CN115109268A - Preparation method and application of photocatalytic material for efficiently degrading oxytetracycline - Google Patents
Preparation method and application of photocatalytic material for efficiently degrading oxytetracycline Download PDFInfo
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- CN115109268A CN115109268A CN202210919951.3A CN202210919951A CN115109268A CN 115109268 A CN115109268 A CN 115109268A CN 202210919951 A CN202210919951 A CN 202210919951A CN 115109268 A CN115109268 A CN 115109268A
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- 239000004100 Oxytetracycline Substances 0.000 title claims abstract description 26
- 229960000625 oxytetracycline Drugs 0.000 title claims abstract description 26
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 title claims abstract description 26
- 235000019366 oxytetracycline Nutrition 0.000 title claims abstract description 26
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000000593 degrading effect Effects 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 8
- 229940063650 terramycin Drugs 0.000 description 8
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- 238000003917 TEM image Methods 0.000 description 4
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- 239000006228 supernatant Substances 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
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- 239000002243 precursor Substances 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 206010067623 Radiation interaction Diseases 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
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- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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]
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a preparation method and application of a photocatalytic material for efficiently degrading oxytetracycline, wherein the preparation method comprises the following steps: dissolving a ZIF-67 sample in ethanol; obtaining ZIF-67p after ultrasonic treatment; dissolving AgNO3 in ethanol; slowly dripping a ZIF-67p solution under violent stirring to obtain a purple solution; centrifugally washing with ethanol for 3 times after stirring; drying to obtain a purple product; dissolving the purple product in ethanol, and performing ultrasonic treatment; dissolving NaBH4 in ethanol; mixing the two solutions; stirring at room temperature; centrifugally washing with ethanol to obtain a purple black product; and drying to obtain an Ag-ZIF-67p sample. The invention adopts an ultrasonic reduction method to synthesize a new material with better performance of photocatalytic degradation of the oxytetracycline, the preparation method adopted by the invention is simple and has high efficiency, the obtained material has regular appearance and uniform size, and the effect of degrading the oxytetracycline is good.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method and application of a photocatalytic material for efficiently degrading oxytetracycline.
Background
The residual terramycin in the environment is mainly from inevitable loss in the process of producing terramycin in factories, antibiotic waste discarded by hospitals, terramycin discharged from human and animal excrements and urine, and the like. Currently, surface water and drinking water are detected in many parts of the world, and the hazards of oxytetracycline abuse are: 1. pathogenic microorganisms have increased resistance to antibiotics, causing serious harm to the ecological balance and human health. 2. Antibiotics are teratogenic and carcinogenic in the ecological environment. 3. Complexing with metal ions produces toxic effects. Therefore, there is an urgent need for efficient methods and catalysts for the degradation of oxytetracycline. Because oxytetracycline has antimicrobial activity, it is difficult to achieve desirable results using conventional biological treatment techniques. The photocatalytic oxidation technology has the unique properties of directly utilizing solar energy as a light source to drive reaction, having no secondary pollution and the like, and has the advantages of mild reaction conditions, high reaction speed, high mineralization rate and the like when used for treating organic pollutants.
The Metal Organic Frameworks (MOFs) are novel porous crystal materials synthesized by coordination of metal ions or metal clusters and organic ligands, ZIF-67 is three-dimensional porous Co-based MOFs consisting of Co2+ coordination clusters and 2-methylimidazole, and the microporous structure of the ZIF-67 has the excellent characteristics of large specific surface area, high porosity, good crystallinity and the like, so that the ZIF-67 can be widely applied to the fields of gas storage, catalysis, clean energy, sensing and the like. The large surface area and microporous structure of ZIF-67 have also attracted great interest in the field of photocatalysis, but the lower photocatalytic activity of pure ZIF-67 has largely limited the use of ZIF-67 in photocatalytic processes. Ag is considered as a relatively industrially promising doping material, while silver nanoparticles (Ag-NPs) can enhance the photocatalytic activity of semiconductors under visible light due to the localized surface plasmon resonance effect (LSPR) of electromagnetic radiation interaction. Therefore, Ag-NPs are introduced and then compounded with ZIF-67 to prepare the Ag-ZIF-67p, so that the performance of photocatalytic degradation of oxytetracycline is effectively improved.
