CN116351420A - Heterogeneous photo-Fenton catalytic degradation dye copper ferrite fiber and preparation method thereof - Google Patents
Heterogeneous photo-Fenton catalytic degradation dye copper ferrite fiber and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 115
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 113
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000000835 fiber Substances 0.000 title claims abstract description 104
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 230000015556 catabolic process Effects 0.000 title claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 238000009987 spinning Methods 0.000 claims abstract description 26
- 230000005415 magnetization Effects 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960002303 citric acid monohydrate Drugs 0.000 claims abstract description 16
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 229960004887 ferric hydroxide Drugs 0.000 claims description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 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 claims description 4
- 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 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000005750 Copper hydroxide Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000975 dye Substances 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 239000001045 blue dye Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000928 Yellow copper Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C02F2305/10—Photocatalysts
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a heterogeneous photo Fenton catalytic degradation dye copper ferrite fiber and a preparation method thereof. According to the invention, an iron source, a copper source and citric acid monohydrate (CA) are used as raw materials, a sol-gel preparation technology is adopted for the specific iron source and the copper source, a specific solvent is adopted for preparing a copper ferrite precursor spinning solution with uniformity and good spinnability, and the copper ferrite fiber is prepared by an electrostatic spinning technology, so that the fiber is good in continuity, fluffy and high in saturation magnetization, and can be used for carrying out heterogeneous Fenton-like catalytic degradation on methylene blue fuel in an environment with pH value of 3, the degradation rate reaches 93.94% after 2.5 hours, and the copper ferrite precursor spinning solution is easy to recover after use and cannot cause secondary pollution. The preparation method has the advantages of simple process flow, low raw material cost and adjustable precursor sol preparation process, and the obtained fiber is an excellent heterogeneous photo-Fenton catalyst.
Description
Technical Field
The invention relates to a heterogeneous photo-Fenton catalytic degradation dye copper ferrite fiber and a preparation method thereof, belonging to the technical field of inorganic functional material synthesis.
Background
In recent years, with the continuous development of industry, pollution problems are increasingly severe, and serious influences are caused on soil, water and the like. However, it is difficult to achieve zero pollutant generation from the source in industrial production, so how to treat the pollutant generated in production becomes a focus of industrial attention. The shortage of water resources has made water treatment increasingly important, both for industry and for civilian use. In order to solve the problem of water treatment, advanced oxidation techniques (Advanced Oxidation Processes, AOPs) are commonly used, which are techniques for degrading pollutant and toxic macromolecular organic substances into low-toxic or non-toxic small molecules by generating highly oxidative hydroxyl radicals (OH). Can be classified into electrochemical, photochemical, fenton, etc., and differ in the manner in which they generate free radicals and in the reaction conditions. Wherein Fenton method is carried out by Fe 2+ And H 2 O 2 Hydroxyl radical generated by the reaction is subjected to organic degradation, and Fe is removed by Fenton-like method 2+ And H 2 O 2 In addition to dopingOther metals (e.g., copper, zinc, etc.) are present and the reaction conditions are altered (e.g., electro-Fenton process, UV/Fenton process, etc.). The traditional homogeneous Fenton oxidation technology and the homogeneous Fenton-like oxidation technology both use soluble ions as catalysts, are difficult to recover, and react to generate a large amount of iron mud to cause secondary pollution, and the heterogeneous Fenton-like oxidation technology adopt solid-phase catalysts to participate in the reaction, so that the recovery is convenient after the reaction, and the iron mud is not generated.
Spinel type ferrite with MFe 2 O 4 M is a divalent metal ion, a cubic phase crystal, which is also known as a magnetic spinel, because it is usually magnetic. Common spinel ferrites are Fe 3 O 4 、ZnFe 2 O 4 、CuFe 2 O 4 、CoFe 2 O 4 、NiFe 2 O 4 Etc., of CuFe therein 2 O 4 The magnetic material has better magnetism and better catalytic performance, and the composition elements Fe and Cu are easy to obtain, low in price, better in light absorption capacity and stable in structure. Therefore, the copper ferrite has great application potential in AOPs, and the heterogeneous Fenton-like oxidation technology with the participation of the copper ferrite can achieve the purposes of easy recovery and separation of the catalyst and secondary pollution avoidance.
