CN115430416B - ZrO2Preparation method of OMS-2 and application of OMS-2 in degrading organic pollutants - Google Patents
ZrO2Preparation method of OMS-2 and application of OMS-2 in degrading organic pollutants Download PDFInfo
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- CN115430416B CN115430416B CN202210917602.8A CN202210917602A CN115430416B CN 115430416 B CN115430416 B CN 115430416B CN 202210917602 A CN202210917602 A CN 202210917602A CN 115430416 B CN115430416 B CN 115430416B
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- estriol
- peroxymonosulfate
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- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 title claims abstract 7
- 238000000034 method Methods 0.000 title claims description 8
- 239000002957 persistent organic pollutant Substances 0.000 title abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- PROQIPRRNZUXQM-UHFFFAOYSA-N (16alpha,17betaOH)-Estra-1,3,5(10)-triene-3,16,17-triol Natural products OC1=CC=C2C3CCC(C)(C(C(O)C4)O)C4C3CCC2=C1 PROQIPRRNZUXQM-UHFFFAOYSA-N 0.000 claims description 32
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 claims description 32
- 229960001348 estriol Drugs 0.000 claims description 32
- 238000000862 absorption spectrum Methods 0.000 claims description 12
- 230000031700 light absorption Effects 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 229940088597 hormone Drugs 0.000 abstract description 4
- 239000005556 hormone Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract description 3
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 229940088710 antibiotic agent Drugs 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 32
- 230000015556 catabolic process Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- QYAPHLRPFNSDNH-MRFRVZCGSA-N (4s,4as,5as,6s,12ar)-7-chloro-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O QYAPHLRPFNSDNH-MRFRVZCGSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229940063650 terramycin Drugs 0.000 description 7
- 239000004098 Tetracycline Substances 0.000 description 5
- 229960002180 tetracycline Drugs 0.000 description 5
- 235000019364 tetracycline Nutrition 0.000 description 5
- 229930101283 tetracycline Natural products 0.000 description 5
- 150000003522 tetracyclines Chemical class 0.000 description 5
- 239000004100 Oxytetracycline Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 4
- 229960000625 oxytetracycline Drugs 0.000 description 4
- 235000019366 oxytetracycline Nutrition 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGQYJDHTHFAPRN-UHFFFAOYSA-N 2-fluoro-6-(trifluoromethyl)benzonitrile Chemical compound FC1=CC=CC(C(F)(F)F)=C1C#N OGQYJDHTHFAPRN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229960003185 chlortetracycline hydrochloride Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 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 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003911 water pollution 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an OMS-2 catalyst doped with zirconium dioxide (ZrO 2) and application thereof in degrading organic pollutants, and the application of zirconium dioxide (ZrO 2) in modifying OMS-2 can efficiently degrade pollutants in water. The catalyst prepared by the invention is doped into OMS-2 by zirconium dioxide (ZrO 2), can be used for catalyzing and activating peroxymonosulfate to release a large amount of active free radicals, so that hormone, antibiotics and organic dye are efficiently oxidized and degraded, and simultaneously, the catalyst has excellent cycle performance and can be reused.
Description
Technical Field
The invention discloses a preparation method of a ZrO 2/OMS-2 catalyst, and application of the catalyst in degrading organic pollutants, belonging to the water pollution control technology.
Background
In the past decades, sewage treatment has attracted great attention due to the influence of the sewage treatment on public health, estriol is a hormone which can influence the normal dynamic balance, growth and development and reproduction functions of organisms, can enter the organisms to interfere with the synthesis, secretion and metabolism of the hormones of the organisms, and even can influence the nerves and immune systems, and has become a focus of home and abroad as a novel persistent organic pollutant. Recently, advanced oxidation processes have become one of the research hotspots due to their great degradation ability to organic dyes in water. Sulfate produced by Persulfate (PS) or Peroxymonosulfate (PMS) activation is the primary active species in the highest order oxidation process.
Manganese oxide octahedral molecular sieve (OMS-2) is widely used as a high-efficiency catalyst for organic dye degradation due to its unique nanorod structure, low cost and excellent catalytic activity. In order to increase the catalytic activity of OMS-2, several strategies have been developed, such as α -MnO 2 nanowires, nanorods, nanotubes, and flower-like spherical Mn 2O3; co, ce and Cu-OMS-2 are used as catalysts in the post-plasma catalysis of acetaldehyde degradation; co-doped K-OMS-2 nanofibers for carbon monoxide oxidation, and the like.
