CN106345532A - Three-dimensional specific recognition type POPD/TiO2/SiO2@Fe3O4/FAC blotting nanoreactor and preparation method thereof - Google Patents
Three-dimensional specific recognition type POPD/TiO2/SiO2@Fe3O4/FAC blotting nanoreactor and preparation method thereof Download PDFInfo
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- CN106345532A CN106345532A CN201610607379.1A CN201610607379A CN106345532A CN 106345532 A CN106345532 A CN 106345532A CN 201610607379 A CN201610607379 A CN 201610607379A CN 106345532 A CN106345532 A CN 106345532A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title abstract 8
- 229910052681 coesite Inorganic materials 0.000 title abstract 6
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 6
- 239000000377 silicon dioxide Substances 0.000 title abstract 6
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 6
- 229910052682 stishovite Inorganic materials 0.000 title abstract 6
- 229910052905 tridymite Inorganic materials 0.000 title abstract 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 33
- 238000013019 agitation Methods 0.000 claims description 29
- 230000001699 photocatalysis Effects 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 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 claims description 22
- 230000015556 catabolic process Effects 0.000 claims description 22
- 229960004745 danofloxacin mesylate Drugs 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 239000010881 fly ash Substances 0.000 claims description 19
- 230000005855 radiation Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000007146 photocatalysis Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000010883 coal ash Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- PZJWYUDBXNNVLZ-UHFFFAOYSA-N 1-cyclopropyl-7-(4-ethylpiperazin-1-yl)-6-fluoro-4-oxoquinoline-3-carboxylic acid;hydrochloride Chemical compound Cl.C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 PZJWYUDBXNNVLZ-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 230000004044 response Effects 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- TZBAVQKIEKDGFH-UHFFFAOYSA-N n-[2-(diethylamino)ethyl]-1-benzothiophene-2-carboxamide;hydrochloride Chemical compound [Cl-].C1=CC=C2SC(C(=O)NCC[NH+](CC)CC)=CC2=C1 TZBAVQKIEKDGFH-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- JGAALXVSFDPKRK-UHFFFAOYSA-N CC(C=C)(C)C.C(O)C(CC)(CO)CO Chemical group CC(C=C)(C)C.C(O)C(CC)(CO)CO JGAALXVSFDPKRK-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- 239000003292 glue Substances 0.000 claims 1
- 230000004298 light response Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000012698 light-induced step-growth polymerization Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000006552 photochemical reaction Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004098 Tetracycline Substances 0.000 description 3
- 238000005276 aerator Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229960002180 tetracycline Drugs 0.000 description 3
- 229930101283 tetracycline Natural products 0.000 description 3
- 235000019364 tetracycline Nutrition 0.000 description 3
- 150000003522 tetracyclines Chemical class 0.000 description 3
- QMLVECGLEOSESV-RYUDHWBXSA-N Danofloxacin Chemical compound C([C@@H]1C[C@H]2CN1C)N2C(C(=CC=1C(=O)C(C(O)=O)=C2)F)=CC=1N2C1CC1 QMLVECGLEOSESV-RYUDHWBXSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000003854 Surface Print Methods 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229960004385 danofloxacin Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ICFXCSLDPCMWJI-UHFFFAOYSA-N 2,3-dimethylbut-2-enoic acid;2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CC(C)=C(C)C(O)=O.CCC(CO)(CO)CO ICFXCSLDPCMWJI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000004987 o-phenylenediamines Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
- B01J31/067—Molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a three-dimensional specific recognition type POPD/TiO2/SiO2@Fe3O4/FAC blotting nanoreactor and a preparation method thereof. The preparation method includes the steps of firstly, preparing modified FAC; secondly, preparing Fe3O4; thirdly, preparing SiO2@Fe3O4/FAC; fourthly, preparing TiO2/SiO2@Fe3O4/FAC; fifthly, preparing the POPD/TiO2/SiO2@Fe3O4/FAC blotting nanoreactor. The preparation method is capable of preparing the three-dimensional specific recognition type POPD/TiO2/SiO2@Fe3O4/FAC blotting nanoreactor through a visible light-induced polymerization method.
Description
Technical field
The invention belongs to technical field of environmental material preparation is and in particular to a kind of popd/tio of three-dimensional single-minded identification2/
sio2@fe3o4/ fac trace nano-reactor and preparation method thereof, and three-dimensional single-minded identification/selective photocatalysis degraded first sulphur
The research of sour Danofloxacin.
Background technology
tio2A kind of common inorganic catalysis material, stable chemical nature, nontoxic, there is biocompatibility, thus
It has been widely used in various fields such as catalysis, electronics, environment, medical treatment and shown tempting prospect.Since 1976-
Between 1977, find that Polychlorinated biphenyls and cyanide can be in tio2Since upper photocatalytic degradation, with tio2Semi-conducting material is photocatalysis
Agent, with clean energy resource preparation and the scientific research as target for the environmental pollution improvement, has attracted chemistry, environment and energy field science
The high interest of worker.But common tio2Can not comform the difficult problem of selective removal specific objective thing in multi-pollutant, because
This, we introduce surface imprinted technology.But general surface trace tio2Photocatalyst, because the covering of surface imprinted layer, can be led
Causing its photocatalytic activity to substantially reduce, for this reason, considering hybrid inorganic-organic structure, poly-o-phenylenediamine (popd) can be drawn
Enter in surface imprinted layer, popd can be with tio2Form specific hybrid structure, this is conducive to light induced electron and photo-induced hole
Transfer, can make its photocatalytic activity be improved.
