CN108212217B - Catalyst for degrading chlorophenol pollutants, preparation method and application - Google Patents
Catalyst for degrading chlorophenol pollutants, preparation method and application Download PDFInfo
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- CN108212217B CN108212217B CN201810050114.5A CN201810050114A CN108212217B CN 108212217 B CN108212217 B CN 108212217B CN 201810050114 A CN201810050114 A CN 201810050114A CN 108212217 B CN108212217 B CN 108212217B
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- potassium persulfate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 29
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 29
- 230000000593 degrading effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 239000002262 Schiff base Substances 0.000 claims abstract description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 37
- -1 3, 5-dibromo salicylaldehyde Schiff base Chemical class 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- JHZOXYGFQMROFJ-UHFFFAOYSA-N 3,5-dibromo-2-hydroxybenzaldehyde Chemical compound OC1=C(Br)C=C(Br)C=C1C=O JHZOXYGFQMROFJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000005576 amination reaction Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000010355 oscillation Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims description 40
- 229960003500 triclosan Drugs 0.000 claims description 40
- 239000010949 copper Substances 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOVMHWSVVCQD-UHFFFAOYSA-N 2-benzyl-3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1CC1=CC=CC=C1 ZAMOVMHWSVVCQD-UHFFFAOYSA-N 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 7
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 5
- 230000004913 activation Effects 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
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- 238000006731 degradation reaction Methods 0.000 description 45
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- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
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- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- SBMDBLZQVGUFAI-UHFFFAOYSA-N 4-benzyl-2-chlorophenol Chemical compound C1=C(Cl)C(O)=CC=C1CC1=CC=CC=C1 SBMDBLZQVGUFAI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
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- 150000002815 nickel Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013379 physicochemical characterization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C02F2101/34—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
- C02F2101/36—Organic compounds containing halogen
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for degrading chlorophenol pollutants, a preparation method and application, and belongs to the field of environmental functional materials and catalysis. The catalyst is prepared by the following steps: firstly, carrying out reaction on amination reduction graphene oxide and 3, 5-dibromo salicylaldehyde in an ethanol system to synthesize 3, 5-dibromo salicylaldehyde Schiff base; and then reacting the monohydrate copper acetate with 3, 5-dibromo salicylaldehyde Schiff base in an ethanol system to synthesize the Schiff base-copper complex. The catalyst can activate potassium persulfate to degrade chlorophenol pollutants in an aqueous solution, and the step of removing the chlorophenol pollutants comprises the following steps: a) respectively preparing a catalyst and potassium persulfate into solutions by adopting deionized water; b) mixing the catalyst solution, the potassium persulfate solution and the water solution containing chlorophenol pollutants, adding the mixture into deionized water for reaction, and reacting under the conditions of light shielding and oscillation. The preparation method is simple, and the activation of the potassium persulfate by the catalyst under the conditions of low energy consumption, low pollution and mild condition is realized.
Description
Technical Field
The invention belongs to the field of environmental functional materials and catalysis, relates to a preparation method and application of a novel nano-material immobilized heterogeneous catalyst, and particularly relates to a graphene immobilized Schiff base-copper complex catalyst for activating persulfate in a water phase to degrade chlorophenols at normal temperature and normal pressure and a preparation method thereof.
Background
Transition metal complexes have been widely studied as homogeneous catalysts, but these complexes have problems of difficult recovery and metal ion contamination during practical use.
Schiff base (Schiff base) is mainly an organic compound containing imine or azomethine characteristic group (-RC ═ N-), and is generally formed by condensation of amine and active carbonyl or aldehyde group. Schiff bases are currently used in a wide variety of fields, including the field of biological activity, for anti-tumor and anti-viral purposes; applications in the field of analytical chemistry include identification, identification and quantitative analysis of metal ions; in the field of functional materials, Schiff bases can be used for preparing synthetic liquid crystal materials; in the corrosion field, certain aromatic schiff bases are often used as corrosion inhibitors for copper; in the field of medicine, Schiff base has the functions of bacteriostasis and sterilization; in the field of catalysis, copper, cobalt and nickel complexes of schiff bases have been used as catalysts.
In recent years, many studies have been made on the degradation of various target pollutants by using Schiff base metal complexes as catalysts. Meng et al have studied the ability of a series of Schiff base metal complexes to catalyze and degrade benzoquinone, wherein the complex metals include Cu, Fe, Co, Mn, etc.; zhu and the like research the effect of catalyzing and degrading DMP by the Cu complex; mihara H. et al investigated the degradation of isocyanides by Ga/Yb complexes; the catalytic degradation of nitrobenzene by Pt complexes was studied by Parida K. The researches show that the Schiff base metal complex has good catalytic capability and is an excellent broad-spectrum catalyst. However, the reaction conditions of the catalytic degradation reaction of the homogeneous schiff base metal complex as the catalyst are mostly limited to be carried out in the organic phase, and certain external heating or pressurization is required, and certain secondary pollution of metal ions is caused, which becomes the limit of further popularization and application of the schiff base metal complex catalyst.
