CN114130364A - Efficient and safe method for adsorbing and degrading tetracycline by using mixed metal organic framework material - Google Patents

Efficient and safe method for adsorbing and degrading tetracycline by using mixed metal organic framework material Download PDF

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CN114130364A
CN114130364A CN202111410467.XA CN202111410467A CN114130364A CN 114130364 A CN114130364 A CN 114130364A CN 202111410467 A CN202111410467 A CN 202111410467A CN 114130364 A CN114130364 A CN 114130364A
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tetracycline
metal organic
organic framework
mixed metal
framework material
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孙丽慧
苏悦
贺雷雨
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Dalian University of Technology
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic 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
    • 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
    • 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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Abstract

A high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material belongs to the field of antibiotic wastewater treatment, and a cobalt-doped MIL-53(Fe) metal organic framework material is synthesized by a solvothermal method; dispersing the obtained MIL-53(Fe, Co) in tetracycline aqueous solution, placing in a shaking table for mechanical stirring, and adsorbing or adding Persulfate (PS) to form a metal organic framework material/PS advanced oxidation system for tetracyclineRemoval is performed. The method utilizes the cobalt-doped mixed metal organic framework material to adsorb and degrade the tetracycline simultaneously, has simple, convenient, efficient and rapid operation, can be repeatedly utilized, has low ecological toxicity and has high application value. Introduction of cobalt ions into the MIL-53(Fe) structure not only changes the MIL-53(Fe) surface and structure, but also can react with Co2+And the coordination is firm, so that the harm caused by leaching of transition metal ions in a homogeneous reaction is greatly relieved.

Description

Efficient and safe method for adsorbing and degrading tetracycline by using mixed metal organic framework material
Technical Field
The invention relates to the field of antibiotic wastewater treatment, in particular to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material.
Background
Tetracycline (TC) has received much attention as the most widely used class of antibiotics in the breeding and animal husbandry, which causes pollution problems. At present, the speed of tetracycline entering the environment is far higher than the degradation speed of tetracycline, and if the tetracycline is not controlled, the tetracycline can be enriched and accumulated in organisms through a food chain, so that drug resistance genes are spread, and the health of human beings is finally harmed. The advanced oxidation technology has wide application prospect by generating high-activity oxygen free radicals to oxidize macromolecular organic pollutants into harmless mineralized products. In recent years, Persulfate (PS) -based advanced oxidation technologies have received attention from a large number of environmental workers in the removal of degradation of nonbiodegradable organic matter.
The metal organic framework material is a series of porous materials formed by self-assembling inorganic metal ions and organic ligands, and has good prospects in the fields of good topological structure, high porosity, large specific surface area, selective adsorption on small molecules, excellent optical, electric and magnetic properties and the like, removal of pollutants in aqueous solution and the like. Of these, MIL-53 is more representative of its excellent thermal stability and unique "breathing" phenomenon. In recent years, a series of studies have been carried out by researchers incorporating second or third metal ions into MOF matrices to modify the coordination environment and electronic properties of active sites.
PS can generate SO with high activity4 -Further degrading the organic matter by radical oxidation or direct electron transfer. MIL-53 materials incorporate divalent and trivalent transition metal ions, such as CO2+、Fe3+Etc., these transition metals can activate PS to promote advanced oxidation reactions. Furthermore, the incorporation of transition metals into MOFs materials can result in Co2+Are strongly coordinated so as to be able to be in Co2+Used in common solvents without leaching.
Most of the current researches concern the efficient removal method of tetracycline antibiotics, but ignore the change of the ecotoxicity generated to microorganisms in the degradation process of the antibiotics.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an efficient and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, which is simple, convenient, efficient and rapid to operate, and the mixed metal organic framework material can be recycled and has low ecological toxicity.
