CN108745308A - A kind of conductive traces Ag@PANI/CoFe2O4The preparation method and applications of/C - Google Patents
A kind of conductive traces Ag@PANI/CoFe2O4The preparation method and applications of/C Download PDFInfo
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- CN108745308A CN108745308A CN201810428360.XA CN201810428360A CN108745308A CN 108745308 A CN108745308 A CN 108745308A CN 201810428360 A CN201810428360 A CN 201810428360A CN 108745308 A CN108745308 A CN 108745308A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 91
- 239000004098 Tetracycline Substances 0.000 claims abstract description 34
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 32
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 32
- 229960002180 tetracycline Drugs 0.000 claims abstract description 31
- 229930101283 tetracycline Natural products 0.000 claims abstract description 31
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000013019 agitation Methods 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 9
- 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 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 238000006552 photochemical reaction Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000003760 hair shine Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 9
- 239000002028 Biomass Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 69
- 238000001179 sorption measurement Methods 0.000 description 18
- 206010001497 Agitation Diseases 0.000 description 17
- MYDXUJMODAZBGN-UHFFFAOYSA-N 6-bromo-5-methyl-2-methylsulfanyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=C(Br)C(=O)N2NC(SC)=NC2=N1 MYDXUJMODAZBGN-UHFFFAOYSA-N 0.000 description 11
- 229960004745 danofloxacin mesylate Drugs 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002322 conducting polymer Substances 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005276 aerator Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- -1 Danofloxacin mesylates Chemical class 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229960004385 danofloxacin Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940040944 tetracyclines Drugs 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- 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
- B01J35/39—Photocatalytic properties
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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Abstract
The invention belongs to environmentally conscious materials synthesis technical fields, and in particular to a kind of preparation method of the conductive traces Ag@PANI/CoFe2O4/C with good photocatalytic activity and selectivity；First using the C that corncob converts as carrier load C oFe again2O4CoFe is synthesized2O4Simultaneously loaded Ag has synthesized Ag@PANI by/C, simultaneously synthesizing PANI, then has synthesized final material by template molecule of tetracycline.Advantage of the invention is that：Imprinted layer uses grafting, visible light-initiated method step by step, has the advantages such as bonding success rate is high, polymerization speed is fast, realizes the selective removal of tetracycline；The method that Ag@PANI use external synthesis, are generally introduced has the advantages such as accounting is controllable, preservation is complete, photocatalysis performance is good, is promoted while realizing photocatalytic activity and selectivity；Abandoned biomass（Corncob）Use not only embody the meaning of the treatment of wastes with processes of wastes against one another and also reduce production cost.
Description
Technical field
The invention belongs to environmentally conscious materials synthesis technical fields, and in particular to a kind of conductive traces Ag@PANI/CoFe2O4/ C's
The research of preparation method and its selective absorption/photocatalytic degradation tetracycline.
Background technology
CoFe2O4As novel semiconductor material, there is good photocatalytic activity and Magneto separate characteristic, be special both at home and abroad
One of the active material of family's scholar's research.But common CoFe2O4Cannot from numerous substances selective removal specific objective object, this
Seriously constrain CoFe2O4Functionalized application.And the introducing of surface imprinted technology can well solve CoFe2O4Function
Change application.
Surface imprinted technology is to polymerize template molecule in polymer monomer solution with crosslinking agent, obtains solid Jie
Matter, then by either physically or chemically eluting the template molecule removed in medium, obtaining " trace " has target molecule space knot
The surface imprinted polymer of structure and binding site, it can be envisaged that：Under the conditions of solution environmental, a series of function monomer and template
Molecule meets, and can make these by hydrogen bond, electrostatic interaction, hydrophobic effect and other non-covalent interactions between them
Functional molecular can arrange in the form of with template molecule the structure mutually order state of complementation to each other.But use surface
When engram technology modifies common catalysis material, light degradation activity is caused to substantially reduce since active site is capped, and
Conducting polymer is introduced in surface imprinted layer can efficiently solve the above problem.
Conducting polymer, also known as conducting polymer can effectively conductive semiconductor quilts with good electric conductivity
Light induced electron caused by excitation, and then the separative efficiency of light induced electron-photo-induced hole of material is improved, to improve material
Photocatalytic activity.
In addition, carbon material has good specific surface area and chemical property is stablized, it is extraordinary carrier material, on it
Load C oFe2O4CoFe can be improved2O4Dispersibility, inhibit CoFe2O4Reunion, can also be material load or cladding
More binding sites are provided, while the specific surface area of material can also be increased, improve its adsorption capacity.And corncob is as allusion quotation
The waste biomass material of type, the meaning of the treatment of wastes with processes of wastes against one another can not only be embodied by being converted into carbon material as raw material, additionally it is possible to
Production cost is reduced, there is huge development potentiality.In the prior art in surface imprinted layer conducting polymer introducing, generally adopt
The method being polymerize together with imprinted polymer and conducting polymer, but this method poor controllability, it cannot be guaranteed that conducting polymer
Accounting, integrality and success rate, and it is of high cost；Therefore it needs one kind that can reduce cost, improve synthesis success rate and gathers
The preparation method of sum velocity.
