CN111569949B - Preparation method and application of magnetic temperature-sensitive imprinting material polymerized by microwave initiation - Google Patents
Preparation method and application of magnetic temperature-sensitive imprinting material polymerized by microwave initiation Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 title description 3
- 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 abstract description 54
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 40
- 230000001699 photocatalysis Effects 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003760 magnetic stirring Methods 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
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- 239000000047 product Substances 0.000 claims description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000004098 Tetracycline Substances 0.000 description 8
- 239000000696 magnetic material Substances 0.000 description 8
- 229960002180 tetracycline Drugs 0.000 description 8
- 229930101283 tetracycline Natural products 0.000 description 8
- 235000019364 tetracycline Nutrition 0.000 description 8
- 150000003522 tetracyclines Chemical class 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
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- 238000001179 sorption measurement Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to the technical field of environmental material synthesis, and particularly relates to a preparation method of a magnetic temperature-sensitive imprinting material for microwave-initiated polymerization and application of the magnetic temperature-sensitive imprinting material in selective controllable photocatalytic degradation of ciprofloxacin; the method comprises the following specific steps: the magnetic carbon material is synthesized by a ball milling-calcining method and subjected to surface modification, meanwhile Ag-POPD is synthesized and is used as a functional monomer, and the magnetic thermosensitive imprinting material is prepared by using a surface imprinting technology of microwave initiated polymerization and N-isopropyl acrylamide as a thermosensitive monomer. The synthesized magnetic thermosensitive imprinting material has good magnetic separation characteristics and high photocatalytic activity, can selectively remove ciprofloxacin residues from a plurality of substances, can realize controllable adjustment of a photocatalytic degradation process, and has wide prospect and application value.
Description
Technical Field
The invention belongs to the technical field of environmental material synthesis, and particularly relates to a preparation method of a magnetic temperature-sensitive imprinting material for microwave-initiated polymerization and application of the magnetic temperature-sensitive imprinting material in selective controllable photocatalytic degradation of ciprofloxacin.
Background
The photocatalysis technology is used as a green oxidation technology and is widely applied to the field of water pollution treatment. However, with the development of society, specific removal of specific pollutants existing in some special water environments is needed, and in addition, if controllable adjustment of photocatalytic degradation process can be realized, the method has important significance in the functional application of the photocatalytic technology in the field of water pollution treatment. Therefore, on one hand, the surface imprinting technology and the photocatalysis technology are combined, and the selective and efficient removal of specific target pollutants in the water environment is realized by utilizing the specific adsorptivity of the surface imprinting technology and the efficient degradation activity of the photocatalysis technology. Furthermore, a supported organic semiconductor (such as silver-supported poly-o-phenylenediamine (Ag-POPD)) is taken as a functional monomer to be introduced into the surface imprinting layer, so that the problem that the photocatalytic activity of the traditional imprinting photocatalytic material is reduced due to the fact that the surface imprinting layer covers the photocatalytic active site is solved. On the other hand, the temperature sensitive material can change its own state by changing the temperature of the external environment, such as: n-isopropyl acrylamide (PNIPAM) with a critical temperature of 32 ℃. When the ambient temperature is higher than 32 ℃, the hydrophobic effect plays a dominant role, and the PNIPAM is converted into a contracted state; when the ambient temperature is below 32 ℃, the hydrophilic effect dominates and PNIPAM transitions to the expanded state. Thus, the incorporation of PNIPAM into the surface imprinting layer allows for the controlled tuning of the selective photocatalytic process by varying the ambient temperature.
In addition, it is known that a suitable carrier has the effects of improving separation recovery efficiency, increasing binding sites, increasing specific surface area, and the like for a composite material. Therefore, if the waste biomass material can be further converted into the carrier material, the significance of treating waste with waste can be reflected, the production cost can be reduced, and the method has great development potential. Therefore, the magnetic carbon material with good magnetic separation characteristic and larger specific surface area is synthesized by using the corncob and the iron source as raw materials through a ball milling-calcining method.
