CN111185233A - Preparation method and application of heterogeneous Fenton-like catalyst for degrading antibiotics in water environment - Google Patents
Preparation method and application of heterogeneous Fenton-like catalyst for degrading antibiotics in water environment Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 title abstract description 6
- 229940088710 antibiotic agent Drugs 0.000 title abstract description 6
- 230000000593 degrading effect Effects 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000013177 MIL-101 Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 229960001180 norfloxacin Drugs 0.000 claims description 19
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 abstract description 5
- 239000013179 MIL-101(Fe) Substances 0.000 abstract description 4
- 230000003115 biocidal effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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- Water Supply & Treatment (AREA)
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Abstract
The invention relates to a preparation method and application of a heterogeneous Fenton-like catalyst for degrading antibiotics in a water environment, wherein the catalyst prepared by the method is a Ce-doped MIL-101(Fe) metal organic framework (Fe/Ce-MIL-101). The catalyst is of an octahedral structure, and not only has the advantages of universality of MOF materials, such as large specific surface area, rich pore diameters and the like, but also can change secondary structural units of MOF due to the doping of Ce, so that the material is high in degradation efficiency, wide in pH range and good in stability. The raw materials of the invention are easy to obtain, the preparation process is simple, and the Fenton-like catalytic performance is high, so the invention has good application prospect in the aspect of the application of heterogeneous Fenton-like catalytic degradation antibiotics. The Fe/Ce-MIL-101 in the invention has excellent performance in the Fenton-like catalytic degradation antibiotic reaction, and is a Fenton-like catalyst with a very promising prospect.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, relates to a preparation method and application of a heterogeneous Fenton-like catalyst for degrading antibiotics in a water environment, and particularly relates to preparation of a Fe/Ce-MIL-101 Fenton-like catalyst and degradation of norfloxacin by the same.
Background
Antibiotics have been widely used in clinical medicine since their discovery. Norfloxacin is a fluoroquinolone antibiotic that is widely used in the treatment of common inflammation. However, norfloxacin is difficult to be degraded by light and biodegrade, so that norfloxacin gradually accumulates when being discharged into the natural environment and influences the survival of organisms and even the self health of human beings.
The common treatment methods of the sewage comprise adsorption, high-efficiency biodegradation and the like, but the treatment effect is not ideal. The Fenton method can be applied to various sewage treatments because the process can generate free radicals with high oxidation potential such as hydroxyl free radicals, and the Fenton method is a promising strategy because of mild conditions, simple operation, cheap materials and the like. However, for the traditional homogeneous fenton, not only certain requirements are required for the pH range of the reaction, but also the disadvantages that the catalyst is difficult to recover, and the iron ion loss causes secondary pollution and the like exist. In order to overcome the defects, a heterogeneous Fenton-like catalysis method which is wide in pH application range, good in stability and easy to recover is adopted to replace a homogeneous Fenton catalysis method. The solid Fenton-like catalysts commonly used at present are mainly iron oxides and other metal oxides, but the catalysts still have the defects of poor catalytic effect and poor recycling performance.
The invention is based on the background that on the basis of the familiarity of the MIL-101(Fe) metal organic framework, the expected catalyst material can be obtained by a hydrothermal method in one step, namely, by doping Ce (NO) in the MIL-101(Fe) synthesis process3)3·6H2O，Ce3+After entering secondary structure unit in MIL-101(Fe), the catalyst can not only act with oxidant of inner ball or outer ballThe electric charge transfer can even affect Fe3+Coordination of (2) to Fe3+Fe as an active center in MOF as a Lewis acid catalyst by partially unsaturated coordination around it3+With H as a Lewis guest2O2Obtain stronger affinity between the active center and H in the reaction process2O2The active hydroxyl free radical (. OH) is rapidly contacted and rapidly generated, thereby improving the Fenton-like catalytic performance of the material.
Disclosure of Invention
The invention relates to a preparation method and application of a Fenton-like catalyst for antibiotic degradation, wherein cerium nitrate hexahydrate, ferric nitrate hexahydrate and terephthalic acid are used for synthesizing Fe/Ce-MIL-101 with an octahedral structure according to a certain proportion. The catalyst has an influence on secondary structure units in the MOF due to the doping of Ce, so that the catalyst shows excellent performance in the aspects of sewage treatment, particularly antibiotic degradation. The preparation method is simple, the raw materials are easy to obtain, the energy consumption is low, and the method has bright prospect in the application aspect of future Fenton-like catalysis.
In order to realize the purpose, the preparation method of the high-efficiency Fenton-like catalyst Fe/Ce-MIL-101 comprises the following steps:
(1) 0.412g of terephthalic acid was weighed out, and 1.245g of FeCl was weighed out3·6H2O and 0.105g Ce (NO)3)3·6H2O is co-placed in a beaker, i.e. FeCl3·6H2O and Ce (NO)3)3·6H2The molar ratio of O is 95: 5, 30mL of N, N-dimethylformamide are added, and the mixture is stirred until the mixture is completely dissolved.