Invention content
For overcome the deficiencies in the prior art, present invention firstly provides a kind of conductive traces Ag@PANI/CoFe2O4/ C, by
Modified porous carbon (C), CoFe2O4And the surface imprinted layer of the alternative identification tetracycline containing Ag and PANI is combined；
The modified porous carbon (C) is transformed by corncob, the CoFe2O4It is supported on the surface of C；The Ag is supported on
The surface of PANI, the surface imprinted layer are coated on CoFe2O4The surface of/C, the Ag@PANI are embedded in surface imprinted layer and work as
In；Conductive traces Ag@PANI/CoFe2O4It is 25 emu/g that/C, which has good Magneto separate characteristic, magnetic saturation intensity,；By 0.1g
Conductive traces Ag@PANI/CoFe2O4Photocatalytic degradations of/the C for the tetracycline of 100mL 20mg/L, in the simulation of 2h
Sunlight irradiation declines solution rate and has reached 83%；In addition, the conductive traces Ag@PANI/CoFe of the present invention2O4/ C also has good
Selective absorption/photocatalytic degradation capability.
The present invention also provides a kind of preparation methods of conductive traces Ag@PANI/CoFe2O4/C, carry out as steps described below：
Step 1：The synthesis of modified porous carbon (C)：
Corncob is put into tube furnace first and carries out first time calcination reaction under nitrogen atmosphere, is cooled down again after reaction
To room temperature, KOH solution is used in combination to impregnate, is then washed with deionized water to neutrality, drying moves in tube furnace, under nitrogen atmosphere
Second of calcination reaction is carried out, is cooled to room temperature after reaction, solid sample is taken out, is mixed with the concentrated sulfuric acid and deionized water, it is quiet
It postpones and is washed with deionized water to neutrality, drying is to get to modified porous carbon.
Step 2：CoFe2O4The synthesis of/C：
By Co (NO3)2·6H2O and Fe (NO3)3·9H2O is dissolved in deionized water, is carried out ultrasound at a certain temperature and is stirred
It mixes, C is added and continues to be stirred by ultrasonic, is eventually adding NaOH and continues to be stirred by ultrasonic, be transferred in autoclave and carry out hydro-thermal reaction,
It washs, is dried in vacuo to get to CoFe with deionized water and ethyl alcohol respectively after reaction2O4/C。
Step 3：The synthesis of Ag@PANI：
Aniline is added in HCl solution, stirs, obtains solution A；Ammonium persulfate is added drop-wise in HCl solution, is stirred,
Obtain solution B；Solution B is poured into solution A, continues to stir, solid product is obtained by the reaction in standing, and solid product is used respectively
HCl solution, deionized water and acetone washing, drying is to get to PANI；
Above-mentioned PANI is added in the beaker containing silver nitrate solution, is stirred by ultrasonic, it is later that sodium borohydride is molten
Liquid is added in beaker, is continued to be stirred by ultrasonic, is obtained solid product, is washed with deionized, and drying is to get to Ag@PANI.
Step 4：Conductive traces Ag@PANI/CoFe2O4The synthesis of/C：
By PEG-4000 and CoFe2O4/ C is add to deionized water, and ultrasonic agitation obtains solution C；By Ag@PANI and
Tetracycline is added in dimethyl sulfoxide, and ultrasonic agitation obtains solution D；Then solution C and solution D are mixed, is added to photochemistry
In reaction bulb, and trimethylolpropane trimethacrylate and 784 photoinitiators, under nitrogen atmosphere, magnetic agitation is added and makes
It is irradiated with tungsten lamp, after reaction, deionized water is added in washing, and under air atmosphere, magnetic agitation is simultaneously irradiated using tungsten lamp, instead
It after answering, is washed, to get to conductive traces Ag@PANI/CoFe after vacuum drying2O4/C。
Step 5：Non- trace Ag@PANI/CoFe2O4The synthesis of/C：
By PEG-4000 and CoFe2O4/ C is add to deionized water, and ultrasonic agitation obtains solution E；Ag@PANI are added
Enter into dimethyl sulfoxide, is stirred by ultrasonic, obtains solution F；Then solution E and solution F are mixed, is added to photochemical reaction bottle
In, and trimethylolpropane trimethacrylate and 784 photoinitiators is added, under nitrogen range, magnetic agitation simultaneously uses tungsten lamp
Irradiation, after reaction, is washed, to get to non-trace Ag@PANI/CoFe after vacuum drying2O4/C。
Preferably, a concentration of 0.3g/mL of the KOH solution described in step 1, soaking time 6h；The KOH and corncob
Mass ratio be 4：1；The amount ratio of the concentrated sulfuric acid, deionized water and solid sample is 10mL：300mL：1g；The standing
Time is for 24 hours.