At present, the preparation technology of the copper ferrite material is usually a hydrothermal method, the prepared copper ferrite is in a powdery form, and when the powdery catalyst is used for sewage treatment, the problems of poor dispersibility and easy agglomeration are encountered. And the current preparation method of copper ferrite is difficult to simultaneously meet the requirements of high saturation magnetization and difficult agglomeration. For example, cuFe for activating Peroxomonosulphate (PMS) to degrade tetrabromobisphenol A 2 O 4 The magnetic nano powder (Applied Catalysis B: environmental 129 (2013), 153-162) is in a powder shape, is easy to agglomerate when in use, and has poor dispersibility; magnetic CuFe for catalytic dye-reduction 2 O 4 @SiO 2 The fiber membrane (Journal of Colloid and Interface Science 538 (2019), 620-629) is prepared by mixing CuFe 2 O 4 Powder loading to SiO 2 On the fiber film, the obtained composite material has low saturation magnetization and is preparedThe preparation process is complicated. There are also some patent documents reporting about the preparation and application of copper ferrite and its composite materials, for example: chinese patent document CN112063431A, CN105632756B, CN111841540A, CN113877581B, CN20106948085B, etc. Therein, chinese patent document CN112063431A discloses a magnetic CuFe 2 O 4 The saturation magnetization of the prepared copper ferrite material after roasting at 950 ℃ is only 12.9emu/g, and the magnetization is low.
In summary, most of the reported copper ferrite is nano powder or nano powder is loaded on a substrate or a fiber membrane, and the defects of easy agglomeration of powder, low cycle life, complex structure and low cycle life exist, and saturation magnetization is not high.
Through searching, no report about copper ferrite fiber exists at present, and copper ferrite cannot be spun to prepare the copper ferrite fiber possibly due to technical defects.
Therefore, the invention is provided for solving the problems of easy agglomeration of copper ferrite powder, low saturation magnetization, low cycle service life and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a heterogeneous photo-Fenton catalytic degradation dye copper ferrite fiber and a preparation method thereof.
The method disclosed by the invention is simple in preparation process, low in cost, environment-friendly and safe to operate, and solves the problems of easiness in agglomeration, low saturation magnetization, small specific surface area, low cycle service life and the like of the traditional copper ferrite material.
Summary of the invention:
the invention takes an iron source, a copper source and citric acid monohydrate (CA) as raw materials, adopts a sol-gel preparation technology for the specific iron source and the copper source, and adopts a specific solvent to prepare the uniform copper ferrite precursor spinning solution with good spinnability. Through electrostatic spinning technology, the copper ferrite precursor spinning solution is stretched into filaments under the action of a high-voltage power supply to obtain the required copper ferrite precursor fiber, and the required copper ferrite precursor fiber is subjected to heat treatment through a muffle furnace in air atmosphere to obtain the copper ferrite precursor fiber with good continuity, good flexibility and saturationAnd copper ferrite fibers with higher magnetization. The copper ferrite fiber obtained by the invention can catalyze H by heterogeneous Fenton-like technology 2 O 2 Generates hydroxyl radical and degrades methylene blue dye.
Detailed description of the invention:
the technical scheme of the invention is as follows:
a heterogeneous photo Fenton catalytic degradation dye copper ferrite fiber, the diameter of the fiber is 0.8-2.0 mu m, all the fibers are cubic phases, the copper ferrite is a spinel structure of the cubic phases, the fiber continuity is good, and the saturation magnetization intensity is 20-35emu/g.
The preparation method of the copper ferrite fiber comprises the following steps:
(1) The molar ratio of the iron source to the citric acid monohydrate to the copper source is 2 (2-4) to 1, the ferric iron source, the citric acid monohydrate and the copper source are weighed and sequentially added into deionized water, and the mixture is stirred for 24-36 hours at the temperature of 25-40 ℃ to obtain dark green solution;
(2) Concentrating the solution prepared in the step (1) under reduced pressure at 40-70 ℃ to obtain sol;
(3) Adding the sol prepared in the step (2) into a mixed solvent of water and low-carbon alcohol for dilution, adding a spinning auxiliary agent, stirring for 4 hours, and aging for 6-12 hours to prepare copper ferrite precursor spinning solution;
(4) Carrying out electrostatic spinning on the copper ferrite precursor spinning solution prepared in the step (3), injecting the spinning solution into an injector with a stainless steel needle, and obtaining copper ferrite precursor fibers under the action of high-voltage power supply;
(5) And (3) carrying out heat treatment on the copper ferrite fiber prepared in the step (4) by using a muffle furnace, wherein the heat treatment atmosphere is air, the heating rate is 0.5-5 ℃/min, the heat treatment temperature is 750-850 ℃, and the heat preservation is carried out for 1-5 hours, so as to obtain the copper ferrite fiber of the heterogeneous photo-Fenton catalytic degradation dye.
