CN111617731A - Method for treating antibiotics in water body by coupling magnetic nano material with persulfate - Google Patents
Method for treating antibiotics in water body by coupling magnetic nano material with persulfate Download PDFInfo
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- CN111617731A CN111617731A CN202010400786.1A CN202010400786A CN111617731A CN 111617731 A CN111617731 A CN 111617731A CN 202010400786 A CN202010400786 A CN 202010400786A CN 111617731 A CN111617731 A CN 111617731A
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- 229960003722 doxycycline Drugs 0.000 claims description 6
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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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- B01J35/33—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
Abstract
The invention discloses a method for treating antibiotics in water by utilizing magnetic cobalt nanoparticles to limit the range of nitrogen-doped porous carbon material coupled persulfate system, which comprises the following steps: and (3) limiting magnetic cobalt nanoparticles in a nitrogen-doped porous carbon material, oscillating, mixing and adsorbing the nitrogen-doped porous carbon material and the water containing the antibiotics, and adding a certain amount of persulfate to complete the degradation of the antibiotics in the water. Finally, the material was sucked out with a commercial magnet and washed for reuse. The magnetic cobalt nanoparticles are confined in the nitrogen-doped porous carbon material, and comprise magnetic cobalt nanoparticles and the nitrogen-doped porous carbon material, and the magnetic cobalt nanoparticles are confined in the nitrogen-doped porous carbon material. The method for treating the antibiotics in the water body by utilizing the magnetic cobalt nanoparticles to confine the magnetic cobalt nanoparticles in the nitrogen-doped porous carbon material coupled persulfate system has the advantages of simple treatment process, convenience in operation, simple equipment, low cost, high treatment efficiency, good removal effect, high recycling rate, cleanness and no pollution, is a treatment method which can be widely adopted and can effectively remove the antibiotics, and has high application value and commercial value.
Description
Technical Field
The invention belongs to the field of antibiotic-containing water treatment, relates to a method for treating antibiotics in water, and particularly relates to a method for treating antibiotics in water by utilizing a nitrogen-doped porous carbon material coupled persulfate system in a confined mode of magnetic cobalt nanoparticles.
Background
The large volume production and consumption of Pharmaceutical and Personal Care Products (PPCPs) has posed a threat to the aquatic environment and human health over the last several decades. The advanced oxidation method is a method for generating Reactive Oxygen Species (ROS) and is widely used for solution treatment due to high mineralization degree of organic pollutants and simple operation. Persulfate (PMS) is a typical oxidant, and is activated to generate active oxygen by using methods such as irradiation, heating, ultrasonic waves, transition metal catalysis and the like, so that the solution remediation is realized. Compared with a physical or chemical method, the catalytic method has high activation efficiency, can reduce the input of external energy and chemical reagents, and greatly reduces the application cost. Notably, persulfates may participate in two electron transfer reactions (E)0(HSO5 -/SO4 2-) 1.75VNHE), this singlet oxygen (c: (a)1O2) The induced oxidation reaction has higher catalytic performance and is less interfered by water.
