CN112619680A - Preparation method of carbon nitride-based oxytetracycline residue scavenger - Google Patents
Preparation method of carbon nitride-based oxytetracycline residue scavenger Download PDFInfo
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- carbon nitride
- oxytetracycline
- deionized water
- residue scavenger
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- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical group C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 title claims abstract description 30
- 239000002516 radical scavenger Substances 0.000 title claims abstract description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 40
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 32
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000527 sonication Methods 0.000 claims 1
- 230000003115 biocidal effect Effects 0.000 abstract description 9
- 229910052737 gold Inorganic materials 0.000 abstract description 7
- 239000010931 gold Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000004100 Oxytetracycline Substances 0.000 description 6
- 229960000625 oxytetracycline Drugs 0.000 description 6
- 235000019366 oxytetracycline Nutrition 0.000 description 6
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940063650 terramycin Drugs 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
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- 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
- C02F2101/34—Organic compounds containing oxygen
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- 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
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- 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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- C09K2101/00—Agricultural use
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention disclosesA preparation method of the carbon nitride-based oxytetracycline residue scavenger is provided, which comprises the following steps: firstly, MoS2、g‑C3N4Mixing with deionized water, and performing ultrasonic treatment; putting the mixture into a high-pressure kettle for hydrothermal reaction to obtain MoS2/g‑C3N4A complex; mixing MoS2/g‑C3N4Dispersing the compound in a mixed solution of deionized water and methanol, stirring, adding a chloroauric acid solution into the solution, irradiating the chloroauric acid solution by using a xenon lamp, and blowing by using an air pump; washing and drying to obtain AuNPs/MoS2/g‑C3N4The triphase composite material is the oxytetracycline residue scavenger. Using nano gold and MoS2Doubly sensitized g-C3N4The composite material can remove antibiotic residues, the preparation process has low requirement on equipment, the reaction condition is mild, and the synthesis process is simple and easy to realize.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a carbon nitride-based oxytetracycline residue scavenger.
Background
Antibiotic residues, one of the most serious environmental pollutants, have been attracting much attention as the potential threats to human health and the ecosystem have become increasingly serious. Terramycin is a broad-spectrum antibiotic, has wide application in the aquaculture and livestock and poultry breeding industry, and is one of the antibiotics with the largest global yield. Due to the long half-life period, a large amount of oxytetracycline discharged in water and soil environment is not easy to biodegrade, so that a large amount of oxytetracycline remains in the environment. In addition, the residue of terramycin can provide a good propagation and dissemination environment for drug-resistant bacteria and drug-resistant genes, and the two potential antibiotic resistances pose serious health threats to human and animals. In recent years, the high incidence of drug-resistant bacteria worldwide has shown that antibiotic resistance is one of the most major health challenges in the 21 st century. Therefore, the search for effective antibiotic residue elimination methods is urgent.
g-C3N4Is a typical non-metallic photocatalyst, has the advantages of difficult decomposition, difficult water dissolution, strong alkali and strong acid corrosion resistance, low price, easy obtainment, energy conservation, environmental protection and the likeAdvantages, due to its unique chemical properties and thermal stability, surround g-C3N4The synthesis of composite photocatalytic materials is becoming a research hotspot in the field of photocatalysis. But the practical application is greatly limited due to the defects of increased forbidden band width, low visible light capturing capability, easy recombination of photo-generated electrons and the like. MoS2Has the characteristics of good photosensitivity, high photoelectric response rate, high catalytic activity and the like, and is widely applied to the field of photocatalysis. In addition, the gold nanoparticles (AuNPs) have excellent optical properties and electron transport properties, and are a commonly used noble metal co-catalyst. In order to develop an efficient oxytetracycline residue photocatalytic degradation material, research on a material based on MoS2g-C double sensitized with AgNPs3N4Composite materials are particularly important.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon nitride-based oxytetracycline residue scavenger, which can efficiently catalyze and degrade oxytetracycline residues.
