CN113336295A - Nano Pd/C3N4/Fe3O4Application in photodegradation of tetracycline - Google Patents
Nano Pd/C3N4/Fe3O4Application in photodegradation of tetracycline Download PDFInfo
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- 239000004098 Tetracycline Substances 0.000 title claims abstract description 20
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 20
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 23
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
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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
- 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
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
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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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
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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
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Abstract
The invention discloses nano Pd/C3N4/Fe3O4The application of the compound in photodegradation of tetracycline. Adopts a hydrothermal method to prepare Pd/C3N4/Fe3O4The magnetic composite photocatalyst is applied to photocatalytic degradation of tetracycline in wastewater. The invention has the advantages that: (1) the raw materials for preparing the photocatalytic material are easy to obtain, and the process flow is simple and convenient; (2) the photocatalytic degradation effect is good, and the degradation rate reaches 98%; (3) after the reaction is finished, the magnetic property of the catalytic material is utilized to separate the catalytic material from the reaction system, and the catalytic material is easy to recycle.
Description
Technical field
The invention relates to a composite nano material for photodegradation of tetracyclineBelonging to the technical field of resources and environment. The method is suitable for the nano Pd/C3N4/Fe3O4Is a composite nano photocatalytic material and can be used in the occasions of realizing the photocatalytic degradation of tetracycline under the natural illumination condition.
Two background art
Antibiotics are magical drugs discovered in the twentieth century, and are widely used in the pharmaceutical and aquaculture industries [ tensor. 67-79]. However, since decades of discovery, due to The abuse of antibiotics and their metabolites into The aqueous environment, it has become an environmental contaminant that is mobile and resistant to degradation, and is inadvertently transported from municipal and aquaculture wastewater to natural waters, becoming a long-term environmental safety hazard [ R Huang, P Ding, D huangang, et al, antibiotic polarization processes public health in China [ J ]. The Lancet, 2015, 385: 773-. According to investigation, antibiotic residues are generally detected in agricultural soil and aquaculture water in China [ great clouds, the current situation of tetracycline antibiotic pollution and the progress of source research in agricultural soil in China [ J ]. the ecological environment report, 2018, 27: 1774-1782], in which tetracycline antibiotics occur most frequently. The tetracycline antibiotic pollutants are stable under natural conditions, and a large amount of residual bacteria with strong drug resistance in the environment can easily generate bacteria with strong drug resistance, so that the bacteria directly or indirectly cause harm to a human body and even further influence the whole ecological system. Therefore, the contamination problem represented by the tetracycline antibiotics has become a serious global threat. In the face of severe pollution situation, researchers find an ideal technology for energy regeneration and environmental remediation by using solar energy.
Photocatalytic studies are chemical branches involving the chemical action of light, commonly used to describe chemical reactions caused by ultraviolet light (wavelength 100-400nm) visible light (400-750nm) or infrared radiation (750-2500 nm). Since 1972, Fujishima and Honda issued on photocatalytic water on TiO2 electrode could be regarded as the beginning of photocatalytic applications, scientists have conducted more intensive research and study on photocatalytic behavior from various fields. The photocatalytic degradation technology is developed rapidly, pollutants are adsorbed on the surface of a photocatalyst, and under the irradiation of ultraviolet light or visible light, the pollutants are decomposed into small molecules such as carbon dioxide, water and the like.
The most challenging and valuable direction in the research of photocatalytic degradation technology is the research of photocatalysts. Photocatalysts (or photocatalysts) are known as photocatalysts, which do not themselves change or become consumed throughout a chemical reaction. Over the past decade, a broad class of semiconductor photocatalysts, mainly transition metal oxides and organometallic complexes [ Z Li, Y Zhi, P Shao, et al].Applied Catalysis B：Environmental，2019，245：334-342]The solar energy is developed vigorously, and the possibility is provided for effectively utilizing inexhaustible solar energy. In consideration of energy conservation and environmental protection, the metal-free photocatalytic material is more environment-friendly, and researchers turn the attention to inorganic non-metallic materials such as graphite carbonitride (g-C)3N4) Has photocatalytic activity under ultraviolet or visible light irradiation.
g-C3N4The magnetic composite nano photocatalytic material has excellent dispersibility in water, which means that the magnetic composite nano photocatalytic material can degrade pollutants more efficiently as a photocatalytic material, but brings inconvenience to the recovery process.