The technical scheme of the invention is to provide a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, which comprises the following steps:
1) weighing ferric chloride hexahydrate, cobalt chloride hexahydrate and terephthalic acid according to a proportion, dispersing in 35mL of organic solvent, and then ultrasonically mixing uniformly until the ferric chloride hexahydrate, the cobalt chloride hexahydrate and the terephthalic acid are completely dissolved;
2) transferring the mixed solution obtained in the step 1) into a polytetrafluoroethylene lining for solvothermal reaction;
3) after the solvothermal reaction in the step 2) is finished, naturally cooling to room temperature, and then centrifuging, washing and drying a reaction product to obtain a cobalt-doped mixed metal organic framework material MIL-53(Fe, Co);
4) dispersing the obtained cobalt-doped mixed metal organic framework material MIL-53(Fe, Co) in a tetracycline solution, placing the tetracycline solution in a shaking table, and mechanically stirring to obtain a suspension solution;
5) the tetracycline is removed by adsorbing or adding Persulfate (PS) to form a metal organic framework material/PS high-grade oxidation system.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein the molar ratio of ferric chloride hexahydrate and cobalt chloride hexahydrate is 2:1, 1:2 and 1:4 respectively, and the molar ratio of the total molar weight of the ferric chloride hexahydrate and the cobalt chloride hexahydrate to the molar weight of terephthalic acid is 1: 1.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein an organic solvent is N, N-dimethylformamide.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein the ultrasonic treatment time in the step 1) is 30min, and the temperature is room temperature.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein the solvothermal reaction temperature in the step 2) is 150 ℃, and the solvothermal reaction time is 24 hours.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein the rotation speed required by centrifugation in the step 3) is 8000r/min, pure water is adopted for washing, ultrasonic treatment is carried out for 5min, the washing frequency is 3 times, the drying temperature is 70 ℃, and the drying time is 10 hours.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein the mass-volume ratio of the mixed metal organic framework material MIL-53(Fe, Co) to a tetracycline solution is 10 mg: 20mL, and the reaction temperature is 20 ℃, 30 ℃ and 40 ℃.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein the initial concentrations of tetracycline solutions are respectively 10, 20, 40, 80, 100, 150, 200 and 300mg/L, and the rotating speed of a shaking table is 190 r/min.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein the mass-volume ratio of the mixed metal organic framework material MIL-53(Fe, Co) to a tetracycline solution is 10 mg: 30mL, 10mg of sodium Persulfate (PS), 4-10 of the pH value of the tetracycline solution and 190r/min of the rotation speed in the degradation process.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein a certain amount of mixed metal organic framework material MIL-53(Fe, Co) and a predetermined amount of sodium Persulfate (PS) are weighed and added into a tetracycline solution together, a suspension solution is obtained by stirring, the suspension solution system is placed in a shaking table and oscillated in a dark place, and a reaction solution is taken at intervals for determination.
The invention relates to a high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material, wherein after the tetracycline solution is degraded by using the mixed metal organic framework material MIL-53(Fe, Co), the mixed solution of the tetracycline and the product after reaction is subjected to an escherichia coli ecotoxicity test.
Compared with the prior art, the efficient and safe method for adsorbing and degrading tetracycline by using the mixed metal organic framework material has the following advantages:
1. the tetracycline can be degraded by activating PS to form a metal organic framework material/PS advanced oxidation system, the operation is simple, convenient, efficient and rapid, the mixed metal organic framework material can be recycled, the ecological toxicity is low, and the application value is high;
2. cobalt ions are introduced into the MIL-53(Fe) structure, and the successful introduction of the cobalt ions not only changes the surface and the structure of the MIL-53(Fe), but also the MIL-53(Fe) material can be mixed with Co2+Are strongly coordinated so that the material can be in Co2+The method is used in common solvent without leaching, thereby greatly relieving the harm caused by the leaching of transition metal ions in homogeneous reaction.
By optimizing the conditions of the molar ratio of ferric chloride hexahydrate and cobalt chloride hexahydrate, pH and the like, the following conclusions can be made: when the molar ratio of ferric chloride hexahydrate to cobalt chloride hexahydrate is 1:2, the optimal activation effect is achieved; when the dosage of the MIL-53(Fe, Co) material is 10mg and the pH is 6, the tetracycline degradation rate can reach 92% within 20 min.
In the degradation process provided by the invention, the inhibition rate of the sample solution to escherichia coli is within the confidence interval of the standard curve, which indicates that the degradation product of tetracycline is non-toxic, and indicates that the method is environment-friendly.
