CN114192139A - Epsilon-MnO2Preparation method of porous hexagonal tablet and application of porous hexagonal tablet in degrading bisphenol A in water - Google Patents
Epsilon-MnO2Preparation method of porous hexagonal tablet and application of porous hexagonal tablet in degrading bisphenol A in water Download PDFInfo
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- CN114192139A CN114192139A CN202111482294.2A CN202111482294A CN114192139A CN 114192139 A CN114192139 A CN 114192139A CN 202111482294 A CN202111482294 A CN 202111482294A CN 114192139 A CN114192139 A CN 114192139A
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 14
- 230000000593 degrading effect Effects 0.000 title description 5
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000002351 wastewater Substances 0.000 claims abstract description 21
- 229910006343 ε-MnO2 Inorganic materials 0.000 claims abstract description 19
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical group C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 239000004021 humic acid Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MSBWDNNCBOLXGS-UHFFFAOYSA-L manganese(2+);diacetate;hydrate Chemical group O.[Mn+2].CC([O-])=O.CC([O-])=O MSBWDNNCBOLXGS-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 229910009112 xH2O Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 9
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000006872 improvement Effects 0.000 description 6
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229940011871 estrogen Drugs 0.000 description 2
- 239000000262 estrogen Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 102000015694 estrogen receptors Human genes 0.000 description 1
- 108010038795 estrogen receptors Proteins 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/40—
-
- B01J35/613—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Abstract
The invention discloses epsilon-MnO2The application of the porous hexagonal sheet nanometer material in the treatment of bisphenol A-containing wastewater is to add epsilon-MnO2Uniformly dispersing the porous hexagonal sheet nano material serving as a catalyst in the bisphenol A-containing wastewater, adding peroxymonosulfate serving as an oxidant, performing degradation reaction for 20-30min, and filtering to remove the catalyst. The invention adopts cheap inorganic salt and alkali as raw materials and hydrothermal reaction as a process, and has the advantages of high integral valenceLow cost, rich yield and the like. epsilon-MnO of synthesized hexagonal plate2The diameter is 100-200nm and the thickness is about 20 nm. The specific surface area of the nano material is 36.24m2/g, and the average pore radius is 8.48 nm. Before and after the catalyst participates in the catalytic reaction, the comparison of XRD spectrograms has no obvious change, which shows that the catalyst prepared by the invention has good stability.
Description
Technical Field
The invention relates to epsilon-MnO2A preparation method of a porous hexagonal tablet and application thereof in degrading bisphenol A in water belong to the field of water treatment.
Background
Bisphenol a (bpa), a common hazardous organic material, has been widely used in the industrial production of epoxy resins and polycarbonate plastics. In addition, bisphenol a is believed to be a complex that disturbs estrogen and binds to estrogen receptors in the human body, thereby affecting estrogen secretion. Removal of bisphenol a should therefore be of great concern.
Heretofore, various treatment methods have been employed to solve the contamination of bisphenol A, such as adsorption, membrane filtration, biological treatment, photocatalytic treatment method and the like. However, these methods have some disadvantages such as low processing efficiency and the need for secondary processing, etc. And advanced oxidation technology based on sulfate radical (SO 4-) is used for efficiently removing organic pollutants, and can degrade and mineralize the organic pollutants in water into small molecular substances.
Recently, manganese-based materials have been widely reported to activate Peroxymonosulfate (PMS) for degradation of organic pollutants in water, because manganese-based materials have unique Mn2+/Mn4+The oxidation-reduction cycle is beneficial to the catalytic activation of PMS.
Disclosure of Invention
In view of the above-mentioned problems, the present invention provides an epsilon-MnO2A preparation method and application of a porous hexagonal sheet nano material.
To achieve the above object, the epsilon-MnO synthesized by the present invention2The width of the porous hexagonal plate is 100-200nm, the thickness is about 20nm, and the specific surface area is 36.24m2In terms of/g, the mean pore radius is 8.48 nm.
In addition, the invention also provides the epsilon-MnO2The preparation method of the porous hexagonal sheet comprises the following steps:
1) preparing a manganese salt solution and a strong alkali solution at normal temperature, dropwise adding the manganese salt solution into the strong alkali solution, and continuously stirring to obtain a brown solution. Then adding a certain amount of glucose into the mixed solution, and stirring to turn the solution into gray.