(2) Transferring the solution in the step (1) into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, and performing reaction at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 110 ℃, and the temperature is kept for 20 hours.
(3) And taking out the reaction kettle, naturally cooling to room temperature, carrying out suction filtration, washing with DMF (dimethyl formamide) and ethanol for three times respectively, and placing the obtained yellowish-brown solid in a vacuum oven to dry at 100 ℃ overnight to obtain Fe/Ce-MIL-101.
(4) 27mg of Fe/Ce-MIL-101 from step (3) was weighed out, charged into a photophobic reactor containing 80mL of norfloxacin (100mg/L), and then 90mM of H was added2O2The reaction was initiated, and 1mL of sample was taken from the solution at regular intervals and filtered through a 0.22 μm membrane, and the taken sample was tested with a uv-vis spectrophotometer to determine the removal efficiency of norfloxacin by the catalyst.
The Fe/Ce-MIL-101 catalyst prepared by the method can be used as a Fenton-like catalyst with excellent performance, and has high specific surface area and good norfloxacin removal rate.
The Fe/Ce-MIL-101 catalyst prepared by the method has the advantages of simple synthesis process, low energy consumption and good recycling performance, can be synthesized in large quantities, and can be applied to Fenton-like catalysis in a large scale.
Drawings
FIG. 1 SEM image of Fe/Ce-MIL-101 catalyst obtained in specific example 1, clearly showing that the catalyst has an octahedral structure.
The XRD pattern of the Fe/Ce-MIL-101 catalyst obtained in the specific example 1 in FIG. 2 shows that the XRD pattern of the material is consistent with that of MIL-101, which shows that the doping of Ce element does not influence the crystal structure of MOF.
FIG. 3 shows a performance diagram of degrading norfloxacin by using the Fe/Ce-MIL-101 catalyst obtained in the specific example 1, wherein the material can achieve a removal rate of about 88% in 30min and has a very good Fenton-like catalytic performance.
FIG. 4 shows the stable norfloxacin cycle of the Fe/Ce-MIL-101 catalyst obtained in example 1, which maintains a high removal rate after 5 cycles.
Detailed Description
In order to make the technical solution and the implementation objects and advantages of the present invention more clear, the technical solution of the present invention is fully and clearly described below with reference to the accompanying drawings of the specific embodiments of the present invention. The embodiments described below are only some of the embodiments of the present invention, and not all of them. The embodiments described in the present invention, without any inventive step, are all other embodiments within the scope of the present invention.
The present invention will be described in detail with reference to specific examples.
Example 1
(1) 0.412g of terephthalic acid was weighed out and 1.286g of FeCl were taken out3·6H2O and 0.064g Ce (NO)3)3·6H2O is co-placed in a beaker, i.e. FeCl3·6H2O and Ce (NO)3)3·6H2The molar ratio of O was 97: 3, 30mL of N, N-dimethylformamide was added, and the mixture was stirred until completely dissolved.
(2) Transferring the solution in the step (1) into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, and performing reaction at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 110 ℃, and the temperature is kept for 20 hours.
(3) And taking out the reaction kettle, naturally cooling to room temperature, carrying out suction filtration, washing with DMF (dimethyl formamide) and ethanol for three times respectively, and placing the obtained yellowish-brown solid in a vacuum oven to dry at 100 ℃ overnight to obtain Fe/Ce-MIL-101.
(4) 27mg of Fe/Ce-MIL-101 from step (3) was weighed out, charged into a photophobic reactor containing 80mL of norfloxacin (100mg/L), and then 90mM of H was added2O2The reaction was initiated, and 1mL of sample was taken from the solution at regular intervals and filtered through a 0.22 μm membrane, and the taken sample was tested with a uv-vis spectrophotometer to determine the removal efficiency of norfloxacin by the catalyst.
Example 2
(1) 0.412g of terephthalic acid was weighed out, and 1.245g of FeCl was weighed out3·6H2O and 0.105g Ce (NO)3)3·6H2O is co-placed in a beaker, i.e. FeCl3·6H2O and Ce (NO)3)3·6H2The molar ratio of O is 95: 5, 30mL of N, N-dimethylformamide are added, and the mixture is stirred until the mixture is completely dissolved.
(2) Transferring the solution in the step (1) into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, and performing reaction at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 110 ℃, and the temperature is kept for 20 hours.
(3) And taking out the reaction kettle, naturally cooling to room temperature, carrying out suction filtration, washing with DMF (dimethyl formamide) and ethanol for three times respectively, and placing the obtained yellowish-brown solid in a vacuum oven to dry at 100 ℃ overnight to obtain Fe/Ce-MIL-101.
