CN110961159B - Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof - Google Patents
Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910017061 Fe Co Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 35
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 35
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 19
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 17
- 238000004043 dyeing Methods 0.000 claims description 13
- 238000007639 printing Methods 0.000 claims description 12
- 239000000356 contaminant Substances 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000004065 wastewater treatment Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 238000002835 absorbance Methods 0.000 description 13
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- 230000000694 effects Effects 0.000 description 10
- 230000003213 activating effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 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 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 3
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- 238000004064 recycling Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- -1 papermaking Substances 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
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- 238000007146 photocatalysis Methods 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
-
- 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
- C02F2101/345—Phenols
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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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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Abstract
The invention discloses a supported Fe-Co/ZIF-67 bimetallic catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding Co into ZIF-67 solution 2+ And Fe 3+ With a combined OH-containing radical ‑ The pH of the ZIF-67 solution is adjusted by the solution, the solid phase part obtained after the operation is collected after the reaction under the ultrasonic wave, and the Fe-Co/ZIF-67 bimetallic catalyst is obtained by calcining. The catalyst can be used for wastewater treatment under various pH values, the preparation method is simple, the prepared catalyst is high in catalytic efficiency, the applicable water quality treatment range is wide, and the catalyst is a novel high-efficiency catalyst material integrating high efficiency, economy, environmental protection and recyclability.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a supported Fe-Co/ZIF-67 bimetallic catalyst and a preparation method and application thereof.
Background
Along with the rapid development of industry, people's lives become more and more colorful, and industries such as textile, papermaking, leather making and the like have important significance for enriching the lives of people. However, printing and dyeing wastewater from textile, paper, leather, etc. industries also represents one of the major threats affecting natural ecological environment and human health. The printing and dyeing wastewater mainly comes from wastewater generated in the production processes of dyeing, printing and dyeing, finishing and the like of a printing and dyeing mill mainly processing cotton, wool, synthetic fibers and blended products thereof. The printing and dyeing wastewater has the characteristics of large water quantity, high organic pollutant content, complex components, high alkalinity, large water quality change and the like, and belongs to one of industrial wastewater difficult to treat. At present, the main pollutants in printing and dyeing are auxiliaries and residual dyes. Most of dye compounds in the dye wastewater are aromatic and heterocyclic compounds, have complex molecular structures, and have the properties of high stability and difficult biodegradation.
The persulfate oxidation technology is a new emerging technology for generating SO by activating persulfate 4 · - So as to remove the organic matters difficult to degrade in the water. SO (SO) 4 · - Mainly produced by activated Persulfate (PS), wherein the PS comprises Permonosulfate (PMS) and Peroxodisulfate (PDS), and the structures of the PS comprise O-O bonds, and the Persulfate advanced oxidation technology needs to excite the Persulfate to produce SO by virtue of the activation technology to exert strong oxidation property of the Persulfate 4 · - The commonly used activation methods mainly comprise a thermal activation method, a photoactivation method, a transition metal catalyst activation method and the like, and the development of a persulfate activator which is efficient and does not cause secondary pollution is still an important challenge in the field. The research shows that cobalt, copper, iron and manganese can be used as activators of persulfate. Compared with other transition metals, iron is low in toxicity, cheap and easy to obtain, but the Fenton system of iron has a narrow applicable pH (about 3) and can form a large amount of iron sludge, so that the application of the Fenton system in actual wastewater treatment is severely limited; cobalt element has multiple variable valence states and coordination environment, and the applicable pH range is wide, but the cobalt element is Co 2+ Co used and having biotoxicity 2+ The concentration is far higher than the discharge standard in water, and secondary pollution is easily caused, so that the iron and the cobalt can be combined by designing different structures or compositions to realize more efficient catalytic benefit.