At present, many researches and reports on applying a photocatalysis technology to water pollution treatment are available, some researches and reports on combining a surface imprinting technology and a photocatalysis technology to water pollution treatment are available, and various reports on introducing an organic semiconductor as a functional monomer into a surface imprinting layer and realizing selective photocatalysis removal of specific target pollutants by the organic semiconductor are available, and in addition, some reports on applying a temperature sensitive material to photocatalysis removal of the organic pollutants are available, however, the researches on combining a temperature sensitive material, a photocatalysis material and a surface imprinting material are not available; in addition, the ball milling-calcining method is utilized to convert the waste biomass into the magnetic carbon material, and the research of applying the magnetic carbon material to the field of photocatalysis wastewater treatment is not reported. Therefore, the prepared magnetic temperature-sensitive imprinting material has good magnetic separation characteristic and high photocatalytic activity, can selectively remove ciprofloxacin from a plurality of substances, and can realize controllable adjustment of the photocatalytic process, and has wide prospect and application value.
Disclosure of Invention
The invention prepares the magnetic temperature-sensitive imprinting material with good magnetic separation characteristic, good photocatalytic activity, good selectivity and controllable regulation of the photocatalytic process by taking a ball milling-calcining method, a surface imprinting technology, a microwave initiated polymerization method and the like as synthesis means.
The invention firstly provides a magnetic temperature-sensitive imprinting material capable of removing specific target objects in a controllable and selective way, wherein the composite material is formed by compositing a magnetic carbon material and a surface temperature-sensitive imprinting layer; the magnetic carbon material is formed by converting corncobs and iron sources; the surface temperature-sensitive imprinting layer is formed by combining Ag-POPD, PNIPAM and trimethylolpropane trimethacrylate; the magnetic temperature-sensitive imprinting material has good magnetic separation characteristic and stability, and the magnetic saturation strength is 3.95emu/g; 0.1g of the magnetic temperature-sensitive imprinting material is used for photocatalytic degradation of 100mL of 10mg/L ciprofloxacin solution, and the degradation rate of 90min reaches 73.25% under the irradiation of a xenon lamp at 25 ℃; furthermore, degradation data for different contaminants show: compared with a magnetic non-imprinting material, the magnetic temperature-sensitive imprinting material also has good selective photocatalytic degradation capability on ciprofloxacin; moreover, compared with the magnetic common imprinting material, the magnetic temperature-sensitive imprinting material has obvious degradation rate change on the same pollutant at different temperatures, which indicates that the magnetic temperature-sensitive imprinting material can realize controllable adjustment of the photocatalysis process by adjusting the environmental temperature.
The invention also provides a magnetic temperature-sensitive imprinting material polymerized by microwave initiation, which is prepared according to the following steps:
(1) Synthesis of carboxyl modified magnetic carbon material:
adding corncob, cetyl trimethyl ammonium bromide and ferric nitrate nonahydrate into absolute ethyl alcohol, performing ball milling reaction for a period of time, drying a product after the reaction is finished, and calcining the product for a period of time in a tubular furnace under a hydrogen atmosphere to obtain the corn cob/ferric nitrate composite material: a magnetic carbon material; then amino and carboxyl are modified in sequence to obtain a carboxyl modified magnetic carbon material for later use;
(2) Synthesis of Ag-POPD:
firstly, generating poly-o-phenylenediamine (POPD) through o-phenylenediamine self-polymerization, and carrying out Ag loading on the poly-o-phenylenediamine to obtain Ag-POPD for later use;
(3) Synthesis of magnetic temperature-sensitive blotting material:
firstly, adding the carboxyl modified magnetic carbon material prepared in the step (1) and the Ag-POPD prepared in the step (2) into dimethyl sulfoxide, carrying out a first magnetic stirring reaction at a certain temperature, adding ciprofloxacin after the reaction is finished, carrying out a second magnetic stirring reaction at a certain temperature, introducing nitrogen after the reaction is finished, and then adding N-isopropyl acrylamide, trimethylolpropane trimethacrylate and azodiisoheptanenitrile to obtain a reaction solution; then, the reaction liquid is put into a microwave reactor, and is subjected to a third magnetic stirring reaction under the conditions of a certain temperature, a certain microwave power and nitrogen atmosphere, after the reaction is finished, distilled water and absolute ethyl alcohol are respectively used for washing samples, solid products are added into distilled water, and the solid products are put into a photocatalytic reactor again, and are subjected to a fourth magnetic stirring reaction under the conditions of a certain temperature and air atmosphere after being lighted, after the reaction is finished, distilled water and absolute ethyl alcohol are respectively used for washing samples, and the samples are dried, so that the preparation method is obtained: magnetic temperature sensitive blotting material.