According to the present invention, it is preferable that in the step (1), the molar ratio of the iron source to citric acid monohydrate is 1 (1.4 to 1.6).
According to the present invention, preferably, in the step (1), the iron source is one or a combination of two or more of ferric hydroxide, ferric chloride hexahydrate, ferric chloride anhydrous, ferric nitrate nonahydrate, or ferric nitrate anhydrous.
The ferric hydroxide is ferric hydroxide precipitate, and is prepared on site when in use.
According to the present invention, preferably, in the step (1), the copper source is one or a combination of two or more of copper acetate, copper hydroxide or copper oxalate.
According to the present invention, it is preferable that in the step (1), the iron source and the copper source are not nitrate at the same time.
According to the present invention, it is preferable that in the step (1), the mass ratio of the iron source to deionized water is 1 (5 to 10) in g/mL.
According to the present invention, it is preferable that the reduced pressure concentration temperature in the step (2) is 45 to 50 ℃.
According to the present invention, it is preferable that in the step (2), the mass ratio of water to the lower alcohol in the mixed solvent is 1 (1 to 4).
Further preferably, in the step (2), the mass ratio of water to lower alcohol in the mixed solvent is 1:2.
According to the present invention, in the step (2), the lower alcohol is preferably one or a combination of two or more of methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isopropanol and tert-butanol.
Further preferably, the lower alcohol is methanol or ethanol.
According to the present invention, it is preferable that the amount of the spinning aid added in the step (3) is 0.1 to 0.3% by mass of the sol.
More preferably, in the step (3), the amount of the spinning aid added is 0.22 to 0.27% by mass of the sol.
According to the present invention, it is preferable that the stirring temperature in the step (3) is 20 to 45 ℃.
According to the present invention, preferably, in the step (4), the electrospinning parameters are: the ambient temperature is 25-40 ℃, the ambient relative humidity is 15-25%, the syringe advancing speed is 0.5-4 mL/h, the distance between the receiver and the needle is 10-25 cm, and the applied voltage is 8-35 kV.
It is further preferred that the relative humidity of the environment is 15-20%, the advancing speed of the injector is 1.5-3 mL/h, the applied voltage is 10-15 kV, and the distance from the needle to the receiving device is 10-15 cm.
According to the present invention, it is preferable that the stainless steel needle in the step (4) has an inner diameter of 0.3 to 0.5mm.
According to the invention, in the step (5), the heating rate of the heat treatment is 2 ℃/min, the heat treatment temperature is 800 ℃, the heat is preserved for 1-3 hours after reaching the target temperature, and the heat is cooled to the room temperature along with the furnace after the heat preservation is finished.
The heterogeneous copper ferrite fiber for photocatalytic degradation of dye is prepared by the method.
The application of the heterogeneous photo-Fenton catalytic degradation dye copper ferrite fiber is used for sewage treatment, magnetic separation, catalysis or energy storage; as heterogeneous Fenton-like catalyst, the methylene blue wastewater is degraded under visible light, the concentration of methyl blue in the methylene blue wastewater is 8-15 ppm, and the dosage of copper ferrite fiber is 0.5-1 mg/mL.
According to the invention, it is preferred that 30mg of copper ferrite fibres have a degradation rate of 93.94% at 2.5h for 50mL of methylene blue solution with a concentration of 10ppm under visible light.
When the precursor sol is prepared, the ligand, the copper source and the iron source form a linear molecular structure, and the linear molecular structure enables the prepared sol to have good spinnability, and the fiber with good continuity and good quality is easier to obtain.
