CN113262799B - FeOOH cladding Mn 3 O 4 Composite material, preparation method and application thereof - Google Patents
FeOOH cladding Mn 3 O 4 Composite material, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910002588 FeOOH Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000005253 cladding Methods 0.000 title claims description 3
- 239000011572 manganese Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- AJTFTYHGFWNENF-UHFFFAOYSA-N azanium;hydroxy sulfate Chemical compound [NH4+].OOS([O-])(=O)=O AJTFTYHGFWNENF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims 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 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BUFQZEHPOKLSTP-UHFFFAOYSA-M sodium;oxido hydrogen sulfate Chemical compound [Na+].OS(=O)(=O)O[O-] BUFQZEHPOKLSTP-UHFFFAOYSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011282 treatment Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- 239000000356 contaminant Substances 0.000 description 23
- 239000011550 stock solution Substances 0.000 description 22
- 239000000975 dye Substances 0.000 description 16
- 229910021538 borax Inorganic materials 0.000 description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 11
- 239000004327 boric acid Substances 0.000 description 11
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000004328 sodium tetraborate Substances 0.000 description 11
- 235000010339 sodium tetraborate Nutrition 0.000 description 11
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 11
- 235000019345 sodium thiosulphate Nutrition 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- -1 sulfate radical Chemical class 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000123 paper 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
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/23—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- 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 technical field of water treatment functional materials, and particularly relates to a FeOOH coated Mn 3 O 4 Composite materials, methods of making and uses thereof. The invention aims to provide a catalyst with high efficiency, high speed and high stability. The invention provides a FeOOH coated Mn 3 O 4 The preparation method of the composite material comprises the following steps: (1) Sequentially dissolving alkali and ferrate in deionized water to form solution A; (2) Dissolving a manganese source in deionized water, and continuously stirring and heating to 90 ℃ to form a solution B; (3) The prepared solution A is dropwise poured into the solution B, the mixture is reacted for 2 hours at 90 ℃ under the stirring condition, the prepared compound solution is cooled to the room temperature, the deionized water and the absolute ethyl alcohol are used for washing away unreacted ions in the solution, and the solution is dried to constant weight at 70 ℃ to obtain the FeOOH coated Mn 3 O 4 A composite material. The method is simple, the prepared iron-manganese-based composite catalytic material has high catalytic efficiency, the dye rhodamine B in PMS degradation water can be activated rapidly, and the catalyst can be recycled and continuously used.
Description
Technical Field
The invention belongs to the technical field of water treatment functional materials, and particularly relates to a FeOOH coated Mn 3 O 4 Composite materials, methods of making and uses thereof.
Background
Dyes are a necessity in industry and there are many industries where there is a large amount of dye waste water emissions per day, such as in the leather, paper and textile industries. It is counted that the dye types adopted in the industry at present are more than 10 ten thousand, and dye wastewater is produced annuallyOver 70 ten thousand tons. If the dye wastewater is not effectively treated and discharged into the environment, serious pollution of water body can be directly caused. Furthermore, dyes are difficult to remove effectively under natural conditions due to the complexity of their structure. Thus, decolorization and degradation of dyes is one of the major environmental problems currently faced. In recent years, advanced oxidation technology has been applied as an efficient, environmentally friendly water treatment technology in various water treatment processes, including: pretreatment, advanced treatment, sterilization, disinfection and other links. However, it is common to use H 2 O 2 The advanced oxidation technology for generating hydroxyl free radicals by the oxidant has the advantages of low free radical yield, large oxidant consumption, narrow pH application range and limitation of application in water treatment.
Heterogeneous Fenton-like reaction based on sulfate radical is a process with application prospect at present, and more researches are involved. However, compared with homogeneous phase reaction, the heterogeneous phase method has slower reaction rate, low oxidant utilization efficiency, and how to accelerate the redox cycle of transition metal in the reaction, and improve the utilization efficiency of the oxidant in the reaction is a core problem for improving the heterogeneous phase Fenton-like reaction efficiency. Therefore, the development of a high-efficiency, rapid and high-stability catalyst for activating persulfate to generate free radicals and removing pollutants is expected to become a novel water treatment technology.
Disclosure of Invention
The invention aims to provide a catalyst with high efficiency, high speed and high stability.