Additionally, the thought based on the treatment of wastes with processes of wastes against one another, can be using the flyash (fac) reclaiming from solid waste as load
Body.In order to improve the separation and recovery ability of catalysis material further, we are in fac and tio2Magnetic material is introduced between layer
Material fe3o4, fe3o4Introducing can greatly lift the separation and recovery ability of catalysis material, reduces cost.It is well known that
tio2With fe3o4Directly contact, can produce photoetch effect, this can affect the photocatalytic activity of catalysis material.Therefore, we
Selection uses sio2Insulating barrier is completely cutting off tio2With fe3o4Contact, inhibit the generation of photoetch well.
Therefore, inventor first passes through screening and surface modification modifies the flyash (modified being prepared for modification
Fac), it is prepared for fe using solvent-thermal method simultaneously3o4, recycle sol-gel process to be prepared for sio2@fe3o4/ fac is then again logical
Cross sol-gel process in sio2@fe3o4The Surface coating of/fac tio2Semiconductor layer, is prepared for tio2/sio2@fe3o4/ fac,
The method finally utilizing visible light polymerization, in conjunction with surface imprinted technology, preparation has had three-dimensional single-minded identification ability
Popd/tio2/sio2@fe3o4/ fac trace nano-reactor.This photocatalytic nanometer reactor not only has good Magneto separate
Characteristic, also has high light catalysis activity, selective removal Danofloxacin mesylate in multi-pollutant of simultaneously can also comforming.
Content of the invention
The present invention, with solvent-thermal method, sol-gel process and visible light polymerization method as preparation means, prints in conjunction with surface
Mark technology, prepares a kind of popd/tio of three-dimensional single-minded identification2/sio2@fe3o4The preparation side of/fac trace nano-reactor
Method.Have an advantage in that (1) achieves the method for visible light polymerization to prepare trace nano-reactor；(2) surface imprinted layer
The presence of middle popd, has had successfully formed popd and tio2Hybrid structure is so as to photocatalytic activity effectively improves；(3) surface print
Being introduced into of trace layer makes nano-reactor have three-dimensional single-minded identification ability it is achieved that degradation selectivity methanesulfonic acid reaches in biphasic solution
The purpose of promise sand star；(4) use sio2Isolation layer has successfully coated fe3o4, and make fe3o4With tio2Isolation, reacts making nanometer
Utensil is magnetic to prevent photoetch to act on simultaneously；(5) construct and both there is high light catalysis activity, there is preferable selection again
Property, there is the nano-reactor of good Magneto separate characteristic simultaneously.
The technical solution used in the present invention is:
A kind of popd/tio of three-dimensional single-minded identification2/sio2@fe3o4/ fac trace nano-reactor, described nanometer is anti-
Answer device by flyash (fac), fe3o4、sio2Layer, tio2Layer, popd and can three-dimensional single-minded identification Danofloxacin mesylate table
Face imprinted layer is composited；Described sio2It is coated on the outer surface of fac；Described fe3o4It is wrapped in sio2Layer is internal；Described tio2
It is coated on sio2@fe3o4The outer surface of/fac；Described surface imprinted layer is coated on tio2/sio2@fe3o4The outer surface of/fac；Institute
State popd to be embedded in the middle of surface imprinted layer；Surface imprinted layer is by popd, trimethylol-propane trimethacrylate and removal
The trace hole composition staying after Enrofloxacin HCL；By this popd/tio of 0.1g2/sio2@fe3o4/ fac trace nanometer is reacted
Device is used for the Photocatalytic Activity for Degradation of the Danofloxacin mesylate solution of 100ml 20mg/l, and in 1h, degradation rate reaches
81.6%.
A kind of popd/tio of three-dimensional single-minded identification2/sio2@fe3o4The preparation method of/fac trace nano-reactor, presses
Carry out according to following step:
Step 1: the preparation of modified coal ash (modified fac):
Filter out flyash (fac) with sub-sieve；Again the flyash filtering out is added in hydrochloric acid, carries out mechanical agitation
Collect and washed product after a, after being dried, obtain the flyash of acid activation；By the flyash of acid activation and 3- aminopropyl three ethoxy
Base silane is added in toluene, mechanical agitation b under nitrogen atmosphere, and reaction is collected and washed product after terminating, and obtains after being dried
Amidized flyash, is designated as nh2-fac；Afterwards again by nh2- fac is added to the n containing succinic anhydride, n- dimethylformamide
In, carry out mechanical agitation c, reaction is collected and washed product after terminating, and obtains modified coal ash (modified after being dried
fac)；
Step 2:fe3o4Preparation:
By fecl3·6h2O and sodium acetate are added in ethylene glycol, and magnetic agitation, to being completely dissolved, obtains solution, by solution
Load and in reactor, carry out constant temperature thermal response, after reaction terminates, take out reactor and be cooled to room temperature, collect and washed product
Afterwards, vacuum drying obtains fe3o4；
Step 3:sio2@fe3o4The preparation of/fac:
First dehydrated alcohol and tetraethyl orthosilicate are put in there-necked flask, carry out closing stirring a, obtain mixed liquor a；To
It is added dropwise over the ammonia second solution containing dehydrated alcohol, deionized water and ammonia, with the instillation of ammonia second solution in mixed liquor a
Solution graduates into milky；Carry out closing stirring b, after stirring, add fe3o4, obtain mixed liquor b, carry out closing stirring c, envelope
Add modified coal ash after closing stirring c, obtain mixed liquor c, collect and washed product after carrying out closing stirring d, vacuum drying
Obtain sio afterwards2@fe3o4/fac；
Step 4:tio2/sio2@fe3o4The preparation of/fac:
Tetra-n-butyl titanate and dehydrated alcohol are put in there-necked flask, obtains mixed liquor d, closing stirring；Again thereto
It is added dropwise over the hydrochloric acid second solution containing dehydrated alcohol, distilled water and hydrochloric acid, obtains mixed liquor e, closing stirring is formed to colloidal sol；
Sio is added in colloidal sol2@fe3o4/ fac, closing stirring, it is aged after forming gel, calcined with tube furnace after vacuum drying again, Gu
Body product is designated as tio2/sio2@fe3o4/fac；
Step 5:popd/tio2/sio2@fe3o4The preparation of/fac trace nano-reactor:
First by tio2/sio2@fe3o4/ fac and Macrogol 4000 are added in distilled water, ultrasonic after, stand-by, be designated as
Modified tio2/sio2@fe3o4/fac；
Again Enrofloxacin HCL and o-phenylenediamine are dissolved in toluene, add trimethylol propane trimethyl acrylic acid
Ester, double (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes, obtain mixed liquor f, then add modification in mixed liquor f
tio2/sio2@fe3o4/ fac, puts in photo catalysis reactor, opens and uses radiation of visible light under magnetic agitation, nitrogen atmosphere, instead
After should terminating, with Magnet separation solid product, solid product is added in distilled water, obtains mixed liquor g, then by mixed liquor g
It is placed in photo catalysis reactor, opens magnetic agitation, under air atmosphere, then with radiation of visible light, collecting reaction product simultaneously washs
After be vacuum dried, that is, obtain popd/tio2/sio2@fe3o4/ fac trace nano-reactor.