The invention has the technical characteristics and excellent effects that:
1. the invention takes an iron source, a copper source and citric acid monohydrate (CA) as raw materials, adopts a sol-gel preparation technology for the specific iron source and the copper source, and adopts a specific solvent to prepare the uniform copper ferrite precursor spinning solution with good spinnability. The copper ferrite fiber is prepared by the electrostatic spinning technology, and the obtained product has high purity, good crystallinity, uniform grain, small fiber diameter, good continuity and fluffiness, and can play the roles of self-supporting, difficult agglomeration and strong recoverability when being applied to sewage treatment.
2. The copper ferrite fiber prepared by the invention has good catalytic performance and magnetism, the good catalytic performance can be applied to sewage treatment to degrade pollutants, and the good magnetism is beneficial to recycling the copper ferrite fiber after use.
3. The copper ferrite fiber prepared by the invention is used for heterogeneous Fenton-like oxidation technology, and can achieve the purposes of self-supporting, uneasy agglomeration, easy recovery, magnetic separation and secondary pollution prevention while degrading pollutants.
Drawings
FIG. 1 is a photograph of a copper ferrite precursor fiber obtained in example 1 of the present invention.
FIG. 2 is a photograph showing the appearance of copper ferrite fibers obtained in example 1 and comparative examples 7 to 9.
FIG. 3 is an SEM photograph of copper ferrite fibers prepared in example 1 and comparative examples 7-9.
FIG. 4 is an XRD pattern of the copper ferrite fibers obtained in example 1 and comparative examples 7 to 9.
FIG. 5 shows hysteresis loops of the copper ferrite fibers obtained in example 1 and comparative examples 7 to 9.
FIG. 6 is a graph showing the catalytic degradation of methylene blue dye by copper ferrite fiber in test example 4 of the present invention.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
In the examples, the ferric hydroxide is prepared as follows:
8.08g of ferric nitrate nonahydrate is taken and dissolved in 50mL of deionized water, and magnetically stirred at room temperature until a yellow clear solution is formed; and (3) maintaining magnetic stirring, dropwise adding 6mL of ammonia water to form dark brown precipitate, stopping stirring until the magneton turns slightly, centrifuging to obtain precipitate, and washing with deionized water to obtain ferric hydroxide precipitate.
Example 1:
a preparation method of heterogeneous photo Fenton catalytic degradation dye copper ferrite fiber comprises the following steps:
(1) In a molar ratio of Fe 3+ :CA:Cu 2+ Iron hydroxide precipitate, citric acid monohydrate, copper acetate were weighed in a ratio of =2:3:1, dissolved in deionized water, and stirred at room temperature for 24Obtaining a clear solution after h, carrying out reduced pressure distillation on the solution at 50 ℃ until the solution is 15g to obtain sol, preparing a mixed solvent according to the mass ratio of water to ethanol of 1:2, adding 15g of sol into 10g of mixed solvent, adding 0.06g of polyethylene oxide (PEO) with the number average molecular weight of 100 ten thousand, stirring for 4h, and then aging for 12h to obtain dark green copper ferrite precursor spinning solution;
(2) And (3) filling the precursor spinning solution obtained in the step (1) into a syringe with a needle head with the inner diameter of 0.3mm, and connecting a high-voltage power supply to perform electrostatic spinning. The electrostatic spinning parameters are as follows: applying voltage of 12kV, relative humidity of 25%, ambient temperature of 25 ℃, syringe advancing speed of 2.0mL/h, distance between needle and receiver of 15cm, collecting yellow copper ferrite precursor fiber;
(3) And (3) carrying out heat treatment on the fiber prepared in the step (2) under the air condition by using a muffle furnace, carrying out heat treatment on the fiber to 800 ℃ at a heating rate of 2 ℃/min, preserving heat for 3 hours, and cooling to room temperature along with the furnace to obtain the black purple copper ferrite fiber.
The saturated magnetization intensity of the copper ferrite fiber prepared by the embodiment reaches 26.14emu/g, the fiber diameter is 0.8-2.0 mu m, all the fibers are cubic phases, the fiber quality is good, and the fluffiness is good.