2) Transferring the gray solution into a 100mL reaction kettle, placing the reaction kettle in an oven preheated to 180 ℃ for reaction for 20 hours to obtain gray powder, and filtering, washing, centrifuging and drying the gray powder to obtain precursor powder.
3) Calcining the precursor powder in air at 300 ℃ for 3h at the heating rate of 1 ℃/min to finally obtain the product of epsilon-MnO2A perforated hexagonal sheet.
As an improvement, manganese acetate monohydrate is used as the manganese salt, and potassium hydroxide is used as the strong base.
As an improvement, manganese acetate monohydrate is adopted as the manganese salt in the step 1), and the molar concentration of the manganese salt is 0.15-0.25 mol/L. The strong alkaline solution is potassium hydroxide with the molar concentration of 1.5-2 mol/L. Stirring for 20-30min, and adding glucose with concentration of 0.005-0.006 mol.
As a modification, in the step 2), the preheating temperature of the oven is about 180-. Washing with ethanol for 5-6 times, centrifuging at 7000r/min, and vacuum drying at 55-65 deg.C for 6-8 h.
As a modification, the calcination temperature in the air in the step 3) is 250-350 ℃.
Finally, the invention also provides epsilon-MnO2The application of the porous hexagonal sheet nano material in the treatment of bisphenol A-containing wastewater.
As an improvement, the pH value of the wastewater containing the antibiotics is 3-9, and the concentration of bisphenol A in the wastewater is 20-30 mg/L.
As an improvement, the specific test steps are as follows: adding epsilon-MnO2Uniformly dispersing the porous hexagonal sheet nano material serving as a catalyst in the bisphenol A-containing wastewater, adding Peroxymonosulfate (PMS) serving as an oxidant, performing degradation reaction for 30-40min, and filtering to remove the catalyst.
As an improvement, in the waste water containing bisphenol A, epsilon-MnO2The adding amount of the porous hexagonal plate nano material is 0.1 g/L; the addition amount of Peroxymonosulfate (PMS) is 2 mM;potassium hydrogen persulfate is used as the peroxymonosulfate.
Compared with the prior art, the epsilon-MnO prepared by the invention2When the porous hexagonal sheet nano material is used as a catalyst for bisphenol A wastewater treatment, Mn (II) is used as a starting site for activating peroxymonosulfate, and the specific reaction formula is as follows 1-5. A large amount of sulfate radicals and hydroxyl radicals are generated, bisphenol A in the wastewater can be degraded quickly and efficiently, and the degradation efficiency is better in the range of pH 3-9. In addition, the invention summarizes the influence of inorganic anions and humic acid on the degradation reaction and summarizes the effect of the catalyst on the action of different oxidants.
Mn(II)+HSO5-→Mn(III)+OH-+SO4- (1)
Mn(III)+HSO5-→Mn(II)+H++SO5-- (2)
Mn(III)+HSO5-→Mn(IV)+SO42-+HO. (3)
SO5-+-2OH-→2SO42-+2HO·+O2 (4)
HO·+BPA→CO2+H2O (5)
Mn(II)+HSO5 -→Mn(III)+OH-+SO4 ·- (1)
Mn(III)+HSO5 -→Mn(II)+H++SO5 ·- (2)
Mn(III)+HSO5 -→Mn(IV)+SO4 2-+HO· (3)
So5 ·-+2OH-→2SO4 2-+2HO·+O2 (4)
HO·+BPA→CO2+H2O (5)
The invention adopts cheap inorganic salt and alkali as raw materials and hydrothermal reaction as a process, and has the advantages of low price, rich yield and the like. The obtained epsilon-MnO2The comparison of XRD spectrograms of the porous hexagonal plate nano material before and after the porous hexagonal plate nano material participates in catalytic reaction is unchanged, which shows that the catalyst prepared by the inventionHas good structural stability.
Drawings
FIG. 1 shows ε -MnO obtained in example 1 of the present invention2SEM and TEM images of porous hexagonal plate nanomaterials;
FIG. 2 shows ε -MnO obtained in example 1 of the present invention2XRD pattern of the porous hexagonal plate nano material;
FIG. 3 shows ε -MnO obtained in example 1 of the present invention2N2 adsorption-desorption curve of porous hexagonal plate nanomaterial.
FIG. 4 is a graph showing the time course of catalytic degradation of bisphenol A by various substances;
the figures respectively include: potassium hydrogen Persulfate (PMS), epsilon-MnO2、ε-MnO2+Potassium hydrogen Peroxymonosulfate (PMS):
FIG. 5 shows ε -MnO obtained in example 1 of the present invention2The effect graph of the porous hexagonal plate for degrading the bisphenol A-containing wastewater with different initial pH values is shown.
