CN117563623A - Preparation method and application of copper-manganese composite ferrite microwave catalyst capable of forming oxygen vacancies - Google Patents
Preparation method and application of copper-manganese composite ferrite microwave catalyst capable of forming oxygen vacancies Download PDFInfo
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- CN117563623A CN117563623A CN202311415099.7A CN202311415099A CN117563623A CN 117563623 A CN117563623 A CN 117563623A CN 202311415099 A CN202311415099 A CN 202311415099A CN 117563623 A CN117563623 A CN 117563623A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 17
- 239000001301 oxygen Substances 0.000 title abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000011572 manganese Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 27
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 15
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000011565 manganese chloride Substances 0.000 claims abstract description 15
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 15
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229960003280 cupric chloride Drugs 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229940032296 ferric chloride Drugs 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000004098 Tetracycline Substances 0.000 description 19
- 235000019364 tetracycline Nutrition 0.000 description 19
- 150000003522 tetracyclines Chemical class 0.000 description 19
- 229960002180 tetracycline Drugs 0.000 description 17
- 229930101283 tetracycline Natural products 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000975 co-precipitation Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000036962 time dependent Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- PMATZTZNYRCHOR-CGLBZJNRSA-N Cyclosporin A Chemical compound CC[C@@H]1NC(=O)[C@H]([C@H](O)[C@H](C)C\C=C\C)N(C)C(=O)[C@H](C(C)C)N(C)C(=O)[C@H](CC(C)C)N(C)C(=O)[C@H](CC(C)C)N(C)C(=O)[C@@H](C)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)N(C)C(=O)[C@H](C(C)C)NC(=O)[C@H](CC(C)C)N(C)C(=O)CN(C)C1=O PMATZTZNYRCHOR-CGLBZJNRSA-N 0.000 description 1
- 229930105110 Cyclosporin A Natural products 0.000 description 1
- 108010036949 Cyclosporine Proteins 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229960001265 ciclosporin Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229930182912 cyclosporin Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
-
- 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
-
- 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
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the field of microwave catalysis, and particularly relates to a preparation method and application of a copper-manganese composite ferrite microwave catalyst capable of forming oxygen vacancies. The preparation method of the catalyst comprises the following steps: (1) Adding ferric chloride, cupric chloride and manganese chloride into deionized water to obtain a precursor aqueous solution, adding urea, and stirring; (2) Dropwise adding a sodium hydroxide aqueous solution into the precursor aqueous solution obtained in the step (1), stirring, adjusting the pH value to 11-12 to obtain a suspension, and continuously stirring; (3) Carrying out suction filtration, washing and drying treatment on the suspension obtained in the step (2) to obtain a solid substance; (4) Grinding and sintering the solid substance obtained in the step (3) to obtain the copper-manganese composite ferrite microwave catalyst. The preparation method has the advantages of simple process flow, short process time, high safety and better microwave catalytic activity and stability than that of single manganese ferrite and copper ferrite.
Description
Technical Field
The invention belongs to the technical field of microwave catalysis, and particularly relates to a preparation method and application of a copper-manganese composite ferrite microwave catalyst capable of forming oxygen vacancies.
Background
The residue of antibiotics in the water environment not only can pollute the water, but also can cause microbial drug resistance, thereby destroying the natural ecosystem and even threatening the health of human beings. Therefore, measures are urgently needed to cope with antibiotic residues in water bodies. Among various technologies, the microwave catalytic technology has the advantages of short reaction time and high efficiency. The ferrite can strongly absorb microwaves under the radiation of the microwaves, generates hot spots on the surface to oxidize and decompose pollutants, can generate various active groups under the thermal action of the microwaves, can keep good stability, and becomes a research hot spot in the field of microwave catalysis. MnFe with tetrahedral and octahedral structure 2 O 4 Shows good microwave catalytic activity. MnFe in aqueous solution under microwave radiation 2 O 4 Can absorb microwave energy and create a number of "hot spots" on the surface where organic contaminants adhering to the "hot spots" can be oxidized and decomposed. However, single ferrite as a catalyst material tends to have certain limitations such as easy agglomeration, poor dispersibility, small specific surface area, and the like.