In recent years, zeolite imidazole Framework materials (ZIFs) are taken as branches of Metal Organic Frameworks (MOFs), and have different zeolite-like topologies from other MOFs due to unique coordination modes, and the ZIFs has the characteristics of high crystallinity, large specific surface area, regular structure and the like of common MOFs, high thermal stability and high chemical stability of traditional zeolites, and has potential application values in many aspects such as gas storage and separation, chemical sensors, photocatalysis and the like, so that the ZIFs are concerned by researchers. The ZIF-67 material is a tetrahedron formed by cobalt ions and four imidazole organic ligands through nitrogen bridging, wherein nitrogen atoms are positioned at the center of the tetrahedron, and metal ions are positioned at the top points of the tetrahedron. The superiority of the ZIFs material in the aspect of catalysis inspires more researchers to explore the catalytic performance of the ZIFs composite material. However, ZIF-67 has one important drawback: the poor structural stability in water has made it extremely limited in the field of wastewater treatment.
In conclusion, the construction of the efficient and stable multiphase Fenton-like catalyst has important significance for wastewater treatment, especially printing and dyeing wastewater treatment.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method of the multi-metal catalyst, which can prepare an efficient and stable catalyst.
The invention also provides a catalyst prepared by the method.
The invention also provides the application of the catalyst.
The preparation method according to the embodiment of the first aspect of the invention comprises the following steps:
s1, taking the ZIF-67 solution, and adding the solution into the ZIF-67 solutionAdding Co therein 2+ And Fe 3+ With a combined OH content - Adjusting the pH value of the ZIF-67 solution to 9.5-11.5, and carrying out ultrasonic reaction (preferably, the ultrasonic power is 80-90W) for 1.5-3.5 h;
s2, collecting the solid phase part obtained after the operation, and calcining to obtain a Fe-Co/ZIF-67 bimetallic catalyst;
wherein, in the step S1, co 2+ And Fe 3+ The molar ratio of (1-3) to (1-3).
According to some embodiments of the present invention, the Fe-Co mass fraction of the Fe-Co/ZIF-67 bimetallic catalyst is between (5-15)%.
According to some embodiments of the invention, the calcination in step S2 is performed at (450 to 550) deg.c for (3.5 to 5.5) h in an air atmosphere.
According to some embodiments of the invention, the method further comprises a ZIF-67 preparation step, as follows: mixing 2-methylimidazole and cobalt salt, and reacting to prepare a ZIF-67 material; wherein the molar ratio of the 2-methylimidazole to the cobalt salt is (9-10); preferably 9.6.
According to some embodiments of the present invention, the preparing step of ZIF-67 further comprises filtering, washing, drying, grinding the reacted product, and collecting the product as ZIF-67 material.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects: the invention can prepare the bimetallic catalyst with good catalytic performance and high recycling performance by a simple water phase synthesis method; in the method, the ZIF-67 is taken as a template, iron and cobalt are loaded on the ZIF-67 in a coprecipitation mode, and a magnetic Fe-Co/ZIF-67 bimetallic catalyst is obtained by calcination; the catalyst of the invention has simple reaction process and easy operation, and the obtained catalyst has good magnetism, high recycling rate, no secondary pollution and good industrial application prospect.
The supported Fe-Co/ZIF-67 bimetallic catalyst according to the second aspect of the embodiment of the invention is prepared by the above method.
The catalyst provided by the embodiment of the invention has at least the following beneficial effects: the catalyst fully utilizes the characteristics of large specific surface area of ZIF-67, wide application range of pH of Co, low toxicity of Fe, high-efficiency catalytic activity and the like, has wide applicability to wastewater quality, good catalytic performance and high recycling performance, and has good magnetism and easy separation and recovery.
According to an embodiment of the third aspect of the present invention, the use of the above catalyst for the preparation of an organic contaminant degradation catalyst.
According to some embodiments of the invention, the organic contaminants comprise dye-based organic contaminants.
According to some embodiments of the invention, the organic contaminant comprises at least one of methylene blue or rhodamine B.
The application of the embodiment of the invention has at least the following beneficial effects: the catalyst provided by the scheme of the invention has a good degradation effect on organic pollutants, particularly has a good adsorption degradation effect on colored substances and refractory substances in wastewater, and the catalyst after the action is easy to separate, recycle and utilize.
A treatment method of printing and dyeing wastewater comprises the following steps: the catalyst and persulfate are added into the printing and dyeing wastewater.
According to some embodiments of the invention, the persulfate is sodium persulfate.
According to some embodiments of the invention, the catalyst is added in an amount of not less than 0.5g/L, preferably the amount of catalyst added is (1-1.5) g/L.