The technical scheme adopted by the invention is that the preparation method of the carbon nitride-based oxytetracycline residue scavenger is implemented according to the following steps:
step 1, MoS2、g-C3N4Mixing with deionized water, and performing ultrasonic treatment; then putting the mixture into a high-pressure kettle for hydrothermal reaction to obtain MoS2/g-C3N4A complex;
step 2, MoS2/g-C3N4Dispersing the compound in a mixed solution of deionized water and methanol, stirring, adding a chloroauric acid solution into the solution, irradiating the chloroauric acid solution by using a xenon lamp under the condition of magnetic stirring, and blowing by using an air pump; after the irradiation is finished, washing and drying the reaction product by using deionized water to obtain AuNPs/MoS2/g-C3N4The triphase composite material is the oxytetracycline residue scavenger.
The present invention is also characterized in that,
in step 1, MoS2、g-C3N4And deionized water in a mass ratio of 1:99～199：39601。
in the step 1, the hydrothermal reaction temperature is 150-170 ℃, and the hydrothermal reaction time is 10 h.
In the step 1, the ultrasonic treatment time is 1 h.
In step 2, the mass concentration of the chloroauric acid solution is 4.586 mM/ml.
In step 2, MoS2/g-C3N4The mass ratio of the compound to the mixed solution to the chloroauric acid solution is 0.8000: 48.0895: 0.1650, respectively; the volume ratio of deionized water to methanol in the mixed solution is 4: 1.
in the step 2, the stirring time is 1 h; the irradiation time was 30 min.
The invention has the beneficial effects that:
the method of the invention utilizes nano-gold and MoS2Doubly sensitized g-C3N4The composite material can remove antibiotic residues, the preparation process has low requirement on equipment, the reaction condition is mild, and the synthesis process is simple and easy to realize; three-phase composite photocatalytic material AuNPs/MoS prepared by adopting method2/g-C3N4The visible light capturing capability is high, the separation of electrons and holes is realized, the transmission effect is good, and the photocatalytic degradation performance is high; the method can provide reliable reference basis for preparing other multiphase photocatalytic materials based on the nitrogen carbide.
Drawings
FIG. 1 shows AuNPs/MoS prepared in example 1 of the present invention2/g-C3N4SEM image of three-phase composite;
FIG. 2 is g-C3N4SEM picture of (1);
FIG. 3 shows AuNPs/MoS prepared in example 1 of the present invention2/g-C3N4FT-IR spectrum of three-phase composite material;
FIG. 4 is a 10% AuNPs/0.5% MoS prepared according to example 1 of the present invention2/g-C3N4Three-phase composite material and g-C3N4Ultraviolet diffuse reflectance spectrum of (a);
FIG. 5 is a 10% AuNPs/0.5% MoS prepared according to example 1 of the present invention2/g-C3N4Three-phase composite material and g-C3N4Impedance analysis graph of (a);
FIG. 6 shows AuNPs/MoS prepared in example 1 of the present invention2/g-C3N4Analyzing a spectrogram of a product of the photocatalytic degradation of the oxytetracycline by the three-phase composite material by ultraviolet and visible light;
FIG. 7 is a 5% AuNPs/1% MoS prepared according to the invention2/g-C3N4Ultraviolet and visible light analysis spectrogram of a product of photocatalytic degradation of oxytetracycline by a three-phase composite material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a carbon nitride-based oxytetracycline residue scavenger, which is implemented by MoS2And g-C3N4Starting from the product, MoS is prepared by hydrothermal method2/g-C3N4The AuNPs/MoS is prepared from the composite photocatalytic material by photo-reduction method using chloroauric acid as gold source2/g-C3N4The triphase composite material is the oxytetracycline residue scavenger;
the method is implemented according to the following steps:
step 1, MoS2、g-C3N4Mixing with deionized water, and performing ultrasonic treatment for 1 h; then putting the obtained product into an autoclave for hydrothermal reaction, taking out the autoclave after the reaction is finished, and opening the autoclave in a fume hood to obtain MoS2/g-C3N4A complex;
MoS2、g-C3N4and deionized water in a mass ratio of 1: 99-199: 39601, respectively;
the hydrothermal reaction temperature is 150-170 ℃, and the hydrothermal reaction time is 10 hours;
step 2, MoS2/g-C3N4Dispersing the compound in a mixed solution of deionized water and methanol, stirring at normal temperature for 1h, adding chloroauric acid solution into the solution, irradiating the mixed solution for 30min by using a xenon lamp (250W) under the condition of magnetic stirring, and blowing by using an air pump; after the irradiation is finished, washing and drying the reaction product by using deionized waterDrying to obtain AuNPs/MoS2/g-C3N4The triphase composite material is the oxytetracycline residue scavenger;
the mass concentration of the chloroauric acid solution is 4.586 mM/ml;
MoS2/g-C3N4the mass ratio of the compound to the mixed solution to the chloroauric acid solution is 0.8000: 48.0895: 0.1650, respectively;
the volume ratio of deionized water to methanol in the mixed solution is 4: 1.