Graphene is a good nano-catalyst support. The functionalized graphene can react with aldehyde or ketone to generate Schiff base and metal complexes, and the Schiff base metal complexes are proved to have good catalytic capability in the advanced oxidation process, so that the research on the degradation of organic pollutants by the Schiff base-metal complexes taking graphene as a carrier is significant.
Chinese patent application No. CN201310416149.3, published as 2013.12.18, discloses a graphene oxide supported schiff base palladium catalyst and a preparation method and application thereof, wherein the preparation method in the application is as follows: adding amidated graphene oxide into an ethanol solution containing an aldehyde-based compound or a ketone-based compound, carrying out ultrasonic oscillation and stirring reaction, cooling and separating a product, carrying out freeze drying to obtain graphene oxide supported Schiff base, adding the graphene oxide supported Schiff base into an ethanol solution of palladium salt, and carrying out reaction to finally obtain the graphene oxide supported Schiff base palladium catalyst. However, the catalyst needs to perform catalytic reaction at 85 ℃ by taking DMF as a reaction solvent, and the limitation of catalytic reaction conditions of Schiff base supported metal catalysts in the prior art is not overcome. Chinese patent No. CN201510343950.9, published by the grant of 2017.11.03, discloses a manganese schiff base-graphene oxide composite and a preparation method thereof, in which aminated graphene oxide is reacted with salicylaldehyde to obtain graphene oxide with schiff base grafted on the surface, and then the graphene oxide with schiff base grafted on the surface is reacted with manganese acetate tetrahydrate to obtain the manganese schiff base-graphene oxide composite. The product not only has the function of synergistically catalyzing the curing of cyanate, but also can effectively improve the heat resistance of resin.
Persulfate (PS) is used as a common oxidant, and sulfate radicals are mainly generated in the advanced oxidation process to achieve the purpose of degrading pollutants. However, persulfate has little ability to degrade contaminants under natural conditions, and thus requires external means to activate PS. Common activation modes are: a metal ion activation method, an ultraviolet activation method, a heat activation method, and a carbon material activation method. However, the existing activation methods have more or less drawbacks such as secondary pollution, large energy consumption, severe reaction conditions, and the like.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that in the prior art, most of reaction conditions of catalytic degradation reaction of a Schiff base metal complex catalyst are limited to be carried out in an organic phase, certain external heating or pressurization is needed, and certain secondary pollution of metal ions is caused, the invention aims to provide a graphene-immobilized Schiff base-copper complex catalyst and a preparation method thereof, and application of the catalyst in the process of activating persulfate to degrade chlorophenols.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a catalyst for degrading chlorophenol pollutants, which is prepared according to the following steps:
firstly, carrying out reaction on amination reduction graphene oxide and 3, 5-dibromo salicylaldehyde in an ethanol system to synthesize 3, 5-dibromo salicylaldehyde Schiff base; and then reacting the monohydrate copper acetate with 3, 5-dibromo salicylaldehyde Schiff base in an ethanol system to synthesize the Schiff base-copper complex.
As a further improvement of the invention, the mass fraction of the copper element in the catalyst is 5-7%.
As a further improvement of the method, the reaction temperature of the amination reduction graphene oxide and 3, 5-dibromo salicylaldehyde is 60-70 ℃; the reaction time is 10-12 h; the reaction temperature of the copper acetate monohydrate and the 3, 5-dibromo salicylaldehyde Schiff base is 60-70 ℃; the reaction time is 10-12 h.
As a further improvement of the invention, the catalyst is applied to activate potassium persulfate to degrade chlorophenol pollutants in an aqueous solution.
As a further improvement of the invention, the step of degrading the chlorophenol pollutants is as follows:
a) respectively preparing a catalyst and potassium persulfate into solutions by adopting deionized water;
b) mixing the catalyst solution, the potassium persulfate solution and the water solution containing chlorophenol pollutants, adding the mixture into deionized water to form a reaction solution, and reacting under the conditions of light shielding and oscillation.
As a further improvement of the invention, the concentration of the catalyst in the reaction solution of the step b) is more than or equal to 10 mg/L; the concentration ratio of potassium persulfate to chlorophenol pollutants in the reaction solution is more than or equal to 5: 1.
as a further improvement of the invention, the reaction temperature in the step b) is 15-30 ℃.
As a further improvement of the invention, the chlorophenol-type pollutants comprise triclosan, benzylchlorophenol and 2, 4, 6-trichlorophenol.