ZrO 2 has rich oxygen-containing surface functional groups and unsaturated Zr 4+-O2 -, which is more favorable for PMS activation, leads to rapid degradation after doping into OMS-2, simultaneously can not be rapidly degraded by OMS-2 alone in the process of treating hormone sewage, has low degradation degree, and can degrade 95% of pollutants into nontoxic micromolecule substances in a short time after nano zirconia is introduced. Meanwhile, zrO 2 is small in size, the specific surface area can be increased after doping with OMS-2, more active sites are provided, and the stability of the catalyst is improved. As zirconium dioxide is a weak acid oxide, the zirconium dioxide has enough stability to alkali solution and some acid solutions, and the doped catalyst can keep good degradation effect in estriol solutions with different pH values.
The invention synthesizes the ZrO 2 doped manganese oxide octahedral molecular sieve (ZrO 2/OMS-2-X) catalyst for the first time, generates active free radicals for degrading organic matters in aqueous solution after being activated by peroxymonosulfate, and converts toxic substances into nontoxic micromolecular substances. In addition, the ZrO 2/OMS-2-X catalyst also successfully degraded estriol five times without significant reduction in catalytic activity.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a ZrO 2/OMS-2 catalyst, which comprises the following steps:
(1) Adding ZrO 2 powder into a manganese sulfate monohydrate solution, adding a potassium permanganate solution, and carrying out reflux reaction for 20-30h at 90-120 ℃;
(2) And (3) washing and drying the product obtained in the step (1), and calcining at 200-400 ℃ in air atmosphere to obtain ZrO 2/OMS-2-X.
The mass concentration of the manganese sulfate monohydrate solution is 1.0-2.0g/L, and meanwhile, concentrated nitric acid is added into the solution to ensure that the PH=1-6 of the solution, and the mass concentration of the potassium permanganate is 0.1-1.0g/L.
The adding amount of the ZrO 2 powder is controlled to be 4.5-95% of the mole ratio of Zr to Mn.
The adding amount of ZrO 2 powder is controlled to be 4.5%, 9%, 18%, 27%, 45%, 60%, 75%, 90% or 95% of the mole ratio of Zr to Mn.
The invention also provides an application of the prepared ZrO 2/OMS-2 in degrading organic pollutants by activating peroxymonosulfate.
The organic pollutants comprise any one or more of estriol, rhodamine B, tetracycline, aureomycin hydrochloride and oxytetracycline.
The ZrO 2/OMS-2 catalyst prepared by the invention can generate a plurality of active free radicals in the catalytic degradation process so as to degrade pollutants.
The catalyst disclosed by the invention is a ZrO 2/OMS-2-X (X is the addition amount of Zr) catalyst obtained by doping ZrO 2 with different molar ratios in OMS-2, and a catalytic performance test shows that the catalyst can effectively promote the degradation process after being doped with ZrO 2 and can effectively degrade various pollutants.
The technical scheme of the invention is applied to the degradation of organic pollutants by free radicals generated by activating peroxymonosulfate with ZrO 2/OMS-2-X.
The organic pollutants comprise any one or more of estriol, tetracycline, aureomycin hydrochloride and oxytetracycline.
The ZrO 2/OMS-2-X is black powder, can be repeatedly used in the catalytic process, has an excellent catalytic effect on degradation of estriol, is low in dosage, can save cost, and has a good application prospect in the field of degradation of organic pollutants.
Drawings
FIG. 1 is a scanning electron diffraction pattern of ZrO 2/OMS-2-27% prepared in example 1.
FIG. 2 is an X-ray diffraction pattern of ZrO 2/OMS-2-27% obtained in example 1.
FIG. 3 is a graph showing the rate of degradation of estriol by ZrO 2/OMS-2-X in example 2.
FIG. 4 is a graph showing the ultraviolet-visible light absorption spectrum of ZrO 2/OMS-2-27% in example 3 for catalyzing the degradation of estriol by peroxymonosulfate.
FIG. 5 shows the electron paramagnetic resonance spectrum of ZrO 2/OMS-2-27% in example 3.