To achieve the above object, the present invention provides a FeOOH coated Mn 3 O 4 The preparation method of the composite material comprises the following steps:
(1) Sequentially dissolving alkali and ferrate in deionized water to form solution A;
(2) Dissolving a manganese source in deionized water, and continuously stirring and heating to 70-90 ℃ to form a solution B;
(3) The prepared solution A is poured into the solution B drop by drop, the solution B reacts for 1 to 3 hours at the temperature of 70 to 90 ℃ under the stirring condition, the prepared compound solution is cooled to the room temperature, the deionized water and the absolute ethyl alcohol are used for washing out unreacted ions in the solution, and the solution is dried to constant weight at the temperature of 60 to 80 ℃ to obtain the FeOOH coated Mn3O4 compound material;
preferably, in the step (2), the manganese source is dissolved in deionized water, and the solution B is formed by continuously stirring and heating to 90 ℃.
Preferably, in step (3), the reaction is carried out for 2 hours at 90℃with stirring.
Preferably, in step (3), the drying temperature is 70 ℃.
Specifically, the alkali is NaOH or KOH.
Further, the ferrate is K 2 FeO 4 Or/and Na 2 FeO 4 。
Specifically, the manganese source is one or more of manganese chloride, manganese sulfate and manganese nitrate.
Preferably, in the solution A, the alkali liquor is NaOH.
The invention also provides FeOOH coated Mn prepared by the method 3 O 4 A composite material.
Specifically, the FeOOH coats Mn 3 O 4 The microstructure of the composite material is a sheet structure, the width is 40-50 nm, and the thickness of a single sheet is about 8-10 nm.
Specifically, feOOH and Mn 3 O 4 The mass ratio of (2) is 1:4-4:1.
Preferably, feOOH and Mn 3 O 4 The mass ratio of (2) is 2:3.
The invention also provides the FeOOH coated Mn 3 O 4 The application of the composite material in activating PMS to remove dye wastewater.
Specifically, the dye is rhodamine B.
Further, the application comprises the following steps: coating prepared FeOOH with Mn 3 O 4 The composite material was added to the dye-containing wastewater while PMS was added and stirred at room temperature.
Further, the PMS is at least one of potassium hydrogen peroxymonosulfate, sodium hydrogen peroxymonosulfate, or ammonium hydrogen peroxymonosulfate.
Specifically, the FeOOH coats Mn 3 O 4 The usage amount of the composite material is 0.2-0.4 g/L.
Preferably, the FeOOH coats Mn 3 O 4 The usage amount of the composite material is 0.3-0.4 g/L.
Specifically, the initial concentration of rhodamine B is 20-100 mg/L.
Preferably, the initial concentration of rhodamine B is 20-50 mg/L.
Specifically, the amount of PMS used is 0.325 to 1.3mM.
Preferably, the amount of PMS used is 0.65 to 1.3mM.
Most preferably, the PMS is used in an amount of 1.3mM.
FeOOH coating Mn 3 O 4 The chemical reactions involved in the composite preparation are as follows:
MnCl 2 +2NaOH→Mn(OH) 2 +2NaCl (1)
9Mn(OH) 2 +2K 2 FeO 4 →3Mn 3 O 4 +2FeOOH+4KOH+6H 2 O (2)
the invention has the beneficial effects that: the method is simple, the prepared iron-manganese-based composite catalytic material has high catalytic efficiency, the dye rhodamine B in PMS degradation water can be activated rapidly, and the catalyst can be recycled and continuously used. Aiming at the defects of the heterogeneous Fenton reaction at present, the invention prepares the FeOOH coated Mn through a one-step reaction method 3 O 4 The preparation method of the novel composite material is simple and easy to operate, and can be used for batch preparation. Can rapidly activate KHSO 5 The dye rhodamine B in water is degraded, and meanwhile, the catalyst can be recycled and continuously used. The catalyst prepared by the invention has higher PMS catalytic activity and is suitable for dye and antibiotic wastewater with higher concentration. In addition, sulfate radical with strong oxidability and other various oxygen active species can be generated in the process, the utilization rate of the radical is high, the reaction rate is high, and the pollutant removing effect is obvious. FeOOH coated Mn according to the present invention 3 O 4 The composite material realizes the synergistic effect of different metal compounds, promotes the transfer of electrons, is less influenced by water quality conditions, and reduces catalysisChemical and oxidant drug amounts.
Drawings
FIG. 1FeOOH coated Mn 3 O 4 High resolution transmission electron microscopy (a) and transmission electron microscopy (b) of the composite material.
FIG. 2 is a pure FeOOH and a different FeOOH: mn 3 O 4 Mass ratio X-ray diffraction pattern 20MF-80MF (1:4-4:1) MF.