In step 1, the size that described sub-sieve filters out fac is 76～125 μm.
In step 1, in the preparation process of the flyash of described acid activation, concentration in hydrochloric acid for the flyash is 0.05g/
ml；The concentration of hydrochloric acid is 1mol/l；The temperature of mechanical agitation a is 80 DEG C, and the time is 3h；Described nh2In the preparation process of-fac,
The amount ratio of fac, 3- aminopropyl triethoxysilane of acid activation and toluene is 3g:3ml:100ml；Machinery under nitrogen atmosphere
The temperature of stirring b is 80 DEG C, and the time is 12h；In the preparation process of described modified coal ash, nh2- fac, succinic anhydride and n, n-
The consumption of dimethylformamide is 1.2g, 0.003mol and 30ml；The temperature of mechanical agitation c is 25 DEG C, and the time is 24h.
In step 2, fecl3·6h2The amount ratio of o, sodium acetate and ethylene glycol is 1.35g:3.6g:50ml；Described magnetic force stirs
The temperature mixed is 25 DEG C；Described reactor reaction temperature is 200 DEG C, and the response time is 8h.
In step 3, when preparing mixed liquor a, the volume ratio of described dehydrated alcohol and tetraethyl orthosilicate is 9:2；Described ammonia
In second solution, the volume ratio of dehydrated alcohol, deionized water and ammonia is 36:3:10, and the concentration of described ammonia is 14.78mol/
l；The volume ratio of the dehydrated alcohol in ammonia second solution and the dehydrated alcohol in mixed liquor a is 1:1；When preparing mixed liquor b, made
Fe3o4Amount ratio with the dehydrated alcohol in the mixed liquor a being used is 0.5g:36ml；When preparing mixed liquor c, used
Modified coal ash and the mixed liquor a that used in the amount ratio of dehydrated alcohol be 1g:36ml；The temperature of described closing stirring
It is 40 DEG C；The time of described closing stirring a is 15min；The time for adding of described ammonia second solution is 10～15min；Described
The time of closing stirring b is 10min；The time of described closing stirring c is 30min；The time of described closing stirring d is 6h.
In step 4, when preparing mixed liquor d, the dehydrated alcohol being used and the volume ratio of tetra-n-butyl titanate are 3.6:1；
When preparing mixed liquor e, the sio that used2@fe3o4The amount ratio of the dehydrated alcohol in/fac and mixed liquor d is 1g:36ml；Institute
The volume ratio stating dehydrated alcohol, deionized water and hydrochloric acid in hydrochloric acid second solution is 36:3:0.2, the anhydrous second in hydrochloric acid second solution
The volume ratio of the dehydrated alcohol in alcohol and mixed liquor d is 1:1；The concentration of described hydrochloric acid is 1mol/l；Described closing stirring
Temperature is 40 DEG C；Preparing closing mixing time during mixed liquor d is 15min；The time for adding of described hydrochloric acid second solution is 10
～15min；After described formation gel, digestion time is 2h；Calcining heat in described tube furnace is 500 DEG C, and calcination time is
4h, heating rate is 5 DEG C/min.
In step 5, in modified tio2/sio2@fe3o4In/fac preparation process, tio2/sio2@fe3o4/ fac, poly- second two
The amount ratio of alcohol 4000 and distilled water is 0.5g:2.5g:15ml；Described ultrasonic time is 0.5h；When preparing mixed liquor f, made
Enrofloxacin HCL, o-phenylenediamine, toluene, trimethylol-propane trimethacrylate and double (1- (2,4 difluorobenzene
Base) -3- pyrrole radicals) titanocenes amount ratio be 0.05g:1～10mmol:15ml:0.7ml:0.005g；Described modification
tio2/sio2@fe3o4The volume ratio of the distilled water in/fac and the toluene in mixed liquor f is 1:1；Distilled water in mixed liquor g
With modified tio2/sio2@fe3o4The volume ratio of the distilled water in/fac is 40:3；The rotating speed of described magnetic agitation is
600rpm/min, uses radiation of visible light reaction temperature to be 30 DEG C, when being reacted with radiation of visible light under nitrogen atmosphere under nitrogen atmosphere
Between be 5～30min；Under air atmosphere use radiation of visible light reaction temperature be 30 DEG C, air atmosphere radiation of visible light anti-
It is 2h between seasonable.