FIG. 6 shows ε -MnO obtained in example 1 of the present invention2When the porous hexagonal piece degrades the bisphenol A, the effect is influenced by inorganic anions and humic acid.
FIG. 7 shows ε -MnO obtained in example 1 of the present invention2And (3) when the porous hexagonal piece degrades the bisphenol A, the effect of the effect on different oxidants is shown.
FIG. 8 shows ε -MnO obtained in example 1 of the present invention2TOC graph of porous hexagonal piece degradation bisphenol A;
Detailed Description
The following examples are further illustrative of the present invention as to the technical content of the present invention, but the essence of the present invention is not limited to the following examples, and one of ordinary skill in the art can and should understand that any simple changes or substitutions based on the essence of the present invention should fall within the protection scope of the present invention.
Example 1:
Epsilon-MnO2The application of the porous hexagonal plate nano material in the treatment of bisphenol A-containing wastewater comprises the following steps:
step one, preparing epsilon-MnO2Porous hexagonal sheetRice material
1) 1.225g of manganese acetate monohydrate was weighed out and dissolved in 25mL of water to obtain solution A. 2.8 g of potassium hydroxide was weighed out and dissolved in 25mL of water, and after complete dissolution and cooling, solution B was obtained. The solution A was added dropwise to the solution B and stirring was continued for 20min to form a brown precipitate. 0.056 mol of glucose is weighed and added into the solution, and after stirring for 10min, the solution turns grey.
2) The gray solution was transferred to a 100mL autoclave and placed in an oven preheated to 180 ℃ for 20 h. And filtering, washing and centrifuging the obtained gray precipitate, and then drying in vacuum at 60 ℃ for 12h to obtain precursor powder.
3) And calcining the precursor powder in air at 300 ℃ for 3h, wherein the heating rate is 1 ℃/min. The final product is epsilon-MnO 2 porous hexagonal plate.
Step two, epsilon-MnO2Catalytic degradation of bisphenol A wastewater by porous hexagonal sheets
Adding epsilon-MnO into 50mL of water sample containing 30mg/L bisphenol A25mg of porous hexagonal piece, 30mg of potassium hydrogen Persulfate (PMS) is added, the reaction is carried out under the conditions of 25 ℃ and pH 7, the shaking table is fully vibrated, samples are taken at certain time intervals and filtered, the norfloxacin content in the aqueous solution is detected, and when the reaction time is 30min, the detection removal efficiency reaches 93 percent (as shown in figure 4).
The epsilon-MnO obtained in example 1 was2And (5) carrying out performance test on the porous hexagonal sheet nanometer material.
The morphology of the catalyst is characterized by using an FE I-Quanta 200 Scanning Electron Microscope (SEM), and the concentration of bisphenol A in a treated water sample is detected by using a UV-2550 ultraviolet-visible spectrophotometer.
Wherein, by the scheme 1 (. epsilon. -MnO)2SEM and TEM images of the porous hexagonal plate) it can clearly be seen that the product is a nanomaterial, the morphology is hexagonal plate and contains porous structures.
FIG. 2 is an XRD spectrum, which proves that the phase structure of the synthetic material is epsilon-MnO2The structure and XRD patterns before and after reaction have no obvious change, thus proving the stability of the structure of the synthetic catalyst.
FIG. 3 is an N2 adsorption-desorption curve, tableMing epsilon-MnO2Has a specific surface area of 36.24m2In terms of/g, the mean pore radius is 8.48 nm.
Example 2:
Epsilon-MnO2Use of porous hexagonal plates for treating bisphenol a wastewater of different pH. The method comprises the following steps:
step one, preparing bisphenol A solutions with different initial pH values, wherein the initial pH values are 3,5,7 and 9 respectively. 50mL of each of four bisphenol A aqueous solutions having different pH values was taken, and 5mg of. epsilon. -MnO was added thereto2Adding 30mg of potassium hydrogen Persulfate (PMS) into the porous hexagonal sheet nano material, fully oscillating the porous hexagonal sheet nano material in a table concentrator at the temperature of 25 ℃ at the rotating speed of 200r/min, sampling and filtering the porous hexagonal sheet nano material at certain time intervals, detecting the content of the bisphenol A in the aqueous solution, wherein the reaction time is 30min, and finding that the reaction has only slight influence on catalytic reaction when the pH is 3,7 and 9, and the degradation effect on the bisphenol A can reach more than 90%. At pH 5, the degradation effect of bisphenol a was suppressed to some extent (see fig. 5).