Example 2:
a preparation method of heterogeneous photo Fenton catalytic degradation dye copper ferrite fiber comprises the following steps:
(1) In a molar ratio of Fe 3+ :CA:Cu 2+ Weighing ferric nitrate nonahydrate, citric acid monohydrate and copper acetate in a ratio of (2:3:1), dissolving in deionized water, stirring at room temperature for 24 hours to obtain a clear solution, carrying out reduced pressure distillation on the solution at 50 ℃ until 15g of solution is obtained, preparing a mixed solvent with a mass ratio of water to ethanol of 1:2, adding 15g of solution into 10g of mixed solvent, adding 0.06g of polyethylene oxide (PEO) with a number average molecular weight of 100 ten thousand, stirring for 4 hours, and then aging for 12 hours to obtain a dark green copper ferrite precursor spinning solution;
(2) Filling the precursor spinning solution prepared in the step (1) into a syringe with a needle head with an inner diameter of 0.3mm, and carrying out electrostatic spinning under a high-voltage power supply, wherein the electrostatic spinning parameters are as follows: the environment temperature is 25 ℃, the relative humidity is 25%, the applied voltage is 12kV, the distance between the needle head and the receiving device is 15cm, and the obtained copper ferrite precursor fiber is yellow;
(3) And (3) carrying out heat treatment on the fiber prepared in the step (2) by using a muffle furnace, wherein the sintering atmosphere is air, heating to 800 ℃ at a heating rate of 2 ℃/min, preserving heat for 3 hours, and cooling to room temperature along with the furnace to obtain the copper ferrite fiber.
The saturation magnetization of the copper ferrite fiber prepared in the embodiment is equivalent to that of the embodiment 1, the fiber diameter is 0.8-2.0 mu m, all the fibers are cubic phases, the fiber quality is good, and the fluffiness is good.
Example 3:
the preparation method as described in example 1 is different in that:
copper acetate was replaced by copper hydroxide, and the procedure of example 1 was followed.
The saturation magnetization of the copper ferrite fiber prepared in this example was 25.86emu/g, which is equivalent to that of the copper ferrite fiber prepared in example 1.
Example 4:
the preparation method as described in example 1 is different in that:
ethanol was replaced with methanol and the procedure of example 1 was followed.
The saturation magnetization of the copper ferrite fiber prepared in this example is equivalent to that of example 1.
Example 5:
the preparation method as described in example 1 is different in that:
in step (3), the temperature was raised to 750℃at a heating rate of 2℃per minute and kept at that temperature for 3 hours, followed by cooling to room temperature in a furnace, and the other steps were performed as in example 1.
The saturation magnetization of the copper ferrite fiber prepared in this example is equivalent to that of example 1.
Example 6:
the preparation method as described in example 1 is different in that:
in step (3), the temperature was raised to 850℃at a heating rate of 2℃per minute and kept at that temperature for 3 hours, followed by cooling to room temperature in a furnace, and the other steps were performed as in example 1.
The saturation magnetization of the copper ferrite fiber prepared in this example is equivalent to that of example 1.
Comparative example 1:
the preparation method as described in example 1 is different in that:
the mixed solvent of water and ethanol is changed into deionized water, the spinnability of the obtained copper ferrite precursor spinning solution is poor, the ejected fibers are easy to break, the fibers are slow to solidify, and the solution is easy to drip.
Comparative example 2:
the preparation method as described in example 1 is different in that:
the mixed solvent of water and ethanol is changed into ethanol, the prepared mixed solution can not dissolve the concentrated copper ferrite precursor sol, and the copper ferrite precursor can be separated out along with the addition of the solvent.
Comparative example 3:
the preparation method as described in example 1 is different in that:
the ambient humidity was 32%. When the relative humidity of the environment is 32%, the spinnability of the spinning solution is poor, dripping is easy to occur, the solvent is not completely volatilized, and the ejected fiber is easy to adhere and is not fluffy.
Comparative example 4:
the preparation method as described in example 1 is different in that:
the ambient humidity was 35%. When the ambient relative humidity is 35%, the dripping is serious in the spinning process, and the spinnability of the spinning solution is poor. The reason is that the relative humidity of the environment is too high, after precursor sol is stretched into filaments under the action of high-voltage power supply, the solvent in the sol cannot volatilize in time, so that the fibers are difficult to form, the formed fibers are serious in moisture absorption, adhesion is generated, the adhesion is difficult to collect, and the precursor sol is hardened and crushed after heat treatment.
