CN113145145A - Cobalt phosphate catalyst capable of efficiently activating PMS (permanent magnet synchronous motor), and preparation method and application thereof - Google Patents
Cobalt phosphate catalyst capable of efficiently activating PMS (permanent magnet synchronous motor), and preparation method and application thereof Download PDFInfo
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- CN113145145A CN113145145A CN202110365431.8A CN202110365431A CN113145145A CN 113145145 A CN113145145 A CN 113145145A CN 202110365431 A CN202110365431 A CN 202110365431A CN 113145145 A CN113145145 A CN 113145145A
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- 229910000152 cobalt phosphate Inorganic materials 0.000 title claims abstract description 47
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003213 activating effect Effects 0.000 title claims abstract description 11
- 230000001360 synchronised effect Effects 0.000 title abstract description 3
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 31
- 231100000719 pollutant Toxicity 0.000 claims abstract description 31
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 239000003242 anti bacterial agent Substances 0.000 claims description 16
- 229940088710 antibiotic agent Drugs 0.000 claims description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 14
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000002135 nanosheet Substances 0.000 claims description 12
- 229960001180 norfloxacin Drugs 0.000 claims description 8
- 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 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- 229960001699 ofloxacin Drugs 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229960001680 ibuprofen Drugs 0.000 claims description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 4
- 229940107698 malachite green Drugs 0.000 claims description 4
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 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 2
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 description 33
- 239000000975 dye Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- JLQUFIHWVLZVTJ-UHFFFAOYSA-N carbosulfan Chemical compound CCCCN(CCCC)SN(C)C(=O)OC1=CC=CC2=C1OC(C)(C)C2 JLQUFIHWVLZVTJ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036963 noncompetitive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- 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
- C01P2002/70—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
- 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
- C02F2101/308—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention relates to a cobalt phosphate catalyst capable of efficiently activating PMS (permanent magnet synchronous motor), a preparation method and application thereof. The preparation method is simple, green and environment-friendly, and can efficiently and quickly realize pollutant degradation.
Description
Technical Field
The invention belongs to the technical field of inorganic catalysis, and particularly relates to a cobalt phosphate catalyst capable of efficiently activating PMS, and a preparation method and application thereof.
Background
The waste water often contains high concentration of toxic and non-degradable dyes, which threatens human health. Common wastewater treatment methods are biological processes, filtration and coagulation/flocculation/precipitation, etc., which have good effects on removing pollutants, but are energy intensive, costly, non-competitive in the face of large wastewater treatment demands, and may cause secondary pollution due to excessive use of chemicals.
In recent years, the sulfate-based advanced oxidation process (SR-AOP) has received much attention, has entered the field of vision, and has been successfully applied to the degradation of pollutants. Because the Peroxymonosulfate (PMS) can be activated to generate high-activity free radicals such as sulfate free radicals and hydroxyl free radicals, the peroxymonosulfate can oxidize and decompose refractory water pollutants.
A cobalt-based catalyst has been studied and reported in large quantities as a catalyst effective for activating PMS. The floriform CoSiOx catalyst with controllable morphology is prepared by the Marsupena marshal and the like, a large number of cobalt hydroxyl groups exist on the surface, the generation rate of free radicals is accelerated in the PMS activation process, the degradation rate is improved, and the excellent degradation rate is shown for various dyes.
Among the studies of various cobalt-based catalysts, the studies of cobalt phosphate have been focused on the direction of energy storage, such as sodium ion batteries, supercapacitors, etc., and there have been few studies and reports related thereto as a catalyst for activating PMS.