Drawings
FIG. 1 is an X-ray diffraction pattern of MIL-53(Fe, Co) materials prepared according to the present invention at different molar ratios;
FIG. 2 is a Fourier infrared spectrum of MIL-53(Fe, Co) materials of different molar ratios prepared in accordance with the present invention;
FIG. 3 is a graph showing the effect of Co addition on material properties;
FIG. 4 is MIL-53(Fe)1Co2) Adsorption isotherms for adsorption of TC;
FIG. 5 is a graph of the effect of different initial pH on tetracycline degradation;
FIG. 6 is a graph of toxicity profile of tetracycline degradation process against E.coli.
Detailed Description
The invention provides a high-efficiency and safe method for adsorbing and degrading tetracycline by using mixed metal organic framework material, which is further described in detail by combining the attached drawings and the detailed description:
example one
Preparation of MIL-53(Fe)
Dispersing 805mg of ferric chloride hexahydrate and 744mg of terephthalic acid in 30mL of DMF, and then carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed; and transferring the mixed solution into a polytetrafluoroethylene lining, reacting for 24 hours at a constant temperature of 150 ℃, and naturally cooling to room temperature. The centrifuged product was washed with pure water 3 times and dried at 70 ℃ for 10 hours.
Example two
Preparation of MIL-53(Fe, Co)
Dispersing a certain amount of ferric chloride hexahydrate, cobalt chloride hexahydrate and 332mg of terephthalic acid in 35mLDMF, and then carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed; and transferring the mixed solution into a polytetrafluoroethylene lining, reacting for 24 hours at a constant temperature of 150 ℃, and naturally cooling to room temperature. The centrifuged product was washed with pure water 3 times and dried at 70 ℃ for 10 hours. Wherein the ratio of the total molar amount of ferric chloride hexahydrate and cobalt chloride hexahydrate to the molar amount of terephthalic acid is 1: 1. The molar ratio of ferric chloride hexahydrate to cobalt chloride hexahydrate is 2:1, 1:2, 1:4, and is respectively named MIL-53(Fe)2Co1)、MIL-53(Fe1Co1)、MIL-53(Fe1Co2)、MIL-53(Fe1Co4)。
And (4) analyzing results:
x-ray diffraction analysis was performed on MIL-53(Fe) of example one and MIL-53(Fe, Co) of example two at different mass ratios, and the results are shown in FIG. 1. The main diffraction peak between the MIL-53(Fe) and each sample with different amounts of iron and cobalt does not change obviously, which shows that the crystal structure is not changed by adding the cobalt, and the crystal structure of the MIL-53(Fe) is well preserved. However, the introduction of cobalt caused the peak intensities to disappear or decrease to different degrees, indicating that the crystallinity of the sample was reduced.
FIG. 2 is a Fourier infrared spectrum of MIL-53(Fe) and MIL-53(Fe, Co) at different mass ratios. As can be seen, the FTIR spectra of MIL-53(Fe) and MIL-53(Fe, Co) samples are substantially consistent, which indicates that the doping of cobalt does not affect the types of main functional groups. Meanwhile, the MIL-53(Fe, Co) sample is 1577cm-1There appears a distinct absorption peak, probably due to the introduction of cobalt, which may confirm that cobalt and H are present during the material preparation process2The carboxyl group in BDC undergoes a coordination reaction.
The MIL-53(Fe, Co) materials prepared in the above example two were applied to adsorb and degrade tetracycline solutions, respectively, to obtain the following test examples:
test example 1 influence of Co addition amount on Material Properties:
taking 8 Erlenmeyer flasks, pouring 30mL tetracycline solution with concentration of 100mg/L, respectively, adding 10mg MIL-53(Fe) into No. 1 and No. 2 Erlenmeyer flasks respectively2Co1) Adding 10mg MIL-53(Fe) into No. 3 and No. 4 conical flasks respectively1Co1) Adding 10mg MIL-53(Fe) into No. 5 and No. 6 conical flasks respectively1Co2) Adding 10mg MIL-53(Fe) into No. 7 and No. 8 conical flasks respectively1Co4) (ii) a Subsequently, 10mg of sodium Persulfate (PS) is added into conical flasks No. 2, No. 4, No. 6 and No. 8 respectively; placing all the conical flasks in a shaking table and shaking at 190rpm for 1 h; after sampling and diluting, filtering the mixture by a 0.22 mu m disposable filter head, and measuring the absorbance at 358nm by an ultraviolet-visible spectrophotometer.