In step 1～5, the temperature being dried is 50 DEG C, and drying time is 12h；In step 1～5, vacuum drying temperature
Degree is 30 DEG C, and drying time is 12h.
Additionally, this popd/tio2/sio2@fe3o4/ fac trace nano-reactor also have preferably three-dimensional single-minded identification/
Selective photocatalysis degradation capability
The technological merit of the present invention:
(1) achieve the method for visible light polymerization to prepare trace nano-reactor.
(2) in surface imprinted layer popd presence, had successfully formed popd and tio2Hybrid structure is so as to photocatalysis are lived
Property effectively improves.
(3) being introduced into of surface imprinted layer makes nano-reactor have three-dimensional single-minded identification ability it is achieved that in biphasic solution
The purpose of degradation selectivity Danofloxacin mesylate.
(4) use sio2Isolation layer has successfully coated fe3o4, and make fe3o4With tio2Isolation, has making nano-reactor
Photoetch is prevented to act on while magnetic.
Brief description
Fig. 1 is the xrd spectrogram of different samples, and wherein, curve a is fac, and curve b is tio2/sio2@fe3o4/ fac, curve
C is popd/tio2/sio2@fe3o4/ fac trace nano-reactor；
Fig. 2 is the ft-ir spectrogram of different samples, and curve a is fac, and curve b is tio2/sio2@fe3o4/ fac, curve c are
popd/tio2/sio2@fe3o4/ fac trace nano-reactor；
Fig. 3 is popd/tio2/sio2@fe3o4The nitrogen adsorption of/fac trace nano-reactor-desorption isotherm figure, inserts
Figure is popd/tio2/sio2@fe3o4The graph of pore diameter distribution of/fac trace nano-reactor；
Fig. 4 is the sem spectrogram of different samples；
Fig. 5 is the solid ultraviolet diffusing reflectance spectra figure of different samples；
Fig. 6 is popd/tio2/sio2@fe3o4The magnetization curve of/fac trace nano-reactor, illustration is popd/tio2/
sio2@fe3o4The Magneto separate photo of/fac trace nano-reactor；
Fig. 7 is the adsorption capacity investigation figure of different photocatalysts, and wherein, curve a is tio2/sio2@fe3o4/ fac, curve
B is popd/tio2/sio2@fe3o4/ fac trace nano-reactor；
Fig. 8 is different o-phenylenediamine additions to popd/tio2/sio2@fe3o4The light of/fac trace nano-reactor is urged
Change the impact of activity；
Fig. 9 causes polymerization time to popd/tio for different visible light2/sio2@fe3o4/ fac trace nano-reactor
The impact of photocatalytic activity；
Figure 10 is that the photocatalytic activity contrast of different samples is investigated, and wherein, curve a is tio2/sio2@fe3o4/ fac, bent
Line b is popd/tio2/sio2@fe3o4/ fac non-imprinted material, curve c is popd/tio2/sio2@fe3o4/ fac trace nanometer
Reactor；
Figure 11 is that different samples are investigated to the degradation selectivity ability of different pollutant, and wherein, a is tio2/sio2@
fe3o4/ fac, b are popd/tio2/sio2@fe3o4/ fac non-imprinted material, c is popd/tio2/sio2@fe3o4/ fac trace
Nano-reactor；
In Figure 12, figure a is popd/tio under different cycle-indexes2/sio2@fe3o4The degraded of/fac trace nano-reactor
Rate is investigated, and figure b is popd/tio2/sio2@fe3o4Ft-ir spectrum after 1 time and 5 times degraded for/the fac trace nano-reactor
Figure.
Specific embodiment
With reference to being embodied as example, the present invention will be further described.
Adsorption activity is evaluated: carries out in dw-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), but not
Open the light source, the Danofloxacin mesylate solution of 100ml 20mg/l is added in reactor and measures its initial value, be subsequently adding
The sample of 0.1g, design temperature is 30 DEG C, does not turn on light, stuffiness, opens magnetic agitation (rotating speed is 600rpm/min), interval
10min sample analysis, take the supernatant to measure its concentration in ultraviolet spectrophotometer after being separated with Magnet, and pass through formula: q=
(c0- c) v/m calculates its adsorption capacity q, wherein c0For Danofloxacin mesylate initial concentration, c is first when reaching adsorption equilibrium
The concentration of sulfonic acid Danofloxacin solution, v is the volume of solution, and m is the quality of the sample adding.
Photocatalytic activity evaluation: carry out in dw-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), can
See light irradiation, 100ml 20mg/l Danofloxacin mesylate solution is added in reactor and measures its initial value, be subsequently adding
The sample of 0.1g, opens magnetic agitation (rotating speed be 600rpm/min) and opens aerator and be passed through air (flow is 2ml/
Min), design temperature is 30 DEG C, is spaced 10min sample analysis, takes the supernatant in ultraviolet after being separated with Magnet in During Illumination
Its concentration of spectrophotometric determination, and pass through formula: dr=(c0-c)×100/c0Calculate its degradation rate dr, wherein c0For reaching
Concentration after adsorption equilibrium, the concentration of the Danofloxacin mesylate solution that c measures for t, t is the response time.