One of the methods of improving the activity of a single ferrite catalyst is multicomponent complexing or doping, one of which is the formation of oxygen vacancies that can promote the production of active species. Patent CN202110160476.1 discloses a method for preparing a cobalt ferrite photocatalyst containing oxygen vacancies, which shows good photocatalytic activitySex. Improving MnFe 2 O 4 The study of microwave catalytic technology to form oxygen vacancies has not been reported. At present, common preparation methods of ferrite include a hydrothermal method, a solvothermal method, a microwave-assisted hydrothermal method, a sol-gel method, a microemulsion method, a coprecipitation method and the like. The different preparation methods have a significant effect on the catalytic performance of ferrite. Patent CN202310806573.2 discloses a preparation method of lanthanum ferrite photocatalytic material, which adopts a hydrothermal method, wherein nitrate is selected as metal salt, the hydrothermal reaction time is 18-22h, and the service life is long; patent CN201810042672.7 discloses a preparation method of a manganese ferrite magnetic nano rod, which is to obtain precursor gel by igniting and burning precursor solution, and then calcine the precursor gel to obtain the manganese ferrite magnetic nano rod, wherein the preparation process is complex and the safety coefficient is low.
Disclosure of Invention
The invention aims at a preparation method and application of a copper-manganese composite ferrite microwave catalyst which can form oxygen vacancies and has good and stable catalytic activity. The invention replaces the traditional hydrothermal method with the high-efficiency and rapid coprecipitation method to prepare the copper-manganese composite ferrite microwave catalyst containing oxygen vacancies, so as to solve the problems of long catalyst synthesis time, low safety coefficient, high economic cost and the like in the preparation method in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a copper-manganese composite ferrite microwave catalyst, which comprises the following steps:
(1) Adding ferric chloride, cupric chloride and manganese chloride into deionized water according to a certain proportion to obtain a precursor aqueous solution, adding urea, and stirring, wherein the concentration of ferric chloride in the precursor aqueous solution is 0.02-0.1mol/L, the concentration of cupric chloride is 0.0025-0.0375mol/L, the concentration of manganese chloride is 0.0025-0.0375mol/L, and the concentration of urea is 0.1-0.4mol/L;
(2) Dropwise adding a sodium hydroxide aqueous solution into the precursor aqueous solution obtained in the step (1), stirring, adjusting the pH value to 11-12 to obtain a suspension, and continuously stirring;
(3) Carrying out suction filtration, washing and drying treatment on the suspension obtained in the step (2) to obtain a solid substance;
(4) Grinding and sintering the solid substance obtained in the step (3) to obtain the copper-manganese composite ferrite microwave catalyst.
In the above technical solution, in step (1), the stirring time is 30min.
In the above technical scheme, in step (1), the ferric chloride, cupric chloride and manganese chloride are FeCl respectively 3 ·6H 2 O、CuCl 2 ·2H 2 O、MnCl 2 ·4H 2 O。
In the above technical scheme, in step (1), further, in the precursor aqueous solution, the molar ratio of ferric chloride to urea is 4:1-15.
In the above technical scheme, in step (2), the concentration of the aqueous sodium hydroxide solution is 0.1-1mol/L.
In the above technical scheme, in step (2), the stirring time is 30min.
In the above technical scheme, in step (3), the temperature of the drying treatment is 60-90 ℃.
In the above technical scheme, in step (4), the sintering temperature is 300-550 ℃, and the sintering time is 0.5-2h.
The invention also provides a copper-manganese composite ferrite microwave catalyst prepared by the preparation method, wherein the molar ratio of iron to copper to manganese in the catalyst is 4:0.5:1.5-4:1.5:0.5.
The invention also provides an application of the copper-manganese composite ferrite microwave catalyst in degradation of organic matters in wastewater.
The beneficial effects of the invention are as follows:
1. the invention is realized by combining Cu 2+ Doped into MnFe 2 O 4 ，Cu 2+ Can be doped into MnFe due to smaller ionic radius 2 O 4 Lattice influencing the distribution of ferrite tetrahedral and octahedral cations, mnFe 2 O 4 The spinel structure does not containThe metal with the same ionic radius can cause defects and distortion so as to introduce oxygen vacancies, wherein the oxygen vacancies can activate lattice oxygen to participate in catalytic reaction, can adsorb and degrade organic pollutants so as to improve catalytic activity, are beneficial to the formation of active oxygen and are doped with Cu 2+ MnFe of (2) 2 O 4 Has stable chemical property.
2. The catalyst provided by the invention can be used for degrading organic matters in wastewater under the induction of microwaves, no additional reagent such as hydrogen peroxide, persulfate and other oxidants are needed in the wastewater, and the catalyst has good stability.