Disclosure of the invention
The invention aims to provide a method for recycling and comprehensively utilizing waste vegetable oil, which has the advantages of simple preparation process of a composite material, safe and efficient photodegradation process of tetracycline in water, easy separation and recovery of the composite photocatalytic material and cyclic utilization.
The technical solution for realizing the purpose of the invention is as follows: non-toxic and harmless graphite phase C as non-metallic semiconductor with strong visible light response3N4Is certainly an ideal material for effectively utilizing solar energy, but C3N4The method also has some inherent defects, including low light absorption rate, poor charge transfer efficiency and difficult separation and recovery in a water system, and in order to solve the defects and obtain a more efficient, green and energy-saving photocatalytic material, the invention introduces other components to form the composite photocatalyst; the Pd metal nano-particles are considered to have excellent electron capture capacity and can rapidly separate C under the irradiation of visible light3N4The generated electrons enhance the photocatalytic capacity; with nano Fe3O4The Pd/C as carrier can endow the composite catalyst with excellent magnetism3N4/Fe3O4Under the action of an external magnetic field, the magnetic composite photocatalyst can realize the rapid separation of the catalyst and the wastewater, thereby not only reducing the loss of the catalyst in the degradation process, but also saving a large amount of energy consumed by the traditional separation mode such as high-speed centrifugation.
The invention relates to a method for converting waste vegetable oil by the synergistic catalysis of a eutectic system, and specifically takes Pd/C prepared by a hydrothermal method as a specific measure3N4/Fe3O4The magnetic composite material is a catalyst, a photodegradation reaction is carried out under the irradiation of simulated sunlight of a 250W xenon lamp, tetracycline antibiotics are effectively degraded in a low-concentration alkaline water environment, the degradation rate reaches 98%, after the reaction is finished, the magnetic property of the composite material is utilized, an external magnetic field is applied to separate the composite material from a reaction system, the separated composite material can be directly recycled without treatment, the degradation rate is still more than 80% after 6 times of circulation, and the preparation process of the composite material is as follows:
step 1) grinding a certain amount of melamine, then putting the ground melamine into a porcelain boat, putting the porcelain boat into a muffle furnace, setting a temperature-raising program, raising the temperature in the furnace from 20 ℃ to 550 ℃ within 2 hours, then maintaining the temperature at 550 ℃, keeping the temperature for 3 hours, cooling the temperature in the furnace from 550 ℃ to 20 ℃, changing the powder in the porcelain boat from white to light yellow, grinding the powder, putting the ground powder into the muffle furnace again, raising the temperature to 550 ℃ at the same temperature-raising rate, keeping the temperature for 5 hours, cooling to room temperature, taking out the ground powder, and grinding the powder again to obtain the powdery C3N4；
Step 2) weighing 0.79mmol of polyvinylpyrrolidone, and weighing 0.062mmol of polyvinylpyrrolidone with the concentration of 0.01128 mol.L-1H of (A) to (B)2PdCl4Stirring the solution in a beaker until the solution is completely dissolved; weighing 1.00mmol of sodium borohydride, completely dissolving with 1-2ml of deionized water, and dropwise adding into the solution to reduce Pd2+(ii) a Continuously stirring for 30min after all the Pd nanoparticles are dripped, and obtaining a black Pd nanoparticle solution;
step 3) taking 1.19mmol of FeCl3·6H2O, 2.25mmol of polyvinylpyrrolidone with average molecular weight of 40000Da, 3.63mmol of urea and 15mL of 1, 2-propylene glycol, stirring the mixture on a magnetic stirrer until the mixture is completely dissolved to obtain yellow clear solution, adding a proper amount of C3N4And (2) continuously stirring, obtaining a uniform solution by taking ultrasonic dispersion as an assistant, finally adding the Pd nanoparticles obtained by treatment in 1.2.2, stirring for 30min, then transferring the solution into a 50mL high-pressure reaction kettle, reacting at 190 ℃ for 16h, cooling to room temperature, pouring out a product from the kettle, sequentially washing with deionized water and absolute ethyl alcohol to obtain a black magnetic composite photocatalyst, and drying for later use.