Preferably, the heating rate of the first time calcining described in step 1 is 5 DEG C/min, and calcination temperature is 400 DEG C, calcining
Time is 1h；The heating rate of second of calcining is 5 DEG C/min, and calcination temperature is 850 DEG C, calcination time 1h.
Preferably, the Co (NO described in step 23)2·6H2O、Fe(NO3)3·9H2O, the use of deionized water, C and NaOH
Amount is than being 2mmol：4mmol：15mL：100mg：8g；The temperature is 30 DEG C, ultrasonic power 50W, and speed of agitator is
600rpm/min, reaction time 30min；The temperature of the hydro-thermal reaction is 180 DEG C, reaction time 8h.
Preferably, the concentration of HCl solution described in step 3 is 2mol/L；The volume ratio of the molten aniline and HCl solution is
5.56：50；The amount ratio of the ammonium persulfate and HCl solution is 10.27g：312mL；It is stirred in the solution A and solution B
Temperature is 30 DEG C, and speed of agitator is 600rpm/min, and the reaction time is 30min；After the solution A and solution B mixing
Whipping temp be 30 DEG C, speed of agitator 600rpm/min, reaction time 10h；The temperature for standing reaction is 30 DEG C,
Time of repose is 5h.
Preferably, the amount ratio of the PANI described in step 3, silver nitrate solution and sodium borohydride solution is 2.45g：320mL：
The concentration of 384mL, silver nitrate solution and sodium borohydride solution is 0.025mol/L；The temperature of the ultrasound is 30 DEG C,
Ultrasonic power is 50W；The rotating speed of the stirring is 600rpm/min, and the reaction time is 1h.
Preferably, PEG-4000, CoFe described in step 42O4/ C and the amount ratio of deionized water are 5g：1g：20mL；Institute
The amount ratio for stating Ag@PANI, tetracycline and dimethyl sulfoxide is 0.1g：0.2g：60mL；The trimethylolpropane tris acrylic acid
Ester, 784 photoinitiators and under air atmosphere tungsten lamp pre-irradiation deionized water amount ratio be 1mL：0.01g：200 mL；It is described
The temperature of ultrasound and stirring in solution A and solution B is 30 DEG C, and ultrasonic power is 50W；The speed of agitator is
600rpm/min, reaction time are 30min；The temperature of the irradiation of tungsten lamp under nitrogen atmosphere is 30 DEG C, and magnetic agitation turns
Speed is 600rpm/min, nitrogen flow rate 2mL/min, irradiation time 10min；The irradiation of the tungsten lamp under air atmosphere
Temperature is 30 DEG C, and magnetic agitation rotating speed is 600rpm/min, air velocity 2mL/min, irradiation time 2h.
Preferably, PEG-4000, CoFe in the solution E described in step 52O4/ C and the amount ratio of deionized water are 5g：1g：
20mL；The amount ratio of Ag@PANI and dimethyl sulfoxide is 0.1g in the solution F：60mL；The trimethylolpropane tris third
The amount ratio of olefin(e) acid ester and 784 photoinitiators is 1mL：0.01g；The temperature of the solution E and ultrasound and stirring in solution F is equal
It it is 30 DEG C, ultrasonic power is 50W, and speed of agitator is 600rpm/min, and the reaction time is 30min；The tungsten lamp irradiation
Temperature be 30 DEG C, magnetic agitation rotating speed 600rpm/min, nitrogen flow rate 2mL/min, irradiation time 10min.
Preferably, in step 1~5, the temperature of the drying is 60 DEG C, and drying time is 12h.
Preferably, in step 1~5, the vacuum drying temperature is 30 DEG C, and drying time is 12h.
Beneficial effects of the present invention：
(1) introducing of the surface imprinted layer of the present invention makes material have selective absorption/photocatalytic degradation capability, realizes four
The selective removal of ring element, and the synthesis of surface imprinted layer uses grafting, visible light-initiated method step by step, and it is existing
The synthesis of surface imprinted layer is compared, and there is bonding to have higher success rate, the faster advantage of polymerization speed；
(2) introducings of the Ag@PANI in surface imprinted layer makes material selective while also having in the present invention
Preferable photocatalytic activity, the method that incorporation way uses external synthesis, is generally introduced, compared with prior art, tool
Have that Ag@PANI accountings are controllable, it is complete to preserve, have higher success rate, the advantage that the photocatalysis performance of integral material is good.
(3) use of waste biomass material (corncob), compared with existing carbon source, waste biomass material (corncob)
Use, the meaning of the treatment of wastes with processes of wastes against one another can not only be embodied, additionally it is possible to reduce production cost.
Description of the drawings
Fig. 1 is conductive traces Ag@PANI/CoFe2O4The XRD spectra of/C.