FIG. 3 is an experiment (a) of dye wastewater removal by activating PMS in different systems; different FeOOH: mn 3 O 4 The mass ratio of activated PMS to dye-removal wastewater experiment (b).
FIG. 4 is a screen of different catalyst concentrations for activating PMS to remove RhB, with the horizontal and vertical tables showing reaction time min; (a); screening experiments (b) with different RhB concentrations; screening experiments (c) for different PMS concentrations.
FIG. 5FeOOH coated Mn 3 O 4 The composite material was subjected to multiple replicates.
FIG. 6 is SO 4 -· And OH (a); 1 O 2 electron spin resonance spectrum (b).
Detailed Description
Preparation example FeOOH coated Mn 3 O 4 Preparation of composite materials
The method comprises the following steps: (1) 18mmol NaOH and a certain amount of K 2 FeO 4 Sequentially dissolving in 30mL of deionized water to form solution A; (2) 9mmol MnCl 2 ·4H 2 O is dissolved in 70mL of deionized water, and is continuously stirred and heated to 90 ℃ in a water bath to form solution B; (3) The prepared solution A is dropwise poured into the solution B, the mixture is continuously stirred at 90 ℃ for reaction for 2 hours, the prepared compound solution is cooled to room temperature, the deionized water and the absolute ethyl alcohol are used for washing away unreacted ions in the solution, and the solution is dried at 70 ℃ to constant weight, thus obtaining the FeOOH coated Mn 3 O 4 A composite material.
To examine different K 2 FeO 4 Influence of addition amount on final product activation PMS to remove dye, and MnCl is maintained 2 ·4H 2 On the premise of unchanged O dosage, 2mmol, 5.14mmol, 11.56mmol and 30.8 mmol are respectively added according to the mass ratio of FeOOH accounting for 20%, 40%, 60% and 80% of the final product4mmol of K 2 FeO 4 The prepared materials were labeled 20MF, 40MF, 60MF, 80MF. K (K) 2 FeO 4 And MnCl 2 ·4H 2 The O molar ratio is 1:4.5, 1:1.75, 1.28:1, and 3.43:1 respectively. In order to compare the catalytic effect of the composite material, the method is adopted without adding MnCl 2 ·4H 2 O, 2mmol of K 2 FeO 4 And 4mmol of NaOH were dissolved in water and heated at 90℃for 2 hours to prepare FeOOH, designated as 100F. FeOOH coating Mn 3 O 4 (2:3) the microstructure of the composite material is shown in figure 1. The XRD patterns of the different mass ratios of FeOOH and Mn3O4 are shown in FIG. 2.
EXAMPLE 1 PMS degradation of RhB alone
5mL of RhB stock solution (1 g/L) was removed and added to a 250mL beaker, and the mixture was placed in a thermostat water bath after being put into a rotor and stirred for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, the results of which are shown in FIG. 3 a.
EXAMPLE 2FeOOH coating of Mn 3 O 4 (0:1) composite activation PMS degradation RhB
Weighing 20mg of FeOOH coated Mn 3 O 4 (0:1) the composite material was sonicated in 80mL of water for 5min, after being dispersed uniformly, was added to a 250mL beaker along with 5mL RhB stock solution (1 g/L), placed in a rotor, and placed in a thermostatic water bath for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, the results of which are shown in FIG. 3 a.
EXAMPLE 3FeOOH coating of Mn 3 O 4 (1:0) composite activated PMS degradation RhB
Weighing 20mg of FeOOH coated Mn 3 O 4 (1:0) the composite material was sonicated in 80mL of water for 5min, after being dispersed uniformly, was added to a 250mL beaker along with 5mL RhB stock solution (1 g/L), placed in a rotor, and placed in a thermostatic waterbath for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, the results of which are shown in FIG. 3 a.
EXAMPLE 4FeOOH coating of Mn 3 O 4 (2:3) composite activated PMS degradation RhB
Weighing 20mg of FeOOH coated Mn 3 O 4 (2:3) the composite material was sonicated in 80mL of water for 5min, after being dispersed uniformly, was added to a 250mL beaker along with 5mL RhB stock solution (1 g/L), placed in a rotor, and placed in a thermostatic water bath for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, the results of which are shown in FIG. 3 a.
