalyst has the advantages of simple and convenient preparation method, simple operation, cheap and easily obtained raw materials and the like
(2) AgCl/Bi prepared by the invention12O15Cl6/g-C3N4The three-way catalyst is a photocatalyst with efficient photocatalytic performance under visible light. Using oxygen-enriched bismuth oxyhalide Bi12O15Cl6And AgCl pair g-C capable of generating surface plasma resonance effect3N4Is modified to increase g-C3N4The adsorption capacity and the separation efficiency of the photo-generated electron hole pairs under the irradiation of visible light, and further the photocatalytic performance of the photo-generated electron hole pairs is improved.
(3) The novel AgCl/Bi prepared by the invention12O15Cl6/g-C3N4The three-way catalyst has better photocatalytic performance and adsorption capacity than g-C3N4The method is improved, and the prepared photocatalyst shows higher stability.
(4) Using the prepared novel AgCl/Bi12O15Cl6/g-C3N4Three-way catalyst for degrading tetracycline under irradiation of lightAnd after 80min, the degradation effect of more than 75.4 percent can be achieved, and excellent photocatalytic performance is shown.
Drawings
FIG. 1 is a graph of g-C prepared in example 1 of the present invention3N4、Bi12O15Cl6The X-ray diffraction patterns of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts;
FIG. 2 is an SEM photograph of a 15A/BOCl/CN ternary composite catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph of g-C prepared in example 1 of the present invention3N4、Bi12O15Cl6Ultraviolet-visible diffuse reflection spectrograms of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts;
FIG. 4 shows g-C prepared in example 1 of the present invention3N4、Bi12O15Cl6Band gap diagrams of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts;
FIG. 5 shows g-C prepared in example 1 of the present invention3N4、Bi12O15Cl6And the degradation effect of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts on 20 mg/L tetracycline is shown.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
this example provides an AgCl/Bi12O15Cl6/g-C3N4The preparation method and the application of the ternary composite catalytic material are as follows:
（1）g-C3N4the preparation of (1):
20 g of urea were weighed, placed in a covered alumina crucible, heated to 550 ℃ in an electric furnace at a rate of 5 ℃/min, and held for 4 h. Cooling to room temperature after the reaction is finished, grinding the obtained light yellow powder and collecting to obtain g-C3N4A sample;
（2）Bi12O15Cl6the preparation of (1):
weigh 1 mmol of Bi (NO)3)3•5H2O, which was dissolved in 10 mL of ethylene glycol with vigorous stirring to form a homogeneous solution A. Simultaneously weigh 0.33 mmol of NH4Cl, dissolved in 35 mL of distilled water to form solution B. The solution A was slowly added to the solution B with vigorous stirring and stirred at room temperature for 1 h. After the stirring was completed, it was transferred to an autoclave and heated at 160 ℃ for 12 hours. 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 at 60 ℃ overnight. Then, the obtained white solid powder was calcined in an electric furnace at 400 ℃ for 5 hours at a heating rate of 2 ℃/min. After the reaction is finished, light yellow Bi is obtained12O15Cl6Grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi12O15Cl6/g-C3N4preparing a binary composite material:
weigh 0.5g of g-C3N4In a 150 mL beaker, 30mL of methanol was measured and sonicated for 30 min. Further weigh 0.25g of Bi12O15Cl6Dissolving it in g-C3N4Continuing to perform ultrasonic treatment for 30 min. After which stirring was continued in a fume hood for 24 h. After evaporation of the methanol, the resulting product was collected and dried at 60 ℃ overnight to obtain Bi12O15Cl6/g-C3N4Binary composite material marked as BOCl/CN;
（4）AgCl/Bi12O15Cl6/g-C3N4preparing a ternary composite catalytic material:
weighing 0.5g of Bi prepared by the method12O15Cl6/g-C3N4Dissolving the binary composite material into 30mL of deionized water, and then carrying out ultrasonic dispersion for 30 min;
② placing 0.52 mmol potassium chloride in the solution, then continuing stirring for 30 min at room temperature to obtain suspension;
③ AgNO3The solution was added drop by drop to the suspension from step 2 and stirring was continued at room temperature for 4 h. Adding AgNO3Molar amount of (2) and chlorine in step (ii)The molar amount of the source is the same.