The transition metal particle coupled persulfate system provides a new idea for the field of environmental remediation. Although the traditional transition metal catalyst has high activity, metal ions are inevitably released in a water body in the heterogeneous reaction process to cause secondary pollution. The metal particles are spatially confined with a stable non-metallic material, which effectively solves the problem of metal precipitation while maintaining high activity of the metal material. The Metal Organic Framework (MOF) material is a novel porous functional material constructed by metal ions or metal cluster units and organic ligands, and is also an ideal carrier of the limited-domain transition metal particles. Due to its weak stability, MOFs are difficult to apply directly to water treatment. Pyrolyzing MOFs in an inert gas produces a composite of porous carbon-confined metal nanoparticles. In general, interconnected micro-channels in MOFs are suitable for serving as a guest-isolated metal source, effectively avoiding diffusion and agglomeration of metals during pyrolysis, and the abundance of nitrogen atoms in nitrogen-containing organic ligands (e.g., ZIFs series) helps to generate nitrogen-doped carbon to stabilize small metal clusters. The existing MOF material has the problems of poor stability, low catalytic activity, difficulty in recycling and the like. Therefore, how to comprehensively improve the problems and the defects existing in the traditional MOF material and obtain a space-limited catalytic material based on the MOF material, which has good stability, high catalytic activity and easy recovery and reuse, has very important significance for improving the application range of the MOF material in the treatment of water containing antibiotics.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a method for coupling a magnetic cobalt nanoparticle confinement in a nitrogen-doped porous carbon material with a persulfate system, which has the advantages of good removal effect, high recycling rate, cleanness and no pollution.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for treating antibiotics in a water body by utilizing magnetic cobalt nanoparticles to limit the range of nitrogen-doped porous carbon materials coupled with a persulfate system is characterized by comprising the following steps: and (3) limiting magnetic cobalt nanoparticles in a nitrogen-doped porous carbon material, oscillating, mixing and adsorbing the nitrogen-doped porous carbon material and the water containing the antibiotics, and adding a certain amount of persulfate to complete the degradation of the antibiotics in the water. Finally, the material was sucked out with a commercial magnet and washed for reuse. The magnetic cobalt nanoparticles are confined in the nitrogen-doped porous carbon material, and comprise magnetic cobalt nanoparticles and the nitrogen-doped porous carbon material.
In the method, the magnetic cobalt nanoparticles are limited to 335.52m of the specific surface area of the nitrogen-doped porous carbon material2/g。
In a further improvement of the above method, the method for preparing the porous carbon material doped with nitrogen and confined by the magnetic cobalt nanoparticles is characterized by comprising the following steps:
s1, cobalt nitrate hexahydrate and di-methylimidazole are respectively dissolved in an organic solvent;
s2, slowly adding the di-methylimidazole solution obtained in the step S1 into a cobalt nitrate hexahydrate solution, and stirring to obtain a purple self-sacrifice template (a zeolite imidazole framework, ZIF-67);
and S3, calcining the self-sacrifice template in a nitrogen atmosphere to obtain the magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material.
In a further improvement of the above process, the molar ratio of cobalt chloride hexahydrate to bis-methylimidazole is 1: 4; the molar ratio of the cobalt chloride hexahydrate, the dimethyl imidazole and the organic solvent is 1: 4: 494; the organic solvent is methanol.
In the above method, further improvement, in step S2, the rotation speed of the stirring is 100r/min to 200 r/min; the stirring time is 20 h.
In a further improvement of the above method, the stirring step to obtain ZIF-67 further comprises the following steps: and centrifuging, washing and drying the product generated after stirring. The rotating speed of the centrifugation is 3000 r/min-5000 r/min; methanol is adopted for washing; the washing times are 3-5 times; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 8-12 h.
In step S3, the calcination reaction is started at 10-30 deg.c and heated at a rate of 5 deg.c/min to 300 deg.c in nitrogen atmosphere and maintained for 1 hr, and then heated to 800 deg.c and maintained for 2 hr before being naturally cooled.
In a further improvement of the above method, the calcination reaction further comprises the following steps: washing, magnetically recovering and drying a reaction product obtained after the calcination reaction is finished; deionized water is adopted for washing; the washing times are 3-5 times; the magnetic recovery adopts a commercial magnet; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 8-12 h.
In the method, the mass volume ratio of the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material to the water containing the antibiotics is 0.2 g: 1L.
In the method, the antibiotics in the water body containing the antibiotics are tetracycline hydrochloride, oxytetracycline, chlortetracycline and doxycycline; the concentration of the antibiotics in the water body containing the antibiotics is 5 mg/L-70 mg/L; the pH value of the water body containing the antibiotics is 2-12.
In the method, the rotation speed of the oscillating adsorption is further improved to be 200 r/min-300 r/min; the time of the oscillating adsorption is 0.5 h.
In the above method, further improvement, after the oscillating adsorption is completed, the method further comprises the following steps: adding a certain amount of Persulfate (PMS) to perform catalytic degradation reaction on the reaction product after the oscillation adsorption is finished; the time of the catalytic reaction is 0.5 h. The adding amount of the persulfate is 0.05 g/L-0.4 g/L.
