CN117123222A - Preparation method of Co/CNT catalyst and application of Co/CNT catalyst in degradation of organic pollutants - Google Patents
Preparation method of Co/CNT catalyst and application of Co/CNT catalyst in degradation of organic pollutants Download PDFInfo
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- CN117123222A CN117123222A CN202310151639.9A CN202310151639A CN117123222A CN 117123222 A CN117123222 A CN 117123222A CN 202310151639 A CN202310151639 A CN 202310151639A CN 117123222 A CN117123222 A CN 117123222A
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- aminophenol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 title claims description 23
- 230000015556 catabolic process Effects 0.000 title claims description 21
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 95
- 239000000243 solution Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 claims abstract description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 7
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 53
- 229940018563 3-aminophenol Drugs 0.000 claims description 53
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 22
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 12
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 12
- 229960003405 ciprofloxacin Drugs 0.000 claims description 11
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims description 11
- 229960004306 sulfadiazine Drugs 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 3
- 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 description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- 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 description 2
- 230000000593 degrading effect Effects 0.000 abstract description 14
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 229940088710 antibiotic agent Drugs 0.000 abstract 1
- 239000000975 dye Substances 0.000 abstract 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract 1
- 238000000862 absorption spectrum Methods 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000031700 light absorption Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 230000003115 biocidal effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- -1 CNT activated peroxymonosulfate Chemical class 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 230000004913 activation Effects 0.000 description 1
- 231100000569 acute exposure Toxicity 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000010019 sublethal effect Effects 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of Co/CNT catalyst and application in degrading organic pollutant, when the catalyst is prepared, S1, adding water into carbon nano tube, mixing, adding water into cobalt nitrate hexahydrate to dissolve cobalt nitrate to prepare cobalt nitrate aqueous solution, adding cobalt nitrate solution into mixed solution of carbon nano tube and water, carrying out ultrasonic treatment at normal temperature, and then cooling to 0 ℃ for stirring and mixing; s2, dissolving sodium borohydride in water, then dropwise adding the solution into the mixed solution obtained in the step S1, continuously stirring and mixing at the temperature of 0 ℃, and finally filtering, washing and vacuum drying to obtain the Co/CNT catalyst. The catalyst prepared by the invention is doped into a Carbon Nano Tube (CNT) by cobalt (Co), can be used for catalyzing and activating peroxymonosulfate to release a large amount of active free radicals, so that antibiotics and organic dyes are efficiently oxidized and degraded, and simultaneously, the catalyst has excellent cycle performance and can be reused.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of Co/CNT and application of Co/CNT in degrading organic pollutants.
Background
The high-concentration antibiotic acute exposure has a certain lethal and sublethal effect on aquatic organisms, the normal growth of the aquatic organisms can be influenced under the long-term exposure of the environmental concentration, and the antibiotic pollutants have the characteristics of stable structure and difficult damage, and the effect of removal is difficult to achieve through simple filtration, biological treatment, chemical treatment and other modes, so the degradation of the antibiotic organic pollutants has become a focus. In recent years, advanced oxidation processes to degrade organic contaminants in water have become one of the research hotspots. Whereas the sulphate produced by Persulfate (PS) or Peroxomonosulphate (PMS) activation is the main active species in the highest oxidation processes.
Carbon Nanotubes (CNTs) are widely used as efficient catalysts for research in various fields due to their unique nanotube structure, low cost, and excellent catalytic activity. However, carbon Nanotubes (CNT) themselves cannot effectively activate Persulfates (PS) or Persulfates (PMS) to effect effective degradation of the antibiotic-based organic contaminants.
Disclosure of Invention
The invention provides a preparation method of Co/CNT and application thereof in degrading organic pollutants; the activity of catalyzing and degrading antibiotic organic pollutants is improved by doping Carbon Nano Tubes (CNTs) with cobalt (Co), and the catalyst is maintained to have stable catalytic activity.