Collecting the precipitate, centrifugally washing the precipitate for 6 times by using absolute ethyl alcohol and distilled water, collecting the product, dispersing the product into a culture dish containing the absolute ethyl alcohol, placing the culture dish into an oven, and drying the culture dish at 60 ℃ for 12 hours to obtain 15% AgCl/Bi, wherein the centrifugal speed is 8000 r/min and the centrifugal time is 5 min12O15Cl6/g-C3N4The ternary composite catalytic material is marked as 15A/BOCl/CN.
Three 250 mL tetracycline solutions with a concentration of 20 mg/L were prepared, and 0.05 g-C was added separately3N4BOCl/CN and 15A/BOCl/CN. The photocatalyst is uniformly dispersed by ultrasonic treatment for 15 min under the dark condition, and then the solution is stirred by magnetic force for 40 min under the dark condition to reach the adsorption-desorption balance; then, a 300W xenon lamp with a 420 nm optical filter is used as a visible light source for carrying out photocatalytic reaction, the total time of the photocatalytic reaction is 80min, samples are taken every 20 min, supernatant liquid is taken after centrifugal separation to measure the absorbance, and the maximum absorption wavelength of tetracycline is 357 nm. Then, the time (t) is used as an abscissa, and the concentration ratio of tetracycline at t is used as an ordinate to draw a curve, the degradation performance of the three-way catalyst is tested (see figure 5), and the degradation rate of the catalyst prepared by the method to tetracycline can reach 75.4% within 80 min.
FIG. 1 is an XRD pattern (a: g-C) of the sample prepared in example 13N4, b: Bi12O15Cl6And c: BOCl/CN and 15A/BOCl/CN). As can be seen from the figure, the sample was clearly observed to have good crystal phase growth and a strong and sharp diffraction peak. Monomers g to C3N4The diffraction peaks at 13.04 ° and 27.40 ° correspond to the (001) and (002) crystal planes, respectively, corresponding to the standard card JCPDS number 87-1526. In the ternary complex 15A/BOCl/CN, it can be seen that it is classified as g-C3N4、Bi12O15Cl6And characteristic peaks of AgCl which respectively correspond to cards JCPDS number 87-1526, JCPDS No.70-0249 and JCPDS No.85-1355, and illustrate that Bi12O15Cl6And AgCl was successfully loaded to g-C3N4The above.
FIG. 2 isSEM image of 15A/BOCl/CN ternary composite catalyst prepared in example 1, and it can be seen that Bi appears in a needle-leaf shape12O15Cl6And AgCl in particulate form to g-C3N4And (4) nano-chips.
FIG. 3 is g-C prepared in example 13N4、Bi12O15Cl6The ultraviolet-visible diffuse reflection spectrogram of the BOCl/CN and 15A/BOCl/CN ternary composite catalyst can be known as g-C3N4Has a light absorption edge of 470 nm, a light absorption edge of 500 nm and a light absorption edge of 510 nm for BOCl/CN and 15A/BOCl/CN, respectively, compared with the monomer g-C3N4All have red shifts, which indicate that Bi12O15Cl6Incorporation of AgCl increases g-C3N4Utilization ratio of visible light.
FIG. 4 is g-C prepared in example 13N4、Bi12O15Cl6The band gap diagrams of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts are shown in the figure, g-C3N4、Bi12O15Cl6The band gap values of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts are 2.74 eV, 2.36 eV, 2.67 eV and 2.63 eV, respectively, which shows that Bi12O15Cl6And loading of AgCl to g-C3N4The band gap is narrowed, the separation of the photo-generated electron hole pairs is promoted, and the utilization rate of visible light is improved.
FIG. 5 is g-C prepared in example 13N4、Bi12O15Cl6And the degradation effect of the BOCl/CN and 15A/BOCl/CN ternary composite catalysts on 20 mg/L tetracycline is shown. g-C after 80min of visible light irradiation3N4、Bi12O15Cl6、Bi12O15Cl6/g-C3N4And AgCl/Bi12O15Cl6/g-C3N4The degradation rates of the ternary composite material to 20 mg/L tetracycline are respectively 30.7%, 63% and 75.4%, which shows that Bi12O15Cl6Incorporation of AgCl increases g-C3N4The photocatalytic ability of (c).