Example 3:
Epsilon-MnO2Application of porous hexagonal sheets to treatment of bisphenol A in wastewater under different anion and humic acid conditions. The method comprises the following steps:
respectively adding 5mg of epsilon-MnO 2 porous hexagonal sheet material into four 50mL water samples containing 30mg/L bisphenol A, respectively adding different amounts of sodium bicarbonate, sodium nitrate, sodium chloride and humic acid, respectively adding 30mg of potassium hydrogen Persulfate (PMS), and starting the reaction. The reaction conditions were 25 ℃, pH 7, shaking table shaking, reaction time 30 min. The results were obtained that the addition of sodium bicarbonate, sodium nitrate and humic acid all inhibited the degradation of bisphenol A, while sodium chloride slightly promoted the degradation of bisphenol A (see FIG. 6).
Example 4:
Epsilon-MnO2The use of porous hexagonal plates for treating bisphenol A in wastewater with the addition of an oxidizing agent. The method comprises the following steps:
adding 5mg of epsilon-MnO into three 50mL water samples containing 30mg/L bisphenol A respectively2Adding 2mM hydrogen peroxide (H) to the porous hexagonal plate material2O2) Potassium Persulfate (PS) and Potassium Monopersulfate (PMS). The reaction conditions were 25 ℃, pH 7, shaking table shaking, reaction time 30 min. As a result, the effect of degrading bisphenol A was PMS>PS>H2O2(see fig. 7).
Example 5:
Epsilon-MnO2TOC test of bisphenol A in wastewater treated by porous hexagonal plates under PMS (PMS) activation conditions. The method comprises the following steps:
to 100mL of a water sample containing 30mg/L of bisphenol A, 10mg of. epsilon. -MnO was added2A2 mM potassium hydrogen Peroxymonosulfate (PMS) was added to the porous hexagonal sheet. The reaction conditions were 25 ℃, pH 7, shaking table shaking, reaction time 2 h. Samples were taken every 10min and filtered for TOC. The obtained results are shown in FIG. 8.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made on the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (11)
1. Epsilon-MnO prepared based on hydrothermal method2The porous hexagonal plate is characterized in that the porous hexagonal plate is made of KOH and Mn (CH)3COOH)2Reacting at normal temperature to generate Mn (OH)2·xH2O, then calcining at 300 ℃ in the air under hydrothermal conditions to obtain epsilon-MnO with a porous structure2. epsilon-MnO of synthesized hexagonal plate2The diameter is 100-200nm and the thickness is about 20 nm. The specific surface area of the nano material is 36.24m2/g, and the average pore radius is 8.48 nm.
2. The epsilon-MnO of claim 12The preparation method of the porous hexagonal sheet is characterized by comprising the following steps of:
1) manganese salt was dissolved in water to give solution a. And preparing a strong base solution B. The solution A is added into the solution B drop by drop, and stirring is continuously carried out during the addition, so that brown precipitate is generated.
2) Adding a certain amount of glucose into the mixed solution, and stirring to uniformly mix the glucose and the mixed solution. And transferring the precursor powder into a 100mL polytetrafluoroethylene reaction kettle, putting the kettle into a baking oven preheated to 180 ℃ for reaction for 20 hours to obtain gray solid powder, and filtering, washing, centrifuging and drying to obtain precursor powder.
3) Calcining the precursor powder for 3h at 300 ℃ in the air atmosphere to obtain epsilon-MnO2A perforated hexagonal sheet.
3. An epsilon-MnO as defined in claim 22The preparation method of the porous hexagonal tablet is characterized in that in the step 1), the molar concentration of manganese salt in the solution A is 0.15-0.25mol/L, the molar concentration of strong alkali solution is 1.5-2mol/L, the manganese salt and the strong alkali solution are added dropwise at a constant speed, and the mixed solution is stirred for about 20 min.
4. An epsilon-MnO as defined in claim 22The preparation method of the porous hexagonal tablet is characterized in that in the step 1), the manganese salt is manganese acetate monohydrate, and the alkali is potassium hydroxide.
5. An epsilon-MnO as defined in claim 22The preparation method of the porous hexagonal piece is characterized in that in the step 2), the glucose is added in an amount of 0.005-0.006mol, and the temperature of an oven needs to be preheated to 180 ℃. Washing with ethanol, and vacuum drying at 55-65 deg.C for 6 h.