FIG. 6 is a graph showing the cyclic degradation rate of ZrO 2/OMS-2-27% catalyzed degradation of estriol from peroxymonosulfate in example 3.
FIG. 7 is an ultraviolet-visible light absorption spectrum of ZrO 2/OMS-2-27% catalytic peroxymonosulfate degradation terramycin prepared in example 4.
FIG. 8 is an ultraviolet-visible light absorption spectrum of the ZrO 2/OMS-2-27% activated peroxymonosulfate degradation aureomycin hydrochloride prepared in example 5.
FIG. 9 is a graph comparing the rates of degradation of estriol by the catalyst ZrO 2/OMS-2-27% prepared according to the present invention and by a physically mixed catalyst.
Detailed Description
Comparative example 1
The preparation method of OMS-2 comprises the following steps:
Step 1, 5.85g of potassium permanganate is dissolved in 100ml of deionized water, and a deep purple solution is obtained at room temperature.
Step 2, 8.8g of manganese sulfate monohydrate was added to 30ml of deionized water, and 3ml of concentrated nitric acid was added at room temperature.
And 3, slowly adding the solution obtained in the step 1 into the solution obtained in the step 2.
And 4, refluxing the solution obtained in the step 3 for 24 hours at 100 ℃.
And 5, filtering, separating, washing and drying the catalyst obtained in the step 4.
And 6, calcining the catalyst obtained in the step 5 in air at 300 ℃ to obtain a catalyst which is named OMS-2.
Example 1
Step 1, dissolving potassium permanganate in 100ml of deionized water, and obtaining a deep purple solution at room temperature.
Step 2, manganese sulfate monohydrate was added to 30ml of deionized water, and 3ml of concentrated nitric acid was added at room temperature.
And 3, adding ZrO 2 powder into the solution in the step 2, and stirring, wherein the adding mass of the ZrO 2 powder is respectively 0.5g, 0.9g, 1.9g, 2.9g, 4.9g, 6.5g, 8.2g, 9.8g and 10.4g.
And 4, respectively and slowly adding the solutions obtained in the step 1 into the solutions obtained in the step 3.
And 5, respectively refluxing the solutions obtained in the step 4 at 100 ℃ for 24 hours.
And 6, respectively filtering, separating, washing and drying the product obtained in the step 5.
Step 7, calcining the catalyst obtained in step 6 in air at 300 ℃ to obtain ZrO 2/OMS-2-X, wherein X is 4.5%, 9%, 18%, 27%, 45%, 60%, 75%, 90%, or 95% respectively.
Example 2
Use of catalyst OMS-2 of comparative example 1, catalyst ZrO 2/OMS-2-X of example 1 (x=4.5%, 9%, 18%, 27%, 45%, 60%, 75%, 90%, 95%) according to the invention for degradation of estriol.
The steps of the reaction for degrading estriol by using the catalyst OMS-2 are as follows:
Step 1: estriol solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, and the above catalyst was added at 0.25g/L, respectively, and stirred for 10min;
Step 2: testing and recording the absorption peak value of the estriol at the moment;
step 3: the peroxomonosulfate (0.25 g/L) was rapidly added to the round bottom flask, and 3mL of the mixture was taken out and added to the cuvette at regular intervals, and the peak of the ultraviolet-visible light absorption spectrum of tetracycline was measured by an ultraviolet-visible photometer.
FIG. 3 is a graph showing the comparison of the rates of degradation of estriol by the catalysts OMS-2 and ZrO 2/OMS-2-X (X=4.5%, 9%, 18%, 27%, 45%, 60%, 75%, 90%, 95%) prepared according to the present application, from which it can be seen that the catalyst after doping ZrO 2 has a better degradation effect than OMS-2, but the more the non-doping amount, the better the degradation effect, the degradation effect is when the doping amount is 4.5%, 9%, 18%, 27%, 45% according to the degradation effect of the Total Organic Carbon (TOC), which is significantly better than OMS-2, and is substantially completely degraded in 7-9 minutes. In the application, electron scanning diffraction is carried out by taking 27% doping amount as an example, as shown in fig. 1, and fig. 1 is a scanning electron diffraction picture of ZrO 2/OMS-2-27% prepared in example 1, and the obtained catalyst can be observed to have a rod-shaped structure. FIG. 2 is an X-ray diffraction pattern of ZrO 2/OMS-2-X catalyst prepared in example 1, in which the synthesized catalyst was observed to have the corresponding crystal planes of ZrO 2 and the original crystal plane characteristics of OMS-2 were retained, indicating that ZrO 2 was successfully doped on OMS-2. In fact, the inventors believe that at doping levels of 4.5%, 9%, 18%, 45%, the corresponding crystal planes of ZrO 2 in OMS-2 are still achieved.
