CN109704432B - One-pot method for preparing UIO-66-NH2Method for preparing functional monomer composite material and application of functional monomer composite material in adsorption of antibiotics - Google Patents
One-pot method for preparing UIO-66-NH2Method for preparing functional monomer composite material and application of functional monomer composite material in adsorption of antibiotics Download PDFInfo
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- CN109704432B CN109704432B CN201910061266.XA CN201910061266A CN109704432B CN 109704432 B CN109704432 B CN 109704432B CN 201910061266 A CN201910061266 A CN 201910061266A CN 109704432 B CN109704432 B CN 109704432B
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Abstract
The invention discloses a one-pot method for preparing UIO-66-NH2The method of/functional monomer composite material includes the steps of dissolving functional monomer, zirconium source and organic ligand in N, N-dimethyl formamide ultrasonically, adding ethylene glycol dimethacrylate as cross-linking agent and azodiisobutyronitrile as initiator, transferring to stainless steel reactor with tetrafluoroethylene lining, reaction at 100 deg.c to coordinate and bond mutually, cooling, washing, centrifuging and drying to obtain target product UIO-66-NH2Functional monomer composite material and application of the composite material as an adsorbent in adsorbing macrolide antibiotics are disclosed. The invention prepares UIO-66-NH by a one-pot method2The functional monomer composite material has good physical and chemical stability, simple preparation process and environmental friendliness, and has high removal efficiency and large adsorption capacity for macrolide antibiotics in the environment.
Description
Technical Field
The invention belongs to a metal organic framework UIO-66-NH2The technical field of composite materials, in particular to a one-pot method for preparing UIO-66-NH2Method for preparing/functional monomer composite material and application of functional monomer composite material in adsorption of macrolide antibioticsApplication in biotin.
Background
The macrolide antibiotics are a group of antibiotics with 14-16-membered macrolide structures in molecules, and are widely applied to livestock and poultry treatment because the antibiotics have good antibacterial effects on gram-positive bacteria and mycoplasma in clinic and are easy to absorb. Meanwhile, due to the long-term overuse of macrolide antibiotic drugs, the macrolide antibiotic drugs are continuously accumulated in the environment, so that the health of human bodies is harmed. Numerous scholars at home and abroad have made many studies on the removal of macrolide pollutants, and the separation of substances by using efficient adsorbents becomes one of key technologies.
The metal organic framework material has the characteristics of large specific surface area, easy modification and the like, is considered to be an adsorption material with great advantages, and is particularly prominent in UIO series framework materials. However, UIO-66 and UIO-66-NH2The removal effect on macrolide antibiotics is poor and can only reach about 10%. Therefore, the improvement of the adsorption efficiency of the UIO series framework materials to the macrolide antibiotics in the environment becomes a research hotspot.
Disclosure of Invention
The present invention is directed to the existing UIO-66-NH2Provides a simple and low-cost one-pot method for preparing UIO-66-NH for the problem of poor treatment effect of macrolide antibiotics2A method for preparing a functional monomer composite material and application thereof in adsorbing macrolide antibiotics.
The invention adopts the following technical scheme that the UIO-66-NH is prepared by a one-pot method to solve the technical problems2The method for preparing the functional monomer composite material is characterized by comprising the following specific steps: ultrasonic dissolving functional monomer, zirconium source and organic ligand in N, N-dimethyl formamide simultaneously, adding cross-linking agent ethylene glycol dimethacrylate and initiator azobisisobutyronitrile, transferring into stainless steel reaction kettle with tetrafluoroethylene lining, reacting at 100-150 deg.C for mutual coordination bonding, cooling, washing, dissolving,Centrifuging and drying to obtain a target product UIO-66-NH2A functional monomer composite material, the pore diameter of the composite material is 0.6-2.9nm, the specific surface area is 629-1233m2/g。
Further preferably, the feeding molar ratio of the zirconium source to the organic ligand is 1: 0.5-3.
Further preferably, the washing solvent used in the washing process after cooling is one or more of methanol, N-dimethylformamide or ethanol.
Further preferably, the centrifugation rate in the centrifugation process is 6000-.
UIO-66-NH described in the invention2The functional monomer composite material is used as an adsorbent for adsorbing macrolide antibiotics.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares UIO-66-NH by a one-pot method2The functional monomer composite material has good physical and chemical stability, simple preparation process and environmental friendliness, has high removal efficiency and large adsorption capacity for macrolide antibiotics in the environment, and has wide prospect in the aspect of industrial application of macrolide antibiotics in the treatment environment.
Drawings
FIG. 1 is the UIO-66-NH prepared in example 12SEM image of/functional monomer composite.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Accurately weighing 0.2332g of zirconium tetrachloride and 0.1661g of 2-amino terephthalic acid in 50mL of N, N-dimethylformamide, adding 0.2073g of 2-acrylamide-2-methylpropanesulfonic acid, 0.88mL of crosslinking agent ethylene glycol dimethacrylate and 10mg of initiator azobisisobutyronitrile, simultaneously carrying out ultrasonic treatment for 30min, transferring the mixture to a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, reacting at 120 ℃ for 24h, and cooling to a temperature of 50 hAfter room temperature, it was washed three times with methanol at 6000rpm and dried to give UIO-66-NH2Functional monomer composite material.
Example 2
Accurately weighing 0.4664g of zirconium tetrachloride and 0.1661g of 2-amino terephthalic acid in 50mL of N, N-dimethylformamide, adding 0.2073g of 2-acrylamide-2-methylpropanesulfonic acid, 0.88mL of crosslinking agent ethylene glycol dimethacrylate and 10mg of initiator azobisisobutyronitrile, simultaneously carrying out ultrasonic treatment for 30min, transferring the mixture to a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, carrying out reaction at 120 ℃ for 24h, cooling to room temperature, carrying out centrifugal washing with methanol at 6000rpm for three times, and drying to obtain UIO-66-NH2Functional monomer composite material.
