CN115337964B - Cobalt-iron modified ZIF-8 composite material and preparation method and application thereof - Google Patents
Cobalt-iron modified ZIF-8 composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- -1 Cobalt-iron modified ZIF-8 Chemical class 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 29
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 32
- 239000004202 carbamide Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001291 vacuum drying Methods 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 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 12
- 229960001180 norfloxacin Drugs 0.000 claims description 12
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000004098 Tetracycline Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229960002180 tetracycline Drugs 0.000 claims description 4
- 229930101283 tetracycline Natural products 0.000 claims description 4
- 235000019364 tetracycline Nutrition 0.000 claims description 4
- 150000003522 tetracyclines Chemical class 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 5
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 96
- 239000000243 solution Substances 0.000 description 86
- 238000003756 stirring Methods 0.000 description 55
- 239000000843 powder Substances 0.000 description 46
- 238000005303 weighing Methods 0.000 description 27
- 230000003197 catalytic effect Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 239000011701 zinc Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 238000003889 chemical engineering Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
-
- 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
- B01J2531/845—Cobalt
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation and application of MOFs derivative composite materials, and in particular relates to a cobalt-iron modified ZIF-8 composite material and a preparation method thereof, wherein the ZIF-8 is taken as a template, and Co (NO 3 ) 2 ·6H 2 O is used as cobalt source, fe (NO) 3 ) 3 ·9H 2 O is used as an iron source, and the cobalt-iron modified ZIF-8 composite material is obtained by modifying the ZIF-8 with cobalt iron, so that the activated persulfate performance of the ZIF-8 can be remarkably improved, the morphology structure of the ZIF-8 is reserved, and the composite material can be used for catalyzing and degrading organic pollutants in wastewater.
Description
Technical Field
The invention belongs to the technical field of magnetic composite catalytic materials, and particularly relates to a cobalt-iron modified ZIF-8 composite material, and a preparation method and application thereof.
Background
Antibiotics have been widely used in medical and livestock industries due to their high antibacterial and bactericidal effects, however, the increasing types and amounts thereof inevitably lead to the enhancement of bacterial resistance and serious pollution problems. Thus, the development of a technology for treating sewage containing antibiotics is urgent. Catalytic degradation of refractory organic pollutants in sewage is an effective way to solve the problem of water pollution at present, and improvement of capture and degradation capability of refractory organic matters in sewage is critical.
Metal Organic Frameworks (MOFs) are novel hybrid materials with highly ordered porous structures formed by coordination of metal ions or metal ion clusters and organic ligands. The ZIF-8 is a zinc-based MOF material with a zeolite crystal form and ordered pore channels and high hydrothermal stability, has a three-dimensional porous structure and good adsorption performance, and has been widely applied to the fields of separation, adsorption and catalysis. In addition, ZIF-8 can be rapidly synthesized in different solution systems and has therefore become one of the most studied MOF materials.
To further increase the functionality of ZIF-8, researchers have prepared ZIF-8 based composites, such as Au@ZIF-8 (Kim H, trinh B T, kim K H, et al Au@ZIF-8SERS paper for food spoilage detection[J)].Biosensors and Bioelectronics,2021,179:113063.)、g-C 3 N 4 @ZIF-8(Yuan X,Qu S,Huang X,et al.Design of core-shelled g-C 3 N 4 @ZIF-8photocatalyst with enhanced tetracycline adsorption for boosting photocatalytic degradation[J].Chemical Engineering Journal,2021,416:129148.)、Fe/ZIF-8(Yang H,Hu S,Zhao H,et al.High-performance Fe-doped ZIF-8adsorbent for capturing tetracycline from aqueous solution[J].Journal of Hazardous Materials,2021,416:126046.)、Fe 3 O 4 @ZIF-8(Jiang X,Su S,Rao J,et al.Magnetic metal-organic framework(Fe 3 O 4 @ZIF-8)core-shell composite for the efficient removal of Pb(II)and Cu(II)from water[J]Journal of Environmental Chemical Engineering,2021,9 (5): 105959.) and Co/ZIF-8 (Cong S, shen Q, shan M, et al enhanced permeability in mixed matrix membranes for CO) 2 capture through the structural regulation of the amino-functionalized Co/ZIF-8heterometallic nanoparticles[J]Chemical Engineering Journal,2020, 383:123137), etc.