According to some embodiments of the invention, the persulfate is added in an amount of not less than 8mmol/L, preferably in an amount of 12mmol/L.
According to some embodiments of the invention, the concentration of the organic contaminant is no greater than 30mg/L.
According to some embodiments of the present invention, the treatment method further comprises a step of recovering the catalyst after the treatment of the printing and dyeing wastewater by adsorption with a magnet.
According to the water treatment method provided by the embodiment of the invention, at least the following beneficial effects exist: the catalyst has high catalytic efficiency, is suitable for wide water quality treatment range, and is a novel high-efficiency catalyst material integrating high efficiency, economy, environmental protection and recyclability.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an XRD pattern of a ZIF-67 precursor material and an Fe-Co/ZIF-67 bimetallic catalyst prepared in example 1 of the present invention;
FIG. 2 is a SEM image of ZIF-67 precursor material prepared in example 1 of the present invention at different magnifications;
FIG. 3 is SEM images of different magnifications of Fe-Co/ZIF-67 bimetallic catalyst prepared in example 1 of the present invention;
FIG. 4 is an electron micrograph of a Fe-Co/ZIF-67 bimetallic catalyst prepared in example 1 of the present invention;
FIG. 5 is a graph showing the relationship between concentration and absorbance of a methylene blue solution in example 2 of the present invention.
Detailed Description
In order to explain the technical contents, the objects and the effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
The first embodiment of the invention is as follows: a preparation method of a supported Fe-Co/ZIF-67 bimetallic catalyst comprises the following steps:
1. 3.94g of 2-methylimidazole and 1.50g of cobalt acetate are weighed, respectively dissolved in 20mL of distilled water, then the two solutions are mixed, magnetically stirred at room temperature for 120min (the stirring speed can be 120-130 r/min, in the embodiment, 125 r/min), kept stand for 10min, filtered by a vacuum pump, a solvent filter (an organic filter membrane with the pore diameter of 0.45 mu m is used as the filter), washed by distilled water and ethanol for 3 times respectively, the obtained materials are collected, and placed in an oven to be set at 60 ℃ for vacuum drying for 12h.
2. Dissolving 0.900g of the prepared ZIF-67 material in 20ml of distilled water, respectively dissolving 0.4735g of ferric nitrate nonahydrate and 0.1706g of cobalt nitrate hexahydrate in 10ml of distilled water, mixing the two solutions with the ZIF-67 solution, adding 1.0mol/L NaOH solution, and adjusting the pH value of the solution to 10. After the solution is stirred uniformly, the solution is placed in an ultrasonic cleaning instrument for ultrasonic treatment (the ultrasonic power is 85W) for 2 hours. After the completion of the ultrasonication, the solution was allowed to stand for 10min, and suction filtration was carried out with a vacuum pump, the filter was a solvent filter (using an organic filter membrane having a pore size of 0.45 μm), and the solution was washed 3 times with distilled water and ethanol, respectively, and the obtained material was collected and placed in an oven and vacuum-dried at 120 ℃ for 12 hours. The obtained Fe-Co/ZIF-67 material is calcined for 4 hours at 500 ℃ in the air atmosphere to obtain a black-purple powdery sample, namely the magnetic Fe-Co/ZIF-67 bimetallic catalyst. The molar ratio of Fe to Co in the catalyst is 2.
The ZIF-67 precursor material prepared by the above operations and the Fe-Co/ZIF-67 bimetallic catalyst were subjected to characterization by X-Ray Diffractometer (XRD), and the results are shown in FIG. 1. The upper curve in FIG. 1 is the XRD curve of the ZIF-67 precursor material, and the lower curve is the XRD curve of the Fe-Co/ZIF-67 bimetallic catalyst, and it can be seen from the XRD curve that the zeolite imidazolate framework structure of ZIF-67 is destroyed in the process of loading Fe and Co bimetallic, and the Fe and Co metals are mainly Fe 3 O 4 And Co 3 O 4 Is supported on ZIF-67.