In a further improvement of the above method, after completion of the catalytic reaction, the material is precipitated and collected by a commercial magnet. Soaking the collected reacted materials in water, placing the materials in an ultrasonic cleaning instrument for ultrasonic cleaning for 0.5-2 h, and drying the collected materials after cleaning. The cleaning times are 3-5 times; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 8-12 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for treating antibiotics in water by coupling a magnetic cobalt nanoparticle confinement in a nitrogen-doped porous carbon material with a persulfate system. The method has the advantages of simple treatment process, convenient operation, simple equipment, low cost, high treatment efficiency, good removal effect, high repeated utilization rate, cleanness and no pollution, can be widely adopted, can efficiently remove the antibiotics in the water body, and has very high application value and commercial value.
(2) The magnetic cobalt nanoparticle confinement adopted by the invention in the nitrogen-doped porous carbon material comprises magnetic cobalt nanoparticles and nitrogen-doped porous carbon, wherein the magnetic cobalt nanoparticles are confined in the nitrogen-doped porous carbon. The nitrogen-doped porous carbon skeleton with high porosity and high surface area is beneficial to uniform distribution of the magnetic cobalt nanoparticles, and promotes the mass transfer process of the magnetic cobalt nanoparticles confined between the nitrogen-doped porous carbon and antibiotic molecules. Magnetic cobalt nanoparticles are confined in nitrogen-doped porous carbon, which is critical to the stability of the catalyst. The electron transfer between nitrogen and cobalt elements enables the magnetic cobalt nanoparticles to be confined in the nitrogen-doped porous carbon material, and the magnetic cobalt nanoparticles can effectively catalyze persulfate to generate active oxygen species, so that antibiotics in a water body can be efficiently degraded. In addition, the magnetic cobalt nanoparticles allow the catalyst to be efficiently separated and recycled. Compared with the prior art, the magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material has the advantages of good dispersibility, good stability, high catalytic activity, easiness in recycling and the like, can realize efficient degradation of antibiotics, and has a good application prospect.
(3) In the invention, influence factors of the magnetic cobalt nanoparticles confined in a nitrogen-doped porous carbon material coupled persulfate system are researched. The performance of the magnetic cobalt nanoparticle confinement on the nitrogen-doped porous carbon material is optimized by researching the addition of persulfate, the addition of the magnetic cobalt nanoparticle confinement on the nitrogen-doped porous carbon material, the concentration of tetracycline hydrochloride and the initial pH value of the tetracycline hydrochloride. In addition, the invention researches the performance of the magnetic cobalt nanoparticles in catalyzing and degrading other typical antibiotics such as aureomycin, terramycin and doxycycline by limiting the nitrogen-doped porous carbon material. Therefore, the method optimizes the reaction conditions for removing the antibiotic by the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material, and has important significance for promoting the wide application of the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material.
(4) In the invention, the recycling performance of the magnetic cobalt nanoparticles confined to the nitrogen-doped porous carbon material is researched. The material after degradation reaction can be recycled only by simple magnetic recovery and ultrasonic cleaning. The method for removing the antibiotics in the water body by utilizing the magnetic cobalt nanoparticles to confine the nitrogen-doped porous carbon material has the advantages of simple operation, good removal effect, simple recovery, high recycling rate and the like, and has wide prospect in industrial application.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a microscopic morphology of the magnetic cobalt nanoparticles confined to the nitrogen-doped porous carbon material (Co @ NC-800) prepared in example 1 of the present invention, wherein (a) is a low-power scanning electron microscope image, (b) is a high-power scanning electron microscope image, (c) is a transmission electron microscope image, and (d) is a high-resolution transmission electron microscope image and an electron diffraction image (upper right corner).
FIG. 2 is a graph of the catalytic degradation of tetracycline hydrochloride by magnetic cobalt nanoparticles confined to a nitrogen-doped porous carbon material (Co @ NC-800) at different dosages of persulfate according to example 1 of the present invention.
FIG. 3 is a graph showing the catalytic degradation of the magnetic cobalt nanoparticles confined to a nitrogen-doped porous carbon material (Co @ NC-800) with tetracycline hydrochloride of different concentrations in example 2 of the present invention.