3. The microwave catalyst prepared by the invention is Cu under microwave radiation 2+ 、Mn 2+ 、Fe 3+ The organic wastewater is effectively degraded under the synergistic effect, and the degradation rate of the tetracycline can reach 96.14% in 6min under the microwave radiation.
4. The preparation method has the advantages of simple operation, short process time, high safety and low cost.
Drawings
FIG. 1 is an XRD pattern of a copper-manganese composite ferrite microwave catalyst prepared in example 1;
FIG. 2 is an SEM image of the copper-manganese composite ferrite microwave catalyst prepared in example 1;
FIG. 3 is an XPS diagram of the copper-manganese composite ferrite microwave catalyst prepared in example 1, wherein a is a full spectrum, b is an XPS measurement spectrum of Cu, c is an XPS measurement spectrum of Fe, d is an XPS measurement spectrum of Mn, and e is an XPS measurement spectrum of O;
FIG. 4 is a comparison of the activities of the different metal element composite ferrite microwave catalysts prepared in example 1 and comparative examples 1-4 for microwave catalytic degradation of tetracycline;
FIG. 5 is a comparison of the activity of the catalysts prepared in example 1, comparative examples 5-8 for microwave catalytic degradation of tetracyclines;
FIG. 6 shows the activity of the catalyst prepared in example 1 to catalyze the degradation of tetracycline after repeated use;
FIG. 7 is a comparison of the activity of the catalysts prepared in example 1 and comparative examples 9-10 for microwave-catalyzed degradation of tetracyclines.
Detailed Description
The following detailed description of the embodiments of the present invention will provide for the implementation of the present invention, but it should be apparent that the embodiments described are merely some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, all materials used in the examples of the present invention were commercially available or prepared according to conventional methods well known to those skilled in the art.
Example 1
(1) Adopting a coprecipitation method, firstly dissolving 1.0812g of ferric chloride, 0.17048g of copper chloride, 0.19791g of manganese chloride and 0.9g of urea in 100mL of deionized water to obtain a precursor aqueous solution containing 0.04mol/L of ferric chloride, 0.01mol/L of copper chloride, 0.01mol/L of manganese chloride and 0.15mol/L of urea;
(2) Dropwise adding 1mol/L sodium hydroxide solution into the precursor aqueous solution, adjusting the pH value to 11-12, and stirring for 30min to obtain a suspension;
(3) Filtering the obtained suspension, washing with deionized water and absolute ethyl alcohol for several times, and drying in a 60 ℃ oven for 8 hours to obtain a solid substance;
(4) Calcining the obtained solid substance in a muffle furnace at 450 ℃ for 1h to obtain the copper-manganese composite ferrite microwave catalyst with the molar ratio of Fe, cu and Mn of 4:1:1, wherein the catalyst is expressed as Cu 0.5 Mn 0.5 Fe 2 O 4 。
FIG. 1 shows a microwave catalyst Cu obtained in example 1 0.5 Mn 0.5 Fe 2 O 4 As can be seen from FIG. 1, the obtained product is Cu-Mn bi-metal composite ferrite CuFe 2 O 4 And MnFe 2 O 4 The diffraction peaks of (2) correspond to JCPDS 77-0010 and JCPDS 73-1964 respectively, no other impurity peak is found, and the diffraction peaks are sharp to prove that the crystallinity of the prepared catalyst sample is good.
FIG. 2 shows a microwave catalyst Cu obtained in example 1 0.5 Mn 0.5 Fe 2 O 4 As can be seen from FIG. 1, the obtained microwave catalyst Cu 0.5 Mn 0.5 Fe 2 O 4 The surface is rough, the interface structure is compact and ordered, more active sites can be provided, and microwave energy can be effectively absorbed.
FIG. 3 shows a microwave catalyst Cu obtained in example 1 0.5 Mn 0.5 Fe 2 O 4 As can be seen from FIG. 3, the Fe, mn, cu and O elements of the obtained sample coexist, and three main peaks respectively correspond to lattice oxygen of the metal oxide in the XPS image of O1s (Fe-O, mn-O and Cu-O are represented as O Latt ) Oxygen vacancies (expressed as OVs) and surface hydroxyl species (expressed as O-H). The synthesized catalyst is successfully proved to contain oxygen vacancies, and analysis data in advantage software shows that the total area of three morphological peaks of O element is 15978.96, wherein the characteristic peak area of the oxygen vacancies is 5425.79, and the content of the O element is 33.95 percent according to the peak area ratio (5425.79/15978.96).