As a further improvement of the invention, the preparation method of the catalyst for degrading chlorophenol pollutants comprises the following steps:
(1) dispersing aminated reduced graphene oxide (TEPA-rGO) in absolute ethyl alcohol;
(2) dissolving 3, 5-dibromo salicylaldehyde in absolute ethyl alcohol, dropwise adding the mixture into the system in the step (1), stirring, condensing, refluxing, heating to react, cooling, performing suction filtration after the reaction is finished, drying a filter cake, and collecting to obtain an intermediate product;
(3) weighing the intermediate product obtained in the step (3) and dispersing the intermediate product into absolute ethyl alcohol;
(4) dissolving copper acetate monohydrate in absolute ethyl alcohol, stirring, condensing, refluxing, heating for reaction, cooling, filtering, drying and collecting a filter cake after the reaction is finished, thus obtaining the graphene-immobilized Schiff base-copper complex catalyst.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the catalyst for degrading chlorophenol pollutants is a graphene-immobilized Schiff base-copper complex catalyst, and is a high-efficiency heterogeneous nano catalyst. The catalyst was subjected to structural characterization: the element analysis and XPS show that the content ratio of C, N, O, Cu element in the catalyst indicates the generation of copper complex; the mass fraction of the copper element in the catalyst is 5-7% by flame atomic absorption spectrometry; analysis by a Scanning Electron Microscope (SEM) shows that the rougher surface of the catalyst brings larger specific surface area and more possible reaction sites in the process from the graphene to the intermediate product and then to the catalyst; transmission Electron Microscope (TEM) analysis shows that more new groups and complexes are generated on the surface of graphene in the process from the graphene to an intermediate product and then to a catalyst.
(2) According to the application of the catalyst for degrading the chlorophenol pollutants, the catalyst activates potassium persulfate to realize higher removal rate of the chlorophenol pollutants, and the removal rate can reach about 90%; the stability of the catalyst is characterized by the change of the concentration of Cu ions in the solution, and the Cu ion concentration in the water phase does not obviously change before and after the reaction under the neutral condition, so that the ion leaching rate of the catalyst is low. Therefore, the catalyst can not generate water pollution caused by metal ion release in the using process.
(3) The application of the catalyst for degrading the chlorophenol pollutants realizes the activation of potassium persulfate of the catalyst under the conditions of low energy consumption, low pollution and mild conditions so as to remove the chlorophenol pollutants in a water body.
(4) The application of the catalyst for degrading chlorophenol pollutants not only realizes the catalytic reaction of the Schiff base metal complex catalyst under mild conditions, but also overcomes the defects that persulfate cannot be activated under natural conditions and needs to be added under external conditions, and further overcomes the defects of secondary pollution, high energy consumption and harsh reaction conditions caused by persulfate activation.
(5) The preparation method of the catalyst for degrading chlorophenol pollutants comprises the steps of synthesizing graphene-immobilized Schiff base by using aminated graphene and 3, 5-dibromo salicylaldehyde in an ethanol reaction system at the temperature of 70 ℃, and reacting the Schiff base with copper acetate in an ethanol solution at the temperature of 70 ℃ to finally obtain a black powdery catalyst aminated graphene Schiff base-copper complex. The preparation method is simple, low in cost and energy consumption, green and environment-friendly in preparation process, and beneficial to industrial popularization.
(6) The preparation method of the catalyst for degrading chlorophenol pollutants realizes the immobilization of the traditional Schiff base metal complex, fixes the Schiff base metal complex in a graphene mode, and is convenient to recycle, thereby solving the problems of difficult recycling of homogeneous Schiff base metal complex catalyst, metal ion pollution and the like.
Drawings
FIG. 1 is a reaction scheme for the synthesis of Schiff base intermediates of the present invention;
FIG. 2 is a reaction scheme diagram of the synthesis of the end product graphene-supported Schiff base-copper complex catalyst of the present invention;
FIG. 3 is a scanning electron micrograph of TEPA-rGO, Schiff base intermediates, and catalyst in accordance with the present invention;
wherein a is a scanning electron microscope picture of TEPA-rGO at 500 nm; b is a scanning electron microscope image of the Schiff base intermediate at 500 nm; c is a scanning electron microscope image of the catalyst at 500 nm; d is a scanning electron microscope image of TEPA-rGO at 5.00 mu m; e is a scanning electron microscope image of the Schiff base intermediate at 5.00 mu m; f is a scanning electron microscope image of the catalyst at 5.00 mu m; g is a scanning electron micrograph of TEPA-rGO at 50.0 mu m; h is a scanning electron microscope image of the Schiff base intermediate at 50.0 mu m; i is a scanning electron microscope image of the catalyst at 50.0 mu m;
FIG. 4 is a transmission electron micrograph of TEPA-rGO, Schiff base intermediates, and catalyst of the present invention;
wherein a is a transmission electron microscope picture of TEPA-rGO at 100 nm; b is a transmission electron microscope image of the Schiff base intermediate at 100 nm; c is a transmission electron microscope image of the catalyst at 100 nm; d is a transmission electron micrograph of TEPA-rGO at 200 nm; e is a transmission electron microscope image of the Schiff base intermediate at 200 nm; f is a transmission electron microscope image of the catalyst at 200 nm; g is a transmission electron micrograph of TEPA-rGO at 0.5 mu m; h is a transmission electron microscope image of the Schiff base intermediate at 0.5 mu m; i is a transmission electron microscope image of the catalyst at 0.5 mu m;
FIG. 5 is a full scan XPS plot of TEPA-rGO, Schiff base intermediates, catalysts of the present invention;
FIG. 6 is a graph showing the results of a comparison of catalyst + potassium persulfate, and catalyst degradation of triclosan;
FIG. 7 is a graph showing the results of catalyst + potassium persulfate, and catalyst degradation of benzylchlorophenol;
FIG. 8 is a graph showing the comparative results of catalyst + potassium persulfate, and catalyst degradation of 2, 4, 6-trichlorophenol.