Preferably, in the step (1), the dosage ratio of the corncob, the cetyltrimethylammonium bromide, the ferric nitrate nonahydrate and the absolute ethyl alcohol is 10g:1g:4g:100mL; the ball milling reaction time is 24 hours, and the calcination temperature and the calcination time under the hydrogen atmosphere are 650 ℃ and 3 hours respectively.
Preferably, in the step (3), the dosage ratio of the carboxyl modified magnetic carbon material, the Ag-POPD and the dimethyl sulfoxide is 1g:0.5g:100mL; the dosage ratio of the dimethyl sulfoxide, the ciprofloxacin, the N-isopropyl acrylamide, the trimethylolpropane trimethacrylate and the azodiisoheptonitrile is 100mL:0.1g:0.1g:1mL:0.01g.
Preferably, in the step (3), the temperature, time and rotation speed of the first magnetic stirring reaction and the second magnetic stirring reaction are 30 ℃ for 1h and 800rpm/min; the temperature, time and rotating speed of the third magnetic stirring reaction are 40 ℃, 1h and 800rpm/min respectively, and the microwave power is 600W; the dosage ratio of the solid product to distilled water after the microwave reaction is 1-5g:200mL; the temperature, time and rotating speed of the fourth magnetic stirring reaction under the air atmosphere of the photocatalytic reactor are 30 ℃, 5 hours and 800rpm/min respectively.
Synthesis of non-imprinting carbon magnetic material and common imprinting carbon magnetic material:
s1, synthesizing a non-imprinting carbon magnetic material:
firstly, adding a carboxyl modified magnetic carbon material and Ag-POPD into dimethyl sulfoxide, magnetically stirring for a period of time at a certain temperature, introducing nitrogen after the reaction is finished, and then adding N-isopropyl acrylamide, trimethylolpropane trimethacrylate and azo-diisoheptonitrile. Then, the reaction liquid is put into a microwave reactor, and magnetically stirred and reacted for a period of time under the conditions of a certain temperature, a certain microwave power and nitrogen atmosphere. After the reaction is finished, washing the sample with distilled water and absolute ethyl alcohol respectively, and drying the sample to obtain the product: magnetic non-imprinting material.
S2, synthesizing a common imprinting carbon magnetic material:
firstly, adding a carboxyl modified magnetic carbon material and Ag-POPD into dimethyl sulfoxide, magnetically stirring for a period of time at a certain temperature, adding ciprofloxacin after the reaction is finished, magnetically stirring for a period of time at a certain temperature, introducing nitrogen after the reaction is finished, and then adding trimethylolpropane trimethacrylate and azodiisoheptanenitrile. Then, the reaction liquid is put into a microwave reactor, and magnetically stirred and reacted for a period of time under the conditions of a certain temperature, a certain microwave power and nitrogen atmosphere. After the reaction is finished, washing a sample by using distilled water and absolute ethyl alcohol respectively, adding a solid product into distilled water, putting the solid product into a photocatalytic reactor again, turning on a lamp to perform magnetic stirring reaction for a period of time under a certain temperature and air atmosphere, after the reaction is finished, washing the sample by using distilled water and absolute ethyl alcohol respectively, and drying the sample to obtain the catalyst: magnetic plain blotting material.
Preferably, in the step S1, the dosage ratio of the carboxyl modified magnetic carbon material, ag-POPD, dimethyl sulfoxide, N-isopropyl acrylamide, trimethylolpropane trimethacrylate and azobisisoheptonitrile is 1g:0.5g:100mL:0.1g:1mL:0.01g.
Preferably, in step S1, the temperature, time and rotation speed of the first magnetic stirring reaction are 30 ℃, 1h and 800rpm/min respectively; the temperature, time and rotating speed of the third magnetic stirring reaction in the nitrogen atmosphere in the microwave reactor are 40 ℃, 1h and 800rpm/min respectively, and the microwave power is 600W.
Preferably, in the step S2, the dosage ratio of the carboxyl modified magnetic carbon material, ag-POPD, dimethyl sulfoxide, ciprofloxacin, trimethylolpropane trimethacrylate and azodiisoheptanenitrile is 1g:0.5g:100mL:0.1g:1mL:0.01g.