The technical scheme of the invention is that the preparation method of the Co/CNT catalyst comprises the following steps:
s1, adding water into a carbon nano tube, mixing, adding water into cobalt nitrate hexahydrate to dissolve the cobalt nitrate to prepare a cobalt nitrate solution, adding the cobalt nitrate solution into a mixed solution of the carbon nano tube and the water, carrying out ultrasonic treatment at normal temperature, and then cooling to 0 ℃ and stirring and mixing;
s2, dissolving sodium borohydride in water, then dropwise adding the solution into the mixed solution obtained in the step S1, continuously stirring and mixing at the temperature of 0 ℃, and finally filtering, washing and vacuum drying to obtain the Co/CNT catalyst.
Further, the mass ratio of the cobalt nitrate hexahydrate to the carbon nanotubes is 3-29:50-100.
Further, the concentration of the cobalt nitrate solution is 0.01-0.2mol/L.
Further, the ultrasonic treatment time in S1 is 5-20min, and stirring and mixing are carried out for 20-40min at 0 ℃.
Further, the mass ratio of sodium borohydride to carbon nanotubes in S2 is 19-189:50.
Further, the mixture was stirred and mixed at 0℃for 30min in S2.
The invention also provides the Co/CNT catalyst obtained by the preparation method, wherein the mass fraction of cobalt is 0.59% -10.54%.
The invention also relates to application of the Co/CNT in degrading organic pollutants by activating peroxymonosulfate.
Further, the organic pollutants comprise any one or more of 3-aminophenol, sulfamethoxazole, sulfadiazine, ciprofloxacin, rhodamine B and orange II.
The invention has the following beneficial effects:
according to the catalyst provided by the invention, the Co/CNT catalyst obtained by doping a certain amount of Co in the Carbon Nano Tube (CNT) is used, and a catalytic performance test shows that the Co-doped catalyst can effectively promote the degradation process, and the catalyst can effectively degrade various pollutants, and active free radicals are generated after the catalyst is activated by using peroxymonosulfate for degrading organic matters in aqueous solution, so that toxic substances are converted into nontoxic micromolecular substances, and even are directly converted into water and carbon dioxide.
The Co/CNT is black powder, can be repeatedly used in the catalytic process, has excellent catalytic effect on degrading 3-aminophenol, can degrade common organic pollutants such as sulfamethoxazole, sulfadiazine, ciprofloxacin, rhodamine B and orange Huang, and can degrade extremely difficult-to-degrade phenolic organic pollutants such as 3-aminophenol. Compared with other multi-metal catalysts, the single-metal carbon-based catalyst disclosed by the invention is more friendly to the environment, the problems of secondary pollution and the like caused by metal leaching to the natural environment can be effectively avoided, the carbon-based material of the catalyst is a carbon nano tube, a complicated preparation process is not needed, the cost is lower compared with other carbon-based materials, the dosage is less, the cost can be saved, the removal rate of 3-aminophenol can still reach more than 90% after the catalyst is repeatedly used for five times, and the catalyst has good stability and reusability, so that the catalyst has a good application prospect in the field of degrading organic pollutants.
Drawings
FIG. 1 is a transmission electron microscope picture of Co/CNT obtained in example 1.
FIG. 2 is an X-ray diffraction pattern of Co/CNT obtained in example 1.
FIG. 3 is a graph of the comparative rate of degradation of 3-aminophenol by CNT, co/CNT in example 2.
FIG. 4 is a graph showing the comparative rates of Co/ZrO2, co/ZnO, co/MoS2, co/CeO2 and catalyst Co/CNT degradation of 3-aminophenol in example 3.
FIG. 5 is a graph showing the UV-visible absorption spectrum of Co/CNT catalyzed peroxymonosulfate to 3-aminophenol in example 4.
FIG. 6 is an electron paramagnetic resonance spectrum of Co/CNT in example 4.
FIG. 7 is a graph of the cyclic degradation rate of Co/CNT catalyzed peroxymonosulfate to 3-aminophenol in example 4.
FIG. 8 is an ultraviolet-visible light absorption spectrum of Co/CNT catalyzed peroxymonosulfate to sulfamethoxazole prepared in example 5.