Example 3
The catalyst ZrO 2/OMS-2-27% prepared by the invention is used for catalyzing peroxymonosulfate to generate free radical to degrade estriol.
The catalyst ZrO 2/OMS-2-27% catalyzes the reaction of degrading tetracycline by using peroxymonosulfate, and the method comprises the following steps:
step 1: estriol solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, catalyst (0.25 g/L) was added and stirred for 10min;
Step 2: testing and recording the absorption peak value of the estriol at the moment;
Step 3: the persulfate (0.25 g/L) was rapidly added to the round bottom flask, and 3mL of the mixture was taken out and added to the cuvette at a certain interval, and the peak value of the ultraviolet-visible light absorption spectrum of estriol was measured by an ultraviolet-visible light photometer.
Step 4: the zirconium dioxide doped catalyst ZrO 2/OMS-2-27% is centrifuged, washed and dried.
And 5, repeating the steps 1-3 to perform a circulation experiment for 5 times.
FIG. 4 is a graph showing the ultraviolet-visible light absorption spectrum of the free radical-degrading estriol produced by the ZrO 2/OMS-2-27% catalytic peroxymonosulfate prepared by the method, wherein the characteristic peak of the estriol is detected by an ultraviolet-visible light photometer at the wavelength of 278nm, sampling is carried out according to different time intervals, and the reaction is stopped when the peak value of the characteristic peak of the estriol at the wavelength of 278nm is no longer reduced, namely, 9 min.
FIG. 5 shows electron paramagnetic resonance spectra of ZrO 2/OMS-2-27% activated peroxymonosulfate prepared by the present invention, singlet oxygen energy oxidizes 2, 6-tetramethyl-4-piperidinol (TEMP) to produce paramagnetic 4-hydroxy-2, 6-tetramethyl-piperidinoxyl (TEMPO), and the detection and identification are carried out through Electron Paramagnetic Resonance (EPR), and the 1O2,•OH •O2 - has obvious strength and participates in the degradation process of organic matters.
FIG. 6 is a graph of the catalytic degradation rate of the catalyst ZrO 2/OMS-2-27% prepared by the method, which is repeated for 5 times, wherein the catalytic effect can be represented by the degradation rate, and the catalyst can still keep good degradation after 5 times of circulation, so that macromolecular organic pollutants can be converted into green pollution-free micromolecular substances.
Example 4
The catalyst ZrO 2/OMS-2-27% prepared by the invention is used for catalyzing peroxymonosulfate to generate free radical to degrade terramycin.
The catalyst ZrO 2/OMS-2-27% catalyzes the reaction of active species generated by peroxymonosulfate to degrade terramycin, and the steps are as follows:
Step 1: an terramycin solution (50 mL,50 mg/L) was added to a 100mL round bottom flask, cobalt-doped carbon-based catalyst ZrO 2/OMS-2-27% (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording the absorption peak value of the oxytetracycline at the moment;
Step 3: the persulfate (0.25 g/L) was rapidly added to the round bottom flask, and 3mL was taken out and added to the cuvette at regular intervals, and the peak of the oxytetracycline ultraviolet-visible light absorption spectrum was measured with an ultraviolet-visible photometer.
FIG. 7 is an ultraviolet-visible light absorption spectrum of the catalyst ZrO 2/OMS-2-27% prepared by the invention for catalyzing peroxymonosulfate to generate free radical for degrading terramycin, wherein the catalytic effect is that a characteristic peak of terramycin is detected by an ultraviolet-visible light photometer at a wavelength of 353nm, samples are taken according to different time intervals, and the reaction is stopped when the absorbance of terramycin is kept almost unchanged at 373nm, namely 19 min.