Therefore, in recent years, research on preparing a composite material based on ZIF-8 has had some working foundation, but how to prepare the ZIF-8-based composite material more simply and conveniently and how to ensure that the ZIF-8-based composite material has excellent performance and is more beneficial to recycling, and is still one of the key problems of popularization and application.
Disclosure of Invention
The invention provides a cobalt-iron modified ZIF-8 composite material and a preparation method thereof, which have the advantages of simple preparation process, less process flow, good catalytic degradation performance on antibiotics in sewage by an advanced oxidation method, good magnetism and easy recovery.
The technical scheme adopted is as follows:
the invention provides a cobalt-iron modified ZIF-8 composite material, which is prepared according to the following method:
dissolving ferric salt, cobalt salt and urea in water, adding ZIF-8, uniformly dispersing, performing hydrothermal reaction at 100-140 ℃ for 20-30 h (preferably 120 ℃ for 24 h), and performing post-treatment on the obtained reaction solution A to obtain the cobalt-iron modified ZIF-8 composite material; the mass ratio of ZIF-8, ferric salt, cobalt salt and urea is 1:1.5 to 2: 2-3: 2 to 3 (preferably 1:1.8:2.5:2.6); the ferric salt, the cobalt salt, the urea and the ZIF-8 can be respectively dispersed in water and then uniformly mixed or sequentially dissolved and dispersed, so that the dispersion is more uniform.
Further, the ZIF-8 is prepared as follows:
zn (NO) 3 ) 2 ·6H 2 O and dimethylimidazole were dissolved in methanol A, respectively, and the obtained Zn (NO 3 ) 2 ·6H 2 Mixing the methanol solution of O and the methanol solution of dimethylimidazole uniformly, stirring for 4-6 h at 25 ℃, centrifuging the obtained mixed solution, washing the obtained precipitate of methanol B, and drying to obtain the ZIF-8.
Methanol A, B is methanol, and letters are used for distinguishing the methanol used in different stages, so that the description is convenient and has no special meaning.
Further, the Zn (NO 3 ) 2 ·6H 2 The mass ratio of O to dimethylimidazole is 1:1.5 to 2.5 (preferably 1:2.2), stirring for reaction after uniform ultrasonic dispersion, and the ultrasonic power is 60 to 120W.
Further, the Zn (NO 3 ) 2 ·6H 2 The ratio of the total amount of O and the methanol A is 1g: 40-50 mL.
Further, the iron salt is Fe (NO) 3 ) 3 ·9H 2 O, the cobalt salt is Co (NO) 3 ) 3 ·6H 2 O。
Further, the proportion of the ferric salt to the water is 1g: 50-75 mL.
Further, the post-treatment a is: and (3) carrying out suction filtration on the reaction liquid, washing the obtained filter cake with deionized water and ethanol in sequence, and carrying out vacuum drying to obtain the powder.
The invention also recommends that the cobalt-iron modified ZIF-8 composite material is further processed as follows to obtain a calcined cobalt-iron modified ZIF-8 composite material:
grinding and mixing the cobalt-iron modified ZIF-8 composite material and potassium salt, heating to 750-950 ℃ at a speed of 2-5 ℃/min under a protective atmosphere, calcining for 2-3 h (preferably calcining for 2h at 800 ℃) and carrying out post-treatment B on the obtained solid phase to obtain the calcined cobalt-iron modified ZIF-8 composite material; the mass ratio of the cobalt-iron modified ZIF-8 composite material to the potassium salt is 1:1-1.5 (preferably 1:1.5). The catalyst has better catalytic performance and can be recovered magnetically.
Further, the potassium salt is KCl and KNO 3 One or a mixture of two (preferably KNO) 3 )。
Further, the protective atmosphere is a nitrogen atmosphere or an argon atmosphere, preferably a nitrogen atmosphere.