Fig. 4 is a graph showing the catalytic degradation of the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material (Co @ NC-800) to tetracycline hydrochloride solutions with different pH values in example 3 of the present invention, wherein (a) is a catalytic degradation diagram, and (b) is a zeta potential diagram.
FIG. 5 is a graph showing the catalytic degradation of magnetic cobalt nanoparticles confined to a nitrogen-doped porous carbon material (Co @ NC-800) for various antibiotics in example 4 of the present invention.
FIG. 6 is a graph showing the recycling effect of magnetic cobalt nanoparticles confined in a nitrogen-doped porous carbon material (Co @ NC-800) on tetracycline hydrochloride in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
Example 1
A method for treating water containing antibiotics by coupling a magnetic cobalt nanoparticle confinement with a nitrogen-doped porous carbon material (Co @ NC-800) and a persulfate system, in particular to a method for catalytically degrading tetracycline hydrochloride in water by adopting the magnetic cobalt nanoparticle confinement with the nitrogen-doped porous carbon material (Co @ NC-800), which comprises the following steps:
20mg of magnetic cobalt nanoparticles are limited in a nitrogen-doped porous carbon material (Co @ NC-800), added into 100mL of 30mg/L tetracycline hydrochloride solution with the concentration of 5 parts, and subjected to oscillation adsorption for 0.5h at the rotation speed of 200 r/min. After the adsorption balance is achieved, 0.05g/L, 0.1g/L, 0.2g/L, 0.3g/L and 0.4g/L of persulfate are respectively added, and the influence of different amounts of persulfate on the catalytic degradation of tetracycline hydrochloride by the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material is researched.
In this embodiment, the preparation method of the magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material (Co @ NC-800) specifically is a method of stirring and self-crystallizing at room temperature and calcining in an inert gas by using cobalt nitrate hexahydrate and di-methylimidazole as raw materials to prepare the magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material, and includes the following steps:
(1) the cobalt chloride hexahydrate and the bis-methylimidazole were dissolved in methanol respectively in a molar ratio of 1: 4: 494 for cobalt chloride hexahydrate, bis-methylimidazole and methanol and 1: 4 for cobalt chloride hexahydrate and bis-methylimidazole. Slowly adding the di-methylimidazole solution into the cobalt nitrate hexahydrate solution, and stirring for 20 hours (the rotating speed is 100 r/min-200 r/min) to obtain a purple self-sacrifice template (a zeolite imidazole framework, ZIF-67). Centrifuging the generated product at 3000-5000 r/min and washing with methanol for 3-5 times. And finally, drying under the vacuum condition at the drying temperature of 60-100 ℃ for 8-12 h.
(2) And calcining the obtained ZIF-67 solid in a nitrogen atmosphere, wherein the initial temperature of the calcination reaction is 10-30 ℃, the heating rate is 5 ℃/min, heating to 300 ℃ in a nitrogen atmosphere and keeping the temperature for 1h, then continuously heating to 800 ℃ and keeping the temperature for 2h, and then naturally cooling. And after the calcination reaction is finished, washing the reaction product obtained after the calcination reaction for 3-5 times by using deionized water and magnetically recovering. And finally, carrying out vacuum drying at the drying temperature of 60-100 ℃ for 8-12 h to finally obtain the magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material.
Fig. 1 is a microscopic morphology of the magnetic cobalt nanoparticles confined to the nitrogen-doped porous carbon material (Co @ NC-800) prepared in example 1 of the present invention, wherein (a) is a low-power scanning electron microscope image, (b) is a high-power scanning electron microscope image, (c) is a transmission electron microscope image, and (d) is a high-resolution transmission electron microscope image and an electron diffraction image (upper right corner). As shown in the figure, Co @ NC-800 presents a rhombic dodecahedron morphology, with a particle size of about 600nm, a rough surface and inward depressions. The transmission electron micrograph proves that a large number of nano particles exist in the middle. The high resolution transmission plot confirms that the nanoparticles are cobalt nanoparticles surrounded by a carbon layer and the diffraction rings match the (220), (200), (311) and (111) crystal planes of Co (PDF # 15-0806).