FIG. 9 is an ultraviolet-visible light absorption spectrum of Co/CNT activated peroxymonosulfate degradation sulfadiazine prepared in example 6.
FIG. 10 is a graph showing the UV-visible absorption spectrum of Co/CNT activated peroxymonosulfate degraded ciprofloxacin obtained in example 7.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Comparative example 1:
undoped Carbon Nanotubes (CNT) were the comparative catalyst CNT.
Comparative example 2
Step 1, zirconium dioxide (ZrO 2 ) 0.1g was placed in 5ml of deionized water, and an immiscible mixture was obtained at room temperature.
Step 2, 0.146g of cobalt nitrate hexahydrate was dissolved in 1mL of deionized water to give a pink solution.
Step 3, slowly adding the solution obtained in the step 2 into the mixture obtained in the step 1.
And 4, carrying out ultrasonic treatment on the solution obtained in the step 3 for 5min at normal temperature.
And 5, stirring the product obtained in the step 4 at 0 ℃ for 30min.
Step 6, 0.189g of sodium borohydride was dissolved in 1mL of deionized water to give a clear solution.
And 7, dropwise adding the solution obtained in the step 6 into the mixture obtained in the step 5.
And 8, continuously stirring the mixture obtained in the step 7 at 0 ℃ for 30min.
Step 9, filtering the product obtained in the step 8, fully flushing with deionized water, and putting into a vacuum oven at 50 ℃ for drying to obtain Co/ZrO 2 。
Step 10, zirconium dioxide (ZrO 2 ) Respectively change into ZnO and MoS 2 、CeO 2 Repeating the steps 1-9 to obtain catalysts Co/ZnO and Co/MoS respectively 2 、Co/CeO 2 。
Example 1
Step 1, 0.1g of Carbon Nanotubes (CNT) was placed in 5ml of deionized water, and an immiscible mixture was obtained at room temperature.
Step 2, 0.146g of cobalt nitrate hexahydrate was dissolved in 1mL of deionized water to give a pink solution.
Step 3, slowly adding the solution obtained in the step 2 into the mixture obtained in the step 1.
And 4, carrying out ultrasonic treatment on the solution obtained in the step 3 for 5min at normal temperature.
And 5, stirring the product obtained in the step 4 at 0 ℃ for 30min.
Step 6, 0.189g of sodium borohydride was dissolved in 1mL of deionized water to give a clear solution.
And 7, dropwise adding the solution obtained in the step 6 into the mixture obtained in the step 5.
And 8, continuously stirring the mixture obtained in the step 7 at 0 ℃ for 30min.
And 9, filtering the product obtained in the step 8, fully flushing with deionized water, and putting into a vacuum oven at 50 ℃ for drying to obtain Co/CNT.
Fig. 1 is a Co/CNT transmission electron microscope picture prepared in example 1, in which the obtained catalyst was observed to be a nano-tubular structure, and doped cobalt nanoparticles were observed on the tube wall.
Fig. 2 is an X-ray diffraction diagram of the Co/CNT catalyst prepared in example 1, in which the synthesized catalyst was observed to have a corresponding crystal plane of Co, and the original crystal plane characteristics of the CNT were maintained, indicating that Co was successfully doped on the CNT.
Example 2
3-aminophenol was degraded using the catalyst CNT of comparative example 1, the catalyst Co/CNT of example 1.
The steps of the catalyst CNT degradation 3-aminophenol reaction are as follows:
step 1: 3-aminophenol solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, catalyst CNT (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording the absorption peak value of the 3-aminophenol at the moment;
step 3: the persulfate (0.25 g/L) was rapidly added to the round-bottomed flask, 3mL was taken out and added to the cuvette at regular intervals, and the peak of the ultraviolet-visible light absorption spectrum of 3-aminophenol was measured with an ultraviolet-visible photometer.
The catalyst Co/CNT degradation 3-aminophenol reaction comprises the following steps:
step 1: 3-aminophenol solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, catalyst Co/CNT (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording the absorption peak value of the 3-aminophenol at the moment;
step 3: the persulfate (0.25 g/L) was rapidly added to the round-bottomed flask, 3mL was taken out and added to the cuvette at regular intervals, and the peak of the ultraviolet-visible light absorption spectrum of 3-aminophenol was measured with an ultraviolet-visible photometer.