Detailed Description
The present invention is further described with reference to the following specific examples, which are only used to better illustrate the technical solutions and should not be construed as limiting the scope of the present invention.
Example 1
The reagent materials used in this example include aminated reduced graphene oxide (TEPA-rGO), 3, 5-dibromo salicylaldehyde, copper acetate monohydrate, and anhydrous ethanol, wherein the TEPA-rGO nitrogen content is 9.34% and is available from nanjing piofeng nanomaterial science and technology ltd, and the 3, 5-dibromo salicylaldehyde is available from carbofuran; the copper acetate monohydrate was purchased from Nanjing chemical reagents, Inc.; the absolute ethanol is purchased from Nanjing chemical reagents GmbH.
The synthesis process of the graphene-immobilized schiff base-copper complex catalyst in the embodiment is as follows: firstly, carrying out reaction on amination reduction graphene oxide and 3, 5-dibromo salicylaldehyde in an ethanol system to synthesize 3, 5-dibromo salicylaldehyde Schiff base; then, copper acetate monohydrate and 3, 5-dibromo salicylaldehyde Schiff base react in an ethanol system to synthesize the Schiff base-copper complex, and the specific operation steps are as follows:
(1) 500mg of aminated reduced graphene oxide (TEPA-rGO) was weighed, dispersed in 100mL of anhydrous ethanol, ultrasonically dispersed for 30 minutes by an ultrasonic disperser, and the system was transferred to a round bottom flask.
(2) Meanwhile, 373mg of 3, 5-dibromo salicylaldehyde is weighed, dissolved in 100mL of absolute ethyl alcohol, slowly dripped into the previous round-bottom flask, stirred, condensed and refluxed, heated in a water bath, and reacted for 10 hours at the temperature of 60 ℃. And after the reaction is finished, cooling down the system, performing suction filtration by using a vacuum pump, washing a filter cake for 3 times by using absolute ethyl alcohol, drying at the temperature of 50 ℃ for 10 hours, and collecting to obtain black solid powder amination reduction graphene oxide condensation 3, 5-dibromo salicylaldehyde Schiff base.
The chemical reactions that take place in the above steps are shown in FIG. 1, TEPA-rGO and 3, 5-dibromo salicylaldehydeReacting in an ethanol system at the temperature of 60 ℃ for 12 hours to generate intermediate Schiff base. Wherein the reaction process is the amino (-NH) group of TEPA-rGO2) Condensation reaction with aldehyde group in 3, 5-dibromo salicylaldehyde to generate C ═ N bond and one water molecule (H)2O)。
(3) 500mg of the Schiff base is weighed, dispersed in 100mL of absolute ethyl alcohol, ultrasonically dispersed for 15 minutes by using an ultrasonic disperser, and the system is transferred into a round-bottom flask.
(4) Meanwhile, 152mg of monohydrate copper acetate powder is weighed and dissolved in 100mL of absolute ethyl alcohol, and slowly added into the previous round-bottom flask dropwise, stirring is kept, condensation reflux is carried out, water bath heating is carried out, the temperature is kept at 60-70 ℃, and the reaction is carried out for 10 hours. And after the reaction is finished, cooling down the system, performing suction filtration by using a vacuum pump, washing the filter cake for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, drying for 10 hours at the temperature of 50 ℃, and collecting to obtain the black solid powder graphene-immobilized Schiff base-copper complex catalyst.
The chemical reaction in this step is shown in fig. 2, the schiff base intermediate reacts in an ethanol system at 60 ℃, and the final product schiff base-copper complex is generated after 12 hours of reaction. In the reaction process, copper ions and N with lone electron pairs are matched to generate a coordination bond, and a Schiff base-copper complex is generated.
The synthesized product comprises an amination reduction graphene oxide condensation 3, 5-dibromo salicylaldehyde Schiff base intermediate and a Schiff base-copper complex catalyst, and the mass fraction of the copper element in the catalyst is 5% by flame atomic absorption spectrometry.
Physicochemical characterization of the catalyst and the synthesis precursor were analyzed.
And (3) carrying out nano-scale microscopic analysis on the TEPA-rGO, the Schiff base intermediate and the product catalyst by using a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM).
Fig. 3 is a scanning electron microscope image of TEPA-rGO, schiff base intermediate, and catalyst, and according to analysis of fig. 3, in a process from graphene to schiff base intermediate to catalyst, the surface of the nanomaterial becomes rougher and shows smaller particles, which is because the synthesis process of the catalyst is also a process of surface modification of graphene, and the rougher surface of the catalyst brings a larger specific surface area and more possible reaction sites.
Fig. 4 is a transmission electron microscope image of TEPA-rGO, schiff base intermediate, and catalyst, and it is obtained from the map analysis that defect sites appear on the surface of the material in the process from graphene to schiff base intermediate to catalyst, because more new groups and complexes are generated on the surface of graphene, and these sites promote the catalytic reaction on the surface of graphene.