The adsorption equilibrium time point is taken as the zero point of the catalytic reaction. In the catalysis process, 4mL of samples are taken at intervals (when the vibration adsorption is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), and the samples are centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the tetracycline hydrochloride after adsorption, so as to obtain the effect of persulfate with different adding amounts on the catalytic degradation of the tetracycline hydrochloride by the magnetic cobalt nanoparticle confinement in the nitrogen-doped porous carbon material, wherein the result is shown in fig. 2. As can be seen from FIG. 2, the removal rates of tetracycline hydrochloride were 56.69%, 79.56%, 93.59%, 97.25% and 99.99%, respectively, when the persulfate was added at 0.05g/L, 0.1g/L, 0.2g/L, 0.3g/L and 0.4 g/L. The greater the tetracycline hydrochloride dosage, the higher the removal efficiency and the faster the removal rate. When the addition amount of the persulfate is 0.2g/L, the tetracycline hydrochloride removal rate can reach 93.59%, and the addition amount of the persulfate is 0.2g/L in subsequent experiments.
Example 2
A method for treating water containing antibiotics by coupling a magnetic cobalt nanoparticle confinement with a nitrogen-doped porous carbon material (Co @ NC-800) and a persulfate system, in particular to a method for catalytically degrading tetracycline hydrochloride in water by adopting the magnetic cobalt nanoparticle confinement with the nitrogen-doped porous carbon material (Co @ NC-800), which comprises the following steps:
20mg of magnetic cobalt nanoparticles are limited in a nitrogen-doped porous carbon material (Co @ NC-800), added into 100mL of tetracycline hydrochloride solutions with the concentrations of 5mg/L, 10mg/L, 20mg/L, 30mg/L, 50mg/L and 70mg/L respectively, and subjected to oscillation adsorption for 0.5h at the rotation speed of 200 r/min. After the adsorption balance is achieved, 0.2g/L of persulfate is added respectively, and the influence of the initial concentration of different tetracycline hydrochloride on the catalytic performance of the magnetic cobalt nanoparticle confined in the nitrogen-doped porous carbon material is researched.
The adsorption equilibrium time point is taken as the zero point of the catalytic reaction. In the catalysis process, 4mL of samples are taken at intervals (when the vibration adsorption is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), and the samples are centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the tetracycline hydrochloride after adsorption, so as to obtain the degradation effect of the magnetic cobalt nanoparticles on the tetracycline hydrochloride with different concentrations in the nitrogen-doped porous carbon material coupling persulfate system, wherein the result is shown in fig. 3. As is clear from FIG. 3, the tetracycline hydrochloride removal rates at 5mg/L, 10mg/L, 20mg/L, 30mg/L, 50mg/L and 70mg/L were 99.95%, 99.93%, 96.63%, 96.59%, 85.81% and 73.11%, respectively. The greater the tetracycline hydrochloride concentration, the lower the removal efficiency. The magnetic cobalt nanoparticles are confined in the nitrogen-doped porous carbon material, so that the low-concentration tetracycline hydrochloride has extremely high removal rate, and the application of the magnetic cobalt nanoparticles in the actual wastewater treatment is facilitated.
Example 3
A method for treating water containing antibiotics by coupling a magnetic cobalt nanoparticle confinement with a nitrogen-doped porous carbon material (Co @ NC-800) and a persulfate system, in particular to a method for catalytically degrading tetracycline hydrochloride in water by adopting the magnetic cobalt nanoparticle confinement with the nitrogen-doped porous carbon material (Co @ NC-800), which comprises the following steps:
weighing 20mg of magnetic cobalt nanoparticles, confining the magnetic cobalt nanoparticles in a nitrogen-doped porous carbon material (Co @ NC-800), adding the magnetic cobalt nanoparticles into 100mL of tetracycline hydrochloride solution with the concentration of 30mg/L and the pH values of 2, 4, 6, 8, 10 and 12 respectively, and carrying out oscillatory adsorption for 0.5h at the rotation speed of 200 r/min. After the adsorption balance is achieved, 0.2g/L of persulfate is added respectively, and the influence of the initial pH values of different tetracycline hydrochloride on the catalytic performance of the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material is researched.