Example 2:
this example provides an AgCl/Bi12O15Cl6/g-C3N4The preparation method and the application of the ternary composite catalytic material are as follows:
（1）g-C3N4the preparation of (1):
20 g of urea were weighed, placed in a covered alumina crucible, heated to 550 ℃ in an electric furnace at a rate of 5 ℃/min, and held for 4 h. Cooling to room temperature after the reaction is finished, grinding the obtained light yellow powder and collecting to obtain g-C3N4A sample;
（2）Bi12O15Cl6the preparation of (1):
weigh 1 mmol of Bi (NO)3)3•5H2O, which was dissolved in 10 mL of ethylene glycol with vigorous stirring to form a homogeneous solution A. Simultaneously weigh 0.33 mmol of NH4Cl, dissolved in 35 mL of distilled water to form solution B. The solution A was slowly added to the solution B with vigorous stirring and stirred at room temperature for 1 h. After the stirring was completed, it was transferred to an autoclave and heated at 160 ℃ for 12 hours. 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 at 60 ℃ overnight. Then, the obtained white solid powder was calcined in an electric furnace at 400 ℃ for 5 hours at a heating rate of 2 ℃/min. After the reaction is finished, light yellow Bi is obtained12O15Cl6Grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi12O15Cl6/g-C3N4preparing a binary composite material:
weigh 0.5g of g-C3N4In a 150 mL beaker, 30mL of methanol was measured and sonicated for 30 min. Further weigh 0.25g of Bi12O15Cl6Dissolving it in g-C3N4Continuing to perform ultrasonic treatment for 30 min. After which stirring was continued in a fume hood for 24 h. After evaporation of the methanol, the resulting product was collected and dried at 60 ℃ overnight to yield Bi12O15Cl6/g-C3N4Binary composite material marked as BOCl/CN;
（4）AgCl/Bi12O15Cl6/g-C3N4preparing a ternary composite catalytic material:
weighing 0.5g of Bi prepared by the method12O15Cl6/g-C3N4Dissolving the binary composite material into 30mL of deionized water, and then performing ultrasonic dispersion for 40 min;
② placing 0.17 mmol sodium chloride in the solution, then continuing stirring for 40 min at room temperature to obtain suspension;
③ AgNO3The solution was added drop by drop to the suspension from step 2 and stirring was continued at room temperature for 5 h. Adding AgNO3The molar amount of (a) is the same as the molar amount of the chlorine source in the step (ii).
Collecting precipitate, centrifugally washing the precipitate for 5 times with absolute ethyl alcohol and distilled water at 9000 r/min for 7 min, collecting the product, dispersing the product into a culture dish containing absolute ethyl alcohol, placing the culture dish into an oven, and drying the culture dish at 60 ℃ for 12 h to obtain 5% AgCl/Bi12O15Cl6/g-C3N4A three-way composite catalytic material.
Three 250 mL tetracycline solutions with a concentration of 20 mg/L were prepared, and 0.05 g-C was added separately3N4、Bi12O15Cl6/g-C3N4And 5% AgCl/Bi12O15Cl6/g-C3N4The photocatalyst is uniformly dispersed by ultrasonic treatment for 15 min under the dark condition, and then the solution is stirred by magnetic force for 40 min under the dark condition to reach the adsorption-desorption balance; then, a 300W xenon lamp with a 420 nm optical filter is used as a visible light source for carrying out photocatalytic reaction, the total time of the photocatalytic reaction is 80min, samples are taken every 20 min, supernatant liquid is taken after centrifugal separation to measure the absorbance, and the maximum absorption wavelength of tetracycline is 357 nm. And then, drawing a curve by taking time (t) as an abscissa and taking the concentration ratio of tetracycline at t as an ordinate, and testing the degradation performance of the three-way catalyst. The test shows that the 5% AgCl/Bi of the example12O15Cl6/g-C3N4The degradation rate of tetracycline is 73 percent, which shows that Bi12O15Cl6Incorporation of AgCl increases g-C3N4The photocatalytic ability of (c).