Selective evaluation: carry out it is seen that light in dw-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University)
Irradiate, the Binary Mixtures (tetracycline of the Danofloxacin mesylate containing 20mg/l and 20mg/l) of 100ml are added anti-
Answer in device, be subsequently adding the sample of 0.1g, open magnetic agitation (rotating speed be 600rpm/min) and open aerator and be passed through sky
Gas (flow is 2ml/min), design temperature is 30 DEG C, is spaced 10min sample analysis, takes after being separated with Magnet in During Illumination
Layer clear liquid, measures out the concentration of Danofloxacin mesylate and tetracycline in liquid respectively with high performance liquid chromatograph, calculates and does not share the same light
The photodegradation rate dr to different solutions for the catalyst.The parameter setting of high performance liquid chromatograph is: temperature is 25 DEG C, and mobile phase is body
The long-pending methanol than 40:60 and acetic acid solution, flow velocity is 1ml/min, and wavelength is 276nm..
Estimation of stability: carry out it is seen that light in dw-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University)
Irradiate, 100ml 20mg/l Danofloxacin mesylate solution is added in reactor, is subsequently adding the popd/tio of 0.1g2/
sio2@fe3o4/ fac trace nano-reactor, opens magnetic agitation (rotating speed be 600rpm/min) and opens aerator and be passed through
Air (flow is 2ml/min), design temperature is 30 DEG C, after illumination 60min, takes the supernatant to divide in ultraviolet after being separated with Magnet
Its concentration of light photometric determination, and calculate its degradation rate dr, then by the popd/tio after separation2/sio2@fe3o4/ fac trace is received
Rice reactor sample carries out second circulation degradation experiment and calculates its degradation rate dr, until tying after the 5th circulation degradation experiment
Bundle.
Embodiment 1:
(1) preparation of modified coal ash (modified fac): filter out 76 μm to 125 μm of flyash with sub-sieve
(fac)；Again above-mentioned for 5g fac is added in the hydrochloric acid of 100ml 1mol/l, after 80 DEG C of mechanical agitation 3h, product washing, in
The fac of acid activation is obtained after 12h is dried at 50 DEG C；Then again by the 3- aminopropyl-triethoxy of fac and 3ml of 3g acid activation
Silane is added in the toluene of 100ml, mechanical agitation 12h under 80 DEG C of nitrogen atmosphere, after reaction terminates, after product washing,
Nh is obtained after 12h being dried at 50 DEG C2-fac；Afterwards again by the nh of 1.2g2- fac is added to 30ml and contains 0.1mol/l fourth two
In the n of anhydride, n- dimethylformamide, mechanical agitation 24h at 25 DEG C, reaction terminate after washing, be dried at 50 DEG C after 12h i.e.
Obtain modified coal ash (modified fac).
(2)fe3o4Preparation: by the fecl of 1.35g3·6h2The sodium acetate of o and 3.6g is added in the ethylene glycol of 50ml,
At 25 DEG C, magnetic agitation is to being completely dissolved, more above-mentioned solution is loaded in reactor, keeps 8h at 200 DEG C, after reaction terminates,
Take out reactor and be cooled to room temperature, after washed product, be vacuum dried 12h at 30 DEG C, that is, obtain fe3o4.
(3)sio2@fe3o4The preparation of/fac: first the tetraethyl orthosilicate of the dehydrated alcohol of 36ml and 8ml is put into three mouthfuls
In flask, closing stirring 15min at 40 DEG C.Be added dropwise over again (containing 36ml dehydrated alcohol, 3ml deionized water and
10ml14.78mol/l ammonia) ammonia second solution, control between 10min to 15min, the instillation with ammonia second solution is molten
Liquid graduates into milky.After re-closed stirring 10min, add the fe of 0.5g3o4, continue closing stirring 30min, add
The modified fac of 1g, after closing stirring 6h, washed product, it is vacuum dried 12h at 30 DEG C, that is, obtain sio2@fe3o4/
fac.
(4)tio2/sio2@fe3o4The preparation of/fac: the dehydrated alcohol of the tetra-n-butyl titanate of 10ml and 36ml is put into
In there-necked flask, closing stirring 15min at 40 DEG C；Be added dropwise over containing 36ml dehydrated alcohol more thereto, 3ml distilled water and
The hydrochloric acid second solution of 0.2ml 1mol/l hydrochloric acid, controls the joining day between 10min to 15min, continues closing stirring and observes
Formed to colloidal sol, add the sio of 1g2@fe3o4/ fac, is further continued for closing stirring, after forming gel, is aged 2h, true at 30 DEG C
After sky is dried 12h, then with calcining 4h at 500 DEG C of tube furnace, heating rate is 5 DEG C/min, and solid product is designated as tio2/sio2@
fe3o4/fac.
(5)popd/tio2/sio2@fe3o4The preparation of/fac trace nano-reactor: first by the tio of 0.5g2/sio2@
fe3o4The Macrogol 4000 of/fac and 2.5g is added in the distilled water of 15ml, after ultrasonic 0.5h, stand-by, is designated as modification
tio2/sio2@fe3o4/fac；Again the o-phenylenediamine of the Enrofloxacin HCL of 0.05g and 6mmol is dissolved into the toluene of 15ml
In, add the trimethylol-propane trimethacrylate of 0.7ml, double (1- (2,4 difluorobenzene base) -3- pyrroles of 0.005g
Base) titanocenes and above-mentioned modified tio2/sio2@fe3o4/ fac, this mixed liquor is put in photo catalysis reactor, opens magnetic force
Stirring (rotating speed is 600rpm/min), uses radiation of visible light 20min under 30 DEG C of nitrogen atmosphere, after reaction terminates, uses Magnet
Separate solid product, then add it to, in the distilled water of 200ml, be placed in photo catalysis reactor, open magnetic agitation and (turn
Speed is 600rpm/min), under 30 DEG C of air atmosphere, then use radiation of visible light 2h, after product washing, true at 30 DEG C
Sky is dried 12h, that is, obtain popd/tio2/sio2@fe3o4/ fac trace nano-reactor.