(4) 27mg of Fe/Ce-MIL-101 from step (3) was weighed out, charged into a photophobic reactor containing 80mL of norfloxacin (100mg/L), and then 90mM of H was added2O2The reaction was initiated, and 1mL of sample was taken from the solution at regular intervals and filtered through a 0.22 μm membrane, and the taken sample was tested with a uv-vis spectrophotometer to determine the removal efficiency of norfloxacin by the catalyst.
Example 3
(1) 0.412g of terephthalic acid was weighed out, and 1.204g of FeCl was weighed out3·6H2O and 0.146g Ce (NO)3)3·6H2O is co-placed in a beaker, i.e. FeCl3·6H2O and Ce (NO)3)3·6H2The molar ratio of O was 97: 3, 30mL of N, N-dimethylformamide was added, and the mixture was stirred until completely dissolved.
(2) Transferring the solution in the step (1) into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, and performing reaction at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 110 ℃, and the temperature is kept for 20 hours.
(3) And taking out the reaction kettle, naturally cooling to room temperature, carrying out suction filtration, washing with DMF (dimethyl formamide) and ethanol for three times respectively, and placing the obtained yellowish-brown solid in a vacuum oven to dry at 100 ℃ overnight to obtain Fe/Ce-MIL-101.
(4) 27mg of Fe/Ce-MIL-101 from step (3) was weighed out, charged into a photophobic reactor containing 80mL of norfloxacin (100mg/L), and then 90mM of H was added2O2The reaction was initiated, and 1mL of sample was taken from the solution at regular intervals and filtered through a 0.22 μm membrane, and the taken sample was tested with a uv-vis spectrophotometer to determine the removal efficiency of norfloxacin by the catalyst.
Example 4
(1) 0.412g of terephthalic acid was weighed out, and 1.109g of FeCl was weighed out3·6H2O and 0.241g Ce (NO)3)3·6H2O is co-placed in a beaker, i.e. FeCl3·6H2O and Ce (NO)3)3·6H2The molar ratio of O is 90: 10, 30mL of N, N-dimethylformamide are added, and the mixture is stirred until the mixture is completely dissolved.
(2) Transferring the solution in the step (1) into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, and performing reaction at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 110 ℃, and the temperature is kept for 20 hours.
(3) And taking out the reaction kettle, naturally cooling to room temperature, carrying out suction filtration, washing with DMF (dimethyl formamide) and ethanol for three times respectively, and placing the obtained yellowish-brown solid in a vacuum oven to dry at 100 ℃ overnight to obtain Fe/Ce-MIL-101.
(4) 27mg of Fe/Ce-MIL-101 from step (3) was weighed out, charged into a photophobic reactor containing 80mL of norfloxacin (100mg/L), and then 90mM of H was added2O2The reaction was initiated, and 1mL of sample was taken from the solution at regular intervals and filtered through a 0.22 μm membrane, and the taken sample was tested with a uv-vis spectrophotometer to determine the removal efficiency of norfloxacin by the catalyst.
It should be understood that although the present invention has been particularly shown and described with reference to the foregoing embodiments, it will be understood that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The preparation method of the heterogeneous Fenton-like catalyst Fe/Ce-MIL-101 comprises the following steps:
(1) weighing 0.412g terephthalic acid, and then taking certain proportion of FeCl3·6H2O and Ce (NO)3)3·6H2And placing the O into a beaker together, adding 30mLN, N-dimethylformamide, and stirring until the O is completely dissolved.
(2) Transferring the solution in the step (1) into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, and performing reaction at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 110 ℃, and the temperature is kept for 20 hours.
(3) And taking out the reaction kettle, naturally cooling to room temperature, carrying out suction filtration, washing with DMF (dimethyl formamide) and ethanol for three times respectively, and placing the obtained yellowish-brown solid in a vacuum oven to dry at 100 ℃ overnight to obtain Fe/Ce-MIL-101.
(4) Weighing a certain amount of Fe/Ce-MIL-101 obtained in the step (3), adding the Fe/Ce-MIL-101 into a photophobic reactor filled with 80mL of norfloxacin, and then adding a certain amount of H2O2The reaction was initiated, and 1mL of sample was taken from the solution at regular intervals and filtered through a 0.22 μm membrane, and the taken sample was tested with a uv-vis spectrophotometer to determine the removal efficiency of norfloxacin by the catalyst.
2. The method of claim 1, wherein the Ce (NO) is in the step (1)3)3·6H2The proportion of O is 3%, 5%, 7% and 10%.
3. The method of claim 1, wherein the pH of the solution in step (4) is adjusted to 3, 5, 7, and 9 for testing.
4. The method of claim 1, wherein the amount of the catalyst added in step (4) is 0.1g/L, 0.2g/L, 0.3g/L, or 0.6 g/L.
5. The method of claim 1, wherein the step (4) is performed by using H2O2The dosage of the compound is respectively 80Mm, 90Mm, 100Mm and 120 Mm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114669329A (en) * | 2022-03-10 | 2022-06-28 | 南京工业大学 | Transition metal doped MIL-88 aerogel material and preparation method and application thereof |
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