FIG. 3 is a graph showing the comparison of the rates of degradation of 3-aminophenol by Carbon Nanotubes (CNTs) and the catalyst Co/CNTs prepared according to the present invention, and it can be seen from the graph that Carbon Nanotubes (CNTs) without Co doping hardly degrade 3-aminophenol, only 14% of 3-aminophenol is removed within 20min, and the Co/CNT catalyst after Co doping has a 91% removal rate of 3-aminophenol within 20min, which is improved by 6.5 times compared to the degradation effect of Carbon Nanotubes (CNTs) alone.
Example 3
Co/ZrO using the catalyst of comparative example 2 2 、Co/ZnO、Co/MoS 2 、Co/CeO 2 Catalyst Co/CNT from example 1 degrades 3-aminophenol.
Catalyst Co/ZrO 2 、Co/ZnO、Co/MoS 2 、Co/CeO 2 The steps of the reaction for degrading 3-aminophenol are as follows:
step 1: 3-aminophenol solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, and catalyst Co/ZrO was added 2 (0.25 g/L) stirring for 10min;
step 2: testing and recording the absorption peak value of the 3-aminophenol at the moment;
step 3: the persulfate (0.25 g/L) was rapidly added to the round-bottomed flask, 3mL was taken out and added to the cuvette at regular intervals, and the peak of the ultraviolet-visible light absorption spectrum of 3-aminophenol was measured with an ultraviolet-visible photometer.
Step 4: the catalyst Co/ZrO in step 1 2 Respectively change into catalyst Co/ZnO, co/MoS 2 、Co/CeO 2 Repeating the steps 1-3.
The catalyst Co/CNT degradation 3-aminophenol reaction comprises the following steps:
step 1: 3-aminophenol solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, catalyst Co/CNT (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording the absorption peak value of the 3-aminophenol at the moment;
step 3: the persulfate (0.25 g/L) was rapidly added to the round-bottomed flask, 3mL was taken out and added to the cuvette at regular intervals, and the peak of the ultraviolet-visible light absorption spectrum of 3-aminophenol was measured with an ultraviolet-visible photometer.
FIG. 4 is a catalyst Co with other supports doped with cobalt/ZrO 2 、Co/ZnO、Co/MoS 2 、Co/CeO 2 Compared with the rate of degrading 3-aminophenol by the Co/CNT catalyst prepared by the invention, the rate of removing 3-aminophenol by Co/CNT catalyst doped with Co in 20min can be up to 91%, while Co/ZrO 2 、Co/ZnO、Co/MoS 2 、Co/CeO 2 The removal rates of the catalyst Co/CNT prepared by the invention for 3-aminophenol are respectively 30%, 29%, 52% and 56% in the same time, and the catalyst Co/CNT prepared by the invention has better effect of degrading 3-aminophenol and can be completely degraded in the same time. The catalyst Co/CNT prepared by the invention is a single metal carbon-based material and is Co/ZrO 2 、Co/ZnO、Co/MoS 2 、Co/CeO 2 Compared with the bimetallic composite material, the bimetallic composite material can effectively avoid the problems of secondary pollution caused by metal leaching, is more environment-friendly, and has lower cost compared with the catalyst Co/CNT prepared by the bimetallic composite material.
Example 4
The catalyst Co/CNT prepared by the invention is applied to catalyzing peroxymonosulfate to generate free radicals to degrade 3-aminophenol.
The catalyst Co/CNT catalyzes the reaction of the peroxymonosulfate to degrade the 3-aminophenol as follows:
step 1: 3-aminophenol 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 3-aminophenol 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 ultraviolet-visible light absorption spectrum of 3-aminophenol was measured with an ultraviolet-visible photometer.
Step 4: after the peak value of the ultraviolet-visible light absorption spectrum of the 3-aminophenol is reduced, 0.5mL of a high-concentration (2000 mg/L) 3-aminophenol solution is added to the solution obtained in the step 3.