Analyzing the surface layer element composition of the catalyst, the Schiff base intermediate and the graphene by using an X-ray photoelectron spectrometer (XPS), wherein an analysis map is shown in figure 5, and the analysis map is obtained according to the map, copper ions are combined on the surface of the amination reduced graphene oxide in the synthesis process of the catalyst, and compared with the amination reduced graphene oxide and the Schiff base intermediate, the catalyst shows a large amount of Cu element peaks in the map; and the chart of the final synthesized product is greatly changed relative to the baseline of TEPA-rGO and Schiff base intermediates, which shows that the skeleton structure and functional groups of the product are greatly changed relative to graphene; the composition elements of the TEPA-rGO and the Schiff base intermediate are similar, and the spectra are not obviously different.
Elemental analysis and XPS showed that the content ratio of C, N, O, Cu element in the catalyst was 65.58: 9.39: 17.78: 7.26, indicating the formation of a copper complex.
In the literature of preparation, characterization and epoxidation catalytic performance research of graphene oxide-loaded schiff base metal complexes, in the preparation aspect, aminated graphene and acetylacetone are condensed to prepare a catalyst, but in the patent, TEPA-rGO and 3, 5-dibromo salicylaldehyde are condensed to form schiff base intermediates, and then monohydrate copper acetate and the intermediate products are reacted to synthesize the schiff base-copper complexes, so that the products prepared by the method have essential differences from the products in the literature, and different catalytic degradation performances exist, and the catalytic degradation reactions are different: the method in the literature takes acetonitrile as a reaction solution and TBHP as an oxidant, and the reaction time is 7 hours, the reaction temperature is 80 ℃, and the conversion rate of styrene is 94.3%; in the method, the reaction solution is water, the potassium persulfate is an oxidant, the reaction time is 1.5 hours, the reaction temperature is room temperature (25 ℃), and both the triclosan and the benzylchlorophenol reach 90% removal rates.
Therefore, in the literature of preparation, characterization and epoxidation catalytic performance research of graphene oxide supported schiff base metal complexes, the prepared catalyst is suitable for a laboratory condition, is used as a classical organic chemical oxidation reaction (existing in an organic solvent, and has long reaction time, high temperature and complex conditions), and shows a good catalytic degradation effect; however, the method breaks through the limitation of laboratory conditions of classical organic chemical reactions, and the Schiff base metal complex catalyst is used for activating potassium persulfate to show a catalytic degradation effect in a water phase at normal temperature in a short time, so that the method can be better applied to the field of wastewater treatment, and is a qualitative leap compared with the prior art.
Example 2
The reagent materials used in this embodiment are the same as those used in embodiment 1, and the synthesis process of the graphene-supported schiff base-copper complex catalyst in this embodiment is as follows:
(1) 500mg of amination reduction graphene oxide is weighed and dispersed in 100mL of absolute ethyl alcohol, ultrasonic dispersion is carried out for 18 minutes by using an ultrasonic dispersion instrument, and the system is transferred into a round-bottom flask.
(2) Meanwhile, 373mg of 3, 5-dibromo salicylaldehyde is weighed, dissolved in 100mL of absolute ethyl alcohol, slowly dripped into the previous round-bottom flask, stirred, condensed and refluxed, heated in a water bath, and reacted for 11 hours at 65 ℃. After the reaction is finished, cooling down the system, performing suction filtration by using a vacuum pump, washing a filter cake for 3 times by using absolute ethyl alcohol, drying for 10 hours at the temperature of 50 ℃, and collecting to obtain an intermediate product.
(3) 500mg of the intermediate product was weighed, dispersed in 100mL of anhydrous ethanol, ultrasonically dispersed for 30 minutes by an ultrasonic disperser, and the system was transferred to a round-bottom flask.
(4) Meanwhile, 152mg of copper acetate monohydrate powder is weighed and dissolved in 100mL of absolute ethyl alcohol, and slowly added into the previous round-bottom flask dropwise, stirring is kept, condensation reflux is carried out, water bath heating is carried out, the temperature is kept at 65 ℃, and the reaction is carried out for 11 hours. And after the reaction is finished, cooling down the system, performing suction filtration by using a vacuum pump, washing the filter cake for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, drying for 10 hours at the temperature of 50 ℃, and collecting to obtain the graphene-immobilized Schiff base-copper complex catalyst.
The mass fraction of the copper element in the catalyst is 6 percent by flame atomic absorption spectrometry.
Example 3
The reagent materials used in this embodiment are the same as those used in embodiment 1, and the synthesis process of the graphene-supported schiff base-copper complex catalyst in this embodiment is as follows:
(1) 500mg of amination reduction graphene oxide is weighed and dispersed in 100mL of absolute ethyl alcohol, ultrasonic dispersion is carried out for 30 minutes by using an ultrasonic dispersion instrument, and the system is transferred to a round-bottom flask.