Fig. 2 is the FT-IR spectrograms of different samples, a CoFe2O4/ C, b is that Ag@PANI, c are conductive traces Ag@PANI/
CoFe2O4/C。
Fig. 3 is the SEM spectrograms (a, b and c) and EDS spectrograms (d) of different samples, a C, b CoFe2O4/ C, c and d is to lead
Electroblotting Ag@PANI/CoFe2O4/C。
Fig. 4 is conductive traces Ag@PANI/CoFe2O4The magnetization curve of/C.
Fig. 5 is that different samples investigate figure, a CoFe to the adsorption capacity of tetracycline2O4/ C, b is conductive traces Ag@
PANI/CoFe2O4/C。
Fig. 6 is that different samples investigate figure, a CoFe to the Photocatalytic activity of tetracycline2O4/ C, b is Ag@PANI, c
For conductive traces Ag@PANI/CoFe2O4/ C, d is non-trace Ag@PANI/CoFe2O4/C。
Fig. 7 is that different samples investigate figure to the photocatalytic activity comparison of different pollutants, and a is Ag@PANI, and b is conductive prints
Mark Ag@PANI/CoFe2O4/ C, c are non-trace Ag@PANI/CoFe2O4/C。
Specific implementation mode
With reference to specific implementation example, the present invention will be further described.
Adsorption activity is evaluated：Carried out in DW-01 type photochemical reactors, by the tetracycline of 100mL 20mg/L or
Danofloxacin mesylate solution is added in reactor and measures its initial value, and the sample of 0.1g, source of not opening the light, setting is then added
Temperature is 30 DEG C, irradiation of not opening the light, and blowing air (aeration quantity 2mL/min) opens magnetic agitation (rotating speed 600rpm/min),
10min sampling analyses are spaced, its concentration are measured by ultraviolet-visible spectrophotometer, and pass through formula：Q=(C0- C) V/m calculations
Go out its adsorption capacity Q, wherein C0For tetracycline or the initial concentration of Danofloxacin mesylate, C is four when reaching adsorption equilibrium
The concentration of ring element solution or Danofloxacin mesylate solution, V are the volume of solution, and m is the quality for the sample being added.
Photocatalytic activity evaluation：It is carried out in DW-01 type photochemical reactors, 100mL 20mg/L tetracyclines is added
Enter in reactor and measure its initial value, the sample of 0.1g, source of not opening the light then is added, set temperature is 30 DEG C, and do not open the light photograph
It penetrates, blowing air (aeration quantity 2mL/min), opens magnetic agitation (rotating speed 600rpm/min), after reaching adsorption equilibrium, then use
Simulated solar irradiation irradiates, and opens magnetic agitation (rotating speed 600rpm/min) and opens aerator and is passed through air (flow is
2mL/min), set temperature is 30 DEG C, and 20min sampling analyses are spaced in During Illumination, are surveyed by ultraviolet-visible spectrophotometer
Its fixed concentration, and pass through formula：Dr=(C0-C)×100/C0Calculate its photodegradation rate Dr, wherein C0When to reach adsorption equilibrium
Tetracycline concentration, C be t moment measure tetracycline concentration, t is the reaction time.
Selective evaluation：It is carried out in DW-01 type photochemical reactors, 100mL 20mg/L Danofloxacin mesylates is molten
Liquid is added in reactor and measures its initial value, and the sample of 0.1g, source of not opening the light then is added, and set temperature is 30 DEG C, is not opened
Light irradiates, blowing air (aeration quantity 2mL/min), opens magnetic agitation (rotating speed 600rpm/min), after reaching adsorption equilibrium,
It is irradiated again with simulated solar irradiation, open magnetic agitation (rotating speed 600rpm/min) and opens aerator and be passed through air (flow
For 2mL/min), set temperature is 30 DEG C, and 20min sampling analyses are spaced in During Illumination, pass through ultraviolet-visible spectrophotometer
Its concentration is measured, and passes through formula：Dr=(C0-C)×100/C0Calculate its degradation rate Dr, wherein C0When to reach adsorption equilibrium
Danofloxacin mesylate solution concentration, C be t moment measure Danofloxacin mesylate solution concentration, t be reaction when
Between.
Embodiment 1：
(1) synthesis of modified porous carbon (C)：Corncob is put into tube furnace first and carries out calcining under nitrogen atmosphere instead
It answers, setting heating rate is 5 DEG C/min, by room temperature temperature programming to 400 DEG C, and 1h is calcined at 400 DEG C, cold again after reaction
But to room temperature, above-mentioned product is taken out and use KOH solution (0.3g/mL, KOH and corncob calcine for the first time after product matter
Amount is than being 4：1) 6h is impregnated, then above-mentioned acquired solution is washed with deionized water to neutrality, the dry 12h at 60 DEG C, and will be upper
Product moves again in tube furnace after stating drying, under nitrogen atmosphere calcination reaction, and setting heating rate is 5 DEG C/min, by room
Warm temperature programming calcines 1h to 850 DEG C at 850 DEG C, is cooled to room temperature after reaction, takes out solid sample；Then will
The 10mL concentrated sulfuric acids pour into beaker, and 300mL deionized waters are added, then the solid after second of calcining of 1g is added to above-mentioned solution
Sample, immersion are washed with deionized water afterwards for 24 hours to neutrality, and dry 12h is to get to modified porous carbon (C) at 60 DEG C.