The adsorption equilibrium time point is taken as the zero point of the catalytic reaction. In the catalysis process, 4mL of samples are taken at intervals (when the vibration adsorption is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), and the samples are centrifuged. Measuring absorbance of supernatant fluid obtained by centrifugation by an ultraviolet visible spectrophotometer, and determining the concentration of tetracycline hydrochloride after adsorption, thereby obtaining the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material coupling persulfate system for different initial pH valuesThe degradation effect of the tetracycline hydrochloride solution is shown in fig. 4 a. As can be seen from fig. 4a, the pH of the tetracycline hydrochloride solution has an effect on the removal rate of the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material coupled with the persulfate system. In the pH range of 4-10, a high removal rate (90% or more) was obtained, while at pH 2 and 12, the removal rates were 85.4% and 68.9%, respectively. The zeta potential of Co @ NC-800 in tetracycline hydrochloride solutions at different pH values is shown in FIG. 4 b. Zero charge Point (pH) of Co @ NC-800pzc) 8.13, so at pH values of 2 and 12, the tetracycline hydrochloride molecules and Co @ NC-800 are equally charged, and thus the electrostatic repulsion between the Co @ NC-800 and tetracycline hydrochloride molecules results in a lower removal efficiency. Furthermore, HSO5 -At pH 2, predominantly H2SO5Exist in a form that limits HSO5 -Decomposition of (3). At pH 12, Co (OH)2Catalytic performance may be formed and reduced. In conclusion, the magnetic cobalt nanoparticles are confined in the nitrogen-doped porous carbon material coupled persulfate system, and have good removal effect on tetracycline hydrochloride within a wide pH (4-10) range.
Example 4
A method for treating water containing antibiotics by utilizing a coupling system of magnetic cobalt nanoparticles confined in a nitrogen-doped porous carbon material (Co @ NC-800) and persulfate, in particular to a method for catalytically degrading typical antibiotics (such as aureomycin, oxytetracycline and doxycycline) in water by adopting magnetic cobalt nanoparticles confined in a nitrogen-doped porous carbon material (Co @ NC-800), which comprises the following steps:
weighing 20mg of magnetic cobalt nanoparticles, confining the magnetic cobalt nanoparticles in a nitrogen-doped porous carbon material (Co @ NC-800), adding the magnetic cobalt nanoparticles into 100mL of a 30mg/L solution of oxytetracycline, oxytetracycline and doxycycline, and carrying out oscillatory adsorption for 0.5h at the rotation speed of 200 r/min. After adsorption balance is achieved, 0.2g/L of persulfate is added respectively, and the removal effect of the magnetic cobalt nanoparticles in a nitrogen-doped porous carbon material coupling persulfate system on typical antibiotics in water is explored.
The adsorption equilibrium time point is taken as the zero point of the catalytic reaction. In the catalysis process, 4mL of samples are taken at intervals (when the vibration adsorption is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), and the samples are centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the adsorbed antibiotics, so as to obtain the degradation of the magnetic cobalt nanoparticles in the nitrogen-doped porous carbon material coupled persulfate system on the typical antibiotics in the water body, wherein the result is shown in fig. 5. As can be seen from fig. 5, the removal rates of aureomycin, oxytetracycline, and doxycycline by the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material coupled persulfate system are 92.28%, 90.84%, and 90.75%, respectively. Therefore, the magnetic cobalt nanoparticles confined in the nitrogen-doped porous carbon material coupled persulfate system have good removal effect on typical antibiotics in water.
Example 5
A method for treating a water body containing antibiotics by coupling a magnetic cobalt nanoparticle confinement with a nitrogen-doped porous carbon material (Co @ NC-800) with a persulfate system specifically researches the reusability of the magnetic cobalt nanoparticle confinement with the nitrogen-doped porous carbon material for degrading tetracycline hydrochloride in the water body, and comprises the following steps.