FIG. 3 is a graph comparing the effect of MIL-53(Fe, Co) on the adsorption and catalytic degradation of tetracycline at different mass ratios. Compared with MIL-53(Fe), the introduction of cobalt is greatly improved by fourRemoval rate of cyclins. MIL-53(Fe)2Co1)/PS、MIL-53(Fe1Co1)/PS、MIL-53(Fe1Co2) Perps and MIL-53(Fe)1Co4) the/PS can reduce the TC concentration by 69.5 percent, 83.0 percent, 83.6 percent and 81.8 percent respectively. This is probably because, within a certain range, an increase in the cobalt content promotes activation of PS, while a too high Co content may lead to the formation of unknown phases, resulting in a low crystallinity. At the same time, the adsorption amount also shows the same tendency. Thus, MIL-53(Fe) was chosen1Co2) Subsequent experiments were performed to investigate their adsorption and degradation capabilities.
Test example 2MIL-53 (Fe)1Co2) Isothermal adsorption test on TC:
preparing tetracycline solutions with concentrations of 10, 20, 40, 80, 100, 150, 200, 300mg/L, respectively, taking 20mL of each solution and adding 10mg of MIL-53(Fe)1Co2) The materials are reacted at 20 ℃, 30 ℃ and 40 ℃ respectively until the adsorption balance is reached; after sampling and diluting, filtering the mixture by a 0.22 mu m disposable filter head, and measuring the absorbance at 358nm by an ultraviolet-visible spectrophotometer.
The results of fitting adsorption data with Langmuir and Freundlich isotherm models, respectively, are shown in fig. 4. At lower initial concentrations of TC, the equilibrium adsorption capacity increases rapidly first followed by a slower rate of increase. At 40 ℃, the adsorbed amount increased from 17.46mg/g at 10mg/L to 236.47mg/g at 300 mg/L. By comparing the correlation coefficients R2And calculating the amount of adsorption (qm), MIL-53(Fe)1Co2) The adsorption process for TC more closely follows the Langmuir isotherm model, namely MIL-53(Fe)1Co2) The adsorption of TC is monolayer adsorption. The adsorption equilibrium increases with increasing temperature. These results indicate that MIL-53(Fe)1Co2) Adsorption of TC is possible.
Experimental example 3 effect of different initial pH on tetracycline degradation:
preparing 100mg/L tetracycline solutions with pH of 4,5,6,7,8,9, and 10, respectively, each 30mL, and adding 10mg MIL-53(Fe)1Co2) Then adding 10mg of sodium persulfate into each system, and placing the system in a shaking table for oscillation reaction for 2 hours; each timeSamples were taken at intervals for dilution, filtered through a 0.22 μm disposable filter, and the absorbance at 358nm was measured by UV-visible spectrophotometer.
FIG. 5 is a graph of the effect of different initial pH on tetracycline degradation. The results show that MIL-53(Fe)1Co2) the/PS system has a high TC removal efficiency in the acidic range and reaches a maximum at pH 6.
Test example 4 toxicity of tetracycline degradation process to E.coli:
0.3mL of Escherichia coli was added to 100mL of sterile LB medium and incubated at a constant temperature of 120r/min for 10 hours in a shaker at 37 ℃. 0.3mL of cultured Escherichia coli and 6mL of TC solution collected at different degradation times were injected into 24mL of sterile LB medium, and were cultured in a shaker at 37 ℃ and a constant temperature of 160r/min for 14 hours. Samples were taken at regular intervals (2h) and absorbance at 600nm was measured using an ultraviolet spectrophotometer. The absorbance at 600nm is positively correlated with the E.coli density. The blank control sample was replaced with equal quality of sterile water and LB medium, and all manipulations were performed on a clean bench to ensure a sterile environment. Negative control samples were set for each experiment, i.e. no bacterial solution was added to the solution, to demonstrate that there was no bacterial contamination in the experiment. Two sets of parallel experiments were set up.
The toxicity results of the tetracycline degradation process on E.coli are shown in FIG. 6. The inhibition of E.coli is markedly reduced with longer degradation times: coli growth was almost completely inhibited in TC solution; after 45min of degradation, the growth of E.coli was slightly inhibited; after 60min of degradation, the growth of E.coli was essentially the same as in the blank group. As shown by the data, the TC removal rate at 45min of degradation is already 95%, while the inhibition rate to Escherichia coli is only 0.56%, indicating that the degradation product has lower toxicity.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention by those skilled in the art should fall within the protection scope of the present invention without departing from the design spirit of the present invention.