(2)CoFe2O4The synthesis of/C：By the Co (NO of 2mmol3)2·6H2Fe (the NO of O and 4mmol3)3·9H2O is dissolved in
In 15mL deionized waters, ultrasonic (power 50W) is carried out at 30 DEG C and stirs (rotating speed 600rpm/min) 30min, then will
The C of 100mg is added in above-mentioned solution, continues to carry out ultrasonic (power 50W) at 30 DEG C and stirs (rotating speed 600rpm/
Min) 30min, is eventually adding the NaOH of 8g, continues to carry out ultrasonic (power 50W) at 30 DEG C and stirs that (rotating speed is
The solution of 600rpm/min) 30min, gained are transferred in autoclave the progress hydro-thermal reaction 8h at 180 DEG C, after reaction
Multipass is washed with deionized water and ethyl alcohol respectively, is dried in vacuo 12h at 30 DEG C later to get to CoFe2O4/C。
(3) synthesis of Ag@PANI：5.56mL aniline is added in the HCl solution (2mol/L) of 250mL, and at 30 DEG C
Under be stirred (rotating speed 600rpm/min) 30min, acquired solution is denoted as solution A；Then the ammonium persulfate of 10.27g is delayed
Slowly it is added drop-wise in the HCl solution (2mol/L) of 312mL, and is stirred (rotating speed 600rpm/min) at 30 DEG C dropwise
30min is denoted as solution B；Above-mentioned solution is mixed into (solution B is poured into solution A), continues and is stirred (rotating speed at 30 DEG C
For 600rpm/min) 10h, after reaction 5h is stood at 30 DEG C.By solid product respectively with HCl solution (2mol/L), go from
Sub- water and acetone wash multipass, then by product at 60 DEG C dry 12h to get to PANI.The above-mentioned PANI of 2.45g are added again
Into the beaker containing 320mL silver nitrate solutions (0.025mol/L), ultrasonic (power 50W) is carried out at 30 DEG C and is stirred
(rotating speed 600rpm/min) 1h.384mL sodium borohydride solutions (0.025 mol/L) are added dropwise in beaker later, after
Continue and carry out ultrasonic (power 50W) at 30 DEG C and stir (rotating speed is 600 rpm/min) 1h, after reaction by solid product
Be washed with deionized, then by product at 60 DEG C dry 12h to get to Ag@PANI.
(4) conductive traces Ag@PANI/CoFe2O4The synthesis of/C：By the CoFe of the PEG-4000 of 5g and 1g2O4/ C is added to
In the deionized water of 20mL, ultrasonic (power 50W) is carried out at 30 DEG C and stirs (rotating speed 600rpm/min) 30min, is remembered
For solution A；The tetracycline of Ag the@PANI and 0.2g of 0.1g are added in the dimethyl sulfoxide of 60mL, ultrasound is carried out at 30 DEG C
(power 50W) and (rotating speed 600rpm/min) 30min is stirred, is denoted as solution B；Then solution A and solution B are added to light
It chemically reacts in bottle, and the trimethylolpropane trimethacrylate of 1mL and 784 photoinitiators of 0.01 g is added, in nitrogen atmosphere
Under enclosing (flow velocity 2mL/min), 30 DEG C of magnetic agitations (rotating speed 600rpm/min) simultaneously irradiate 10min using tungsten lamp, react it
Afterwards, will reaction solid product absolute ethyl alcohol and deionized water rinse it is multiple, it is anti-that solid sample is transferred to photochemistry again later
It answers in bottle, and the deionized water of 200mL, under air atmosphere (flow velocity 2mL/min), 30 DEG C of magnetic agitations is added thereto
(rotating speed 600rpm/min) and 2h is irradiated using tungsten lamp, after reaction, by reaction solid product absolute ethyl alcohol and deionization
Water rinse is multiple, is dried in vacuo at 30 DEG C after 12h to get to conductive traces Ag@PANI/CoFe2O4/C。
(5) non-trace Ag@PANI/CoFe2O4The synthesis of/C：By the CoFe of the PEG-4000 of 5g and 1g2O4/ C is added to
In the deionized water of 20mL, ultrasonic (power 50W) is carried out at 30 DEG C and stirs (rotating speed 600rpm/min) 30min, is remembered
For solution A；The Ag@PANI of 0.1g are added in the dimethyl sulfoxide of 60mL, ultrasonic (power 50W) is carried out simultaneously at 30 DEG C
(rotating speed 600rpm/min) 30min is stirred, solution B is denoted as；Then solution A and solution B are added to photochemical reaction bottle
In, and the trimethylolpropane trimethacrylate of 1mL and 784 photoinitiators of 0.01g is added, (flow velocity is under nitrogen atmosphere
2mL/min), 30 DEG C of magnetic agitations (rotating speed 600rpm/min) and use tungsten lamp 10 min of irradiation, after reaction, reaction is consolidated
Body product absolute ethyl alcohol and deionized water rinse are multiple, are dried in vacuo at 30 DEG C after 12h to get to non-trace Ag@
PANI/CoFe2O4/C。
(6) sample in 0.1g (4) is taken to carry out dark adsorption test, experimental result ultraviolet-visible in photochemical reactor
Spectrophotometric analysis measures conductive traces Ag@PANI/CoFe2O4/ C to the adsorption capacity of tetracycline 30min dark suction
0.23mg/g can be reached when attached, adsorption capacity starts that adsorption-desorption-absorption fluctuation is presented after dark absorption 30min, shows this
Conductive traces Ag@PANI/CoFe2O4/ C can reach adsorption equilibrium in 30min to tetracycline.