(2) Meanwhile, 373mg of 3, 5-dibromo salicylaldehyde is weighed, dissolved in 100mL of absolute ethyl alcohol, slowly dripped into the previous round-bottom flask, stirred, condensed and refluxed, heated in a water bath, and reacted for 12 hours at the temperature of 70 ℃. After the reaction is finished, cooling down the system, performing suction filtration by using a vacuum pump, washing a filter cake for 3 times by using absolute ethyl alcohol, drying for 10 hours at the temperature of 50 ℃, and collecting to obtain an intermediate product.
(3) 500mg of the intermediate product was weighed, dispersed in 100mL of anhydrous ethanol, ultrasonically dispersed for 30 minutes by an ultrasonic disperser, and the system was transferred to a round-bottom flask.
(4) Meanwhile, 152mg of copper acetate monohydrate powder is weighed and dissolved in 100mL of absolute ethyl alcohol, and slowly added into the previous round-bottom flask dropwise, stirring is kept, condensation reflux is carried out, water bath heating is carried out, the temperature is kept at 70 ℃, and the reaction is carried out for 12 hours. And after the reaction is finished, cooling down the system, performing suction filtration by using a vacuum pump, washing the filter cake for 3 times by using absolute ethyl alcohol, then washing for 3 times by using deionized water, drying for 10 hours at the temperature of 50 ℃, and collecting to obtain the graphene-immobilized Schiff base-copper complex catalyst.
The mass fraction of the copper element in the catalyst is 7 percent by flame atomic absorption spectrometry.
Example 4
The graphene-supported schiff base-copper complex catalyst synthesized in example 1 was subjected to performance test, and this example tests the performance of activating potassium persulfate to degrade chlorophenol antibacterial Triclosan (TCS) in an aqueous persulfate system.
The experimental method is as follows: the experiment for catalytic degradation of triclosan by the catalyst was carried out in a glass cuvette (volume approximately 15 mL). The experiment was carried out in a shaking incubator protected from light, wherein the rotation speed of the shaking incubator was 150rpm, the reaction temperature was 15 ℃, and the reaction time was 90 minutes.
The specific operation steps are as follows:
1) firstly, preparing a catalyst into a mother liquor with the concentration of 1g/L by using deionized water, and preparing potassium persulfate into a mother liquor with the concentration of 10 mmol/L;
2) 0.2mL of catalyst mother liquor with the concentration of 1g/L, 0.2mL of triclosan aqueous solution with the concentration of 1mmol/L and 0.2mL of potassium persulfate aqueous solution (PS) with the concentration of 10mmol/L are added into 9.4mL of deionized water to form a reaction solution, the reaction is immediately carried out, 0.5mL of reaction solution is taken out from a colorimetric tube at the 0 th, 10 th, 20 th, 30 th, 40 th and 60 th min of the reaction, added into 0.5mL of methanol prepared in advance to stop the reaction, centrifuged at the rotation speed of 10000rpm, and 0.5mL of supernatant is taken out to be detected in a high performance liquid chromatograph to detect the concentration of TCS. Meanwhile, a control test is set, and the degradation capability of the single catalyst and the single potassium persulfate to the TCS is researched. Each set of experiments was run in triplicate and the average was taken.
As shown in fig. 6, the catalyst exhibited good ability to activate potassium persulfate to degrade TCS. Under the condition, the degradation rate of TCS in 90min reaches about 50%.
While the TCS is not degraded basically by PS alone within 90min, and the measured degradation rate is within 10%. The result shows that the catalyst can promote the degradation of TCS by PS and greatly accelerate the reaction process. Meanwhile, the catalyst has no degradation effect on the TCS under the condition that the oxidant PS exists, so that the adsorption effect of the catalyst on the TCS in a water phase can be eliminated.
The stability of the catalyst is characterized by the change of the concentration of Cu ions in the solution, and the Cu ion concentration in the water phase does not obviously change before and after the reaction under the neutral condition, so that the ion leaching rate of the catalyst is low.
Example 5
The graphene-supported schiff base-copper complex catalyst synthesized in example 1 was subjected to a performance test, and this example tests the catalytic degradation effect of the catalyst on another chlorophenol substance, namely, benzylchlorophenol (CF).
The experimental method is as follows: the experiment of catalytic degradation of benzyl chlorophenol was carried out in a glass cuvette (volume about 15 mL). The experiment was carried out in a shaking incubator protected from light, wherein the rotation speed of the shaking incubator was 150rpm, the reaction temperature was 25 ℃, and the reaction time was 60 minutes.
The specific operation flow is as follows:
1) firstly, preparing a catalyst into a mother liquor with the concentration of 1g/L by using deionized water, and preparing potassium persulfate into a mother liquor with the concentration of 10 mmol/L;
2) 0.2mL of a CF aqueous solution with the concentration of 1g/L, 0.2mL of a CF aqueous solution with the concentration of 1mmol/L and 0.2mL of a potassium persulfate aqueous solution (PS) with the concentration of 10mmol/L are added into 9.4mL of deionized water to form a reaction solution, the reaction is immediately carried out, 0.5mL of the reaction solution is taken out from a colorimetric tube at the 0 th, 10 th, 20 th, 30 th, 40 th and 60 th min of the reaction, added into 0.5mL of methanol prepared in advance to stop the reaction, centrifuged at the rotation speed of 10000rpm, and 0.5mL of supernatant is taken out and put into a high performance liquid chromatograph to detect the concentration of the benzylchlorophenol. Meanwhile, a control test is set, and the degradation capability of the single catalyst and the single potassium persulfate p-benzylchlorophenol is researched. Each set of experiments was run in triplicate and the average was taken.