Preferably, in the step S2, the temperature, time and rotating speed of the first magnetic stirring reaction and the second magnetic stirring reaction are all 30 ℃, 1h and 800rpm/min; the temperature, time and rotating speed of the third magnetic stirring reaction are 40 ℃, 1h and 800rpm/min respectively, and the microwave power is 600W; the dosage ratio of the solid product to distilled water after the microwave reaction is 1-5g:200mL; the temperature, time and rotating speed of the fourth magnetic stirring reaction under the air atmosphere of the photocatalytic reactor are 30 ℃, 5 hours and 800rpm/min respectively.
The invention has the beneficial effects that:
(1) The invention combines the magnetic carbon material, the temperature sensitive material, the organic semiconductor material and the surface imprinting material by utilizing the surface imprinting technology of microwave initiated polymerization, and the synthesized magnetic temperature sensitive imprinting material can realize the selective controllable degradation of the target ciprofloxacin residue.
(2) According to the invention, the corn cob is used as a carbon source, ferric nitrate nonahydrate is used as an iron source, and the ball milling-calcining method is utilized to synthesize the magnetic carbon material, so that the specific surface area and the magnetic separation characteristic of the composite material are improved.
(3) The invention takes Ag-POPD as a functional monomer and N-isopropyl acrylamide as a temperature-sensitive monomer, and adopts a composite material synthesized by a microwave-initiated polymerization method, and has the advantages of selectivity, controllable regulation of a photocatalysis process and the like.
Drawings
FIG. 1 is an XRD spectrum of different samples; wherein a is a magnetic carbon material, and b is a magnetic temperature-sensitive imprinting material.
FIG. 2 is a FTIR spectrum of different samples; wherein a is a magnetic carbon material, and b is a magnetic temperature-sensitive imprinting material.
FIG. 3 is a TEM and SEM spectra of different samples; a and b are respectively TEM and SEM spectrograms of the magnetic carbon material, and c and d are respectively TEM and SEM spectrograms of the magnetic temperature-sensitive imprinting material;
FIG. 4 is an XPS spectrum of a magnetic temperature sensitive blotting material;
FIG. 5 is a graph of VSM spectra for different materials; wherein a is a magnetic carbon material, and b is a magnetic temperature-sensitive imprinting material.
FIG. 6 is a graph of degradation rate data for ciprofloxacin and tetracycline at different temperatures for different samples; wherein A is at 25deg.C, and B is at 40deg.C; a is a magnetic temperature-sensitive imprinting material, b is a magnetic ordinary imprinting material, and c is a magnetic non-imprinting material.
Fig. 7 is a cycle experiment diagram of the degradation of ciprofloxacin by the magnetic temperature-sensitive blotting material at 25 ℃.
Detailed Description
The invention will be further described with reference to specific examples.
Photocatalytic degradationEvaluation of Activity: in a xenon lamp photocatalytic reactor, 100mL of 10mg/L ciprofloxacin solution or 100mL of 20mg/L tetracycline solution is added into the reactor and the initial value thereof is measured, then 0.1g of sample is added, a light source is not started, the set temperature is 25 ℃ (or 40 ℃), air (aeration rate is 2 mL/min), magnetic stirring (rotation speed is 600 rpm/min) is started, after adsorption equilibrium is reached, the xenon lamp is used for irradiation, the magnetic stirring (rotation speed is 600 rpm/min) is started, an aeration device is started, air (flow rate is 2 mL/min), the set temperature is 25 ℃ (or 40 ℃), sampling analysis is carried out at intervals of 15min in the irradiation process, the concentration is measured by an ultraviolet-visible spectrophotometer, and the concentration is measured by a formula: degradation rate= (C 0 -C)×100/C 0 Calculating the degradation rate, wherein C 0 In order to reach the concentration of ciprofloxacin or tetracycline at adsorption equilibrium, C is the concentration of ciprofloxacin or tetracycline measured at time t, and t is the reaction time.
Evaluation of recyclability: the method is carried out according to the photocatalytic activity evaluation process, except that the reaction temperature is set to 25 ℃, the degradation pollutant is 100mL of 10mg/L ciprofloxacin solution, after the photocatalytic activity experiment is finished, a solid sample is separated and recovered, the sample is ultrasonically cleaned for several times by absolute ethyl alcohol and distilled water, then the sample is subjected to a second photocatalytic activity experiment, the process is repeated for five times, and the degradation rate of each time is calculated.