The morphology of the ZIF-67 precursor material prepared by the above operation and the Fe-Co/ZIF-67 bimetallic catalyst are characterized by a Scanning Electron Microscope (SEM), and the species and content of the component elements in the micro-area of the material are analyzed, and the results are shown in FIGS. 2-4, wherein FIG. 2 is a morphology diagram of the ZIF-67 precursor material under different magnifications; FIG. 3 is a topographical view of a Fe-Co/ZIF-67 bimetallic catalyst at different magnifications; FIG. 4 is an electron micrograph of the Fe-Co/ZIF-67 bimetallic catalyst. As can be seen from FIGS. 2 and 3, during the calcination of the catalyst, the carbon skeleton of ZIF-67 collapsed and was recessed, resulting in a Fe-Co/ZIF-67 bimetallic catalyst with relatively uniform plasmids.
The second embodiment of the invention is as follows: preparation of bimetallic catalysts of different moles: by changing the taken mass of the ferric nitrate nonahydrate and the cobalt nitrate hexahydrate according to the procedure in the above example 1, a Fe-Co/ZIF-67 bimetallic catalyst with a molar ratio of Fe to Co of 1, 2,1, 3, 2.
In order to verify the influence of the molar ratio on the performance of the catalyst, the catalysts prepared by the operations are respectively used for treating methylene blue wastewater, and the specific operations are as follows:
(1) Preparing 20mg/L methylene blue solution, and adding 200mL of the solution into a 500mL beaker;
(2) Adding 200mg of Fe-Co/ZIF-67 bimetallic catalyst into the solution obtained in the step (1) to obtain a mixed solution;
(3) Adding sodium persulfate (Na) with the concentration of 8mmol/L into the mixed solution in the step (2) 2 S 2 O 8 ) A solution;
(4) And (4) stirring the solution in the step (3) properly to fully mix the mixed solution, and carrying out reaction for 120min under the normal-temperature ultrasonic condition.
(5) After the reaction is finished, the catalyst is adsorbed by a magnet, and the supernatant is the treated effluent. The effluent was centrifuged appropriately and the absorbance measured.
Taking a methylene blue standard substance to prepare methylene blue standard solutions with different concentrations, measuring the absorbance of the methylene blue standard solutions, marking corresponding absorbance-concentration coordinate points in a coordinate system, and fitting each point to obtain a standard curve, wherein the result is shown in fig. 5. As can be seen from fig. 5, c =4.4197Abs-0.01705, and R of the curve 2 >0.999, therefore, the concentration and the absorbance have good linear relation, and the concentration value can be accurately calculated according to the equation. Converting the absorbance measured by the operation into a concentration value, and calculating the degradation efficiency of each catalyst according to a degradation efficiency formula of the methyl blue solution:
η＝[(C 0 －C t )/C 0 ]×100％
in the formula: c t The concentration of the methylene blue solution determined during sampling; c 0 The initial concentration of methylene blue solution.
The results of the efficiency of various catalysts at room temperature (25 ℃) to activate persulfate to degrade methylene blue solution are shown in table 1 below:
TABLE 1 Effect of various catalysts activating persulfate at room temperature to degrade methylene blue
As can be seen from the above table, the catalyst prepared by the above operations has a degradation efficiency of 80% or more, wherein the effect is best when the molar ratio of Fe and Co is 2.
Comparative example 1 of the present invention is: the preparation method of the Fe/ZIF-67 composite material is different from the preparation method of the example 1 only in that: in step 2, no cobalt nitrate hexahydrate solution was added to the ZIF-67 material solution.
Comparative example 2 of the present invention is: the preparation method of the Co/ZIF-67 composite material is only different from the preparation method of the example 1 in that: in step 2, no iron nitrate solution was added to the ZIF-67 material solution.