Disclosure of Invention
The invention aims to provide a preparation method and application of a photocatalytic material for efficiently degrading oxytetracycline, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a photocatalytic material for efficiently degrading oxytetracycline mainly comprises the following steps:
step 1: dissolving 350mg of ZIF-67 sample in 12mL of ethanol;
step 2: carrying out ultrasonic treatment for 1h to obtain ZIF-67 p;
and step 3: dissolving 30.57mg of AgNO3 in 4mL of ethanol;
and 4, step 4: slowly dripping the solution in the step 3 into the solution in the step 2ZIF-67p under vigorous stirring to obtain a purple solution;
and 5: stirring for 4h, and centrifuging and washing with ethanol for 3 times;
step 6: drying at 80 ℃ for 12h to obtain a purple product;
and 7: dissolving the purple product obtained in the step 6 in 12mL of ethanol, and then carrying out ultrasonic treatment for 0.5 h;
and step 8: dissolving 68.1mg NaBH4 in 3.8mL ethanol;
and step 9: slowly dripping the solution obtained in the step 8 into the solution obtained in the step 7;
step 10: stirring for 2 hours at room temperature;
step 11: centrifugally washing with ethanol for 4 times to obtain a purple black product;
step 12: and drying the purple black product at 80 ℃ for 1h to obtain an Ag-ZIF-67p sample.
As a further scheme of the invention: the preparation method of the ZIF-67 mainly comprises the following steps:
step 1: 1.4g of cobalt nitrate hexahydrate is dissolved in 80mL of methanol;
step 2: dissolving 1.6g of 2-methylimidazole in 80ml of methanol and pouring the solution into the solution in the step 1;
and step 3: stirring for 6h to form a purple solution;
and 4, step 4: after the reaction is finished, centrifugally washing the mixture for 3 times by using methanol;
and 5: vacuum drying at 100 deg.C for 5h to obtain ZIF-67 sample.
The invention also aims to provide an application of the photocatalytic material in degrading terramycin.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts the ultrasonic reduction method to synthesize a new material with better performance of photocatalytic degradation of terramycin, the preparation method adopted by the invention is simple and has high efficiency, the obtained material has regular shape and uniform size, the effect of degrading terramycin is good, the discovery and research of Ag-ZIF-67p are beneficial to further widening the research field of photocatalytic degradation of other substances, and some ideas are provided for designing and synthesizing novel catalysts or new materials.
Drawings
FIG. 1 is an XRD pattern of ZIF-67, ZIF-67p, Ag-ZIF-67, and Ag-ZIF-67 p.
FIG. 2 is an EDX diagram of Ag-ZIF-67 p.
FIG. 3 is a TEM image of ZIF-67(a), Ag-ZIF-67(b), ZIF-67p (c), and Ag-ZIF-67p (d).
FIG. 4 is an XPS map of Ag-ZIF-67 p.
FIG. 5 is an ultraviolet spectrum of Ag-ZIF-67p catalyst degrading oxytetracycline.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment I provides a high-efficiency oxytetracycline degrading photocatalytic material, and the preparation method mainly comprises the following steps:
the preparation method of ZIF-67 comprises the following steps:
step 1: 1.4g of cobalt nitrate hexahydrate is dissolved in 80mL of methanol;
step 2: dissolving 1.6g of 2-methylimidazole in 80ml of methanol and pouring the solution into the solution in the step 1;
and 3, step 3: stirring for 6h to form a purple solution;
and 4, step 4: after the reaction is finished, centrifugally washing the mixture for 3 times by using methanol;
and 5: vacuum drying at 100 deg.C for 5h to obtain ZIF-67 sample.
The preparation method of the Ag-ZIF-67p comprises the following steps:
step 1: dissolving 350mg of ZIF-67 sample in 12mL of ethanol;
step 2: carrying out ultrasonic treatment for 1h to obtain ZIF-67 p;
step 3: dissolve 30.57mg AgNO3 in 4mL ethanol;
and 4, step 4: slowly dripping the solution in the step 3 into the solution in the step 2ZIF-67p under vigorous stirring to obtain a purple solution;
and 5: stirring for 4h, and centrifuging and washing with ethanol for 3 times;
step 6: drying at 80 ℃ for 12h to obtain a purple product;
and 7: dissolving the purple product obtained in the step 6 in 12mL of ethanol, and then carrying out ultrasonic treatment for 0.5 h;
and 8: dissolving 68.1mg NaBH4 in 3.8mL ethanol;
and step 9: slowly dripping the solution obtained in the step 8 into the solution obtained in the step 7;
step 10: stirring for 2 hours at room temperature;
step 11: centrifugally washing with ethanol for 4 times to obtain a purple black product;
step 12: and drying the purple black product at 80 ℃ for 1h to obtain an Ag-ZIF-67p sample.
FIG. 1 is an XRD pattern of ZIF-67, ZIF-67p, Ag-ZIF-67, and Ag-ZIF-67 p. From FIG. 1, the reflection peak of ZIF-67 is consistent with that of the simulated ZIF-67(CCDC-671073), confirming the successful synthesis of pure ZIF-67. From FIG. 1, the XRD characteristic peaks of the ZIF-67p composite material did not change significantly, indicating that the original crystal structure of ZIF-67 was also maintained after sonication.