The results are shown in fig. 7, where the catalyst exhibited good ability to activate potassium persulfate to degrade CF. Under the condition, the degradation rate of CF in 60min reaches about 90 percent.
While PS alone does not degrade CF substantially within 60min, the degradation rate measured is within 5%. The result shows that the catalyst can promote the degradation of PS to CF and greatly accelerate the reaction process. Meanwhile, the catalyst has no degradation effect on the CF under the condition that an oxidant PS exists, so that the adsorption effect of the catalyst on the CF in a water phase can be eliminated.
Example 6
The graphene-supported schiff base-copper complex catalyst synthesized in example 1 is subjected to performance test, and the catalytic degradation effect of the catalyst on another chlorophenol substance 2, 4, 6-Trichlorophenol (TCP) is tested in this example.
Catalytic degradation of 2, 4, 6-trichlorophenol the catalyst was reacted in a glass cuvette (volume approximately 15 mL). The experiment was carried out in a shaking incubator protected from light, wherein the rotation speed of the shaking incubator was 150rpm, the reaction temperature was 30 ℃ and the reaction time was 30 minutes.
The specific operation flow is as follows:
1) firstly, preparing a catalyst into a mother liquor with the concentration of 1g/L by using deionized water, and preparing potassium persulfate into a mother liquor with the concentration of 10 mmol/L;
2) 0.2mL of catalyst mother liquor with the concentration of 1g/L, 0.2mL of TCP aqueous solution with the concentration of 1mmol/L and 0.2mL of potassium persulfate aqueous solution (PS) with the concentration of 10mmol/L are added into 9.4mL of deionized water to form a reaction solution, the reaction is immediately carried out, 0.5mL of reaction solution is taken out from a colorimetric tube at the 0 th, 10 th, 20 th, 30 th, 40 th and 60 th min of the reaction, added into 0.5mL of methanol prepared in advance to stop the reaction, and centrifuged at the rotation speed of 10000rpm, and 0.5mL of supernatant is taken out to be put into a high performance liquid chromatograph to detect the concentration of TCP. Meanwhile, a control test is set, and the degradation capability of the single catalyst and the single potassium persulfate on the TCP is researched. Each set of experiments was run in triplicate and the average was taken.
The results are shown in fig. 8, where the catalyst exhibited good ability to activate potassium persulfate to degrade TCP. Under the condition, the degradation rate of the TCP in 60min reaches about 80 percent.
And the PS alone does not degrade the TCP basically within 60min, and the measured degradation rate is within 10 percent. The result shows that the catalyst can promote the degradation of PS to TCP and greatly accelerate the reaction process. Under the condition of no oxidant PS, the catalyst has no degradation effect on the TCP, so that the adsorption effect of the catalyst on the TCP in a water phase can be eliminated.
Example 7
The graphene-supported schiff base-copper complex catalyst synthesized in example 1 was subjected to performance test, and this example tests the performance of activating potassium persulfate to degrade chlorophenol antibacterial Triclosan (TCS) in an aqueous persulfate system.
The experimental method is as follows: the experiment for catalytic degradation of triclosan by the catalyst was carried out in a glass cuvette (volume approximately 15 mL). The experiment was carried out in a shaking incubator protected from light, wherein the rotation speed of the shaking incubator was 150rpm, the reaction temperature was 15 ℃, and the reaction time was 90 minutes.
The specific operation steps are as follows:
1) firstly, preparing a catalyst into a mother liquor with the concentration of 1g/L by using deionized water, and preparing potassium persulfate into a mother liquor with the concentration of 10 mmol/L;
2) 0.1mL of catalyst mother liquor with the concentration of 1g/L, 0.2mL of triclosan aqueous solution with the concentration of 1mmol/L and 0.2mL of potassium persulfate aqueous solution (PS) with the concentration of 10mmol/L are added into 9.5mL of deionized water to form a reaction solution, the reaction is immediately carried out, 0.5mL of reaction solution is taken out from a colorimetric tube at the 0 th, 10 th, 20 th, 30 th, 40 th and 60 th min of the reaction, added into 0.5mL of methanol prepared in advance to stop the reaction, centrifuged at the rotation speed of 10000rpm, and 0.5mL of supernatant is taken out to be detected in a high performance liquid chromatograph to detect the concentration of TCS. Meanwhile, a control test is set, and the degradation capability of the single catalyst and the single potassium persulfate to the TCS is researched. Each set of experiments was run in triplicate and the average was taken.
The results show that the catalyst exhibits good ability to activate potassium persulfate to degrade TCS. Under the condition, the degradation rate of TCS in 90min reaches about 25%.