Disclosure of Invention
The invention aims to provide a cobalt phosphate catalyst capable of efficiently activating PMS, and a preparation method and application thereof. The prepared cobalt phosphate is used as a catalyst for efficiently activating the Peroxymonosulfate (PMS), and can effectively accelerate degradation of pollutants such as dye pollutants, antibiotics and the like in a water body by the Peroxymonosulfate (PMS). The preparation method is simple, green and environment-friendly, and can efficiently and quickly realize pollutant degradation.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a cobalt phosphate catalyst capable of efficiently activating PMS comprises the following steps:
(1) respectively preparing a cobalt nitrate solution and a phosphate solution, slowly dropping the cobalt nitrate solution into the phosphate solution under the stirring state, and uniformly stirring;
(2) and transferring the mixture into a hydrothermal kettle, carrying out hydrothermal reaction, washing and drying to obtain a cobalt phosphate nanosheet product.
In a preferred embodiment of the present invention, in step (1), the phosphate is sodium dihydrogen phosphate or ammonium phosphate; the molar concentration ratio of the cobalt nitrate to the phosphate solution is 10 (10-15).
In a preferred embodiment of the present invention, in the step (1), the stirring time is 30 to 60 minutes.
In a preferred embodiment of the present invention, in the step (2), the temperature of the hydrothermal reaction is 120-180 ℃; the hydrothermal time is 6-12 hours; more preferably, the hydrothermal time is 6 hours.
The invention also provides the cobalt phosphate catalyst prepared by the preparation method, and the cobalt phosphate nanosheet is of a cobalt phosphate nanosheet structure.
The invention also protects the cobalt phosphate catalyst used for accelerating the degradation of pollutants such as dye pollutants, antibiotics and the like in water by a Peroxymonosulfate (PMS) system.
In a preferred embodiment of the present invention, the cobalt phosphate catalyst concentration is in the range of 0.1 to 0.5 mol L-1The concentration range of the PMS is 0.1-0.5 mol L-1And the pollutant degradation concentration ranges from 20 ppm to 100 ppm.
In a preferred embodiment of the invention, the dye contaminants are Methylene Blue (MB), Methylene Orange (MO), gold orange ii (oii), rhodamine b (rhb), Malachite Green (MG); the antibiotic pollutants are Norfloxacin (NOR), Ofloxacin (OFR) and ibuprofen.
Compared with the prior art, the invention has the beneficial effects that: the cobalt phosphate nanosheet product is prepared by a one-step hydrothermal method and is used as a cobalt phosphate catalyst for efficiently activating PMS, so that the preparation method is simple, green and environment-friendly; in the degradation process, the cobalt phosphate catalyst can effectively activate PMS, accelerate the speed of degrading pollutants such as dye pollutants, antibiotics and the like in a water body by a Peroxymonosulfate (PMS) system, realize the removal rate of more than 95% of high-concentration dye pollutants within 3 minutes of reaction time, realize the removal rate of more than 99% of other pollutants such as high-concentration antibiotics and the like within 6 minutes of reaction time, show excellent degradation rate, greatly widen the application field of the cobalt phosphate catalyst, and is suitable for wide popularization and application.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is a flow chart of the preparation process of example 1;
FIG. 2 is an X-ray powder diffractogram of cobalt phosphate provided in example 1;
FIG. 3 is an SEM electron micrograph of cobalt phosphate provided in example 1;
FIG. 4 shows that the cobalt phosphate catalyst provided in example 1 activates PMS to accelerate the degradation of various dye contaminants;
FIG. 5 shows that the cobalt phosphate catalyst provided in example 1 activates PMS to accelerate the degradation of contaminants such as antibiotics.
Detailed Description
The process of the present invention is illustrated below by means of specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
the preparation process is shown in figure 1. Weigh 10 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 10 mmol of sodium dihydrogen phosphate dihydrate (NaH)2PO4·2H2O) are respectively placed in a beaker, and deionized water is added for dissolution. Under the stirring state, the cobalt nitrate solution is slowly dripped into the sodium dihydrogen phosphate solution by using a dropper, pink purple precipitate is gradually generated, and stirring is continued for 30 minutes until the cobalt nitrate solution is finally changed into purple. And transferring the purple mixed solution to a 100mL polytetrafluoroethylene hydrothermal kettle, and reacting for 6 hours in an oven at 150 ℃. After the reaction is finished, the reaction product is naturally cooled, the product is separated by using a centrifugal mode, and the product is washed for 3 times by using deionized water and ethanol respectively. And drying in an oven at 60 ℃ for 24 hours to obtain the final cobalt phosphate catalyst.