As can be seen from FIG. 1, representative diffraction peaks (black lines) of Ag-ZIF-67 and Ag-ZIF-67p at 38 ° and 44 ° can be indicated as (111) and (200) planes (JCPDS 87-717) of Ag. As a result, it was found that the Ag-ZIF-67 has a weaker Ag-characteristic peak intensity than Ag-ZIF-67p, which may be associated with a lower Ag-NPs doping amount. The X-ray diffraction peak is very strong as seen from the XRD diagram of figure 1, which shows that the crystal form is well developed.
FIG. 2 is an EDX diagram of Ag-ZIF-67p, further illustrating the structure of the prepared Ag-ZIF-67 p. The EDX elemental diagram confirms the distribution of C, Co, N and Ag elements in the Ag-ZIF-67p, and verifies the formation of the Ag-ZIF-67p again.
FIG. 3 is a TEM image of ZIF-67(a), Ag-ZIF-67(b), ZIF-67p (c), and Ag-ZIF-67p (d). FIG. 3a is a TEM image of synthesized ZIF-67, in which a regular, independent dodecahedron was observed, indicating that ZIF-67 has good crystallinity. As can be seen from FIG. 3b, the Ag-ZIF-67 composite material is formed by reducing the metal precursor Ag solution in MOF matrix, and Ag nanoparticles with average size of about 15nm are formed on the inner and outer surfaces of ZIF-67.
From FIG. 3c, the ultrasonically prepared ZIF-67 still retained the original dodecahedral shape, but a nano-pinna was found around the ZIF-67, indicating that the ultrasonic treatment has an important effect on the morphology of the ZIF-67 during the sample preparation process. From FIG. 3d, Ag-ZIF-67p was obtained by the ultrasonic strategy, in which well-dispersed Ag-NPs were encapsulated in the ZIF-67p and distributed outside the ZIF-67p, which was rarely seen in the previous reports. This morphology not only increases the surface active area, but also increases the loading of active sites and Ag-NPs.
It can be seen from the TEM image of FIG. 3 that the catalyst particles are regular and are assembled from dodecahedrons, and that particles having an average size of about 15nm are formed on both the inner and outer surfaces of the dodecahedrons.
FIG. 4 is an XPS map of Ag-ZIF-67p, which further examined the chemical state of the prepared Ag-ZIF-67 p. XPS measurement spectrum of the Ag-ZIF-67p composite material shows that C element, N element, Co element and Ag element exist, and the analysis is consistent with the analysis of an EDX chart. The peak binding energy of C1s, N1s, and Co2p matched well with the value of ZIF-67. The results show that the Ag-ZIF-67p is successfully prepared. The chemical state of the prepared Ag-ZIF-67p was further examined from the XPS chart of fig. 4, in agreement with the analysis of fig. 2.
The ZIF-67 is changed into the ZIF-67 with a larger specific surface area and a nanometer feather by adopting an ultrasonic method, namely the ZIF-67p, and the ZIF-67p is used for loading a certain amount of Ag-NPs. And reducing the metal precursor (AgNO3) into ZIF-67p by adopting a reduction method to obtain the Ag-ZIF-67p nanometer feather composite metal material. The preparation method not only can enable the Ag-NPs to be formed in the ZIF-67, but also can be formed on the outer surface of the ZIF-67, so that the catalytic activity sites of the composite material are increased. The Ag-NPs modified ZIF-67 nanometer feather composite metal material (Ag-ZIF-67p) has a synergistic catalysis effect on terramycin degradation due to the large porosity and specific surface area, and the electric conductivity and excellent catalytic activity of Ag-NPs.
The second embodiment is an application of a photocatalytic material for efficiently degrading oxytetracycline, and the preparation method mainly comprises the following steps:
step 1: respectively dissolving 1.4g of cobalt nitrate hexahydrate and 1.6g of 2-methylimidazole in 80mL of methanol;
step 2: pouring the methanol solution of 2-methylimidazole into the methanol solution of cobalt nitrate hexahydrate to form a purple solution, and stirring for reacting for 6 hours;
and step 3: after the reaction is finished, centrifugally washing the reactant for 3 times by using methanol, and then carrying out vacuum drying for 5 hours in a vacuum drying oven at the temperature of 100 ℃ to obtain a ZIF-67 sample;
and 4, step 4: dissolving 350mg of ZIF-67 sample in 12mL of ethanol, and carrying out ultrasonic treatment for 1h to obtain a ZIF-67p solution;
and 5: dissolving 30.57mg of AgNO3 in 4mL of ethanol, and then slowly dripping the solution into the ZIF-67p solution obtained in the previous step under vigorous stirring to obtain a mixed solution of silver ions and the ZIF-67 p;
step 6: stirring the mixed solution for 4h, washing with ethanol for 3 times, and drying at 80 ℃ for 12h to obtain a purple product;
and 7: dissolving the purple product obtained in the step 6 in 12mL of ethanol, and then carrying out ultrasonic treatment for 0.5 h;
and 8: dissolving 68.1mg of NaBH4 in 3.8mL of ethanol, slowly dropwise adding the solution into the solution obtained by the treatment in the step 7, and stirring at room temperature for 2 hours;
and step 9: and centrifugally washing the stirred solution with ethanol for 4 times, and drying at 80 ℃ for 1h to obtain a purple black product Ag-ZIF-67p sample.