(7) sample is taken in 0.1g (4) to carry out photocatalytic degradation experiment in photochemical reactor, experimental result with it is ultraviolet-
Visible spectrophotometer is analyzed, and conductive traces Ag@PANI/CoFe are measured2O4/ C to the photodegradation rate of tetracycline 2h simulation
It can reach 83% under sunlight irradiation, show conductive traces Ag PANI/CoFe2O4/ C has stronger photocatalytic activity.
(8) sample in 0.1g (4) is taken to carry out photocatalytic degradation experiment in photochemical reactor, in the simulated solar irradiation of 2h
Under irradiation, conductive traces Ag@PANI/CoFe are measured2O4/ C to the photocatalytic activity of tetracycline and Danofloxacin mesylate,
Show conductive traces Ag@PANI/CoFe2O4/ C has good selectivity absorption/photocatalytic degradation capability.
Fig. 1 is conductive traces Ag@PANI/CoFe2O4The XRD spectra of/C, as can be seen from the figure：CoFe2O45 spread out
It penetrates peak and is located at 30 °, 35.59 °, 43.48 °, 57.20 ° and 62.39 °, these values correspond respectively to CoFe2O4(220),
(311), (400), (511) and (440) crystal face.2 diffraction maximums of Ag are located at 38.45 ° and 76.34 °, these values are right respectively
It should be in (111) and (311) crystal face of Ag.Illustrate CoFe2O4It has successfully been supported on the surface of C, has also illustrated conductive traces Ag
PANI/CoFe2O4/ C is implicitly present in Ag@PANI.；
Fig. 2 is the FT-IR spectrograms of different samples, as can be seen from the figure：Conductive traces Ag@PANI/CoFe2O4The peak of/C
Substantially CoFe is contained2O4The principal character peak of/C and Ag@PANI, this illustrates CoFe2O4/ C and Ag@PANI are present in conductive print
Mark Ag@PANI/CoFe2O4Among/C, conductive traces Ag@PANI/CoFe have been further related to2O4/ C has been successfully synthesized.
Fig. 3 is the SEM spectrograms and EDS spectrograms of different samples, as can be seen from the figure：CoFe2O4/ C is more thick relative to C
It is rough, illustrate in CoFe2O4Successfully it has been supported on the surface of C；With CoFe2O4/ C is compared, conductive traces Ag@PANI/CoFe2O4/
More apparent variation has occurred in the surface of C, and this is mainly due to coated caused by surface imprinted layer.From conductive traces
Ag@PANI/CoFe2O4The EDS spectrograms of/C are can be found that：The content highest of C, this may be C members in carbon material and surface imprinted layer
Caused by element is more；Simultaneously it has also been found that there are O, Fe, Co and Ag from EDS spectrograms, this again shows that conductive traces Ag@
PANI/CoFe2O4/ C has been successfully synthesized.
Fig. 4 is conductive traces Ag@PANI/CoFe2O4The magnetization curve of/C, it can be seen from the figure that conductive traces Ag@
PANI/CoFe2O4It is 25emu/g that/C, which has preferable magnetic saturation intensity, magnetic saturation intensity value, illustrates conductive traces Ag@
PANI/CoFe2O4/ C has good Magneto separate characteristic.
Fig. 5 is that different samples investigate figure to the adsorption capacity of tetracycline, as can be seen from the figure：Secretly absorption 30min's
When, CoFe2O4/ C and conductive traces Ag@PANI/CoFe2O4/ C nearly reaches adsorption equilibrium, therefore, is dropped in next light
It solves in experimentation, dark adsorption time is selected as 30min；Compared to CoFe2O4/ C, conductive traces Ag@PANI/CoFe2O4/ C pairs four
The adsorption capacity higher of ring element, reaches 0.23mg/g, this is because conductive traces Ag@PANI/CoFe2O4/ C has and can select
Caused by the trace hole of property tetracycline adsorption.