Example 2
To 100mL of a tetracycline solution having a concentration of 50mg/L, 0.1g of Cu prepared in example 1 was added 0.5 Mn 0.5 Fe 2 O 4 And (3) after the adsorption of the microwave catalyst reaches equilibrium, placing the catalyst into a microwave reactor, setting the microwave power to 480W, and carrying out microwave reaction for 6min.
The time-dependent degradation rate curve of tetracycline wastewater is shown in fig. 4. From the figure, the copper-manganese composite ferrite microwave catalyst shows obvious advantages, and has the advantages of higher reaction rate and higher degradation rate.
Example 3
To 100mL of a tetracycline solution having a concentration of 50mg/L, 0.1g of Cu prepared in example 1 was added 0.5 Mn 0.5 Fe 2 O 4 Placing the catalyst into a microwave reactor after the adsorption reaches equilibrium, setting the microwave power to 480W, carrying out microwave reaction for 6min, and carrying out microwave reaction on the catalyst Cu 0.5 Mn 0.5 Fe 2 O 4 The recovered, reprocessed 100mL of 50mg/L tetracycline solution, and the repeated use of this 4 times. The results are shown in FIG. 7, and four times of experimental microwave reaction are performed after 6minThe removal rates of the cyclosporin were 96.14%, 86.13%, 84.22%, 83.04% and 80.77%, respectively. Always keep above 80%. The results demonstrate Cu 0.5 Mn 0.5 Fe 2 O 4 The catalyst has good stability.
Comparative examples 1 to 4
According to the preparation method of example 1, 0.1363g of zinc chloride, 0.23973g of cobalt chloride, 0.2033g of magnesium chloride and 0.24143g of aluminum chloride are respectively used for replacing 0.17048g of copper chloride, and a composite ferrite microwave catalyst with the molar ratio of Fe, M and Mn of 4:1:1 is prepared and is expressed as M 0.5 Mn 0.2 Fe 2 O 4 Wherein M is Zn, co, mg, al.
0.1g of M prepared in comparative examples 1 to 4 was added to 100mL of a tetracycline solution having a concentration of 50mg/L, respectively 0.5 Mn 0.5 Fe 2 O 4 And (3) after the adsorption of the microwave catalyst reaches equilibrium, placing the catalyst into a microwave reactor, setting the microwave power to 480W, and carrying out microwave reaction for 6min. The time-dependent degradation rate curve of tetracycline wastewater is shown in fig. 4. From the figure, the copper-manganese composite ferrite microwave catalyst shows obvious advantages, and has the advantages of higher reaction rate and higher degradation rate.
Comparative example 5
(1) Adopting a coprecipitation method, firstly dissolving 2.703g of ferric chloride, 0.17048g of copper chloride, 0.79164g of manganese chloride and 2.4024g of urea in 100mL of deionized water to obtain a precursor aqueous solution containing 0.1mol/L of ferric chloride, 0.01mol/L of copper chloride, 0.04mol/L of manganese chloride and 0.6mol/L of urea;
(2) Dropwise adding 1mol/L sodium hydroxide solution into the precursor aqueous solution, adjusting the pH value to 11-12, and stirring for 30min to obtain a suspension;
(3) Filtering the obtained suspension, washing with deionized water and absolute ethyl alcohol for several times, and drying in a 60 ℃ oven for 8 hours to obtain a solid substance;
(4) Calcining the obtained solid substance in a muffle furnace at 450 ℃ for 1h to obtain the copper-manganese composite ferrite microwave catalyst with the molar ratio of Fe, cu and Mn of 10:1:4, wherein the catalyst is expressed as Cu 0.2 Mn 0.8 Fe 2 O 4 。
Comparative example 6
(1) Adopting a coprecipitation method, firstly dissolving 2.703g of ferric chloride, 0.68192g of copper chloride, 0.19791g of manganese chloride and 0.9g of urea in 100mL of deionized water to obtain a precursor aqueous solution containing 0.1mol/L of ferric chloride, 0.04mol/L of copper chloride, 0.01mol/L of manganese chloride and 0.15mol/L of urea;