Comparative example 5:
the preparation method as described in example 1 is different in that:
the ambient temperature was 15 ℃. When the ambient temperature is 15 ℃, the fiber is difficult to form, and the dripping is serious. The reason is that the environment temperature is too low, the solvent in the sol cannot volatilize in time, so that the fiber is difficult to form, the formed fiber has serious moisture absorption, adhesion is generated, the collection is difficult, and the fiber is hardened and crushed after heat treatment.
Comparative example 6:
the preparation method as described in example 1 is different in that:
copper acetate was exchanged for copper nitrate trihydrate. At this time, in the electrostatic spinning process of the copper ferrite precursor, the dripping is serious, the obtained copper ferrite fiber has serious moisture absorption and is difficult to collect, and the fiber after heat treatment has serious fragmentation.
Comparative example 7:
the preparation method as described in example 1 is different in that:
in step (3), the temperature was raised to 600℃at a heating rate of 2℃per minute and kept at that temperature for 3 hours, followed by cooling to room temperature in the furnace, and the other steps were performed as in example 1.
Although the prepared copper ferrite fiber has good flexibility, the saturation magnetization is 7.84emu/g.
Comparative example 8:
the preparation method as described in example 1 is different in that:
in the step (3), the temperature was raised to 700℃at a heating rate of 2℃per minute and kept at that temperature for 3 hours, followed by cooling to room temperature in a furnace, and the other steps were performed as in example 1.
The prepared copper ferrite fiber has good flexibility and saturation magnetization of 18.53emu/g.
Comparative example 9:
the preparation method as described in example 1 is different in that:
in step (3), the temperature was raised to 900℃at a heating rate of 2℃per minute and kept at that temperature for 3 hours, followed by cooling to room temperature in a furnace, and the other steps were performed as in example 1.
The prepared copper ferrite fiber becomes brittle and friable.
Test example 1
The powder diffraction data of the copper ferrite fibers prepared in example 1 and comparative examples 7 to 9 were tested and plotted as XRD patterns, as shown in FIG. 4. As can be seen from FIG. 4, the fibers of comparative example 7 and comparative example 8 were composed of CuFe when the heat treatment temperature was 600℃and 700 ℃ 2 O 4 、Fe 2 O 3 Two-phase composition, due to low sintering temperature, and presence of non-magnetic impurity Fe 2 O 3 The saturation magnetization intensity of the prepared copper ferrite fiber is low; example 1, comparative example 9 the fibers obtained CuFe at a heat treatment temperature of 800℃and 900 ℃ 2 O 4 The fibers obtained at 900 ℃ are easily broken in a pure phase.
Test example 2
The copper ferrite fibers prepared in example 1 and comparative examples 7 to 9 were tested for magnetic properties and plotted as hysteresis loops, as shown in fig. 5. As can be seen from the graph 5, the higher the heat treatment temperature is, the saturation magnetization of the copper ferrite fiber is correspondingly improved, the saturation magnetization of the copper ferrite fiber is 7.84emu/g at the heat treatment temperature of 600 ℃, the saturation magnetization of the copper ferrite fiber is 26.14emu/g at the heat treatment temperature of 800 ℃, and the fiber obtained at 900 ℃ is easy to crush.
Test example 3
SEM photographs of the copper ferrite fibers prepared in example 1 and comparative examples 7 to 9 were tested, as shown in fig. 3. As can be seen from FIG. 3, the fiber obtained after heat treatment at 600-800 ℃ has good microscopic morphology, good continuity and diameter distribution between 0.8-2.0 μm, and when the heat treatment temperature is higher than 900 ℃, the grains excessively grow large, resulting in the fiber becoming macroscopically brittle.
Test example 4
The copper ferrite fiber prepared in example 1 was used for the catalytic degradation test of methylene blue dye, comprising the following steps:
50mL of methylene blue solution having a concentration of 10ppm was prepared using deionized water as a solvent, and 1M HNO was used 3 Adjusting pH to 3, adding 30mg of copper ferrite fiber prepared in example 1, shaking in the dark for 1 hr, and adding 50uL of 30% H 2 O 2 The solution was irradiated using a 150W xenon lamp. After the beginning of the lamp irradiation, 2mL of the supernatant was taken every 30min to test the methylene blue concentration in the solution, and the treatment result is shown in FIG. 6.