Fig. 6 is that different samples investigate figure to the Photocatalytic activity of tetracycline, as can be seen from the figure：CoFe2O4/ C's
Photocatalytic activity is only 25%, and activity is minimum；Non- trace Ag@PANI/CoFe2O4The activity of/C is that the light of 70%, Ag@PANI is urged
It is 74% to change activity, conductive traces Ag@PANI/CoFe2O4The activity of/C is 83%.By comparing it is found that conductive traces Ag@
PANI/CoFe2O4The photocatalytic activity highest of/C, this is because there is the trace hole for capableing of selective absorption tetracycline to lead for it
It causes, illustrates conductive traces Ag@PANI/CoFe2O4/ C has higher Photocatalytic activity to tetracycline.
Fig. 7 is that different samples investigate figure to the photocatalytic activity comparison of different pollutants, as can be seen from the figure：Ag@
PANI is 74% to the degradation rate of tetracycline, non-trace Ag@PANI/CoFe2O4/ C is 70% to the degradation rate of tetracycline, and is led
Electroblotting Ag@PANI/CoFe2O4/ C can reach 83% to the photocatalytic activity highest of tetracycline, degradation rate.In addition, Ag@
PANI is 66% to the degradation rate of Danofloxacin mesylate, non-trace Ag@PANI/CoFe2O4Drops of/the C to Danofloxacin mesylate
Solution rate is 61%, and conductive traces Ag@PANI/CoFe2O4/ C only has 53% to the degradation rate of Danofloxacin mesylate.Above-mentioned number
It is said that bright conductive traces Ag@PANI/CoFe2O4/ C is best to the degrading activity of tetracycline, lives to the degradation of Danofloxacin mesylate
Property is worst, this is because conductive traces Ag@PANI/CoFe2O4/ C has the trace hole for capableing of selective absorption tetracycline, and
The trace hole is unable to selective absorption Danofloxacin mesylate.The above results show conductive traces Ag@PANI/CoFe2O4/
C has extraordinary selective absorption/photocatalytic degradation removal ability to tetracycline.
Claims (10)
1. a kind of conductive traces Ag@PANI/CoFe2O4/C composite materials, which is characterized in that the composite material is more by being modified
Hole carbon (C), CoFe2O4And the surface imprinted layer of the alternative identification tetracycline containing Ag and PANI is combined；Described
C is transformed by corncob, CoFe2O4It is supported on the surface of C；The Ag is supported on the surface of PANI, and described is surface imprinted
Layer is coated on CoFe2O4The surface of/C, the Ag@PANI are embedded in surface imprinted layer.
2. a kind of preparation method of conductive traces Ag@PANI/CoFe2O4/C, which is characterized in that carry out as steps described below：
The synthesis of the modified porous carbon of step 1.：
Corncob is put into tube furnace first and carries out first time calcination reaction under nitrogen atmosphere, room is cooled to after reaction
Temperature is used in combination KOH solution to impregnate, and is then washed with deionized water to neutrality, drying is moved in tube furnace, carried out under nitrogen atmosphere
Second of calcination reaction is cooled to room temperature after reaction, is taken out solid sample, is mixed with the concentrated sulfuric acid and deionized water, after standing
It is washed with deionized water to neutrality, drying is to get to modified porous carbon.
Step 2. prepares CoFe2O4/C；
The synthesis of step 3.Ag@PANI：
Aniline is added in HCl solution, stirs, obtains solution A；Ammonium persulfate is added drop-wise in HCl solution, stirs, obtains
Solution B；Solution B is poured into solution A, continues to stir, solid product is obtained by the reaction in standing, uses HCl molten respectively solid product
Liquid, deionized water and acetone washing, drying is to get to PANI；PANI is added to containing in silver nitrate solution, is stirred by ultrasonic,
Then sodium borohydride solution is added, continues to be stirred by ultrasonic, obtains solid product, be washed with deionized, drying is to get to Ag@
PANI。
Step 4. conductive traces Ag@PANI/CoFe2O4The synthesis of/C：
By PEG-4000 and CoFe2O4/ C is add to deionized water, and ultrasonic agitation obtains solution C；By Ag@PANI and tetracycline
It is added in dimethyl sulfoxide, is stirred by ultrasonic, obtains solution D；Then solution C and solution D are mixed, is added to photochemical reaction bottle
In, and trimethylolpropane trimethacrylate and 784 photoinitiators, under nitrogen atmosphere, magnetic agitation is added and uses tungsten lamp
Irradiation, after reaction, deionized water is added in washing, and under air atmosphere, magnetic agitation is simultaneously irradiated using tungsten lamp, after reaction,
It is washed, to get to conductive traces Ag@PANI/CoFe after vacuum drying2O4/C。
The non-trace Ag@PANI/CoFe of step 5.2O4The synthesis of/C：
By PEG-4000 and CoFe2O4/ C is add to deionized water, and ultrasonic agitation obtains solution E；Ag@PANI are added to two
In first sulfoxide, ultrasonic agitation obtains solution F；Then solution E and solution F are mixed, is added in photochemical reaction bottle, and added
Enter trimethylolpropane trimethacrylate and 784 photoinitiators, under nitrogen range, magnetic agitation is simultaneously irradiated using tungsten lamp, instead
It after answering, is washed, to get to non-trace Ag@PANI/CoFe after vacuum drying2O4/C。
3. the preparation method of conductive traces Ag@PANI/CoFe2O4/C according to claim 2 a kind of, which is characterized in that
A concentration of 0.3g/mL of KOH solution described in step 1, soaking time 6h；The mass ratio of the KOH and corncob is 4：
1；The amount ratio of the concentrated sulfuric acid, deionized water and solid sample is 10mL：300mL：1g；The time of repose is for 24 hours.