the invention relates to a preparation method of a carbon nitride-based oxytetracycline residue scavenger, which uses nano-gold and MoS2Doubly sensitized g-C3N4The composite material is used for synthesizing the antibiotic residue scavenger, so that the raw material cost is saved, the operation is simple, and the composite material for scavenging antibiotic residues is successfully synthesized.
Example 1
The invention relates to a preparation method of a carbon nitride-based oxytetracycline residue scavenger, which is implemented by the following steps:
weighing MoS20.004 g; taking g-C again3N40.796 g. 0.004g of MoS is taken2And 0.796g g-C3N4Placing the mixture in the same beaker, adding 60mL of deionized water, and carrying out ultrasonic treatment for 1 h. Then, the mixture is placed into an autoclave and kept at 150 ℃ for 10 hours. After the reaction was complete, the autoclave was taken out and opened in a fume hood to obtain 0.5% MoS2/g-C3N4A composite photocatalytic material. 10mL of 48.56mM chloroauric acid solution was prepared (stored under dark and dry conditions). 0.1895g of 0.5% MoS was taken2/g-C3N4The complex was added to a mixed solution of 40mL of deionized water and 10mL of methanol, and stirred at room temperature for 1 hour. Two 2.320mL portions of chloroauric acid solution were accurately measured and added to 0.2g of 0.5% MoS2/g-C3N4In a complex. Under magnetic stirring, it was irradiated with a xenon lamp (250W) for 30min and blown with an air pump.
After the irradiation is finished, the relevant materials are respectively washed and dried, and are marked as 10% AuNPs/0.5% MoS2/g-C3N4。
FIG. 1 shows AuNPs/MoS prepared in example 12/g-C3N4SEM image of three-phase composite material. FIG. 2 shows g-C3N4The SEM image shows that the graphite phase carbon nitride is a layered porous structure, MoS2And AuNPs are better loaded on graphite phase carbon nitride to form 10 percent AuNPs/0.5 percent MoS2/g-C3N4A three-phase composite material.
FIG. 3 is a 10% AuNPs/0.5% MoS prepared in example 12/g-C3N4FT-IR spectrum of three-phase composite material. As can be seen from the figure: 3261 and 3162cm-1The signal can be subjected to N-H stretching vibration, 1200 and 1650cm-1The typical C ═ N heterocyclic ring telescopic mode can be obviously observed in the region, wherein 492cm-1The peak at (A) was attributed to typical Mo-S stretching vibrations, further demonstrating 10% AuNPs/0.5% MoS2/g-C3N4Successful synthesis of three-phase composite materials.
FIG. 4 is a 10% AuNPs/0.5% MoS prepared in example 12/g-C3N4Three-phase composite material and g-C3N4Ultraviolet diffuse reflectance spectroscopy. The ultraviolet diffuse reflection spectrogram is compared and analyzed, the response of the composite material to visible light is improved greatly compared with carbon nitride, and the result shows that the graphite-phase carbon nitride is sensitized and modified by using the nano-gold and the molybdenum disulfide so as to enhance the capturing performance of the composite material to the visible light and obtain a relatively ideal effect.
FIG. 5 is a 10% AuNPs/0.5% MoS prepared in example 12/g-C3N4Three-phase composite material and g-C3N4Impedance analysis chart of (1). The semi-circular arc on the graph shows the reaction rate of the electrode surface, the smaller circular arc means the effective separation of photo-generated electron-hole pairs, the charge transfer efficiency is higher, and the arc radius of the composite material is less than g-C3N4And the impedance values are all less than 50 omega, which indicates that the materials have good photoinduced electron transmission performance.