The composite materials prepared in example 1 and comparative examples 1 and 2 were treated under the same conditions (see the wastewater treatment procedure in example 2) to evaluate the catalytic performance, and the degradation effect of each material on the degradation of methylene blue by activated persulfate was calculated, and the results are shown in table 2 below:
TABLE 2 Effect of different composite Metal catalysts activating persulfate to degrade methylene blue
As can be seen from Table 2, the catalyst degradation efficiency of the example 1 of the invention is improved by more than 8.6% compared with that of the comparative example 1; the improvement is more than 14.5 percent compared with the comparative example 2. In Table 2, the mass of both Fe and Co was 0.05g, 0.3617g in terms of the mass of Fe salt and 0.2492g in terms of the mass of Co salt. In the preparation process of the catalyst, 0.9g of ZIF-67 is used as a carrier, and 0.1g of total metal content is used as an active component, so that when a single-metal catalyst is used as a control group, the mass of the metals Fe and Co is 0.05g; (calculated as Fe salt mass =403.9972 (relative molecular mass of iron nitrate nonahydrate) × 0.05 ÷ 55.845 (relative atomic mass of iron) =0.3617g co salt mass is equal to =291.03 (relative molecular mass of cobalt nitrate hexahydrate) × 0.05 ÷ 58.393 (relative atomic mass of cobalt) =0.2492 g).
The embodiment 3 of the invention is the application of the Fe-Co/ZIF-67 bimetallic catalyst, and the application conditions of the catalyst are verified through different experiments:
A. optimum pH environment for activating persulfate
The treatment of methylene blue wastewater with the Fe-Co/ZIF-67 bimetallic catalyst prepared in example 1 with a molar ratio of 2, comprises the following steps:
(1) Preparing 20mg/L methylene blue solution, and adding 200mL of the solution into a 500mL beaker;
(2) Adding 200mg of Fe-Co/ZIF-67 bimetallic catalyst into the solution obtained in the step (1) to obtain a mixed solution;
(3) Adding sodium persulfate (Na) with over concentration of 8mmol/L into the mixed solution in the step (2) 2 S 2 O 8 ) A solution;
(4) Preparing 1.0mol/L NaOH solution, and respectively adjusting the initial pH of the solution in the step (3) to be 4, 7 and 10.
(5) And (5) stirring the solution obtained in the step (4) properly to fully mix the mixed solution, and reacting for 120min under the normal-temperature ultrasonic condition.
(6) After the reaction is finished, the catalyst is adsorbed by a magnet, and the supernatant is the treated effluent. The effluent was centrifuged appropriately and the absorbance measured.
And converting the absorbance of the solution measured by the experiment into a concentration index. According to the method of example 2, the optimum pH condition for degrading methylene blue by activating persulfate through Fe-Co/ZIF-67 bimetallic catalyst is evaluated, and the results are shown in the following table 3:
TABLE 3 optimum pH environment for Fe-Co/ZIF-67 bimetallic catalyst activated persulfate
As can be seen from the above table, the catalytic activity did not differ greatly under different pH conditions, with pH 4 being the most preferred.
B. Optimum concentration of persulfate
The treatment of methylene blue wastewater with the Fe-Co/ZIF-67 bimetallic catalyst prepared in example 1 with a molar ratio of 2, comprises the following steps:
(1) Preparing 20mg/L methylene blue solution, and adding 200mL of the solution into a 500mL beaker;
(2) Adding 200mg of Fe-Co/ZIF-67 bimetallic catalyst into the solution obtained in the step (1) to obtain a mixed solution;
(3) 4 parts of the mixed solution obtained in the step (2) are respectively added with sodium persulfate (Na) with the concentration of 6, 8, 10 and 12mmol/L 2 S 2 O 8 ) A solution;
(4) Preparing 1.0mol/L NaOH solution, and adjusting the initial pH of the solution in the step (3) to be 4.
(5) And (4) stirring the solution in the step (4) properly to fully mix the mixed solution, and carrying out reaction for 120min under the normal-temperature ultrasonic condition.
(6) After the reaction is finished, the catalyst is adsorbed by a magnet, and the supernatant is the treated effluent. The effluent was centrifuged appropriately and the absorbance measured.
And converting the absorbance of the solution measured by the experiment into a concentration index. According to the method of example 2, the optimum condition for adding the oxidant persulfate to degrade methylene blue by activating the persulfate through the Fe-Co/ZIF-67 bimetallic catalyst is evaluated, and the results are shown in the following table 4:
TABLE 4 optimum amount of oxidant for Fe-Co/ZIF-67 bimetallic catalyst for activating persulfate
| Na 2 S 2 O 8 Concentration of solution (mmol/L) | Concentration of stock solution (mg/L) | Concentration after treatment (mg/L) | Efficiency of degradation (%) |
| 6 | 20 | 5.2886 | 73.56 |
| 8 | 20 | 2.900 | 85.50 |
| 10 | 20 | 1.423 | 92.89 |
| 12 | 20 | 0.5295 | 97.35 |
As can be seen from the above table, na 2 S 2 O 8 The concentration of (b) is preferably 8mol/L or more; preferably 12mol/L.