Further, the post-treatment B is: and washing the solid phase with deionized water and drying to obtain the calcined cobalt-iron modified ZIF-8 composite material.
When the cobalt-iron modified ZIF-8 composite material is used for treating organic pollutant wastewater, an advanced oxidation treatment technology represented by transition metal activated persulfate is adopted.
On the other hand, the invention also provides an application of the cobalt-iron modified ZIF-8 composite material in treating organic pollutant wastewater.
Further, the organic pollutant in the organic pollutant wastewater is one or a mixture of more than two of norfloxacin, tetracycline and bisphenol A, and preferably norfloxacin.
Specifically, the application is as follows: dispersing the cobalt-iron modified ZIF-8 composite material into organic pollutant wastewater, and adding persulfate to catalyze and degrade the organic pollutant.
Further, the concentration of the organic pollutants in the organic pollutant wastewater is 2-50 mg/L. The persulfate is one or a mixture of two of Peroxomonosulfate (PMS) and Peroxodisulfate (PDS). The ratio of the cobalt-iron modified ZIF-8 composite material to the persulfate to the organic pollutant wastewater is 0.2-2 g:0.2 g to 2g:1L.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention can obviously improve the performance of ZIF-8 activated PMS in degrading organic pollutants by a simple method.
(2) In the preparation process of the cobalt-iron modified ZIF-8 composite material, the process steps can be flexibly adjusted according to actual conditions, and the cobalt-iron modified ZIF-8 composite material is endowed with good adsorption performance and catalytic performance.
(3) In the preparation process of the cobalt-iron modified ZIF-8 composite material, through fused salt calcination, the catalytic performance can be improved, and the composite material of the cobalt-iron modified ZIF-8 which can be magnetically recovered and reused can be formed.
Drawings
FIG. 1 is an SEM image of a cobalt-iron modified ZIF-8 composite prepared according to example 1
FIG. 2 is an XRD pattern of a cobalt-iron modified ZIF-8 composite prepared in example 1
FIG. 3 is an SEM image of a molten salt calcined cobalt-iron modified ZIF-8 composite prepared according to example 2
FIG. 4 is an XRD pattern of a composite of molten salt calcined cobalt-iron modified ZIF-8 prepared in example 2
FIG. 5 is a graph showing the comparison of magnetic properties of the cobalt-iron modified ZIF-8 composites prepared in example 1 (a) and example 2 (b)
FIG. 6 is an XRD pattern of a composite of an aerobic molten salt calcined cobalt-iron modified ZIF-8 prepared in comparative example 2
FIG. 7 is an XRD pattern of ZIF-8 prepared in comparative example 3
FIG. 8 is an XRD pattern of a composite of comparative example 4 prepared without the addition of molten salt calcined cobalt-iron modified ZIF-8
Detailed Description
Example 1:
the preparation method of the magnetic composite catalytic material of the embodiment comprises the following steps:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-methylimidazole (2-Meim) were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain the cobalt-iron modified ZIF-8 composite material.
Example 1 is a direct urea process to prepare a cobalt iron modified ZIF-8 composite.
Example 2:
the preparation method of the magnetic composite catalytic material of the embodiment comprises the following steps:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally vacuum drying for 6 hours at 60 ℃ in a vacuum drying box to obtain powder II;
(6) And (3) weighing 0.35g of the powder II obtained in the step (5) and 0.35g of KCl, mixing and grinding, placing into a tube furnace for calcination (the temperature is 800 ℃, the calcination time is 2h, the heating rate is 5 ℃/min, and the nitrogen atmosphere), washing with deionized water for 3 times, and finally, drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the magnetic composite catalytic material.
Example 2 is based on preparing cobalt-iron modified ZIF-8 composite material by urea method, adding the step of calcining in molten salt (1:1) nitrogen atmosphere.
Example 3:
the preparation method of the magnetic composite catalytic material of the embodiment comprises the following steps:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-methylimidazole (2-Meim) were dissolved in 64.5ml of methanol, respectively, and stirred for 3 minutes. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain the cobalt-iron modified ZIF-8 composite material.