EXAMPLE 5FeOOH coating of Mn 3 O 4 (1:4) composite activated PMS degradation RhB
Weighing 20mg of FeOOH coated Mn 3 O 4 (1:4) the composite material was sonicated in 80mL of water for 5min, after being dispersed uniformly, was added to a 250mL beaker along with 5mL RhB stock solution (1 g/L), placed in a rotor, and placed in a thermostatic water bath for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At 5min intervals, 2mL of the solution was taken with a syringe, the unreacted PMS was quenched with sodium thiosulfate after filtration with a 0.45 μm filter and examinedAbsorbance of the remaining contaminants, and the contaminant degradation profile was plotted, the results are shown in fig. 3 b.
EXAMPLE 6FeOOH coating of Mn 3 O 4 (3:2) composite activated PMS degradation RhB
Weighing 20mg of FeOOH coated Mn 3 O 4 (3:2) ultrasonic treatment of the composite material in 80mL of water for 5min, adding the uniformly dispersed composite material and 5mL of RhB stock solution (1 g/L) into a 250mL beaker, putting the mixture into a rotor, and then placing the mixture into a constant-temperature water bath kettle for stirring for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, as shown in FIG. 3 b.
EXAMPLE 7FeOOH coating of Mn 3 O 4 (4:1) composite activated PMS degradation RhB
Weighing 20mg of FeOOH coated Mn 3 O 4 (4:1) the composite material was sonicated in 80mL of water for 5min, after being dispersed uniformly, was added to a 250mL beaker along with 5mL RhB stock solution (1 g/L), placed in a rotor, and placed in a thermostatic water bath for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, as shown in FIG. 3 b.
Through the degradation experiments of examples 1-7, it can be seen from FIG. 3 that FeOOH and Mn are present when the composite material of the present invention catalyzes the optimal effect of degrading pollutants 3 O 4 The mass ratio of (2) is 2:3.
Example 8 screening of initial concentration of catalyst
In order to optimize the initial concentration of the catalyst, 0mg, 5mg, 10mg, 30mg, 40mg FeOOH coated Mn were weighed respectively 3 O 4 (2:3) compoundingThe material is ultrasonically treated in 80mL of water for 5min, and after being uniformly dispersed, the material and 5mL of RhB stock solution (1 g/L) are added into a 250mL beaker, and the mixture is placed into a rotor and then placed into a constant-temperature water bath kettle for stirring for 30min. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, the results of which are shown in FIG. 4 a. The results show that as the concentration of the catalyst increases, the removal effect of the contaminants will increase significantly and when increased to a certain concentration, the removal effect will not increase.
EXAMPLE 9 screening of initial RhB concentration
Weighing 20mg of FeOOH coated Mn 3 O 4 (2:3) ultrasonic treatment of the composite material in 80mL of water for 5min, after uniform dispersion, respectively transferring 2.5mL, 5mL, 7.5mL and 10mL of RhB stock solution (1 g/L) into a 250mL beaker, putting into a rotor, and then placing into a constant-temperature water bath kettle for stirring for 30min in order to optimize the initial concentration of the dye. Then 1mL of PMS stock solution (20 g/L) was added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, the results of which are shown in FIG. 4 b. The results clearly show that the removal effect is reduced with increasing concentration of this RhB.
EXAMPLE 10 screening of PMS addition amount
Weighing 20mg of FeOOH coated Mn 3 O 4 (2:3) the composite material was sonicated in 80mL of water for 5min, after being dispersed uniformly, was added to a 250mL beaker along with 5mL RhB stock solution (1 g/L), placed in a rotor, and placed in a thermostatic water bath for 30min. To optimize the PMS addition, 0mL, 0.5mL, 1mL, 1.5mL, 2mL PMS stock solutions (20 g/L) were removed, respectively, and added dropwise to a beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted solution was then used to adjust the pH of the solution to a pH of 4The volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter, unreacted PMS was quenched with sodium thiosulfate, and the absorbance of the remaining contaminants was measured, and the contaminant degradation profile was plotted, the results of which are shown in FIG. 4 c. As the amount of PMS increases, the removal effect will increase.