(6) sample in 0.1g (5) is taken to carry out dark adsorption test, experimental result ultraviolet spectrometry light in photochemical reaction instrument
Degree meter analysis, records this popd/tio2/sio2@fe3o4/ fac trace nano-reactor is to Danofloxacin mesylate adsorption capacity
5.25mg/g can be reached in the dark absorption of 0.5h, show this popd/tio2/sio2@fe3o4/ fac trace nano-reactor
There is stronger adsorption activity.
(7) sample in 0.1g (5) is taken to carry out photocatalytic degradation test in photochemical reaction instrument, experimental result ultraviolet is divided
Light luminometric analysis, record this popd/tio2/sio2@fe3o4The light to the Danofloxacin mesylate for/fac trace nano-reactor
Degradation rate can reach 81.6% in the radiation of visible light of 1h, shows this popd/tio2/sio2@fe3o4/ fac trace nanometer
Reactor has stronger photocatalytic activity.
(8) sample in 0.1g (5) is taken to carry out photocatalytic degradation test in photochemical reaction instrument, in the radiation of visible light of 1h
Interior, record this popd/tio2/sio2@fe3o4The photocatalysis to material each in the Binary Mixtures for/fac trace nano-reactor
Degradation rate.
(9) sample in 0.1g (5) is taken to carry out photocatalytic degradation test in photochemical reaction instrument, in the radiation of visible light of 1h
Under, circulation experiment 5 times, record this popd/tio each2/sio2@fe3o4/ fac trace nano-reactor is to methanesulfonic acid Da Nuosha
Star degradation rate.
Embodiment 2:
Carry out by the same step of embodiment 1 preparation technology, except for the difference that in step (5), the addition of o-phenylenediamine is respectively
1mmol, 2mmol, 4mmol, 6mmol, 8mmol, 10mmol, to prepare different popd/tio2/sio2@fe3o4/ fac trace
Nano-reactor, the addition investigating different o-phenylenediamines is to popd/tio2/sio2@fe3o4/ fac trace nano-reactor light
The impact of catalysis activity, is investigated the activity of light degradation Danofloxacin mesylate solution by (7) step in embodiment 1.Photocatalysis are imitated
Fruit is as shown in Figure 8 it can be seen that the popd/tio preparing when the addition of o-phenylenediamine is for 6mmol2/sio2@fe3o4/fac
The effect of trace nano-reactor light degradation Danofloxacin mesylate is best.
Embodiment 3:
Carry out by the same step of embodiment 1 preparation technology, except for the difference that under nitrogen atmosphere in step (5) during radiation of visible light
Between be respectively 5min, 10min, 15min, 20min, 25min, 30min, to prepare different popd/tio2/sio2@fe3o4/
Fac trace nano-reactor, investigates different visible light and causes polymerization time to popd/tio2/sio2@fe3o4/ fac trace nanometer
The impact of reactor photocatalytic activity, is investigated the activity of light degradation Danofloxacin mesylate solution by (7) step in embodiment 1.
Photocatalysis effect is as shown in Figure 9 it can be seen that the popd/tio preparing when the visible light polymerization time is for 20min2/sio2@
fe3o4The effect of/fac trace nano-reactor light degradation Danofloxacin mesylate is best.
Fig. 1 is the xrd spectrogram of different samples, as can be seen from the figure: through sio2、fe3o4And tio2Cladding, tio2/
sio2@fe3o4There is the fe of cubic spinel structure in/fac sample3o4With anatase structured tio2.Additionally, through surface print
The cladding of trace layer, popd/tio2/sio2@fe3o4/ fac trace nano-reactor and tio2/sio2@fe3o4The spectrogram of/fac is almost
Equally, this illustrates that the cladding of surface imprinted layer has no effect on the crystalline structure of matrix material.The above results surface: fe3o4And tio2
Do exist in popd/tio2/sio2@fe3o4In/fac trace nano-reactor.
It is found that in figure 3432cm from Fig. 2-1And 1099cm-1Stretching vibration for si-oh and si-o and asymmetric
Stretching vibration absworption peak, in b and c, 2962cm-1Locate as c-h stretching vibration absworption peak, 1637cm-1Feature for c=c or c=o
Absworption peak, 1471cm-1And 1384cm-1It is fe at two3o4With the covalent bond absworption peak of cooh-fac, the above results show fe3o4?
Through successfully passing through sio2It is covered by the surface of fac；Additionally, compared with b, c has had more a lot of other absworption peaks, 1723cm-1Locate as 1 in popd, the absworption peak of c=o in the absworption peak of 2,4 trisubstituted benzenes or trimethylol-propane trimethacrylate,
1017cm-1Locate the stretching vibration absworption peak for c-o in trimethylol-propane trimethacrylate, 939cm-1Locate curved for c-h
Bent vibration absorption peak.Additionally, 1600cm-1And 1450cm-1Between for phenyl ring skeletal vibration absworption peak, 1323cm-1With
1295cm-1It is the stretching vibration absworption peak of c-n-c at two, 1145cm-1Locate the stretching vibration absworption peak for c-c.The above results are demonstrate,proved
Understand that surface imprinted layer has successfully been coated on tio2/sio2@fe3o4The surface of/fac, and being present in of popd is surface imprinted
In layer.
From figure 3, it can be seen that popd/tio2/sio2@fe3o4The isothermal line of/fac trace nano-reactor belongs to the i-th v
Type, illustrates this popd/tio2/sio2@fe3o4/ fac trace nano-reactor has meso-hole structure, and average pore size is about
2.71nm, specific surface area is about 184.15m2/g.The above results illustrate this popd/tio2/sio2@fe3o4/ fac trace nanometer is anti-
Answer and in device, contain the trace hole being capable of three-dimensional single-minded identification Danofloxacin mesylate.