The nano Pd/C of the invention3N4/Fe3O4The application of the compound in photodegradation of tetracycline is characterized in that: adding the magnetic composite photocatalytic material into a tetracycline aqueous solution, firstly carrying out 30min in a dark place, continuously stirring for pretreatment to ensure the adsorption-desorption balance of the tetracycline aqueous solution and the surface of a photocatalyst, then carrying out a photodegradation reaction, using an open beaker as a reaction container, keeping the container under sufficient visible light irradiation, sampling at fixed time intervals, collecting a sample into a sample bottle through a filter membrane, and examining the concentration change through an ultraviolet visible spectrophotometer.
The nano Pd/C of the invention3N4/Fe3O4The application of the compound in photodegradation of tetracycline is characterized in that: after the photocatalytic reaction is finished, the magnetic property of the composite material can be utilized to separate the composite material from a reaction system through a magnet or other external magnetic fields, and the composite material can be directly recycled without treatment.
According to the eutectic system provided by the invention, the waste vegetable oil is synergistically catalyzedThe key technology of the conversion method is that the Pd metal nano-particles have excellent electron capture capacity and can rapidly separate C under the irradiation of visible light3N4The generated electrons enhance the photocatalytic capacity; with nano Fe3O4The Pd/C as carrier can endow the composite catalyst with excellent magnetism3N4/Fe3O4Under the action of an external magnetic field, the magnetic composite photocatalyst can realize the rapid separation of the catalyst and the wastewater, thereby not only reducing the loss of the catalyst in the degradation process, but also saving a large amount of energy consumed by the traditional separation mode such as high-speed centrifugation.
Advantageous effects
(1) The raw materials for preparing the photocatalytic material are easy to obtain, and the process flow is simple and convenient;
(2) the photocatalytic degradation effect is good, and the degradation rate reaches 98%;
(3) after the reaction is finished, the magnetic property of the catalytic material is utilized to separate the catalytic material from the reaction system, and the catalytic material is easy to recycle.
Description of the four figures
FIG. 1 is the XRD pattern of the catalyst (a- -Pd/C)3N4/Fe3O4；b--C3N4/Fe3O4；c--Fe3O4；d--C3N4；e--Recycled Pd/C3N4/Fe3O4)。
FIG. 2 is a wavelength-absorbance relationship of ultraviolet-visible diffuse reflectance spectrum (a); (b) turke map (hv) - (alpha hv)2 relationship
FIG. 3 is a Pd/C catalyst3N4/Fe3O4Separated by a magnet.
Detailed description of the preferred embodiments
The following examples further illustrate the invention in order to provide a better understanding of the invention. The examples do not limit the scope of the invention in any way. Modifications and adaptations of the present invention within the scope of the claims may occur to those skilled in the art and are intended to be within the scope and spirit of the present invention.