Example 3 is a cobalt iron modified ZIF-8 composite material prepared by direct urea method, which is different from example 1 in the amount of methanol (Zn (NO 3 ) 2 ·6H 2 O: the molar ratio of methanol is changed from 1:350 to 1:300
Example 4
The preparation method of the magnetic composite catalytic material of the embodiment comprises the following steps:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally vacuum drying for 6 hours at 60 ℃ in a vacuum drying box to obtain powder II;
(6) And (3) weighing 0.35g of the powder II obtained in the step (5) and 0.525g of KCl, mixing and grinding, placing into a tube furnace for calcination (the temperature is 800 ℃, the calcination time is 2h, the heating rate is 5 ℃/min, and the nitrogen atmosphere), washing with deionized water for 3 times, and finally, drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the magnetic composite catalytic material.
Example 4 is based on urea method to prepare cobalt-iron modified ZIF-8 composite material, and adds the step of calcining in molten salt (1:1.5) nitrogen atmosphere.
Example 5
The preparation method of the magnetic composite catalytic material of the embodiment comprises the following steps:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally vacuum drying for 6 hours at 60 ℃ in a vacuum drying box to obtain powder II;
(6) Weighing 0.35g and 0.35g KNO of the powder II obtained in the step (5) 3 Mixing, grinding, calcining in a tube furnace (800 deg.C for 2 hr, heating at 5 deg.C/min, nitrogen atmosphere),and washing with deionized water for 3 times, and finally drying in vacuum at 60 ℃ for 24 hours in a vacuum drying oven to obtain the magnetic composite catalytic material.
Example 5 is based on the preparation of cobalt-iron modified ZIF-8 composite material by urea method, and KNO is added 3 And calcining the molten salt (1:1) in a nitrogen atmosphere.
Example 6:
the preparation method of the magnetic composite catalytic material of the embodiment comprises the following steps:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 5.2225g of 2-methylimidazole (2-Meim) were each dissolved in 75ml of methanol and stirred for 3 minutes. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally drying in a vacuum drying oven at 60 ℃ for 6 hours to obtain the cobalt-iron modified ZIF-8 composite material.
Example 6 is a direct urea process to prepare cobalt-iron modified ZIF-8 composite material, differing from example 1 in the amount of 2-methylimidazole (Zn (NO 3 ) 2 ·6H 2 O: the molar ratio of the 2-methylimidazole is changed from 1:8 to 1:6
Example 7
The preparation method of the magnetic composite catalytic material of the embodiment comprises the following steps:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally vacuum drying for 6 hours at 60 ℃ in a vacuum drying box to obtain powder II;
(6) And (3) weighing 0.35g of the powder II obtained in the step (5) and 0.35g of KCl, mixing and grinding, placing into a tube furnace for calcination (the temperature is 750 ℃, the calcination time is 2 hours, the heating rate is 5 ℃/min, and the nitrogen atmosphere), washing with deionized water for 3 times, and finally, drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the magnetic composite catalytic material.
Example 7 is based on the urea method for preparing the cobalt-iron modified ZIF-8 composite material, and adds the step of calcining in a molten salt (1:1) nitrogen atmosphere. The calcination temperature was different from that of example 2.
Comparative example 1:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, and ultrasonic stirring in a beaker (ultrasonic time of 10min, power of 60W, stirring time of 240min, and temperature of 25deg.C) to obtain milky suspensionCentrifuging the solution (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally, performing vacuum drying for 6 hours at 60 ℃ in a vacuum drying box to obtain powder II;
(6) And (3) weighing 0.35g of the powder II obtained in the step (5) and 0.7g of KCl, mixing and grinding, placing into a tube furnace for calcination (the temperature is 800 ℃, the calcination time is 2h, the heating rate is 5 ℃/min, and the nitrogen atmosphere), washing with deionized water for 3 times, and finally, drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the magnetic composite catalytic material.
Comparative example 1 increased the amount of potassium salt (KCl).