And 5, repeating the step 3 to perform a circulation experiment for 5 times.
FIG. 5 is a graph showing the ultraviolet-visible light absorption spectrum of the Co/CNT catalytic peroxymonosulfate prepared by the invention to degrade 3-aminophenol, the catalytic effect is detected by an ultraviolet-visible photometer at 282nm wavelength, the characteristic peaks of the 3-aminophenol are sampled at different time intervals, and the reaction is stopped at 20min after the peak value of the characteristic peaks of the 3-aminophenol at 270nm wavelength is no longer reduced.
FIG. 6 shows the electron paramagnetic resonance spectrum of Co/CNT activated peroxymonosulfate prepared according to the present invention, singlet oxygen energy oxidizing 2, 6-tetramethyl-4-piperidinol (TEMP) to paramagnetic 4-hydroxy-2, 6-tetramethyl-piperidyloxy (TEMPO), and detecting and identifying by Electron Paramagnetic Resonance (EPR), in which FIG. O can be seen 2 - ， 1 O 2 ，•OH，•SO 4 - All have obvious strength and participate in the degradation process of organic matters.
FIG. 7 is a graph of the catalytic degradation rate of the catalyst Co/CNT prepared by the invention, 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, and even directly converted into water and carbon dioxide.
Example 5
The catalyst Co/CNT prepared by the invention catalyzes the peroxymonosulfate to produce free radical and degrades sulfamethoxazole.
The catalyst Co/CNT catalyzes the reaction of active species generated by peroxymonosulfate to degrade sulfamethoxazole, and the steps are as follows:
step 1: sulfamethoxazole solution (50 mL,10 mg/L) was added to a 100mL round bottom flask, cobalt-doped carbon-based catalyst Co/CNT (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording the absorption peak value of the sulfamethoxazole 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 the sulfamethoxazole ultraviolet-visible light absorption spectrogram by an ultraviolet-visible light photometer.
FIG. 8 is an ultraviolet-visible light absorption spectrum of the catalyst Co/CNT catalytic peroxymonosulfate prepared by the invention to produce free radical degradation sulfamethoxazole, the catalytic effect detects the characteristic peak of sulfamethoxazole at the wavelength of 266nm by an ultraviolet-visible light photometer, samples are taken according to different time intervals, and the reaction is stopped when the sulfamethoxazole absorbance is kept unchanged almost at the wavelength of 266nm, namely 10 min.
Example 6
The catalyst Co/CNT prepared by the invention is applied to catalyzing peroxymonosulfate to generate free radical to degrade sulfadiazine.
Step 1: sulfadiazine solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, cobalt doped carbon based catalyst Co/CNT (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording the absorption peak value of sulfadiazine 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 a sulfadiazine ultraviolet-visible light absorption spectrum by using an ultraviolet-visible light photometer.
FIG. 9 is a graph showing the absorption spectrum of ultraviolet and visible light of sulfadiazine degraded by free radical generated by Co/CNT catalytic peroxymonosulfate, wherein the catalysis effect is that the characteristic peak of sulfadiazine is detected by an ultraviolet-visible photometer at the wavelength of 265nm, sampling is carried out according to different time intervals, and the reaction is stopped when the sulfadiazine absorbance is kept unchanged almost at the wavelength of 265nm, namely 15 min.
Example 7
The catalyst Co/CNT prepared by the invention is used for catalyzing peroxymonosulfate to generate free radical and degrading ciprofloxacin.
Step 1: ciprofloxacin solution (50 mL,20 mg/L) was added to a 100mL round bottom flask, cobalt-doped carbon-based catalyst Co/CNT (0.25 g/L) was added and stirred for 10min;
step 2: testing and recording the absorption peak value of ciprofloxacin 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 ciprofloxacin was measured by an ultraviolet-visible photometer.
FIG. 10 is a graph showing the ultraviolet-visible light absorption spectrum of the catalyst Co/CNT catalytic peroxymonosulfate prepared by the invention to produce the ciprofloxacin, the catalytic effect is detected by an ultraviolet-visible photometer at the wavelength of 323nm, the characteristic peak of the ciprofloxacin is sampled according to different time intervals, and the reaction is stopped when the absorbance of the ciprofloxacin is kept almost unchanged at the wavelength of 323nm, namely, 20 min.