(2) Dropwise adding 1mol/L sodium hydroxide solution into the precursor aqueous solution, adjusting the pH value to 11-12, and stirring for 30min to obtain a suspension;
(3) Filtering the obtained suspension, washing with deionized water and absolute ethyl alcohol for several times, and drying in a 60 ℃ oven for 8 hours to obtain a solid substance;
(4) The solid material obtained was placed in a muffle furnace at 450 ℃ for calcination for 1h. Finally, the copper-manganese composite ferrite microwave catalyst with the molar ratio of Fe, cu and Mn of 10:4:1 is prepared, and is expressed as Cu 0.8 Mn 0.2 Fe 2 O 4 。
Comparative example 7
Single MnFe 2 O 4 Preparation of a microwave catalyst: adopting a coprecipitation method, firstly dissolving 0.5406g of ferric chloride, 0.19791g of manganese chloride and 0.9g of urea in 100mL of deionized water to obtain a precursor aqueous solution containing 0.02mol/L of ferric chloride, 0.01mol/L of manganese chloride and 0.15mol/L of urea;
dropwise adding 1mol/L sodium hydroxide solution into the precursor aqueous solution, adjusting the pH value to 11-12, and stirring for 30min to obtain a suspension;
carrying out suction filtration on the obtained suspension, washing with deionized water and absolute ethyl alcohol for a plurality of times, and drying in a 60 ℃ oven to obtain a solid substance;
calcining the obtained solid substance in a muffle furnace at 450 ℃ for 1h to obtain the catalyst with the molar ratio of Fe to Mn of 2:1, which is expressed as MnFe 2 O 4 。
Comparative example 8
Single CuFe 2 O 4 Preparation of a microwave catalyst: adopting a coprecipitation method, firstly dissolving 0.5406g of ferric chloride, 0.17048g of copper chloride and 0.9g of urea in 100mL of deionized water to obtain a precursor aqueous solution containing 0.02mol/L of ferric chloride, 0.01mol/L of copper chloride and 0.15mol/L of urea;
dropwise adding 1mol/L sodium hydroxide solution into the precursor aqueous solution, adjusting the pH value to 11-12, and stirring for 30min to obtain a suspension;
carrying out suction filtration on the obtained suspension, washing with deionized water and absolute ethyl alcohol for a plurality of times, and drying in a 60 ℃ oven to obtain a solid substance;
calcining the obtained solid substance in a muffle furnace at 450 ℃ for 1h to obtain the catalyst with the molar ratio of Fe to Cu of 2:1, which is expressed as CuFe 2 O 4 。
And adding 0.1g of the catalyst prepared in the comparative example 5-8 into 100mL of tetracycline solution with the concentration of 50mg/L, placing the catalyst into a microwave reactor after adsorption reaches equilibrium, setting the microwave power to be 480W, and carrying out microwave reaction for 6min.
FIG. 5 is MnFe 2 O 4 、Cu 0.2 Mn 0.8 Fe 2 O 4 、Cu 0.5 Mn 0.5 Fe 2 O 4 、Cu 0.8 Mn 0.2 Fe 2 O 4 、CuFe 2 O 4 Five microwave catalysts show microwave catalytic degradation patterns of tetracycline under microwave radiation. As shown in FIG. 5, when no microwave catalyst is added, only the tetracycline is hardly degraded under microwave radiation, which indicates that the tetracycline is more stable and cannot directly absorb microwaves. After adding the catalyst, radiating the catalyst for 6min by microwave, and then Cu 0.5 Mn 0.5 Fe 2 O 4 The degradation efficiency of the tetracycline reaches 96.14%, and Cu 0.2 Mn 0.8 Fe 2 O 4 、Cu 0.8 Mn 0.2 Fe 2 O 4 、MnFe 2 O 4 、CuFe 2 O 4 The degradation efficiency to the tetracycline is 65.26%, 54.92%, 76.11% and 45.82% respectively. Therefore, in the preparation process of the catalyst, the molar ratio of Fe, cu and Mn can be regulated and controlled by controlling the addition amount of ferric chloride, cupric chloride and manganese chloride, so that the improvement of the microwave catalytic performance is realized.