EXAMPLE 11FeOOH coating of Mn 3 O 4 (2:3) composite reuse experiments
Weighing 20mg of FeOOH coated Mn 3 O 4 (2:3) the composite material was sonicated in 80mL of water for 5min, after being dispersed uniformly, was added to a 250mL beaker along with 5mL RhB stock solution (1 g/L), placed in a rotor, and placed in a thermostatic water bath for 30min. 1mL of PMS stock solution (20 g/L) was removed and added dropwise to the beaker, the pH of the solution was adjusted to 4 using boric acid (0.2M) and sodium tetraborate (0.1M), and the adjusted volume of the solution was made up to 100mL. At intervals of 5min, 2mL of the solution was taken with a syringe, after filtration with a 0.45 μm filter membrane, unreacted PMS was quenched with sodium thiosulfate, the absorbance of the remaining contaminants was measured, a contaminant degradation profile was drawn, and the reacted solution was subjected to centrifugation, separation, washing and drying to perform repeated experiments, the results of which are shown in FIG. 5. The result shows that the catalyst still has higher catalytic activity after 5 times of repeated use.
Example 12 electron paramagnetic resonance characterization of free radicals during the reaction
To confirm that there are different free radical generation during the experiment, the present invention characterizes the free radicals involved in this system by electron paramagnetic resonance, the results of which are shown in fig. 5. The results show that the corresponding characteristic peaks are not generated under the condition that the catalyst is not added, the characteristic peaks of the corresponding free radicals appear after the catalyst is added, and the characteristic peaks of the sulfate radical and the hydroxyl radical are shown in fig. 6a, and the characteristic peak intensity increases with the increase of the reaction time. FIG. 6b is a characteristic peak of singlet oxygen, the peak intensity of which increases with increasing reaction time. This further shows that a large amount of free radicals and active substances are generated in the system, and dye and antibiotic wastewater can be effectively removed.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (13)
1. FeOOH cladding Mn 3 O 4 The preparation method of the composite material is characterized by comprising the following steps:
(1) Sequentially dissolving alkali and ferrate in deionized water to form solution A; (2) Dissolving a manganese source in deionized water, and continuously stirring and heating to 70-90 ℃ to form a solution B; (3) The prepared solution A is dropwise poured into the solution B, the mixture reacts for 1 to 3 hours at the temperature of 70 to 90 ℃ under the stirring condition, the prepared compound solution is cooled to the room temperature, the deionized water and the absolute ethyl alcohol are used for washing out unreacted ions in the solution, and the solution is dried to constant weight at the temperature of 60 to 80 ℃ to obtain FeOOH coated Mn 3 O 4 A composite material.
2. The method of claim 1, wherein in step (2), a manganese source is dissolved in deionized water and heated to 90 ℃ with continuous stirring to form solution B; in the step (3), the reaction is carried out for 2 hours at 90 ℃ under the stirring condition; in step (3), the drying temperature was 70 ℃.
3. The method of claim 1, wherein the base is NaOH or KOH.
4. The method of claim 1, wherein the ferrate is K 2 FeO 4 Or/and Na 2 FeO 4 。
5. The method of claim 1, wherein the manganese source is one or more of manganese chloride, manganese sulfate, and manganese nitrate.
6. The method according to claim 1, wherein in the solution A, the alkali solution is NaOH.
7. The FeOOH coated Mn prepared by the method of any one of claims 1 to 5 3 O 4 A composite material; the FeOOH coats Mn 3 O 4 The microcosmic appearance of the composite material is a flaky structure, the width is 40-50 nm, and the thickness of a single sheet is 8-10 nm; feOOH and Mn 3 O 4 The mass ratio of (2) is 1:4-4:1.
8. The FeOOH-coated Mn of claim 7 3 O 4 A composite material characterized by FeOOH and Mn 3 O 4 The mass ratio of (2) is 2:3.
9. The FeOOH coated Mn of claim 7 3 O 4 The application of the composite material in activating PMS to remove dye wastewater.
10. The use according to claim 9, wherein the dye is rhodamine B.
11. The application according to claim 10, wherein the application comprises the steps of: adding the prepared FeOOH coated Mn3O4 composite material into waste water containing dye, simultaneously adding PMS, and stirring at room temperature;
the PMS is at least one of potassium hydrogen peroxymonosulfate, sodium hydrogen peroxymonosulfate and ammonium hydrogen peroxymonosulfate;
the FeOOH coats Mn 3 O 4 The usage amount of the composite material is 0.2-0.4 g/L;
the initial concentration of rhodamine B is 20-100 mg/L;
the amount of PMS used is 0.325 to 1.3mM.
12. The use according to claim 11, wherein FeOOH coats Mn 3 O 4 The usage amount of the composite material is 0.3-0.4 g/L; the saidThe initial concentration of rhodamine B is 20-50 mg/L; the amount of PMS used is 0.65 to 1.3mM.
13. The use according to claim 12, wherein the PMS is used in an amount of 1.3mM.
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