FIGS. 6 and 7 show AuNPs/MoS at different ratios2/g-C3N4Three-phase compositionUltraviolet and visible light analysis spectrogram of a material photocatalytic degradation oxytetracycline product. The figure clearly shows that the three-phase composite material has stronger removing effect on terramycin, wherein, 10 percent of AuNPs/0.5 percent of MoS2/g-C3N4The composite material can remove the terramycin within 160min by 83.0 percent. Fully proves that the graphite-phase carbon nitride double-sensitized by the nano-gold and the molybdenum disulfide has a good removing effect on the oxytetracycline.
Example 2
The invention relates to a preparation method of a carbon nitride-based oxytetracycline residue scavenger, which is implemented by the following steps:
weighing MoS20.008 g; taking g-C again3N40.796 g. 0.008g of MoS is taken2And 0.796g g-C3N4Placing in the same beaker, adding 60ml of deionized water, and carrying out ultrasonic treatment for 1 h. Then, the mixture is placed into an autoclave and kept at the temperature of 160 ℃ for 10 hours. After the reaction was complete, the autoclave was taken out and opened in a fume hood to obtain 1% MoS2/g-C3N4A composite photocatalytic material. 10mL of 48.56mM chloroauric acid solution was prepared (stored under dark and dry conditions). 0.1778g of 1% MoS was taken2/g-C3N4The complex was added to a mixed solution of 40mL of deionized water and 10mL of methanol, and stirred at room temperature for 1 hour. Two 1.100mL portions of chloroauric acid solution were accurately measured and added to 0.1778g of 1% MoS2/g-C3N4In a complex. Under magnetic stirring, it was irradiated with a xenon lamp (250W) for 30min and blown with an air pump. After the irradiation is finished, the relevant materials are respectively washed and dried, and are marked as 5% AuNPs/1% MoS2/g-C3N4。
Claims (7)
1. A preparation method of carbon nitride-based oxytetracycline residue scavenger is characterized by comprising the following steps:
step 1, MoS2、g-C3N4Mixing with deionized water, and performing ultrasonic treatment; then putting the mixture into a high-pressure kettle for hydrothermal reaction to obtain MoS2/g-C3N4A complex;
step 2, MoS2/g-C3N4Dispersing the compound in a mixed solution of deionized water and methanol, stirring, adding a chloroauric acid solution into the solution, irradiating the chloroauric acid solution by using a xenon lamp under the condition of magnetic stirring, and blowing by using an air pump; after the irradiation is finished, washing and drying the reaction product by using deionized water to obtain AuNPs/MoS2/g-C3N4The triphase composite material is the oxytetracycline residue scavenger.
2. The method for preparing carbon nitride-based oxytetracycline residue scavenger according to claim 1, wherein in step 1, MoS is performed2、g-C3N4And deionized water in a mass ratio of 1: 99-199: 39601.
3. the preparation method of the carbon nitride-based oxytetracycline residue scavenger according to claim 1, wherein in the step 1, the hydrothermal reaction temperature is 150-170 ℃ and the hydrothermal reaction time is 10 hours.
4. The method for preparing the carbon nitride-based oxytetracycline residue scavenger according to claim 1, wherein in step 1, the sonication time is 1 h.
5. The method for preparing a carbon nitride-based oxytetracycline residue scavenger according to claim 1, wherein the mass concentration of the chloroauric acid solution in step 2 is 4.586 mM/ml.
6. The method for preparing carbon nitride-based oxytetracycline residue scavenger according to claim 1, wherein in step 2, MoS is performed2/g-C3N4The mass ratio of the compound to the mixed solution to the chloroauric acid solution is 0.8000: 48.0895: 0.1650, respectively; the volume ratio of deionized water to methanol in the mixed solution is 4: 1.
7. the method for preparing the carbon nitride-based oxytetracycline residue scavenger according to claim 1, wherein in the step 2, the stirring time is 1 h; the irradiation time was 30 min.
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