Comparative example 9
(1) Adopting a coprecipitation method, firstly dissolving 1.5995g of ferric sulfate, 0.24969g of copper sulfate, 0.16902g of manganese sulfate and 0.9g of urea in 100mL of deionized water to obtain a precursor aqueous solution containing 0.04mol/L of ferric sulfate, 0.01mol/L of copper sulfate, 0.01mol/L of manganese sulfate and 0.15mol/L of urea;
(2) Dropwise adding 1mol/L sodium hydroxide solution into the two precursor aqueous solutions, adjusting the pH value to 11-12, and stirring for 30min to obtain a suspension;
(3) Carrying out suction filtration on the obtained suspension, washing with deionized water and absolute ethyl alcohol for a plurality of times, and drying in a 60 ℃ oven for 8 hours to obtain a solid substance;
(4) Calcining the obtained solid substance in a muffle furnace at 450 ℃ for 1h to obtain catalysts with different metal salt raw materials and Fe, cu and Mn molar ratio of 4:1:1, wherein the catalysts are expressed as Cu 0.5 Mn 0.5 Fe 2 O 4 。
Comparative example 10
(1) Firstly, 1.616g of ferric nitrate, 0.24160g of copper nitrate, 0.17895g of manganese nitrate and 0.9g of urea are dissolved in 100mL of deionized water to obtain a precursor aqueous solution containing 0.04mol/L of ferric nitrate, 0.01mol/L of copper nitrate, 0.01mol/L of manganese nitrate and 0.15mol/L of urea;
(2) Dropwise adding 1mol/L sodium hydroxide solution into the two precursor aqueous solutions, adjusting the pH value to 11-12, and stirring for 30min to obtain a suspension;
(3) Carrying out suction filtration on the obtained suspension, washing with deionized water and absolute ethyl alcohol for a plurality of times, and drying in a 60 ℃ oven for 8 hours to obtain a solid substance;
(4) Calcining the obtained solid substance in a muffle furnace at 450 ℃ for 1h to obtain catalysts with different metal salt raw materials and Fe, cu and Mn molar ratio of 4:1:1, wherein the catalysts are expressed as Cu 0.5 Mn 0.5 Fe 2 O 4 。
And adding 0.1g of the catalyst prepared in the comparative example 9-10 into 100mL of tetracycline solution with the concentration of 50mg/L, placing the catalyst into a microwave reactor after adsorption reaches equilibrium, setting the microwave power to be 480W, and carrying out microwave reaction for 6min.
The time-dependent degradation rate curve of tetracycline wastewater is shown in fig. 6. From the figure, it can be seen that the microwave catalyst prepared by taking the chloride salt as the raw material shows obvious advantages, and has faster reaction rate and higher degradation rate.
It should be noted that the above examples are only preferred examples of the present invention and are not limiting to the embodiments. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations or modifications may be made in the various forms based on the above description. Obvious variations or modifications of the embodiments are within the scope of the invention.
Claims (9)
1. The preparation method of the copper-manganese composite ferrite microwave catalyst is characterized by comprising the following steps of:
(1) Adding ferric chloride, cupric chloride and manganese chloride into deionized water to obtain a precursor aqueous solution, adding urea, and stirring, wherein the concentration of ferric chloride in the precursor aqueous solution is 0.02-0.1mol/L, the concentration of cupric chloride is 0.0025-0.0375mol/L, the concentration of manganese chloride is 0.0025-0.0375mol/L, and the concentration of urea is 0.1-0.4mol/L;
(2) Dropwise adding a sodium hydroxide aqueous solution into the precursor aqueous solution obtained in the step (1), stirring, adjusting the pH value to 11-12 to obtain a suspension, and continuously stirring;
(3) Carrying out suction filtration, washing and drying treatment on the suspension obtained in the step (2) to obtain a solid substance;
(4) Grinding and sintering the solid substance obtained in the step (3) to obtain the copper-manganese composite ferrite microwave catalyst.
2. The method according to claim 1, wherein in the step (1), the stirring time is 30 minutes.
3. The method according to claim 1, wherein in the step (1), the molar ratio of the ferric chloride to the urea in the precursor aqueous solution is 4:1-15.
4. The method according to claim 1, wherein in the step (2), the concentration of the aqueous sodium hydroxide solution is 0.1 to 1mol/L.
5. The method according to claim 1, wherein in the step (2), the stirring time is 30 minutes.
6. The method according to claim 1, wherein in the step (3), the temperature of the drying treatment is 60 to 90 ℃.
7. The method according to claim 1, wherein in the step (4), the sintering temperature is 300 to 550 ℃ and the sintering time is 0.5 to 2 hours.
8. A copper-manganese composite ferrite microwave catalyst prepared by the preparation method according to any one of claims 1 to 7, wherein the molar ratio of iron, copper and manganese in the catalyst is 4:0.5:1.5 to 4:1.5:0.5.
9. An application of the copper-manganese composite ferrite microwave catalyst as claimed in claim 8, which is characterized by being applied to degradation of organic matters in wastewater.
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