While the TCS is not degraded basically by PS alone within 90min, and the measured degradation rate is within 10%. The result shows that the catalyst can promote the degradation of TCS by PS and greatly accelerate the reaction process. Meanwhile, the catalyst has no degradation effect on the TCS under the condition that the oxidant PS exists, so that the adsorption effect of the catalyst on the TCS in a water phase can be eliminated.
Example 8
The graphene-supported schiff base-copper complex catalyst synthesized in example 1 was subjected to performance test, and this example tests the performance of activating potassium persulfate to degrade chlorophenol antibacterial Triclosan (TCS) in an aqueous persulfate system.
The experimental method is as follows: the experiment for catalytic degradation of triclosan by the catalyst was carried out in a glass cuvette (volume approximately 15 mL). The experiment was carried out in a shaking incubator protected from light, wherein the rotation speed of the shaking incubator was 150rpm, the reaction temperature was 15 ℃, and the reaction time was 90 minutes.
The specific operation steps are as follows:
1) firstly, preparing a catalyst into a mother liquor with the concentration of 1g/L by using deionized water, and preparing potassium persulfate into a mother liquor with the concentration of 10 mmol/L;
2) 0.2mL of catalyst mother liquor with the concentration of 1g/L, 0.2mL of triclosan aqueous solution with the concentration of 1mmol/L and 0.1mL of potassium persulfate aqueous solution (PS) with the concentration of 10mmol/L are added into 9.5mL of deionized water to form a reaction solution, the reaction is immediately carried out, 0.5mL of reaction solution is taken out from a colorimetric tube at the 0 th, 10 th, 20 th, 30 th, 40 th and 60 th min of the reaction, added into 0.5mL of methanol prepared in advance to stop the reaction, centrifuged at the rotation speed of 10000rpm, and 0.5mL of supernatant is taken out to be detected in a high performance liquid chromatograph to detect the concentration of TCS. Meanwhile, a control test is set, and the degradation capability of the single catalyst and the single potassium persulfate to the triclosan are researched. Each set of experiments was run in triplicate and the average was taken.
The catalyst exhibits good ability to activate potassium persulfate to degrade TCS. Under the condition, the degradation rate of TCS in 90min reaches about 50%.
While the TCS is not degraded basically by PS alone within 90min, and the measured degradation rate is within 10%. The result shows that the catalyst can promote the degradation of TCS by PS and greatly accelerate the reaction process. Meanwhile, the catalyst has no degradation effect on the TCS under the condition that the oxidant PS exists, so that the adsorption effect of the catalyst on the TCS in a water phase can be eliminated.
The present invention and its embodiments have been described in detail in the foregoing for illustrative purposes, and the description is not intended to be limiting, and the embodiments shown in the drawings are only one embodiment of the present invention, and the actual flow is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.
Claims (5)
1. The application of the catalyst for degrading chlorophenol pollutants is characterized in that: the catalyst is applied to activating potassium persulfate to degrade chlorophenol pollutants in an aqueous solution; the catalyst is prepared according to the following steps: firstly, carrying out reaction on amination reduction graphene oxide and 3, 5-dibromo salicylaldehyde in an ethanol system to synthesize 3, 5-dibromo salicylaldehyde Schiff base; reacting copper acetate monohydrate with 3, 5-dibromo salicylaldehyde Schiff base in an ethanol system to synthesize a Schiff base-copper complex, wherein the reaction temperature of amination reduction graphene oxide and 3, 5-dibromo salicylaldehyde is 60-70 ℃; the reaction time is 10-12 h; the reaction temperature of the copper acetate monohydrate and the 3, 5-dibromo salicylaldehyde Schiff base is 60-70 ℃; the reaction time is 10-12 h, and the mass fraction of the copper element in the catalyst is 5-7%.
2. Use of a catalyst for degrading chlorophenol-type contaminants according to claim 1, characterized in that: the steps for degrading the chlorophenol pollutants are as follows:
a) respectively preparing a catalyst and potassium persulfate into solutions by adopting deionized water;
b) mixing the catalyst solution, the potassium persulfate solution and the water solution containing chlorophenol pollutants, adding the mixture into deionized water to form a reaction solution, and reacting under the conditions of light shielding and oscillation.
3. Use of a catalyst for degrading chlorophenol-type contaminants according to claim 2, characterized in that: the concentration of the catalyst in the reaction solution in the step b) is more than or equal to 10 mg/L; the molar concentration ratio of potassium persulfate to chlorophenol pollutants in the reaction solution is more than or equal to 5: 1.
4. use of a catalyst for degrading chlorophenol-type contaminants according to claim 3, characterized in that: the reaction temperature in the step b) is 15-30 ℃.
5. Use of a catalyst for degrading chlorophenol-type contaminants according to claim 4, characterized in that: the chlorophenol pollutants comprise triclosan, benzylchlorophenol and 2, 4, 6-trichlorophenol.
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| CN109851032B (en) * | 2019-03-12 | 2021-11-02 | 河南师范大学 | Method for degrading triclosan by catalyzing hydrogen peroxide oxidation through Schiff base copper complex |
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| CN112169838A (en) * | 2020-11-03 | 2021-01-05 | 南京工程学院 | Honeycomb material supported transition metal oxide catalyst and preparation method thereof |
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