Example 1:
(1) Synthesis of carboxyl modified magnetic carbon material:
10g of corncob, 1g of hexadecyl trimethyl ammonium bromide and 4g of ferric nitrate nonahydrate are added into 100mL of absolute ethyl alcohol, ball milling reaction is carried out for 24h, and the product is calcined for 3h in a tubular furnace at 650 ℃ in a hydrogen atmosphere after being dried, so that the corn cob preparation method is obtained: a magnetic carbon material. 3g of the magnetic carbon material is put into 120mL of toluene, 10mL of 3-aminopropyl triethoxysilane is added, nitrogen is introduced, the mixture is mechanically stirred for 12h at 70 ℃, and the mixture is washed with toluene and methanol, filtered and dried to obtain the magnetic carbon material: amino modified magnetic carbon material. Adding 2g of the amino modified magnetic carbon material into 50mL of N, N-dimethylformamide (containing 1mol/L succinic anhydride), mechanically stirring at room temperature for 24h, washing with the N, N-dimethylformamide, and drying to obtain the amino modified magnetic carbon material: carboxyl modified magnetic carbon material;
(2) Synthesis of Ag-POPD:
2.16g of o-phenylenediamine is dissolved in 30mL of chloroform to prepare an organic phase solution; 2.128g of ammonium persulfate was then dissolved in 30mL of distilled water to prepare an aqueous solution. Then the organic phase is firstly moved into a wide-mouth bottle, then the aqueous phase solution is added into the wide-mouth bottle through glass rod drainage, poly-o-phenylenediamine is formed on the interface between two phases soon, and is diffused to the aqueous phase, the organic phase is placed for 16 hours at room temperature, and then is washed three times by methanol and absolute ethyl alcohol in sequence, and the organic phase is obtained after drying: POPD;
1.45g of the POPD was further added to a beaker containing 320mL of a 0.025mol/L silver nitrate solution, and the above mixed solution was dispersed by ultrasonic while being mechanically stirred for 1 hour. Then 3800 mL of 0.025mol/L sodium borohydride solution is added into a beaker drop by drop, and the solution is mechanically stirred for 1.5 hours; washing the obtained product with distilled water, suction filtering, and drying to obtain the final product: silver-loaded poly-o-phenylenediamine (Ag-POPD);
(3) Synthesis of magnetic temperature-sensitive blotting material:
firstly, adding 1g of carboxyl modified magnetic carbon material and 0.5g of Ag-POPD into 100mL of dimethyl sulfoxide, magnetically stirring for 1h at 30 ℃ (the rotating speed is 800 rpm/min), after the reaction is finished, adding 0.1g of ciprofloxacin, magnetically stirring for 1h at 30 ℃ (the rotating speed is 800 rpm/min), after the reaction is finished, introducing nitrogen, and then adding 0.1g N-isopropyl acrylamide, 1mL of trimethylolpropane trimethacrylate and 0.01g of azo-diisoheptanenitrile. Subsequently, the reaction solution was put into a microwave reactor and magnetically stirred for 1 hour (at a rotation speed of 800 rpm/min) under a nitrogen atmosphere at 40℃and 600W. After the reaction is finished, washing a sample by using distilled water and absolute ethyl alcohol respectively, adding a solid product into 200mL of distilled water, putting into a xenon lamp photocatalytic reactor again, turning on a lamp and magnetically stirring for 5h (the rotating speed is 800 rpm/min) under the atmosphere of 30 ℃, after the reaction is finished, washing the sample by using distilled water and absolute ethyl alcohol respectively, and drying the sample to obtain the product: magnetic temperature sensitive blotting material.
Synthesizing a non-imprinting carbon magnetic material and a common imprinting carbon magnetic material;
s1, synthesizing a non-imprinting carbon magnetic material:
firstly, 1g of carboxyl modified magnetic carbon material and 0.5g of Ag-POPD are added into 100mL of dimethyl sulfoxide, magnetic stirring is carried out for 1h at 30 ℃ (the rotating speed is 800 rpm/min), after the reaction is finished, nitrogen is firstly introduced, and then 0.1. 0.1g N-isopropyl acrylamide, 1mL of trimethylolpropane trimethacrylate and 0.01g of azo-diisoheptanenitrile are added. Subsequently, the reaction solution was put into a microwave reactor and magnetically stirred for 1 hour (at a rotation speed of 800 rpm/min) under a nitrogen atmosphere at 40℃and 600W. After the reaction is finished, washing the sample with distilled water and absolute ethyl alcohol respectively, and drying the sample to obtain the product: magnetic non-imprinting material.