Claims (10)

1. A high-efficiency and safe method for adsorbing and degrading tetracycline by using a mixed metal organic framework material is characterized by comprising the following steps of:
1) weighing ferric chloride hexahydrate, cobalt chloride hexahydrate and terephthalic acid according to a proportion, dispersing in 35mL of organic solvent, and then ultrasonically mixing uniformly until the ferric chloride hexahydrate, the cobalt chloride hexahydrate and the terephthalic acid are completely dissolved;
2) transferring the mixed solution obtained in the step 1) into a polytetrafluoroethylene lining for solvothermal reaction;
3) after the solvothermal reaction in the step 2) is finished, naturally cooling to room temperature, and then centrifuging, washing and drying a reaction product to obtain a cobalt-doped mixed metal organic framework material MIL-53(Fe, Co);
4) dispersing the obtained cobalt-doped mixed metal organic framework material MIL-53(Fe, Co) in a tetracycline solution, placing the tetracycline solution in a shaking table, and mechanically stirring to obtain a suspension solution;
5) the tetracycline is removed by adsorbing or adding Persulfate (PS) to form a metal organic framework material/PS high-grade oxidation system.
2. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as claimed in claim 1, wherein: the molar ratio of the ferric chloride hexahydrate to the cobalt chloride hexahydrate is 2:1, 1:2 and 1:4 respectively, and the ratio of the total molar amount of the ferric chloride hexahydrate and the cobalt chloride hexahydrate to the molar amount of the terephthalic acid is 1: 1.
3. A highly efficient and safe method for adsorbing and degrading tetracycline using mixed metal organic framework materials according to claim 1 or 2, wherein: the organic solvent is N, N-dimethylformamide.
4. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as in claim 3, wherein: the ultrasonic treatment in the step 1) is carried out for 30min at room temperature.
5. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as in claim 4, wherein: the reaction temperature of the solvothermal reaction in the step 2) is 150 ℃, and the reaction time of the solvothermal reaction is 24 hours.
6. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as in claim 5, wherein: the rotation speed required by centrifugation in the step 3) is 8000r/min, pure water is adopted for washing, ultrasonic treatment is carried out for 5min under the washing condition, the washing frequency is 3 times, the drying temperature is 70 ℃, and the drying time is 10 hours.
7. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as in claim 6, wherein: the mass-volume ratio of the mixed metal organic framework material MIL-53(Fe, Co) to the tetracycline solution is 10 mg: 20mL, and the reaction temperature is 20 ℃, 30 ℃ and 40 ℃.
8. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as in claim 7, wherein: the initial concentration of the tetracycline solution is 10, 20, 40, 80, 100, 150, 200 and 300mg/L respectively, and the rotating speed of the shaking table is 190 r/min.
9. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as in claim 6, wherein: the mass-volume ratio of the mixed metal organic framework material MIL-53(Fe, Co) to the tetracycline solution is 10 mg: 30mL, 10mg of sodium Persulfate (PS), 4-10 of the pH value of the tetracycline solution and 190r/min of the rotation speed in the degradation process.
10. A highly efficient and safe method for the adsorption and degradation of tetracycline using mixed metal organic framework materials as claimed in claim 9, wherein: weighing a certain amount of the mixed metal organic framework material MIL-53(Fe, Co) and a predetermined amount of sodium Persulfate (PS) and adding into a tetracycline solution together, stirring to obtain a suspension solution, placing the suspension solution system in a shaking table, oscillating in a dark place, and taking a reaction solution at intervals for determination.
CN202111410467.XA 2021-11-25 2021-11-25 Efficient and safe method for adsorbing and degrading tetracycline by using mixed metal organic framework material Pending CN114130364A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115121226A (en) * 2022-07-11 2022-09-30 徐州医科大学 Preparation method and application of magnetic carbon-based FeCo bimetal organic framework composite material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115121226A (en) * 2022-07-11 2022-09-30 徐州医科大学 Preparation method and application of magnetic carbon-based FeCo bimetal organic framework composite material
CN115121226B (en) * 2022-07-11 2024-04-16 徐州医科大学 Preparation method and application of magnetic carbon-based FeCo bimetal organic framework composite material

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