In summary, the invention adopts a sol-gel preparation technology, adopts a specific solvent to prepare a copper ferrite precursor spinning solution with uniformity and good spinnability, and stretches the copper ferrite precursor spinning solution into filaments under the action of a high-voltage power supply by adopting an electrostatic spinning technology to obtain the required copper ferrite precursor fiber, and the copper ferrite fiber with good continuity, good flexibility and higher saturation magnetization is obtained at the heat treatment temperature of 750-850 ℃, and the degradation rate of 50mL of methylene blue solution with the concentration of 10ppm reaches 93.94% under the irradiation of visible light for 2.5 hours, so that the catalytic performance is high.
Claims (10)
1. A heterogeneous photo Fenton catalytic degradation dye copper ferrite fiber, the diameter of the fiber is 0.8-2.0 mu m, all the fibers are cubic phases, the copper ferrite is a spinel structure of the cubic phases, the fiber continuity is good, and the saturation magnetization intensity is 20-35emu/g.
2. The method for preparing the copper ferrite fiber according to claim 1, comprising the steps of:
(1) The molar ratio of the iron source to the citric acid monohydrate to the copper source is 2 (2-4) to 1, the ferric iron source, the citric acid monohydrate and the copper source are weighed and sequentially added into deionized water, and the mixture is stirred for 24-36 hours at the temperature of 25-40 ℃ to obtain dark green solution;
(2) Concentrating the solution prepared in the step (1) under reduced pressure at 40-70 ℃ to obtain sol;
(3) Adding the sol prepared in the step (2) into a mixed solvent of water and low-carbon alcohol for dilution, adding a spinning auxiliary agent, stirring for 4 hours, and aging for 6-12 hours to prepare copper ferrite precursor spinning solution;
(4) Carrying out electrostatic spinning on the copper ferrite precursor spinning solution prepared in the step (3), injecting the spinning solution into an injector with a stainless steel needle, and obtaining copper ferrite precursor fibers under the action of high-voltage power supply;
(5) And (3) carrying out heat treatment on the copper ferrite fiber prepared in the step (4) by using a muffle furnace, wherein the heat treatment atmosphere is air, the heating rate is 0.5-5 ℃/min, the heat treatment temperature is 750-850 ℃, and the heat preservation is carried out for 1-5 hours, so as to obtain the copper ferrite fiber of the heterogeneous photo-Fenton catalytic degradation dye.
3. The method according to claim 2, wherein in the step (1), the molar ratio of the iron source to citric acid monohydrate is 1 (1.4 to 1.6).
4. The process according to claim 2, wherein in the step (1), the iron source is one or a combination of two or more of ferric hydroxide, ferric chloride hexahydrate, ferric chloride anhydrous, ferric nitrate nonahydrate, and ferric nitrate anhydrous,
the copper source is one or the combination of more than two of copper acetate, copper hydroxide or copper oxalate,
the iron source and the copper source cannot be nitrate at the same time.
5. The preparation method according to claim 2, wherein in the step (1), the mass ratio of the iron source to deionized water is 1 (5-10), and the unit g/mL.
6. The process according to claim 2, wherein in the step (2), the concentration under reduced pressure is at a temperature of 45 to 50 ℃.
7. The preparation method according to claim 2, wherein in the step (2), the mass ratio of water to lower alcohol in the mixed solvent is 1 (1-4); the lower alcohol is one or more of methanol, ethanol, ethylene glycol, n-propanol, n-butanol, isopropanol and tert-butanol.
8. The process according to claim 2, wherein in the step (3), the spinning aid is added in an amount of 0.1 to 0.3% by mass of the sol and the stirring temperature is 20 to 45 ℃.
9. The method according to claim 2, wherein in the step (4), the electrospinning parameters are as follows: the temperature of the environment is 25-40 ℃, the relative humidity of the environment is 15-25%, the advancing speed of the injector is 0.5-4 mL/h, the distance between the receiver and the needle head is 10-25 cm, the applied voltage is 8-35 kV, the inner diameter of the stainless steel needle head is 0.3-0.5 mm, the heating rate of the heat treatment is 2 ℃/min, the heat treatment temperature is 800 ℃, the heat is preserved for 1-3 h after reaching the target temperature, and the stainless steel needle head is cooled to the room temperature along with a furnace after the heat preservation is finished.