S2, synthesizing a common imprinting carbon magnetic material:
firstly, adding 1g of carboxyl modified magnetic carbon material and 0.5g of Ag-POPD into 100mL of dimethyl sulfoxide, magnetically stirring for 1h at 30 ℃ (the rotating speed is 800 rpm/min), after the reaction is finished, adding 0.1g of ciprofloxacin, magnetically stirring for 1h at 30 ℃ (the rotating speed is 800 rpm/min), after the reaction is finished, introducing nitrogen, and then adding 1mL of trimethylolpropane trimethacrylate and 0.01g of azodiisoheptanenitrile. Subsequently, the reaction solution was put into a microwave reactor and magnetically stirred for 1 hour (at a rotation speed of 800 rpm/min) under a nitrogen atmosphere at 40℃and 600W. After the reaction is finished, washing a sample by using distilled water and absolute ethyl alcohol respectively, adding a solid product into 200mL of distilled water, putting into a xenon lamp photocatalytic reactor again, turning on a lamp and magnetically stirring for 5h (the rotating speed is 800 rpm/min) under the atmosphere of 30 ℃, after the reaction is finished, washing the sample by using distilled water and absolute ethyl alcohol respectively, and drying the sample to obtain the product: magnetic plain blotting material.
Figure 1 is an XRD pattern of different samples. As can be seen from the figures: b has four additional characteristic peaks compared with a, located at 37.98 °, 44.14 °, 64.26 ° and 77.286 °, respectively, corresponding to the (111), (200), (220) and (311) crystal planes of face-centered cubic Ag (standard JCPDS cards 65-2871), respectively, indicating: ag and a magnetic carbon material exist in the magnetic temperature-sensitive imprinting material, and the coating of the surface temperature-sensitive imprinting layer does not damage the crystal structures of the Ag and the magnetic carbon material.
FIG. 2 is a schematic view ofFTIR spectra of the different samples, as can be seen from the figure: b has many more characteristic absorption peaks than a, wherein: 3437cm -1 Is 2928cm of the absorption peak of N-H in POPD or PNIPAM or the absorption peak of hydroxyl in the inner interface -1 And 2876cm -1 is-CH 3 and-CH 2 The C-H tensile vibration absorption peak in the group, 1652cm -1 The tensile vibration absorption peak of C=O in PNIPAM or trimethylolpropane trimethacrylate is 1600cm -1 -1450cm -1 Is the characteristic absorption peak of benzene ring in POPD, 1421cm -1 Is the absorption peak of C-N in POPD or PNIPAM, 1367cm -1 Is C-N-C in POPD or C (CH) in PNIPAM 3 ) 2 Is 1338cm -1 And 1317cm -1 Is the absorption peak of C-N-C in POPD, 1164cm -1 And 1116cm -1 Is the tensile vibration absorption peak of C-C. The additional absorption peaks presented above indicate the presence of POPD, PNIPAM and trimethylolpropane trimethacrylate in the magnetic temperature sensitive blotting material. The results of XRD and FTIR are fully demonstrated: magnetic temperature sensitive blotting materials have been successfully prepared.
Fig. 3 is a TEM and SEM spectrum of different samples, from which it can be seen: compared with a, b, c and d, after being covered by the surface temperature-sensitive imprinting layer, the surface of the material is obviously changed, the surface of the magnetic temperature-sensitive imprinting material is flattened, and the result shows that the surface temperature-sensitive imprinting layer is successfully coated on the surface of the magnetic carbon material.
Fig. 4 is an XPS spectrum of the magnetic temperature sensitive blotting material, from which it can be seen that: C. fe, O, N and Ag are all present in the magnetic temperature-sensitive blotting material, and this result again demonstrates that the magnetic temperature-sensitive blotting material has been successfully prepared.
Fig. 5 is a VSM spectrum of different samples, and it can be seen from the graph that the magnetic saturation intensities of a and b are 4.83emu/g and 3.95emu/g, respectively, which indicates that the prepared magnetic temperature-sensitive blotting material has good magnetic separation characteristics.