C. Optimum catalyst reaction dosage
The treatment of methylene blue wastewater with the Fe-Co/ZIF-67 bimetallic catalyst prepared in example 1 with a molar ratio of 2, comprises the following steps:
(1) Preparing 20mg/L methylene blue solution, and adding 200mL of the solution into a 500mL beaker;
(2) Respectively taking 4 parts of the solution in the step (1), and respectively adding 0.25, 0.5, 1.0 and 1.50g/L Fe-Co/ZIF-67 bimetallic catalyst into the solution in the step (1) to obtain a mixed solution;
(3) To the mixed solution in the step (2), 12mmol/L of sodium persulfate (Na) was added 2 S 2 O 8 ) A solution;
(4) Preparing 1.0mol/L NaOH solution, and adjusting the initial pH of the solution in the step (3) to be 4.
(5) And (4) stirring the solution in the step (4) properly to fully mix the mixed solution, and carrying out reaction for 120min under the normal-temperature ultrasonic condition.
(6) After the reaction is finished, the catalyst is adsorbed by a magnet, and the supernatant is the treated effluent. The effluent was centrifuged appropriately and the absorbance measured.
And converting the absorbance of the solution measured by the experiment into a concentration index. The optimum dosage conditions for the Fe-Co/ZIF-67 bimetallic catalyst activated persulfate degradation methylene blue catalyst were evaluated according to the method of example 2, and the results are shown in Table 5 below:
TABLE 5 optimum dosage of Fe-Co/ZIF-67 bimetallic catalyst activated persulfate
| Dosage (g/L) of Fe-Co/ZIF-67 | Concentration of stock solution (mg/L) | Concentration after treatment (mg/L) | Efficiency of degradation (%) |
| 0.25 | 20 | 4.0228 | 79.87 |
| 0.50 | 20 | 3.5455 | 82.27 |
| 1.00 | 20 | 1.5650 | 92.17 |
| 1.50 | 20 | 0.8575 | 95.71 |
As can be seen from the above table, the amount of the catalyst to be added is preferably not less than 0.50 g/L; preferably 1.50g/L.
D. Concentration of methylene blue
The treatment of methylene blue wastewater with the Fe-Co/ZIF-67 bimetallic catalyst prepared in example 1 with a molar ratio of 2, comprises the following steps:
(1) Preparing 5, 10, 15, 20 and 30mg/L methylene blue solution respectively, adding 200mL of the solution into a 500mL beaker to obtain 5 parts of methylene blue solution with different concentrations;
(2) Taking the solution in the step (1), and respectively adding 200mg of Fe-Co/ZIF-67 bimetallic catalyst into the solution in the step (1) to obtain a mixed solution;
(3) To the mixed solution in step (2) was added 12mmol/L sodium persulfate (Na) 2 S 2 O 8 ) A solution;
(4) Preparing 1.0mol/L NaOH solution, and adjusting the initial pH of the solution in the step (3) to be 4.
(5) And (4) stirring the solution in the step (4) properly to fully mix the mixed solution, and carrying out reaction for 120min under the normal-temperature ultrasonic condition.
(6) After the reaction is finished, the catalyst is adsorbed by a magnet, and the supernatant is the treated effluent. The effluent was centrifuged appropriately and the absorbance measured.
And converting the absorbance of the solution measured by the experiment into a concentration index. The Fe-Co/ZIF-67 bimetallic catalyst was evaluated for the degradation of methylene blue at various concentrations by activating persulfate according to the method of example 2. The results are shown in Table 6 below.
TABLE 6 degradation Effect of methylene blue at different concentrations
| Concentration of methylene blue solution (mg/L) | Concentration of stock solution (mg/L) | Concentration after treatment (mg/L) | Degradation efficiency (%) |
| 5 | 5 | 0.005 | 99.90 |
| 10 | 10 | 0.0492 | 99.51 |
| 15 | 15 | 0.0879 | 99.41 |
| 20 | 20 | 0.5295 | 97.35 |
| 30 | 30 | 2.1584 | 92.81 |
As can be seen from the table above, the catalyst of the embodiment of the invention has better degradation effect on methylene blue of 5-30 mg/L.