The obtained Ag-ZIF-67p catalyst can be used for degrading terramycin, and the specific method is as follows:
step 1: 100mL of oxytetracycline solution with the concentration of 30mg/L is prepared in a special glass culture dish for the photocatalytic test, and then 0.03g of Ag-ZIF-67p catalyst is added into the oxytetracycline solution;
step 2: putting the culture dish into an ultrasonic machine, and carrying out ultrasonic treatment for 10min in the dark;
and step 3: placing the culture dish into a photochemical reaction instrument, and standing for 12 hours under a dark condition to ensure that the system achieves adsorption-degradation balance;
and 4, step 4: sampling 5mL of the sample from a glass culture dish under a dark condition, and performing centrifugal separation on the sampled sample to obtain a supernatant;
and 5: turning on a xenon lamp light source in a photochemical reaction instrument to ensure that the oxytetracycline starts to be degraded by photocatalysis under the action of an Ag-ZIF-67p catalyst;
step 6: after the photocatalytic reaction starts, sampling 5mL of the solution from a glass culture dish every 1h, and performing centrifugal separation on the sampled solution to obtain a supernatant;
and 7: and detecting the absorbance of the obtained supernatant at different times by using an ultraviolet-visible spectrophotometer to obtain ultraviolet-visible absorption spectrograms of the oxytetracycline at different irradiation times.
FIG. 5 is an ultraviolet spectrum of the degradation of oxytetracycline by an Ag-ZIF-67p catalyst, showing that the absorbance of oxytetracycline decreases with the increase of degradation time; and 3h, the absorbance is only 0.122, and the degradation rate reaches 90.77%, which shows that the degradation efficiency of the Ag-ZIF-67p catalyst is very high.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (3)
1. A preparation method of a photocatalytic material for efficiently degrading oxytetracycline is characterized by comprising the following steps: the preparation method mainly comprises the following steps:
step 1: dissolving 350mg of ZIF-67 sample in 12mL of ethanol;
step 2: carrying out ultrasonic treatment for 1h to obtain ZIF-67 p;
and step 3: dissolve 30.57mg AgNO3 in 4mL ethanol;
and 4, step 4: slowly dripping the solution in the step 3 into the solution in the step 2ZIF-67p under vigorous stirring to obtain a purple solution;
and 5: stirring for 4h, and centrifuging and washing with ethanol for 3 times;
step 6: drying at 80 ℃ for 12h to obtain a purple product;
and 7: dissolving the purple product obtained in the step 6 in 12mL of ethanol, and then carrying out ultrasonic treatment for 0.5 h;
and 8: dissolving 68.1mg NaBH4 in 3.8mL ethanol;
and step 9: slowly dripping the solution obtained in the step 8 into the solution obtained in the step 7;
step 10: stirring for 2 hours at room temperature;
step 11: centrifugally washing with ethanol for 4 times to obtain a purple black product;
step 12: and drying the purple black product at 80 ℃ for 1h to obtain an Ag-ZIF-67p sample.
2. The preparation method of the photocatalytic material for efficiently degrading the oxytetracycline according to claim 1, characterized in that: the preparation method of the ZIF-67 mainly comprises the following steps:
step 1: 1.4g of cobalt nitrate hexahydrate is dissolved in 80mL of methanol;
step 2: dissolving 1.6g of 2-methylimidazole in 80ml of methanol and pouring the solution into the solution in the step 1;
and step 3: stirring for 6h to form a purple solution;
and 4, step 4: after the reaction is finished, centrifugally washing the mixture for 3 times by using methanol;
and 5: vacuum drying at 100 deg.C for 5h to obtain ZIF-67 sample.
3. The application of the photocatalytic material for efficiently degrading the oxytetracycline is characterized in that: the application of the high-efficiency oxytetracycline degrading photocatalytic material in the degradation of oxytetracycline is provided.
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