Example 1
Take 15gAnd grinding melamine, putting the ground melamine into a porcelain boat, putting the porcelain boat into a muffle furnace, setting a temperature-raising program, raising the temperature in the furnace from 20 ℃ to 550 ℃ within 2h, and then maintaining the temperature at 550 ℃ for 3 h. The constant temperature is ended and the temperature in the furnace is cooled from 550 ℃ to 20 ℃. The powder in the porcelain boat is changed from white to light yellow, the solid is scraped from the porcelain boat and poured into a mortar for grinding, the obtained powder is put into a muffle furnace again, the temperature is raised at the same temperature raising rate, and the constant temperature is kept for 5 hours. Cooling to room temperature, taking out and grinding to obtain powder C3N4。
Example 2
0.79mmol of polyvinylpyrrolidone (PVP) is weighed out, and the 0.062mmol of PVP with the concentration of 0.01128 mol.L is measured-1H of (A) to (B)2PdCl4The solution was stirred in a beaker until completely dissolved. Weighing 1.00mmol of sodium borohydride, completely dissolving with 1-2ml of deionized water, and dropwise adding into the solution to reduce pd2+. And continuously stirring for 30min after all the Pd nanoparticles are dropwise added to obtain a black Pd nanoparticle solution.
Example 3
1.19mmol of FeCl are taken3·6H2O, 2.25mmol of PVP (average molecular weight 40000Da), 3.63mmol of urea and 15mL of 1, 2-propylene glycol, stirring the mixture on a magnetic stirrer until the mixture is completely dissolved to obtain yellow clear solution, and adding a proper amount of C3N4Stirring is continued, ultrasonic dispersion is used as an auxiliary to obtain a uniform solution, and finally the Pd nano particles obtained by the treatment in 1.2.2 are added and stirred for 30 min. The solution was then transferred to a 50mL autoclave and reacted at 190 ℃ for 16 h. And (3) cooling to room temperature, pouring out the product from the kettle, sequentially washing with deionized water and absolute ethyl alcohol to obtain the black magnetic composite photocatalyst, and drying for later use.
Example 4
A typical photodegradation process: recording the absorbance of tetracycline aqueous solutions with different concentrations under the irradiation of 357nm wavelength, and quantitatively obtaining corresponding concentrations according to the Lambert-Beer law to obtain a concentration-absorbance curve; taking 50mg of Pd/C3N4/Fe3O4Adding the magnetic composite photocatalyst into a tetracycline aqueous solution with the concentration of 10mg/L, wherein the pH value of the solution is 11-11.5,the tetracycline aqueous solution is pretreated in the dark (30min, continuous stirring) to ensure the adsorption-desorption balance of the tetracycline aqueous solution and the photocatalyst surface, then the photodegradation reaction is carried out under the irradiation of a 250W xenon lamp simulating sunlight, sampling is carried out after 90min, a sample is collected into a sample bottle through a filter membrane, the concentration change of the obtained sample liquid is examined by an ultraviolet-visible spectrophotometer, and the degradation rate of the sample liquid can be calculated to be 98% by comparing with a standard curve. After the reaction is finished, the magnetism of the catalyst is utilized in time, and the reactant and the catalytic material are separated by the magnet to recycle the catalytic material.
Example 5
The catalytic material recycles light to degrade tetracycline: the first circulation, the catalytic material obtained by separating the magnet in the embodiment 4 is used for a circulation experiment, other conditions are completely consistent with those in the embodiment 4, the obtained sample liquid is checked for concentration change by an ultraviolet-visible spectrophotometer, the degradation rate can be calculated to be 96% by comparing with a standard curve, after the reaction is finished, the magnetism of the catalyst is utilized in time, the reactant and the catalyst are separated by the magnet, and the catalyst is recovered and recycled for the next circulation; similarly, the second to sixth cycles were carried out, and the sixth degradation rate was 80%.