6. An epsilon-MnO as defined in claim 22The preparation method of the porous hexagonal piece is characterized in that in the step 3), the heating rate is 1 ℃/min, and the calcining temperature is 250-.
7. An epsilon-MnO obtainable by the process of claim 1 or any one of claims 2 to 62Use of a porous hexagonal sheet for the treatment of bisphenol a-containing wastewater.
8. The use according to claim 7, wherein the pH of the bisphenol A-containing wastewater is 3 to 9 and the concentration of bisphenol A in the wastewater is 20 to 30 mg/L.
9. The application of claim 7, wherein the specific processing steps are: adding epsilon-MnO2Uniformly dispersing the porous hexagonal sheets serving as a catalyst in the bisphenol A-containing wastewater, adding peroxymonosulfate serving as an oxidant, performing degradation reaction for 30-40min, and filtering to remove the catalyst.
10. Use according to claim 9, characterized in that in the bisphenol a containing waste water, epsilon-MnO2The adding amount of the porous hexagonal piece is 0.1 g/L; the amount of added peroxymonosulfate was 2 mM.
11. Use according to claim 9, characterized in that the type of inorganic anion added to the bisphenol A-containing waste water is HCO3-,NO3-,Cl-. The added natural organic substance is humic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254135A (en) * | 2022-08-01 | 2022-11-01 | 上海交通大学 | Epsilon-MnO 2 @Fe 2 O 3 Catalyst, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087775A1 (en) * | 2000-05-15 | 2001-11-22 | Eveready Battery Company Inc. | A method of preparation of porous manganese dioxide |
| JP2009197325A (en) * | 2008-01-22 | 2009-09-03 | Mitsubishi Materials Corp | Dispersion solution of metal nanoparticle, and method for production thereof |
| CN108735518A (en) * | 2018-05-31 | 2018-11-02 | 济南大学 | A kind of hexagonal flake manganese oxide@nickel oxide composite materials and preparation method thereof |
| CN110975863A (en) * | 2019-12-13 | 2020-04-10 | 中国科学院合肥物质科学研究院 | Spine-shaped nano manganese dioxide/graphene composite material, preparation method and application thereof |
| US20210040334A1 (en) * | 2019-08-05 | 2021-02-11 | The Boeing Company | Systems, compositions, and methods for enhanced electromagnetic shielding and corrosion resistance |
| CN113019359A (en) * | 2021-02-05 | 2021-06-25 | 中国科学院合肥物质科学研究院 | MnO (MnO)2Preparation method and application of triangular plate Fenton catalyst |
-
2021
- 2021-12-07 CN CN202111482294.2A patent/CN114192139A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087775A1 (en) * | 2000-05-15 | 2001-11-22 | Eveready Battery Company Inc. | A method of preparation of porous manganese dioxide |
| JP2009197325A (en) * | 2008-01-22 | 2009-09-03 | Mitsubishi Materials Corp | Dispersion solution of metal nanoparticle, and method for production thereof |
| CN108735518A (en) * | 2018-05-31 | 2018-11-02 | 济南大学 | A kind of hexagonal flake manganese oxide@nickel oxide composite materials and preparation method thereof |
| US20210040334A1 (en) * | 2019-08-05 | 2021-02-11 | The Boeing Company | Systems, compositions, and methods for enhanced electromagnetic shielding and corrosion resistance |
| CN110975863A (en) * | 2019-12-13 | 2020-04-10 | 中国科学院合肥物质科学研究院 | Spine-shaped nano manganese dioxide/graphene composite material, preparation method and application thereof |
| CN113019359A (en) * | 2021-02-05 | 2021-06-25 | 中国科学院合肥物质科学研究院 | MnO (MnO)2Preparation method and application of triangular plate Fenton catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 鲍菊生: "锰氧化物六角形片的制备及电化学性能研究", 《硅酸盐通报》, vol. 38, pages 1002 - 1005 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254135A (en) * | 2022-08-01 | 2022-11-01 | 上海交通大学 | Epsilon-MnO 2 @Fe 2 O 3 Catalyst, preparation method and application thereof |
| CN115254135B (en) * | 2022-08-01 | 2023-12-26 | 上海交通大学 | epsilon-MnO 2 @Fe 2 O 3 Catalyst, preparation method and application thereof |
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