Comparative example 2:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for more than 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally, performing vacuum drying for 6 hours at 60 ℃ in a vacuum drying box to obtain powder II;
(6) And (3) weighing 0.35g of the powder II obtained in the step (5) and 0.35g of KCl, mixing and grinding, placing into a muffle furnace for calcination (the temperature is 800 ℃, the calcination time is 2h, the heating rate is 5 ℃/min, and the air atmosphere), washing with deionized water for 3 times, and finally, vacuum drying in a vacuum drying oven at 60 ℃ for 24 hours to obtain the magnetic composite catalytic material.
Comparative example 2 the calcination atmosphere was an air atmosphere.
Comparative example 3:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min.
(2) Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder ZIF-8;
comparative example 3 is pure ZIF-8.
Comparative example 4:
(1) 3.1542g of Zn (NO) 3 ) 2 ·6H 2 O and 6.9567g of 2-MeIm were dissolved in 75ml of methanol, respectively, and stirred for 3min. Mixing the two solutions, placing in a beaker, ultrasonically stirring (ultrasonic time is 10min, power is 60W, stirring time is 240min, and temperature is 25 ℃) to obtain milky suspension, centrifuging (4000 r/min), washing with methanol for 3 times, and drying to obtain white powder I;
(2) 0.8798g of Fe (NO) 3 ) 3 ·9H 2 O and 1.2676g of Co (NO 3 ) 2 ·6H 2 Dissolving O in 50ml of water, and continuously stirring for 3min to obtain a solution A;
(3) Weighing 1.3079g of urea, adding the urea into the solution A, and continuously stirring for 3min to obtain a solution B;
(4) Weighing 0.5g of the powder I obtained in the step (1), adding the powder I into the solution B, and ultrasonically stirring (the time is 10min, the power is 60W, and the temperature is 25 ℃) to obtain a solution C;
(5) Transferring the solution C in the step (4) into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 100 ℃, filtering and collecting precipitate by a vacuum pump, washing 3 times by using DIW/ethanol, and finally, performing vacuum drying for 6 hours at 60 ℃ in a vacuum drying box to obtain powder II;
(6) And (3) weighing 0.35g of the powder II obtained in the step (5), grinding, placing into a tube furnace for calcination (the temperature is 800 ℃, the calcination time is 2h, the heating rate is 5 ℃/min, and the nitrogen atmosphere), washing with deionized water for 3 times, and finally, drying in vacuum at 60 ℃ for 24 hours in a vacuum drying oven to obtain the magnetic composite catalytic material.
Comparative example 4 calcination in a nitrogen atmosphere without potassium salt
The performance of the cobalt-iron modified ZIF-8 composite material prepared in the embodiment is tested, and the performance test is specifically as follows: magnetic separation performance test of cobalt-iron modified ZIF-8 composite material: 0.05g of the samples prepared in examples 1 and 2 was weighed and placed in a transparent glass bottle filled with deionized water, the mixture was stirred by ultrasonic until the mixture was suspended, and after 15 seconds from the side of the glass bottle, the sample prepared in example 2 was separated from deionized water, the magnetic separation effect was shown in FIG. 5 (see FIG. 5 (b)), and the sample prepared in example 1 was not separated significantly (see FIG. 5 (a)). The sample is obviously separated from deionized water after 15s, and the comparison of the example 1 and the example 2 shows that the material prepared after the calcination of the fused salt has excellent magnetic property and is convenient for recycling after catalytic degradation.
Degradation and adsorption performance test of cobalt-iron modified ZIF-8 composite material: firstly, 50mL of norfloxacin solution with initial concentration of 20mg/L is added into a reaction tube, 0.025g of the magnetic composite catalyst prepared in each example is weighed and added into the 50mL of solution, and after continuous stirring for 30min, the adsorption rate of a sample on the norfloxacin solution is tested; then, 0.025g of Peroxomonosulfate (PMS) was added, and after a certain period of time (10 min, 30min and 60 min), the concentration of norfloxacin remaining in the solution was measured by an ultraviolet spectrophotometer, and the degradation rate (%) of the sample to the norfloxacin solution was calculated.
Table 1 adsorption and catalytic test results for each sample
1. According to the embodiment 1-5, the degradation rate of the composite material of the cobalt-iron modified ZIF-8 in the embodiment to norfloxacin solution for 60min is more than 95%, which indicates that the composite material of the cobalt-iron modified ZIF-8 prepared in the embodiment of the invention has excellent catalytic performance.