4. the preparation method of conductive traces Ag@PANI/CoFe2O4/C according to claim 2 a kind of, which is characterized in that
The heating rate of first time calcining described in step 1 is 5 DEG C/min, and calcination temperature is 400 DEG C, calcination time 1h；It is described
Second calcining heating rate be 5 DEG C/min, calcination temperature be 850 DEG C, calcination time 1h.
5. the preparation method of conductive traces Ag@PANI/CoFe2O4/C according to claim 2 a kind of, which is characterized in that
The concentration of HCl solution described in step 3 is 2mol/L；The volume ratio of the molten aniline and HCl solution is 5.56：50；The mistake
The amount ratio of ammonium sulfate and HCl solution is 10.27g：312mL；Dwell temperature after the reaction is 30 DEG C, and time of repose is
5h。
6. the preparation method of conductive traces Ag@PANI/CoFe2O4/C according to claim 2 a kind of, which is characterized in that
The amount ratio of PANI, silver nitrate solution and sodium borohydride solution described in step 3 are 2.45g：320mL：384mL；The nitric acid
The concentration of silver-colored solution and sodium borohydride solution is 0.025mol/L.
7. the preparation method of conductive traces Ag@PANI/CoFe2O4/C according to claim 2 a kind of, which is characterized in that
PEG-4000, CoFe described in step 42O4/ C and the amount ratio of deionized water are 5g：1g：20mL；Ag@PANI, tetracycline
Amount ratio with dimethyl sulfoxide is 0.1g：0.2g：60mL；The trimethylolpropane trimethacrylate, 784 photoinitiators and
The amount ratio of deionized water is 1mL：0.01g：200mL；The temperature of the irradiation of tungsten lamp under nitrogen atmosphere is 30 DEG C, and magnetic force stirs
Mix rotating speed is 600rpm/min, nitrogen flow rate 2mL/min, irradiation time 10min；The tungsten lamp under air atmosphere shines
The temperature penetrated is 30 DEG C, and magnetic agitation rotating speed is 600rpm/min, air velocity 2mL/min, irradiation time 2h.
8. the preparation method of conductive traces Ag@PANI/CoFe2O4/C according to claim 2 a kind of, which is characterized in that
PEG-4000, CoFe in solution E described in step 52O4/ C and the amount ratio of deionized water are 5g：1g：20mL；The solution F
The amount ratio of middle Ag@PANI and dimethyl sulfoxide is 0.1g：60mL；The trimethylolpropane trimethacrylate and 784 light draws
The amount ratio for sending out agent is 1mL：0.01g；The temperature of the tungsten lamp irradiation is 30 DEG C, magnetic agitation rotating speed 600rpm/min, nitrogen
Gas velocity is 2mL/min, irradiation time 10min.
9. the preparation method of conductive traces Ag@PANI/CoFe2O4/C according to claim 2 a kind of, which is characterized in that
In step 1~5, the temperature of the drying is 60 DEG C, and drying time is 12h；In step 1~5, the vacuum drying temperature
Degree is 30 DEG C, and drying time is 12h.
10. a kind of conductive traces Ag@PANI/CoFe2O4/C according to claim 1-9 any claims are applied to choosing
Selecting property absorption/photocatalytic degradation tetracycline.
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| CN111482202A (en) * | 2020-03-27 | 2020-08-04 | 江苏大学 | Preparation method of temperature-sensitive imprinted Ag-POPD @ carbon magnetic material for controllably treating antibiotic wastewater |
| CN111935965A (en) * | 2020-07-14 | 2020-11-13 | 西安工程大学 | Preparation method of silver/biomass porous carbon electromagnetic wave absorption composite material |
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| CN111935965B (en) * | 2020-07-14 | 2023-04-18 | 西安工程大学 | Preparation method of silver/biomass porous carbon electromagnetic wave absorption composite material |
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