During the degradation process, the concentration of the cobalt phosphate catalyst is 0.2 g L-1PMS concentration of 0.2 g L-1. The dye concentration is 50 ppm, norfloxacin, ofloxacin and ibuprofenThe concentration of the solution was 20 ppm.
As shown in figure 2, the prepared material is verified to be cobalt phosphate nanosheet Co through X-ray powder diffractometer identification3(PO4)2·4H2And O. The morphology of the cobalt phosphate is characterized by using a scanning electron microscope SEM, and as shown in FIG. 3, the prepared cobalt phosphate is in a lamellar shape.
As shown in FIGS. 4-5, at a cobalt phosphate concentration of 0.2 g L-1PMS concentration of 0.2 g L-1Under the condition, the prepared cobalt phosphate nanosheet can effectively activate PMS, rapidly degrade various dyes, antibiotics and the like in the solution, realize the removal rate of more than 95% for dye pollutants in the solution within 3 minutes of reaction time, and realize the removal rate of more than 99% for other pollutants such as antibiotics in the solution within 6 minutes of reaction time.
Example 2:
weigh 10 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 10 mmol of sodium dihydrogen phosphate dihydrate (NaH)2PO4·2H2O) are respectively placed in a beaker, and deionized water is added for dissolution. Under the stirring state, the cobalt nitrate solution is slowly dripped into the sodium dihydrogen phosphate solution by using a dropper, pink purple precipitate is gradually generated, and stirring is continued for 30 minutes until the cobalt nitrate solution is finally changed into purple. And transferring the purple mixed solution into a 100mL polytetrafluoroethylene hydrothermal kettle, and reacting for 6 hours in an oven at the temperature of 120 ℃. After the reaction is finished, the reaction product is naturally cooled, the product is separated by using a centrifugal mode, and the product is washed for 3 times by using deionized water and ethanol respectively. And drying in an oven at 60 ℃ for 24 hours to obtain the final cobalt phosphate catalyst.
During the degradation process, the concentration of the cobalt phosphate catalyst is 0.2 g L-1PMS concentration of 0.2 g L-1. The dye concentration is 50 ppm, and the concentration of norfloxacin, ofloxacin and ibuprofen solution is 20 ppm. Tests prove that the prepared cobalt phosphate nanosheet can effectively activate PMS, rapidly degrade various dyes, antibiotics and the like in a solution, achieve a removal rate of over 95% for dye pollutants in the solution within 3 minutes of reaction time, and achieve a removal rate of over 99% for other pollutants such as antibiotics in the solution within 6 minutes of reaction time.
Example 3:
weigh 10 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 10 mmol of sodium dihydrogen phosphate dihydrate (NaH)2PO4·2H2O) are respectively placed in a beaker, and deionized water is added for dissolution. Under the stirring state, the cobalt nitrate solution is slowly dripped into the sodium dihydrogen phosphate solution by using a dropper, pink purple precipitate is gradually generated, and stirring is continued for 30 minutes until the cobalt nitrate solution is finally changed into purple. And transferring the purple mixed solution into a 100mL polytetrafluoroethylene hydrothermal kettle, and reacting for 6 hours in an oven at 180 ℃. After the reaction is finished, the reaction product is naturally cooled, the product is separated by using a centrifugal mode, and the product is washed for 3 times by using deionized water and ethanol respectively. And drying in an oven at 60 ℃ for 24 hours to obtain the final cobalt phosphate catalyst.
During the degradation process, the concentration of the cobalt phosphate catalyst is 0.2 g L-1PMS concentration of 0.2 g L-1. The dye concentration is 50 ppm, and the concentration of norfloxacin, ofloxacin and ibuprofen solution is 20 ppm. Tests prove that the prepared cobalt phosphate nanosheet can effectively activate PMS, rapidly degrade various dyes, antibiotics and the like in a solution, achieve a removal rate of over 95% for dye pollutants in the solution within 3 minutes of reaction time, and achieve a removal rate of over 99% for other pollutants such as antibiotics in the solution within 6 minutes of reaction time.