FIG. 6 is a graph of degradation rate data for ciprofloxacin and tetracycline at different temperatures for different samples. As can be seen from panels a and B: the degradation rate of the magnetic thermosensitive imprinting material on ciprofloxacin is higher than that of the magnetic non-imprinting material at different temperatures, and the degradation rate of the magnetic thermosensitive imprinting material on tetracycline is lower than that of the magnetic non-imprinting material, so that the prepared magnetic thermosensitive imprinting material has good selectivity on target pollutants; in addition, the degradation rate of the magnetic temperature-sensitive imprinting material to ciprofloxacin and tetracycline is higher than that of the magnetic temperature-sensitive imprinting material at the temperature of 25 ℃ and the degradation rate of the magnetic ordinary imprinting material to ciprofloxacin and tetracycline is not obviously changed at different temperatures. The above results indicate that: the prepared magnetic temperature-sensitive imprinting material not only has good selectivity on target pollutants, but also has controllability in the photocatalytic degradation process.
FIG. 7 is a cycle chart of the degradation of ciprofloxacin by the magnetic temperature sensitive blotting material at 25deg.C. From the graph, after 5 cycles, the degradation rate of the magnetic temperature-sensitive imprinting material is slightly lower than that of the first time, and the result shows that: the magnetic temperature-sensitive imprinting material has good stability.
Description: the above embodiments are only for illustrating the present invention and not for limiting the technical solution described in the present invention; thus, while the invention has been described in detail with reference to the various embodiments described above, it will be understood by those skilled in the art that the invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Claims (9)
1. The preparation method of the magnetic temperature-sensitive imprinting material for microwave initiated polymerization is characterized by comprising the following specific steps:
(1) Adding corncob, cetyl trimethyl ammonium bromide and ferric nitrate nonahydrate into absolute ethyl alcohol, performing ball milling reaction for a period of time, drying a product after the reaction is finished, and calcining the product for a period of time in a tubular furnace under a hydrogen atmosphere to obtain the corn cob/ferric nitrate composite material: a magnetic carbon material; then amino and carboxyl are modified in sequence to obtain a carboxyl modified magnetic carbon material for later use;
(2) Preparing Ag-POPD; firstly, generating poly-o-phenylenediamine by self-polymerization of o-phenylenediamine, and carrying out Ag loading on the poly-o-phenylenediamine to obtain silver-loaded poly-o-phenylenediamine, which is marked as Ag-POPD for later use;
(3) Adding the carboxyl modified magnetic carbon material prepared in the step (1) and the Ag-POPD prepared in the step (2) into dimethyl sulfoxide, carrying out a first magnetic stirring reaction at a certain temperature, adding ciprofloxacin after the reaction is finished, carrying out a second magnetic stirring reaction at a certain temperature, introducing nitrogen after the reaction is finished, and then adding N-isopropyl acrylamide, trimethylolpropane trimethacrylate and azodiisoheptanenitrile to obtain a reaction solution; wherein the dosage ratio of the carboxyl modified magnetic carbon material to the Ag-POPD to the dimethyl sulfoxide is 1g:0.5g:100mL; the dosage ratio of dimethyl sulfoxide, ciprofloxacin, N-isopropyl acrylamide, trimethylolpropane trimethacrylate and azodiisoheptonitrile is 100mL:0.1g:0.1g:1mL:0.01 g;
then, placing the reaction liquid into a microwave reactor, carrying out a third magnetic stirring reaction under a certain temperature, a certain microwave power and a nitrogen atmosphere, washing a sample with distilled water and absolute ethyl alcohol respectively after the reaction is finished, adding a solid product into distilled water, placing the solid product into a photocatalytic reactor again, carrying out a fourth magnetic stirring reaction under the condition of a certain temperature and an air atmosphere after the illumination of a lamp is turned on, washing the sample with distilled water and absolute ethyl alcohol respectively after the reaction is finished, and drying the sample to obtain the magnetic temperature-sensitive imprinting material; the magnetic temperature-sensitive imprinting material is formed by compounding a magnetic carbon material and a surface temperature-sensitive imprinting layer; the surface temperature-sensitive imprinting layer is formed by combining Ag-POPD, N-isopropyl acrylamide and trimethylolpropane trimethacrylate.
2. The method for preparing a magnetic thermosensitive imprinting material for microwave-initiated polymerization according to claim 1, wherein in the step (1), the dosage ratio of corncob, cetyltrimethylammonium bromide, ferric nitrate nonahydrate and absolute ethyl alcohol is 10g:1g:4g:100 And (3) mL.