Fig. 4 is the sem figure of different samples, it can be seen that through sio2、fe3o4、tio2, popd and surface imprinted
The cladding of layer, popd/tio2/sio2@fe3o4/ fac trace nano-reactor still assumes preferable spherical structure.With fac phase
Ratio sio2@fe3o4There is substantial amounts of spherical little particle on the surface of/fac in much places, and fe is described3o4Pass through sio2Successfully
It is coated on the surface of fac.With sio2@fe3o4/ fac compares, tio2/sio2@fe3o4The surface of/fac has been substantially not visible
fe3o4The vestige of nanosphere, illustrates tio2Successfully coat, additionally, from tio2/sio2@fe3o4The indentation, there of/fac microsphere can
Can be clearly seen that the fe at hollow structure and cleaved facet3o4Nanosphere, also demonstrates above-mentioned conclusion.With tio2/sio2@fe3o4/
Fac compares, popd/tio2/sio2@fe3o4A lot of holes can be seen in the surface of/fac trace nano-reactor, this explanation print
Trace layer has successfully been covered by tio2/sio2@fe3o4The surface of/fac.
As can be seen from Figure 5: coating sio2, fe3o4And tio2Afterwards, tio2/sio2@fe3o4/ fac in ultraviolet and
There is preferable absorption visible region, and meanwhile, popd has extraordinary light absorpting ability in visible region, therefore, with tio2/
sio2@fe3o4/ fac compares, popd/tio2/sio2@fe3o4/ fac trace nano-reactor has more preferable visible absorption energy
Power.
Fig. 6 is popd/tio2/sio2@fe3o4The magnetization curve of/fac trace nano-reactor, it can be seen that
popd/tio2/sio2@fe3o4The magnetic saturation intensity of/fac trace nano-reactor is 8.8emu/g, can be more from illustration
Intuitively find out, this popd/tio2/sio2@fe3o4/ fac trace nano-reactor can easily be separated by Magnet.
From Fig. 7, the adsorption curve of different samples can be seen that when adsorbing 0.5h, almost adsorption equilibrium,
Compared to tio2/sio2@fe3o4/ fac, popd/tio2/sio2@fe3o4The adsorption capacity of/fac trace nano-reactor is higher,
Reach 5.25mg/g,.This is due to popd/tio2/sio2@fe3o4/ fac trace nano-reactor has being capable of three-dimensional single-minded knowledge
The trace hole of other Danofloxacin mesylate leads to.
Be can be seen that when there is no catalyst by the photocatalytic activity curve of samples different in Figure 10, degradation rate is very
Low, illustrate that we have extraordinary catalytic effect by prepared catalyst；With tio2/sio2@fe3o4/ fac and popd/tio2/
sio2@fe3o4/ fac non-imprinted material is compared, popd/tio2/sio2@fe3o4The photocatalytic activity of/fac trace nano-reactor
Highest, under the radiation of visible light of 1h, degradation rate can reach 81.6%, and this is the three-dimensional specific recognition ability due to trace hole
And popd and tio2The highlight catalytic active these two aspects effect of hydridization leads to.
It can be seen from figure 11 that popd/tio2/sio2@fe3o4/ fac trace nano-reactor is to Danofloxacin mesylate
Degradation rate will be apparently higher than tio2/sio2@fe3o4/ fac and popd/tio2/sio2@fe3o4/ fac non-imprinted material；And for
For the degraded of tetracycline, tio2/sio2@fe3o4/ fac and popd/tio2/sio2@fe3o4/ fac non-imprinted material is but substantially high
In popd/tio2/sio2@fe3o4/ fac trace nano-reactor；The above results show this popd/tio2/sio2@fe3o4/fac
Trace nano-reactor has extraordinary three-dimensional single-minded identification/selective photocatalysis degraded and goes decapacitation to Danofloxacin mesylate
Power.
From circulation experiment in Figure 12, prepared popd/tio2/sio2@fe3o4/ fac trace nano-reactor is 5
After secondary circulation experiment, still there is preferable Photocatalytic activity, and structure composition does not have significant change, this popd/ is described
tio2/sio2@fe3o4/ fac trace nano-reactor has preferable stability.
Claims (9)
1. a kind of popd/tio of three-dimensional single-minded identification2/sio2@fe3o4/ fac trace nano-reactor is it is characterised in that described
Nano-reactor by flyash (fac), fe3o4、sio2Layer, tio2Layer, popd and promise can be reached by three-dimensional single-minded identification methanesulfonic acid
The surface imprinted layer of Sha Xing is composited；Described sio2It is coated on the outer surface of fac；Described fe3o4It is wrapped in sio2In layer
Portion；Described tio2It is coated on sio2@fe3o4The outer surface of/fac；Described surface imprinted layer is coated on tio2/sio2@fe3o4/fac
Outer surface；Described popd is embedded in the middle of surface imprinted layer；Surface imprinted layer is by popd, trimethylol propane trimethyl propylene
The trace hole composition staying after acid esters and removal Enrofloxacin HCL；By popd/tio described in 0.1g2/sio2@fe3o4/fac
Trace nano-reactor is used for the Photocatalytic Activity for Degradation of the Danofloxacin mesylate solution of 100ml 20mg/l, drops in 1h
Solution rate has reached 81.6%.