Example 3:
this example provides an AgCl/Bi12O15Cl6/g-C3N4The preparation method and the application of the ternary composite catalytic material are as follows:
（1）g-C3N4the preparation of (1):
20 g of urea were weighed, placed in a covered alumina crucible, heated to 550 ℃ in an electric furnace at a rate of 5 ℃/min, and held for 4 h. Cooling to room temperature after the reaction is finished, grinding the obtained light yellow powder and collecting to obtain g-C3N4A sample;
（2）Bi12O15Cl6the preparation of (1):
weigh 1 mmol of Bi (NO)3)3•5H2O, which was dissolved in 10 mL of ethylene glycol with vigorous stirring to form a homogeneous solution A. Simultaneously weigh 0.33 mmol of NH4Cl, dissolved in 35 mL of distilled water to form solution B. The solution A was slowly added to the solution B with vigorous stirring and stirred at room temperature for 1 h. After the stirring was completed, it was transferred to an autoclave and heated at 160 ℃ for 12 hours. 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 at 60 ℃ overnight. Then, the obtained white solid powder was calcined in an electric furnace at 400 ℃ for 5 hours at a heating rate of 2 ℃/min. After the reaction is finished, light yellow Bi is obtained12O15Cl6Grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi12O15Cl6/g-C3N4preparing a binary composite material:
weigh 0.5g of g-C3N4In a 150 mL beaker, 30mL of methanol was measured and sonicated for 30 min. Further weigh 0.25g of Bi12O15Cl6Dissolving it in g-C3N4Solutions ofAnd continuing to perform ultrasonic treatment for 30 min. After which stirring was continued in a fume hood for 24 h. After evaporation of the methanol, the resulting product was collected and dried at 60 ℃ overnight to yield Bi12O15Cl6/g-C3N4Binary composite material marked as BOCl/CN;
（4）AgCl/Bi12O15Cl6/g-C3N4preparing a ternary composite catalytic material:
weighing 0.5g of Bi prepared by the method12O15Cl6/g-C3N4Dissolving the binary composite material into 30mL of deionized water, and then carrying out ultrasonic dispersion for 60 min;
② placing 0.34 mmol sodium chloride in the solution, then continuing stirring for 50 min at room temperature to obtain suspension;
③ AgNO3The solution was added drop by drop to the suspension from step (ii) and stirring was continued at room temperature for 6 h. Adding AgNO3The molar amount of (a) is the same as the molar amount of the chlorine source in the step (ii).
Collecting the precipitate, centrifugally washing the precipitate for 4 times by using absolute ethyl alcohol and distilled water, collecting the product, dispersing the product into a culture dish containing the absolute ethyl alcohol, placing the culture dish into an oven, and drying the culture dish for 12 hours at the temperature of 60 ℃ to obtain 10% AgCl/Bi, wherein the centrifugal speed is 10000 r/min and the centrifugal time is 5 min12O15Cl6/g-C3N4A three-way composite catalytic material.
Three 250 mL tetracycline solutions with a concentration of 20 mg/L were prepared, and 0.05 g-C was added separately3N4、Bi12O15Cl6/g-C3N4And 10% AgCl/Bi12O15Cl6/g-C3N4The photocatalyst is uniformly dispersed by ultrasonic treatment for 15 min under the dark condition, and then the solution is stirred by magnetic force for 40 min under the dark condition to reach the adsorption-desorption balance; then, a 300W xenon lamp with a 420 nm optical filter is used as a visible light source for carrying out photocatalytic reaction, the total time of the photocatalytic reaction is 80min, samples are taken every 20 min, a supernatant is taken after centrifugal separation to measure the absorbance, and the maximum absorption wavelength of tetracycline is measured357 nm. And then, drawing a curve by taking time (t) as an abscissa and taking the concentration ratio of tetracycline at t as an ordinate, and testing the degradation performance of the three-way catalyst. By detection, this example is 10% AgCl/Bi12O15Cl6/g-C3N4The degradation rate of tetracycline is 72.5%, which shows that Bi12O15Cl6Incorporation of AgCl increases g-C3N4The photocatalytic ability of (c).
Claims (8)
1. A ternary composite catalytic material for removing tetracycline from waste water is characterized in that the composite material is AgCl/Bi12O15Cl6/g-C3N4In the composite material Bi12O15Cl6/g-C3N4The mass ratio of the AgCl to the water is 20: 1-10: 3; in the composite material, Bi12O15Cl6And g-C3N4The mass ratio of (A) to (B) is 1: 2.
2. The three-way composite catalytic material for removing tetracycline from wastewater according to claim 1, wherein Bi is12O15Cl6/g-C3N4The mass ratio of the catalyst to AgCl is 20: 3.