Example 4:
weigh 10 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O) and 15 mmol of sodium dihydrogen phosphate dihydrate (NaH)2PO4·2H2O) are respectively placed in a beaker, and deionized water is added for dissolution. Under the stirring state, the cobalt nitrate solution is slowly dripped into the sodium dihydrogen phosphate solution by using a dropper, pink purple precipitate is gradually generated, and stirring is continued for 30 minutes until the cobalt nitrate solution is finally changed into purple. And transferring the purple mixed solution into a 100mL polytetrafluoroethylene hydrothermal kettle, and reacting for 6 hours in an oven at the temperature of 120 ℃. After the reaction is finished, the reaction product is naturally cooled, the product is separated by using a centrifugal mode, and the product is washed for 3 times by using deionized water and ethanol respectively. And drying in an oven at 60 ℃ for 24 hours to obtain the final cobalt phosphate catalyst.
In the degradation process, the concentration of the cobalt phosphate catalyst is 0.2 g L-1, and the concentration of PMS is 0.2 g L-1. The dye concentration is 50 ppm, and the concentration of norfloxacin, ofloxacin and ibuprofen solution is 20 ppm. Tests prove that the prepared cobalt phosphate nanosheet can effectively activate PMS, rapidly degrade various dyes, antibiotics and the like in a solution, achieve a removal rate of over 95% for dye pollutants in the solution within 3 minutes of reaction time, and achieve a removal rate of over 99% for other pollutants such as antibiotics in the solution within 6 minutes of reaction time.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a cobalt phosphate catalyst capable of efficiently activating PMS is characterized by comprising the following steps:
(1) respectively preparing a cobalt nitrate solution and a phosphate solution, slowly dropping the cobalt nitrate solution into the phosphate solution under the stirring state, and uniformly stirring;
(2) and transferring the mixture into a hydrothermal kettle, carrying out hydrothermal reaction, washing and drying to obtain a cobalt phosphate nanosheet product.
2. The production method according to claim 1, wherein in the step (1), the phosphate is sodium dihydrogen phosphate or ammonium phosphate; the molar concentration ratio of the cobalt nitrate to the phosphate solution is 10 (10-15).
3. The production method according to claim 1, wherein in the step (1), the stirring time is 30 to 60 minutes.
4. The method as claimed in claim 1, wherein the temperature of the hydrothermal reaction in step (2) is 120-180 ℃; the hydrothermal time is 6-12 hours; more preferably, the hydrothermal time is 6 hours.
5. The cobalt phosphate catalyst prepared by the preparation method according to any one of claims 1 to 4, wherein the cobalt phosphate nanosheet is of a cobalt phosphate nanosheet structure.
6. The cobalt phosphate catalyst of claim 5, used for accelerating degradation of pollutants such as dye pollutants, antibiotics and the like in a water body by a Peroxymonosulfate (PMS) system.
7. The use of the cobalt phosphate catalyst according to claim 6 for accelerating the degradation of pollutants such as dye pollutants and antibiotics in a water body by a Peroxymonosulfate (PMS) system, wherein the concentration of the cobalt phosphate catalyst is in the range of 0.1-0.5 mol L-1The concentration range of the PMS is 0.1-0.5 mol L-1And the pollutant degradation concentration ranges from 20 ppm to 100 ppm.
8. The cobalt phosphate catalyst according to claim 6 or 7 is used for accelerating the degradation of pollutants such as dye pollutants, antibiotics and the like in a water body by a Peroxymonosulfate (PMS) system, wherein the dye pollutants are Methylene Blue (MB), Methylene Orange (MO), gold orange II (OII), rhodamine B (RhB), Malachite Green (MG); the antibiotic pollutants are Norfloxacin (NOR), Ofloxacin (OFR) and ibuprofen.
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