According to the invention, co element is doped on the basis of the Carbon Nano Tube (CNT), the performance of degrading 3-aminophenol by the material is obviously improved, and compared with the comparative example 1, the Carbon Nano Tube (CNT) without Co can hardly degrade 3-aminophenol, only 14% of 3-aminophenol is removed within 20min, and the Co/CNT catalyst after Co doping has 91% removal rate of 3-aminophenol within 20min, and compared with the degradation effect of the single Carbon Nano Tube (CNT), the degradation effect is improved by 6.5 times. As can be seen from comparative example 2, the Co/CNT prepared by the present invention has a removal rate of 91% for 3-aminophenol within 20min, whereas Co/ZrO 2 、Co/ZnO、Co/MoS 2 、Co/CeO 2 The removal rates of the catalyst Co/CNT prepared by the invention for 3-aminophenol are respectively 30%, 29%, 52% and 56% in the same time, and the catalyst Co/CNT prepared by the invention has better effect of degrading 3-aminophenol and can be completely degraded in the same time. The catalyst Co/CNT prepared by the invention is a single metal carbon-based material and is Co/ZrO 2 、Co/ZnO、Co/MoS 2 、Co/CeO 2 Compared with the bimetal composite material, the bimetal composite material can effectively avoid the problems of secondary pollution and the like caused by metal leaching, and is more environment-friendly. The Co/CNT prepared by the method can still reach more than 90% of 3-aminophenol after being repeatedly used for five times, and the catalyst has good stability and reusability, and has a wider application prospect in the degradation field due to the low dosage, simpler preparation process, low cost and high efficiency.
The foregoing embodiments are merely illustrative of the technical idea and features of the present invention, and the present invention is not limited to the preferred embodiments. Within the technical scope of the present disclosure, the technical solution and the invention concept according to the present disclosure are equivalent to or improved from the above description, and all the equivalent changes or modifications are included in the scope of the present disclosure. .
Claims (9)
1. The preparation method of the Co/CNT catalyst is characterized by comprising the following steps of:
s1, adding water into a carbon nano tube, mixing, adding water into cobalt nitrate hexahydrate to dissolve the cobalt nitrate to prepare a cobalt nitrate aqueous solution, adding the cobalt nitrate aqueous solution into a mixed solution of the carbon nano tube and the water, carrying out ultrasonic treatment at normal temperature, and then cooling to 0 ℃ and stirring and mixing;
s2, dissolving sodium borohydride in water, then dropwise adding the solution into the mixed solution obtained in the step S1, continuously stirring and mixing at the temperature of 0 ℃, and finally filtering, washing and vacuum drying to obtain the Co/CNT catalyst.
2. The method according to claim 1, characterized in that: the mass ratio of the cobalt nitrate hexahydrate to the carbon nano tube is 3-29:50-100.
3. The method according to claim 1, characterized in that: the concentration of the cobalt nitrate solution is 0.01-0.2mol/L.
4. The method according to claim 1, characterized in that: and (2) in the step S1, the ultrasonic treatment time is 5-20min, and stirring and mixing are carried out for 20-40min at the temperature of 0 ℃.
5. The method according to claim 1, characterized in that: and the mass ratio of the sodium borohydride to the carbon nano tube in the S2 is 19-189:500.
6. The method according to claim 1, characterized in that: s2, stirring and mixing for 30min at the temperature of 0 ℃.
7. The Co/CNT catalyst obtained by the preparation method of any one of claims 1-6, wherein the mass fraction of cobalt is 0.59% -10.54%.
8. The use of the Co/CNT catalyst according to claim 7 for the degradation of organic contaminants by activated peroxymonosulfate.
9. The use according to claim 8, characterized in that: the organic pollutant includes 3-aminophenol, sulfamethoxazole, sulfadiazine, ciprofloxacin, rhodamine B and orange II.
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