10. The use of the heterogeneous photoFenton catalytic degradation dye copper ferrite fiber of claim 2 for sewage treatment, magnetic separation, catalysis, energy storage; as heterogeneous Fenton-like catalyst, the methylene blue wastewater is degraded under visible light, the concentration of methyl blue in the methylene blue wastewater is 8-15 ppm, and the dosage of copper ferrite fiber is 0.5-1 mg/mL.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154817A (en) * | 2011-02-15 | 2011-08-17 | 江苏大学 | Silver-loaded copper ferrite magnetic nanometer composite fiber and preparation method and application thereof |
| KR20120064370A (en) * | 2010-12-09 | 2012-06-19 | 한국세라믹기술원 | Nano-fiber making process of tube structure |
| WO2013119179A1 (en) * | 2012-02-10 | 2013-08-15 | Swetree Technologies Ab | Cellulose nanofibril decorated with magnetic nanoparticles |
| CN106948085A (en) * | 2017-05-08 | 2017-07-14 | 湖北工程学院 | A kind of coppe ferrite/carbon nanofiber membrane and preparation method thereof, application |
| CN108439491A (en) * | 2018-05-14 | 2018-08-24 | 太原理工大学 | A kind of preparation method and application having both magnetic and gas-sensitive property ferrous acid cupro-nickel nano material |
-
2023
- 2023-03-31 CN CN202310332721.1A patent/CN116351420A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120064370A (en) * | 2010-12-09 | 2012-06-19 | 한국세라믹기술원 | Nano-fiber making process of tube structure |
| CN102154817A (en) * | 2011-02-15 | 2011-08-17 | 江苏大学 | Silver-loaded copper ferrite magnetic nanometer composite fiber and preparation method and application thereof |
| WO2013119179A1 (en) * | 2012-02-10 | 2013-08-15 | Swetree Technologies Ab | Cellulose nanofibril decorated with magnetic nanoparticles |
| CN106948085A (en) * | 2017-05-08 | 2017-07-14 | 湖北工程学院 | A kind of coppe ferrite/carbon nanofiber membrane and preparation method thereof, application |
| CN108439491A (en) * | 2018-05-14 | 2018-08-24 | 太原理工大学 | A kind of preparation method and application having both magnetic and gas-sensitive property ferrous acid cupro-nickel nano material |
Non-Patent Citations (7)
| Title |
|---|
| SAFARTOOBI A等: "Electrochemical and optical properties of magnetic CuFe2O4 nanofibers grown by PVP and PVA-assisted sol-gel electrospinning", APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING, vol. 128, no. 1, 31 January 2022 (2022-01-31), pages 13 * |
| ZHANG GS等: "CuFe2O4/activated carbon composite: A novel magnetic adsorbent for the removal of acid orange II and catalytic regeneration", CHEMOSPHERE, vol. 68, no. 6, 30 June 2007 (2007-06-30), pages 1058 - 1066, XP022043643, DOI: 10.1016/j.chemosphere.2007.01.081 * |
| 向军等: "Fe-Co-Ni合金/Co_(0.5)Ni_(0.5)Fe_2O_4磁性复合纳米纤维的制备及性能", 中国有色金属学报中国有色金属学报, vol. 23, no. 08, 15 August 2013 (2013-08-15), pages 2259 - 2266 * |
| 张星宇等: "尖晶石型CuFe_2O_4多孔级纳米纤维的制备及在水处理中的应用", 化工管理, no. 25, 31 December 2015 (2015-12-31), pages 203 - 204 * |
| 程魁玉等: "CuFe_2O_4纤维的制备与表征", 科技创新导报, no. 17, 11 June 2009 (2009-06-11), pages 12 * |
| 陆楚楚等: "c-CuFe_2O_4纳米纤维管的制备及可见光响应光催化性能", 功能材料, vol. 48, no. 01, 30 January 2017 (2017-01-30), pages 1172 - 1176 * |
| 黄达明等: "铜铁氧体中空纤维的制备及载银的抗菌性能", 江苏大学学报(自然科学版), vol. 34, no. 01, 31 December 2013 (2013-12-31), pages 116 - 120 * |
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