Example 5
The catalyst ZrO 2/OMS-2-27% prepared by the invention is used for catalyzing peroxymonosulfate to generate free radical and degrading aureomycin hydrochloride.
Step 1: aureomycin hydrochloride solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, cobalt-doped carbon-based catalyst ZrO 2/OMS-2-27% (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording an absorption peak value of the chlortetracycline hydrochloride at the moment;
Step 3: rapidly adding peroxymonosulfate (0.25 g/L) into a round bottom flask, taking out 3mL and adding into a cuvette at certain interval, and measuring peak value of an ultraviolet-visible light absorption spectrum of chlortetracycline hydrochloride by using an ultraviolet-visible light photometer.
FIG. 8 is an ultraviolet-visible light absorption spectrum of the catalyst ZrO 2/OMS-2-27% prepared by the invention for catalyzing peroxymonosulfate to generate free radical for degrading aureomycin hydrochloride, wherein the catalytic effect is that a characteristic peak of aureomycin hydrochloride is detected by an ultraviolet-visible light photometer at a wavelength of 364nm, samples are taken according to different time intervals, and the reaction is terminated when the absorbance of aureomycin hydrochloride is kept almost unchanged at the wavelength of 354nm, namely 22 min.
Example 6
Use of the catalyst ZrO 2/OMS-2-27% of example 1 of the invention, physically mixed ZrO 2 and OMS-2 (mechanically mixed according to the molar ratio n (Zr): n (Mn) =0.27) to catalyze the production of free radical-degrading estriol.
The steps of the reaction for degrading estriol by the catalyst are as follows:
Step 1: estriol solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, and the above catalyst was added at 0.25g/L, respectively, and stirred for 10min;
Step 2: testing and recording the absorption peak value of the estriol at the moment;
step 3: the peroxomonosulfate (0.25 g/L) was rapidly added to the round bottom flask, and 3mL of the mixture was taken out and added to the cuvette at regular intervals, and the peak of the ultraviolet-visible light absorption spectrum of tetracycline was measured by an ultraviolet-visible photometer.
FIG. 9 is a graph comparing the rates of degradation of estriol by ZrO 2/OMS-2-27% and by physical mixing of the catalyst prepared by the invention, and it can be seen from the graph that the degradation effect of directly carrying out physical mixing on ZrO 2 and OMS-2 is poor, only 40% can be degraded in 15min, while the catalyst prepared by chemical reaction has excellent degradation effect and is basically completely degraded in 7-9 min. It can be seen that the catalyst prepared by the invention has a chemical reaction in the preparation process, so that the catalytic effect is enhanced.
Claims (1)
1. The method for degrading estriol by using the ZrO 2/OMS-2 catalyst is characterized by comprising the following steps of:
step 1: adding 50mL of estriol solution and 20mg/L of estriol solution into a 100mL round-bottom flask, respectively adding 0.25g/L of the catalyst, and stirring for 10min;
Step 2: testing and recording the absorption peak value of the estriol at the moment;
Step 3: rapidly adding 0.25 g/L of peroxymonosulfate into a round bottom flask, taking out 3mL of peroxymonosulfate and adding the peroxymonosulfate into a cuvette at certain interval time, and measuring the peak value of an ultraviolet-visible light absorption spectrum of estriol by an ultraviolet-visible light photometer;
the preparation method of the ZrO 2/OMS-2 catalyst comprises the following steps:
step 1, dissolving potassium permanganate in 100ml of deionized water, and obtaining a deep purple solution at room temperature;
Step 2, adding manganese sulfate monohydrate into 30ml of deionized water, and adding 3ml of concentrated nitric acid at room temperature;
step 3, adding ZrO 2 powder into the solution in the step 2, and stirring, wherein the adding mass of the ZrO 2 powder is 2.9g respectively;
step4, slowly adding the solutions obtained in the step 1 into the solutions obtained in the step 3 respectively;
step 5, respectively refluxing the solutions obtained in the step 4 at 100 ℃ for 24 hours;
Step 6, filtering, separating, washing and drying the product obtained in the step 5 respectively;
and 7, calcining the catalyst obtained in the step 6 at 300 ℃ in air to obtain ZrO 2/OMS-2-X, wherein X is 27%.
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