3. A method for preparing the three-way composite catalytic material for removing tetracycline from wastewater according to claim 1 or 2, characterized by comprising the steps of:
（1）g-C3N4the preparation of (1):
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 the speed of 5 ℃/min, and keeping the temperature for 4 hours; cooling to room temperature after the reaction is finished, grinding the obtained light yellow powder and collecting to obtain g-C3N4A sample;
（2）Bi12O15Cl6the preparation of (1):
weigh 1 mmol of Bi (NO)3)3•5H2O, dissolved to 10 mL under vigorous stirringForming a uniform solution A in ethylene glycol; simultaneously weigh 0.33 mmol of NH4Cl, which is dissolved in 35 mL of distilled water to form a solution B; slowly adding the solution A into the solution B under vigorous stirring, and stirring for 1 h at room temperature; after stirring, transferring the mixture into an autoclave, and heating the mixture for 12 hours at 160 ℃; after the reaction is finished, cooling the high-pressure kettle to room temperature, washing the obtained precipitate with ethanol and distilled water for three times, and drying at 60 ℃ overnight; then, calcining the obtained white solid powder in an electric furnace at 400 ℃ for 5 h, wherein the heating rate is 2 ℃/min; after the reaction is finished, light yellow Bi is obtained12O15Cl6Grinding and collecting the powder for later use, and marking the powder as BOCl;
（3）Bi12O15Cl6/g-C3N4preparing a binary composite material:
weigh 0.5g of g-C3N4Measuring 30mL of methanol in a 150 mL beaker, and performing ultrasonic treatment for 30 min; further weigh Bi in an amount of 0.25g12O15Cl6Dissolving it in g-C3N4Continuing to perform ultrasonic treatment for 30 min in the solution; then continuously stirring in a fume hood for 24 hours; after evaporation of the methanol, the resulting product was collected and dried at 60 ℃ overnight to obtain Bi12O15Cl6/g-C3N4Binary composite material marked as BOCl/CN;
（4）AgCl/Bi12O15Cl6/g-C3N4preparing a ternary composite catalytic material:
weighing 0.5g of Bi prepared by the method12O15Cl6/g-C3N4Dissolving the binary composite material into 30mL of deionized water, and then performing ultrasonic dispersion;
secondly, placing 0.17-0.85 mmol of chlorine source in the solution of the first step, and stirring at room temperature to obtain a suspension;
③ AgNO3Dropwise adding the solution into the suspension obtained in the step II, and continuously stirring for 4-8 hours at room temperature; adding AgNO3The molar quantity of the chlorine source is the same as that of the chlorine source in the step II;
collecting the precipitateCentrifuging and washing the substance for 3-6 times by using absolute ethyl alcohol and distilled water, wherein the centrifugal rotating speed is 8000-10000 r/min, the centrifugal time is 5-10 min, collecting a product, dispersing the product into a culture dish containing the absolute ethyl alcohol, and then placing the culture dish into an oven for drying to obtain AgCl/Bi12O15Cl6/g-C3N4The ternary composite catalytic material is marked as A/BOCl/CN.
4. The preparation method of the ternary composite catalytic material for removing tetracycline in wastewater according to claim 3, wherein Bi in step (4) and (r)12O15Cl6/g-C3N4The ultrasonic time of the binary composite material at room temperature is 30-60 min.
5. The preparation method of the ternary composite catalytic material for removing tetracycline from wastewater according to claim 3, wherein the chlorine source in the step (4) and the step (II) is one of potassium chloride or sodium chloride; stirring for 30-60 min at room temperature.
6. Use of the ternary composite catalytic material of claim 1 or 2 in the removal of tetracycline from wastewater under visible light conditions.
7. Use according to claim 6, characterized in that: AgCl/Bi in photocatalytic degradation process12O15Cl6/g-C3N4The dosage 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. Use according to claim 7, characterized in that: 250 mL of tetracycline solution with the concentration of 20 mg/L is prepared, and then 0.05g of AgCl/Bi is weighed12O15Cl6/g-C3N4Adding the ternary composite catalytic material into a tetracycline solution, carrying out ultrasonic treatment for 15 min under a dark condition to uniformly disperse the catalyst, and then carrying out magnetic stirring for 40 min to enable the solution to reach adsorption-desorption balance; then adopt and carryPerforming photocatalytic reaction with a 300W xenon lamp with a 420 nm filter as a visible light source, wherein the total time of the photocatalytic reaction is 80min, taking a sample every 20 min, performing secondary centrifugal separation on the obtained solution at 10000 rpm, centrifuging for 5 min each time, and filtering the supernatant with a 0.45-micrometer filter membrane; finally, testing the absorbance of the filtered clear liquid on an ultraviolet visible spectrophotometer; the absorbance of the filtrate was measured at a wavelength of 357 nm.
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