Preparation method of carbon nitride-based oxytetracycline residue scavenger
阅读说明：本技术 一种基于氮化碳的土霉素残留物清除剂的制备方法 (Preparation method of carbon nitride-based oxytetracycline residue scavenger ) 是由 何仰清 魏娜梅 马占营 杨谦 姚秉华 于 2020-12-08 设计创作，主要内容包括：本发明公开了一种基于氮化碳的土霉素残留物清除剂的制备方法,具体为：首先,将MoS-2、g-C-3N-4和去离子水混合,超声处理；放入高压釜中,进行水热反应,得到MoS-2/g-C-3N-4复合物；将MoS-2/g-C-3N-4复合物分散于去离子水和甲醇的混合溶液中,搅拌,之后向溶液中加入氯金酸溶液,使用氙灯对其照射,并用气泵进行鼓气；洗涤,干燥,得到AuNPs/MoS-2/g-C-3N-4三相复合材料,即为土霉素残留物清除剂。利用纳米金和MoS-2双重敏化的g-C-3N-4复合材料,能对抗生素残留物进行清除,制备过程对设备要求低、反应条件温和,合成工艺简单易于实现。(The invention disclosesA preparation method of the carbon nitride-based oxytetracycline residue scavenger is provided, which comprises the following steps: firstly, MoS 2 、g‑C 3 N 4 Mixing with deionized water, and performing ultrasonic treatment; putting the mixture into a high-pressure kettle for hydrothermal reaction to obtain MoS 2 /g‑C 3 N 4 A complex; mixing MoS 2 /g‑C 3 N 4 Dispersing 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/MoS 2 /g‑C 3 N 4 The triphase composite material is the oxytetracycline residue scavenger. Using nano gold and MoS 2 Doubly sensitized g-C 3 N 4 The 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.)
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.
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。