Example 3
Accurately weighing 0.1166g of zirconium tetrachloride and 0.042g of 2-amino terephthalic acid in 50mL of N, N-dimethylformamide, adding 0.2073g of 2-acrylamide-2-methylpropanesulfonic acid, 0.88mL of crosslinking agent ethylene glycol dimethacrylate and 10mg of initiator azobisisobutyronitrile, simultaneously carrying out ultrasonic treatment for 30min, transferring the mixture to a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, carrying out reaction at 120 ℃ for 24h, cooling to room temperature, carrying out centrifugal washing with methanol at 6000rpm for three times, and drying to obtain UIO-66-NH2Functional monomer composite material.
Example 4
Accurately weighing 0.1166g of zirconium tetrachloride and 0.042g of 2-amino terephthalic acid in 50mL of N, N-dimethylformamide, adding 0.09mL of methacrylic acid, 0.88mL of cross-linking agent ethylene glycol dimethacrylate and 10mg of initiator azobisisobutyronitrile, simultaneously carrying out ultrasonic treatment for 30min, transferring the mixture to a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, reacting for 24h at 100 ℃, cooling to room temperature, carrying out centrifugal washing with ethanol at 6000rpm for three times, and drying to obtain UIO-66-NH2Functional monomer composite material.
Example 5
0.1166g of zirconium tetrachloride and 0.042g of 2-aminoterephthalic acid were accurately weighed into 50mL of N, N-dimethylformamide, and then 0.13mL of hydroxyethyl methacrylate, 0.88mL of crosslinking agent ethylene glycol dimethacrylate and 10mL of crosslinking agent ethylene glycol dimethacrylate were addedSimultaneously ultrasonically treating azodiisobutyronitrile (mg) as an initiator for 30min, transferring the azodiisobutyronitrile into a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, reacting at 150 ℃ for 24h, cooling to room temperature, centrifugally washing with N, N-dimethylformamide at 8000rpm for three times, and drying to obtain UIO-66-NH2Functional monomer composite material.
Example 6
0.01g of UIO-66-NH prepared in example 1 was weighed2The functional monomer composite material is added into 10mL of 100mg/L tylosin tartrate, the mixture is shaken in water bath at 25 ℃ for 1h, clear liquid obtained after filtration and dilution is tested by a T6 new century ultraviolet-visible spectrophotometer, and the adsorption capacity is calculated by a formula.
Example 7
0.01g of UIO-66-NH prepared in example 1 was weighed2The functional monomer composite material is added into 10mL of 100mg/L kitasamycin tartrate, is vibrated in water bath at 25 ℃ for 1h, clear liquid obtained after filtration and dilution is tested by a T6 new century ultraviolet-visible spectrophotometer, and the adsorption capacity is calculated by a formula.
Example 8
0.01g of UIO-66-NH prepared in example 1 was weighed2The functional monomer composite material is added into 10mL of spiramycin containing 50mg/L, is vibrated in water bath at 25 ℃ for 1h, and is filtered and diluted to obtain clear liquid which is tested by a T6 new century ultraviolet-visible spectrophotometer, and the adsorption capacity is calculated by a formula.
Example 9
0.1g of UIO-66-NH prepared in example 1 was weighed out separately2Adding the functional monomer composite material into 30mL of mixed aqueous solution respectively containing 100mg/L of tylosin tartrate, kitasamycin tartrate and spiramycin, oscillating the mixed aqueous solution in water bath at 25 ℃ for 1h, filtering and diluting to obtain clear liquid, testing the clear liquid by a T6 new century ultraviolet-visible spectrophotometer, and calculating the adsorption capacity by a formula.
TABLE 1 UIO-66-NH prepared in example 12Adsorption capacity of functional monomer composite material
The results in Table 1 show that the UIO-66-NH prepared by the present invention2The/functional monomer composite material has high adsorption and removal efficiency on macrolide antibiotics, particularly has high adsorption capacity on tylosin tartrate, and the adsorption capacity is up to 132 mg/g.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (1)
1.UIO-66-NH2The application of/functional monomer composite material in adsorbing macrolide antibiotics is characterized in that the UIO-66-NH2The functional monomer composite material is prepared by a one-pot method, and the specific steps are as follows: weighing 0.2332g of zirconium tetrachloride and 0.1661g of 2-aminoterephthalic acid in 50mL of N, N-dimethylformamide, adding 0.2073g of 2-acrylamide-2-methylpropanesulfonic acid, 0.88mL of crosslinking agent ethylene glycol dimethacrylate and 10mg of initiator azobisisobutyronitrile, carrying out ultrasonic treatment for 30min, transferring the mixture to a stainless steel hydrothermal reaction kettle with a tetrafluoroethylene lining, reacting for 24h at 120 ℃, cooling to room temperature, carrying out centrifugal washing with methanol at 6000rpm for three times, and drying to obtain UIO-66-NH2Functional monomer composite material.
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| CN110479220A (en) * | 2019-08-23 | 2019-11-22 | 河南师范大学 | The method of molecularly imprinted polymer separating and enriching trace sulfamethoxazole pollutant based on supported ion liquid metal organic framework |
| CN110975825B (en) * | 2019-12-31 | 2023-03-28 | 中国科学院合肥物质科学研究院 | Double-ligand zirconium MOFs adsorbent, preparation method and application thereof |
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