3. The method for preparing a magnetic thermosensitive imprinting material for microwave-initiated polymerization according to claim 1, wherein in the step (1), the time of the ball milling reaction is 24 h; the calcination temperature and time under the hydrogen atmosphere were 650 ℃ and 3h, respectively.
4. The method for preparing the magnetic thermosensitive imprinting material by microwave initiated polymerization according to claim 1, wherein the method for preparing Ag-POPD in the step (2) is as follows: 2.16g o-phenylenediamine is dissolved in 30mL chloroform to prepare an organic phase solution; then, 2.128g ammonium persulfate is dissolved in 30mL distilled water to prepare an aqueous solution; then the organic phase is firstly moved into a wide-mouth bottle, then the aqueous phase solution is added into the wide-mouth bottle through glass rod drainage, the poly-o-phenylenediamine is formed on the interface between two phases and is diffused to the aqueous phase, the mixture is placed under the room temperature condition for 16h, and then the mixture is washed three times by methanol and absolute ethyl alcohol in sequence, and the POPD is obtained after drying;
then adding 1.45g POPD into a beaker containing 320mL and 0.025mol/L silver nitrate solution, dispersing the mixed solution by ultrasonic, and mechanically stirring 1 h; then adding 380mL and 0.025mol/L sodium borohydride solution into a beaker dropwise, and mechanically stirring for 1.5h; washing the obtained product with distilled water, suction filtering, and drying to obtain silver-loaded poly-o-phenylenediamine, namely Ag-POPD.
5. The method for preparing a magnetic thermosensitive imprinting material for microwave-initiated polymerization according to claim 1, wherein in the step (3), the temperature, time and rotation speed of the first magnetic stirring reaction and the second magnetic stirring reaction are 30 ℃, 1h and 800rpm/min.
6. The method according to claim 1, wherein in the step (3), the reaction temperature, time and rotation speed of the third magnetic stirring reaction are 40 ℃, 1h and 800rpm/min, respectively, and the microwave power is 600W.
7. The method according to claim 1, wherein in the step (3), the temperature, time and rotation speed of the fourth magnetic stirring reaction under the hollow atmosphere of the photocatalytic reactor are 30 ℃, 5h and 800rpm/min, respectively.
8. The method for preparing a magnetic thermosensitive imprinting material for microwave-initiated polymerization according to claim 1, wherein in the step (3), the dosage ratio of the solid product to distilled water after the microwave reaction is 1-5g:200 And (3) mL.
9. Use of a magnetic temperature-sensitive imprinting material prepared by the method according to any one of claims 1-8 for selectively and controllably degrading ciprofloxacin.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527349A (en) * | 2011-11-28 | 2012-07-04 | 江苏大学 | Magnetic composite material surface imprinting thermosensitive adsorbent, and preparation method and application thereof |
| CN106378195A (en) * | 2016-08-26 | 2017-02-08 | 江苏大学 | Ag-POPD embedded magnetic imprinted light photocatalyst and preparation method thereof |
| CN108144582A (en) * | 2017-12-28 | 2018-06-12 | 中南大学 | A kind of preparation method of biomass-based magnetic active carbon and the magnetic active carbon of preparation |
| CN110252398A (en) * | 2019-05-21 | 2019-09-20 | 江苏大学 | A kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation method and application of/CN composite photo-catalyst |
| CN110252262A (en) * | 2019-07-01 | 2019-09-20 | 河南城建学院 | A kind of magnetism corncob multi-stage porous carbon microsphere surface imprinted material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102527349A (en) * | 2011-11-28 | 2012-07-04 | 江苏大学 | Magnetic composite material surface imprinting thermosensitive adsorbent, and preparation method and application thereof |
| CN106378195A (en) * | 2016-08-26 | 2017-02-08 | 江苏大学 | Ag-POPD embedded magnetic imprinted light photocatalyst and preparation method thereof |
| CN108144582A (en) * | 2017-12-28 | 2018-06-12 | 中南大学 | A kind of preparation method of biomass-based magnetic active carbon and the magnetic active carbon of preparation |
| CN110252398A (en) * | 2019-05-21 | 2019-09-20 | 江苏大学 | A kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation method and application of/CN composite photo-catalyst |
| CN110252262A (en) * | 2019-07-01 | 2019-09-20 | 河南城建学院 | A kind of magnetism corncob multi-stage porous carbon microsphere surface imprinted material and its preparation method and application |
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