Claims (11)
1. A method for treating antibiotics in a water body by utilizing magnetic cobalt nanoparticles to limit the range of nitrogen-doped porous carbon materials coupled with a persulfate system is characterized by comprising the following steps: and (3) limiting magnetic cobalt nanoparticles in a nitrogen-doped porous carbon material, oscillating, mixing and adsorbing the nitrogen-doped porous carbon material and the water containing the antibiotics, and adding a certain amount of persulfate to complete the degradation of the antibiotics in the water. Finally, the material was sucked out with a commercial magnet and washed for reuse. The magnetic cobalt nanoparticles are confined in the nitrogen-doped porous carbon material, and comprise magnetic cobalt nanoparticles and the nitrogen-doped porous carbon material.
2. The magnetic cobalt nanoparticles confinement of nitrogen-doped porous carbon material of claim 1, wherein the ratio of the magnetic cobalt nanoparticles to nitrogen-doped porous carbon materialSurface area 335.52m2/g。
3. A method for preparing a magnetic cobalt nanoparticle-confined nitrogen-doped porous carbon material as claimed in claim 1 or 2, comprising the steps of:
s1, cobalt nitrate hexahydrate and di-methylimidazole are respectively dissolved in an organic solvent;
s2, slowly adding the di-methylimidazole solution obtained in the step S1 into a cobalt nitrate hexahydrate solution, and stirring to obtain a purple self-sacrifice template (a zeolite imidazole framework, ZIF-67);
and S3, calcining the self-sacrifice template in a nitrogen atmosphere to obtain the magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material.
4. The method according to claim 3, wherein the molar ratio of cobalt chloride hexahydrate to bis-methylimidazole is 1: 4; the molar ratio of the cobalt chloride hexahydrate, the dimethyl imidazole and the organic solvent is 1: 4: 494; the organic solvent is methanol.
5. The method according to any one of claims 3 to 4, wherein in step S2, the rotation speed of the stirring is 100 to 200 r/min; the stirring time is 20 h.
The method also comprises the following steps after stirring to obtain the ZIF-67: and centrifuging, washing and drying the product generated after stirring. The rotating speed of the centrifugation is 3000 r/min-5000 r/min; methanol is adopted for washing; the washing times are 3-5 times; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 8-12 h.
6. The preparation method according to any one of claims 3 to 5, wherein in step S3, the calcination reaction is started at a temperature of 10 ℃ to 30 ℃ at a temperature rise rate of 5 ℃/min, heated to 300 ℃ in a nitrogen atmosphere and kept at the temperature for 1h, then continuously heated to 800 ℃ and kept at the temperature for 2h, and finally naturally cooled.
The method also comprises the following steps after the calcination reaction is completed: washing, magnetically recovering and drying a reaction product obtained after the calcination reaction is finished; deionized water is adopted for washing; the washing times are 3-5 times; the magnetic recovery adopts a commercial magnet; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 8-12 h.
7. The method according to any one of claims 1 to 6, wherein the magnetic cobalt nanoparticles are confined to the nitrogen-doped porous carbon material and the antibiotic-containing water body at a mass-to-volume ratio of 0.2 g: 1L.
8. The method according to any one of claims 1 to 6, wherein the antibiotics in the antibiotic-containing water body are tetracycline hydrochloride, oxytetracycline, chlortetracycline and doxycycline; the concentration of the antibiotics in the water body containing the antibiotics is 5 mg/L-70 mg/L; the pH value of the water body containing the antibiotics is 2-12.
9. The method according to any one of claims 1 to 6, wherein the rotation speed of the oscillating adsorption is 200r/min to 300 r/min; the time of the oscillating adsorption is 0.5 h.
10. The method according to any one of claims 1 to 6, further comprising the following steps after the oscillating adsorption is completed: adding a certain amount of Persulfate (PMS) to perform catalytic degradation reaction on the reaction product after the oscillation adsorption is finished; the time of the catalytic reaction is 0.5 h. The adding amount of the persulfate is 0.05 g/L-0.4 g/L.
11. A method according to any one of claims 1 to 6, wherein after completion of the catalytic reaction, the material is separated and collected by a commercial magnet. Soaking the collected reacted materials in water, placing the materials in an ultrasonic cleaning instrument for ultrasonic cleaning for 0.5-2 h, and drying the collected materials after cleaning. The cleaning times are 3-5 times; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 8-12 h.
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