2. The degradation rate of the composite material pair norfloxacin solution can be well improved and the catalytic performance can be improved by using cobalt iron to modify ZIF-8 according to the degradation rate of the embodiment 1 and the comparison 3.
3. The degradation rate of the composite material of the cobalt-iron modified ZIF-8 on the norfloxacin solution is improved by adding potassium salt (KCl) according to the degradation rates of the example 2, the example 4 and the comparative example 4
4. The degradation rate of the potassium salt (KNO) is demonstrated by example 5 and comparative 4 3 ) The addition of the (2) can improve the degradation rate of the composite material of the cobalt-iron modified ZIF-8 on the norfloxacin solution
5. As demonstrated by the degradation rates of example 2 and comparative example 1, too high a potassium salt (KCl) content reduced the degradation rate of the cobalt iron modified ZIF-8 composite material to norfloxacin solution.
6. The degradation rate and the adsorption rate of the composite material of the material cobalt-iron modified ZIF-8 are proved by the degradation rate and the adsorption rate of the composite material of the example 2 and the comparative example 2, and the catalytic degradation and the adsorption performance of the composite material of the material cobalt-iron modified ZIF-8 can be obviously improved by calcining under the inert gas atmosphere.
Claims (10)
1. The cobalt-iron modified ZIF-8 composite material is characterized in that the cobalt-iron modified ZIF-8 composite material is prepared according to the following method:
dissolving ferric salt, cobalt salt and urea in water, adding ZIF-8, uniformly dispersing, performing hydrothermal reaction at 100-140 ℃ for 20-30 h, and performing post-treatment A on the obtained reaction solution to obtain a ZIF-8 composite material; the mass ratio of ZIF-8, ferric salt, cobalt salt and urea is 1:1.5 to 2: 2-3: 2 to 3;
grinding and mixing the ZIF-8 composite material and potassium salt, heating to 750-950 ℃ at a speed of 2-5 ℃/min under a protective atmosphere, calcining for 2-3 h, and carrying out post-treatment B on the obtained solid phase to obtain the cobalt-iron modified ZIF-8 composite material; the mass ratio of the ZIF-8 composite material to the potassium salt is 1:1-1.5.
2. The cobalt-iron modified ZIF-8 composite material of claim 1, wherein: the ferric salt is Fe (NO) 3 ) 3 ·9H 2 O, the cobalt salt is Co (NO) 3 ) 3 ·6H 2 O。
3. The cobalt-iron modified ZIF-8 composite material of claim 1, wherein: the proportion of the ferric salt to the water is 1g: 50-75 mL.
4. The cobalt-iron modified ZIF-8 composite material of claim 1, wherein the post-treatment a is: and (3) carrying out suction filtration on the reaction liquid, washing the obtained filter cake with deionized water and ethanol in sequence, and carrying out vacuum drying to obtain the ZIF-8 composite material.
5. The cobalt-iron modified ZIF-8 composite material of claim 1, wherein: the potassium salt is KCl and KNO 3 One or a mixture of both.
6. The cobalt-iron modified ZIF-8 composite material of claim 1, wherein: the protective atmosphere is nitrogen atmosphere or argon atmosphere.
7. The cobalt-iron modified ZIF-8 composite material of claim 6, wherein: the protective atmosphere is a nitrogen atmosphere.
8. The cobalt-iron modified ZIF-8 composite material of claim 1, wherein the post-treatment B is: and washing the solid phase with deionized water and drying to obtain the cobalt-iron modified ZIF-8 composite material.
9. The use of the cobalt-iron modified ZIF-8 composite material of claim 1 for treating wastewater containing organic pollutants.
10. The use according to claim 9, characterized in that the organic pollutant in the organic pollutant wastewater is one or a mixture of more than two of norfloxacin, tetracycline and bisphenol a; the application is as follows:
dispersing the cobalt-iron modified ZIF-8 composite material into organic pollutant wastewater, and adding persulfate to catalyze and degrade the organic pollutant.
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