Claims (3)
1. Nano Pd/C3N4/Fe3O4The application of the compound in photodegradation of tetracycline is characterized in that: Pd/C prepared by hydrothermal method3N4/Fe3O4The magnetic composite material is a catalyst, a photodegradation reaction is carried out under the irradiation of simulated sunlight of a 250W xenon lamp, tetracycline antibiotics are effectively degraded in a low-concentration alkaline water environment, the degradation rate reaches 98%, after the reaction is finished, the magnetic property of the composite material is utilized, an external magnetic field is applied to separate the composite material from a reaction system, the separated composite material can be directly recycled without treatment, the degradation rate is still more than 80% after 6 times of circulation, and the preparation process of the composite material is as follows:
step 1) grinding a certain amount of melamine, putting the ground melamine into a porcelain boat, putting the porcelain boat into a muffle furnace, setting a temperature rise program, and raising the temperature in the furnace from 20 ℃ to 550 ℃ within 2 hoursThen, the temperature is maintained at 550 ℃, the constant temperature is maintained for 3 hours, the temperature in the furnace is cooled from 550 ℃ to 20 ℃, the powder in the porcelain boat is changed from white to light yellow, the porcelain boat is ground and then put into a muffle furnace again, the temperature is increased to 550 ℃ at the same heating rate, the constant temperature is maintained for 5 hours, the porcelain boat is cooled to room temperature and then ground again, and the powdery C is obtained3N4Standby;
step 2) weighing 0.79mmol of polyvinylpyrrolidone, and weighing 0.062mmol of polyvinylpyrrolidone with the concentration of 0.01128 mol.L-1H of (A) to (B)2PdCl4Stirring the solution in a beaker until the solution is completely dissolved; weighing 1.00mmol of sodium borohydride, completely dissolving with 1-2ml of deionized water, and dropwise adding into the solution to reduce Pd2+(ii) a Stirring for 30min after all the materials are added dropwise to obtain black Pd(0)The nano particle solution is reserved;
step 3) taking 1.19mmol of FeCl3·6H2O, 2.25mmol of polyvinylpyrrolidone with average molecular weight of 40000Da, 3.63mmol of urea and 15mL of 1, 2-propylene glycol, stirring the mixture on a magnetic stirrer until the mixture is completely dissolved to obtain yellow clear solution, and adding a proper amount of C prepared in the step 13N4And (3) continuously stirring, obtaining a uniform solution by taking ultrasonic dispersion as an assistant, finally adding the Pd nanoparticles obtained in the step (2), stirring for 30min, then transferring the solution into a 50mL high-pressure reaction kettle, reacting for 16h at 190 ℃, cooling to room temperature, pouring out a product from the kettle, sequentially washing with deionized water and absolute ethyl alcohol to obtain a black magnetic composite photocatalyst, and drying for later use.
2. The nano Pd/C as in claim 13N4/Fe3O4The application of the compound in photodegradation of tetracycline is characterized in that: adding the magnetic composite photocatalytic material into a tetracycline aqueous solution with the concentration of 10mg/L, wherein the pH value of the solution is 11-11.5, firstly carrying out 30min in a dark place, continuously stirring for pretreatment to ensure the adsorption-desorption balance of the tetracycline aqueous solution and the surface of a photocatalyst, then carrying out a photodegradation reaction, using an open beaker as a reaction container, keeping the container under sufficient visible light irradiation, sampling at fixed time intervals, collecting a sample into a sample bottle through a filter membrane, and carrying out ultraviolet light treatment on the sample bottleSee spectrophotometer to examine the concentration change.
3. The nano Pd/C as in claim 13N4/Fe3O4The application of the compound in photodegradation of tetracycline is characterized in that: after the photocatalytic reaction is finished, the magnetic property of the composite material can be utilized to separate the composite material from a reaction system through a magnet or other external magnetic fields, and the composite material can be directly recycled without treatment.
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| CN113926483A (en) * | 2021-11-22 | 2022-01-14 | 西南林业大学 | Magnetic recovery type double-Fenton Fe3O4Preparation method and application of (E) -Fe-CN composite material |
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| CN113926483B (en) * | 2021-11-22 | 2022-09-16 | 西南林业大学 | Magnetic recovery type double-Fenton Fe 3 O 4 Preparation method and application of (E) -Fe-CN composite material |
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