The precursor ZIF-67 of the Fe-Co/ZIF-67 has simple and convenient preparation conditions, and can be obtained by reaction under the condition of normal temperature. In addition, the target bimetallic catalyst Fe-Co/ZIF-67 can be obtained by high-temperature calcination at 500 ℃ in the air atmosphere, no other byproducts are generated, and the material has good economic and utilization benefits in preparation. The results shown in Table 1 show that Fe-Co/ZIF-67 shows better catalytic activity when the molar ratio of Fe to Co is 2. Meanwhile, as shown in tables 2 to 6, the Fe-Co/ZIF-67 bimetallic catalyst shows better catalytic performance in the reactions of various environmental factors such as pH, the addition amount of oxidant persulfate, the addition amount of the catalyst, the concentration of methylene blue and the like. Under the acidic, neutral and alkaline pH conditions, the Fe-Co/ZIF-67 bimetallic catalyst has the degradation effect of activating persulfate to degrade methylene blue of over 94 percent, when the addition amount of the persulfate is 12mmol/L, the catalyst can activate more sulfuric acid free radicals to degrade the methylene blue, meanwhile, the oxidizing property of the sulfuric acid free radicals activated by the catalyst is extremely strong, and the degradation efficiency of over 92 percent in the reaction process of 5-30 mg/L methylene blue solution. By combining the results of the above examples, the magnetic Fe-Co/ZIF-67 bimetallic catalyst can be used as an efficient metal catalyst to be applied to the wider field of wastewater treatment.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention and the contents of the accompanying drawings, which are directly or indirectly applied to the related technical fields, are included in the scope of the present invention.
Claims (11)
1. A preparation method of a supported Fe-Co/ZIF-67 bimetallic catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, taking a ZIF-67 solution, and adding Co into the ZIF-67 solution 2+ And Fe 3+ With a combined OH content - The pH value of the ZIF-67 solution is adjusted to 9.5-11.5, and ultrasonic reaction is carried out for 1.5-3.5 h;
s2, collecting the solid phase part obtained after the operation, and calcining to obtain a Fe-Co/ZIF-67 bimetallic catalyst;
wherein, in the step S1, co 2+ And Fe 3+ 1;
the method also comprises a ZIF-67 preparation step, which comprises the following steps: mixing 2-methylimidazole and cobalt salt, and reacting to prepare a ZIF-67 material;
wherein the molar ratio of the 2-methylimidazole to the cobalt salt is (9-10): 1.
2. the preparation method of the supported Fe-Co/ZIF-67 bimetallic catalyst of claim 1, characterized in that: the mass fraction of Fe-Co in the Fe-Co/ZIF-67 bimetallic catalyst is between 5 and 15 percent.
3. The preparation method of the supported Fe-Co/ZIF-67 bimetallic catalyst of claim 1, characterized in that: the calcination operation in the step S2 is calcination at (450-550) DEG C for (3.5-5.5) h in an air atmosphere.
4. A load type Fe-Co/ZIF-67 bimetallic catalyst is characterized in that: the catalyst is prepared by the method as claimed in any one of claims 1 to 3.
5. Use of the catalyst of claim 4 in the preparation of an organic contaminant degradation catalyst.
6. Use according to claim 5, characterized in that: the organic contaminants include at least one of methylene blue or rhodamine B.
7. A treatment method of printing and dyeing wastewater is characterized by comprising the following steps: the method comprises the following steps: the catalyst according to claim 4 and persulfate are added to the printing and dyeing wastewater.
8. The processing method according to claim 7, characterized in that: the adding amount of the catalyst is not less than 0.5g/L.
9. The processing method according to claim 8, characterized in that: the addition amount of the catalyst is (1-1.5) g/L.
10. The processing method according to claim 7, characterized in that: the adding amount of the persulfate is not less than 8mmol/L.
11. The processing method according to claim 10, characterized in that: the persulfate addition amount is 12mmol/L.
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