2. the popd/tio of the single-minded identification of the three-dimensional described in a kind of claim 12/sio2@fe3o4/ fac trace nano-reactor
Preparation method is it is characterised in that carry out as steps described below:
Step 1: the preparation of modified coal ash:
Filter out flyash (fac) with sub-sieve；Again the flyash filtering out is added in hydrochloric acid, after carrying out mechanical agitation a
Collect and washed product, after being dried, obtain the flyash of acid activation；By the flyash of acid activation and 3- aminopropyl-triethoxy
Silane is added in toluene, mechanical agitation b under nitrogen atmosphere, and reaction is collected and washed product after terminating, and obtains ammonia after being dried
The flyash of base, is designated as nh2-fac；Afterwards again by nh2- fac is added to the n containing succinic anhydride, n- dimethylformamide
In, carry out mechanical agitation c, reaction is collected and washed product after terminating, and obtains modified coal ash (modified after being dried
fac)；
Step 2:fe3o4Preparation:
By fecl3·6h2O and sodium acetate are added in ethylene glycol, and magnetic agitation, to being completely dissolved, obtains solution, and solution is loaded
Carry out constant temperature thermal response in reactor, after reaction terminates, take out reactor and be cooled to room temperature, after collection washed product, very
Empty drying to obtain fe3o4；
Step 3:sio2@fe3o4The preparation of/fac:
First dehydrated alcohol and tetraethyl orthosilicate are put in there-necked flask, carry out closing stirring a, obtain mixed liquor a；To mixing
It is added dropwise over the ammonia second solution containing dehydrated alcohol, deionized water and ammonia, with the instillation solution of ammonia second solution in liquid a
Graduate into milky；Carry out closing stirring b, after stirring, add fe3o4, obtain mixed liquor b, carry out closing stirring c, closing is stirred
Add modified coal ash after mixing c, obtain mixed liquor c, collect and washed product, after vacuum drying i.e. after carrying out closing stirring d
Obtain sio2@fe3o4/fac；
Step 4:tio2/sio2@fe3o4The preparation of/fac:
Tetra-n-butyl titanate and dehydrated alcohol are put in there-necked flask, obtains mixed liquor d, closing stirring；Again thereto dropwise
Add the hydrochloric acid second solution containing dehydrated alcohol, distilled water and hydrochloric acid, obtain mixed liquor e, closing stirring is formed to colloidal sol；Xiang Rong
Sio is added in glue2@fe3o4/ fac, closing stirring, it is aged after forming gel, calcined with tube furnace after vacuum drying, solid produces again
Thing is designated as tio2/sio2@fe3o4/fac；
Step 5:popd/tio2/sio2@fe3o4The preparation of/fac trace nano-reactor:
First by tio2/sio2@fe3o4/ fac and Macrogol 4000 are added in distilled water, ultrasonic after, stand-by, be designated as modification
Tio2/sio2@fe3o4/fac；
Again Enrofloxacin HCL and o-phenylenediamine are dissolved in toluene, add trimethylol-propane trimethacrylate,
Double (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes, obtain mixed liquor f, then the tio adding modification in mixed liquor f2/
sio2@fe3o4/ fac, puts in photo catalysis reactor, opens and uses radiation of visible light under magnetic agitation, nitrogen atmosphere, and reaction terminates
Afterwards, with Magnet separation solid product, solid product is added in distilled water, obtains mixed liquor g, then mixed liquor g is placed in light
In catalytic reactor, open magnetic agitation, under air atmosphere, then with radiation of visible light, collecting reaction product vacuum after washing
It is dried, that is, obtain popd/tio2/sio2@fe3o4/ fac trace nano-reactor.
3. the popd/tio of a kind of three-dimensional single-minded identification according to claim 22/sio2@fe3o4/ fac trace nanometer is reacted
The preparation method of device is it is characterised in that in step 1, the size that described sub-sieve filters out fac is 76～125 μm.
4. the popd/tio of a kind of three-dimensional single-minded identification according to claim 22/sio2@fe3o4/ fac trace nanometer is reacted
The preparation method of device is it is characterised in that in step 1, in the preparation process of the flyash of described acid activation, flyash is in hydrochloric acid
Concentration be 0.05g/ml；The concentration of hydrochloric acid is 1mol/l；The temperature of mechanical agitation a is 80 DEG C, time 3h；Described nh2-fac
Preparation process in, fac, 3- aminopropyl triethoxysilane of acid activation and the amount ratio of toluene are 3g:3ml:100ml；?
Under nitrogen atmosphere, the temperature of mechanical agitation b is 80 DEG C, and the time is 12h；In the preparation process of described modified coal ash, nh2-fac、
Succinic anhydride and n, the consumption of n- dimethylformamide is 1.2g, 0.003mol and 30ml；The temperature of mechanical agitation c is 25 DEG C,
Time is 24h.
5. the popd/tio of a kind of three-dimensional single-minded identification according to claim 22/sio2@fe3o4/ fac trace nanometer is reacted
The preparation method of device it is characterised in that in step 2, fecl3·6h2The amount ratio of o, sodium acetate and ethylene glycol is 1.35g:
3.6g:50ml；The temperature of described magnetic agitation is 25 DEG C；Described reactor reaction temperature is 200 DEG C, and the response time is 8h.
6. the popd/tio of a kind of three-dimensional single-minded identification according to claim 22/sio2@fe3o4/ fac trace nanometer is reacted
The preparation method of device it is characterised in that in step 3, when preparing mixed liquor a, the volume of described dehydrated alcohol and tetraethyl orthosilicate
Than for 9:2；In described ammonia second solution, the volume ratio of dehydrated alcohol, deionized water and ammonia is 36:3:10, described ammonia
Concentration is 14.78mol/l；The volume ratio of the dehydrated alcohol in ammonia second solution and the dehydrated alcohol in mixed liquor a is 1:1；System
During standby mixed liquor b, the fe being used3o4Amount ratio with the dehydrated alcohol in the mixed liquor a being used is 0.5g:36ml；Preparation
During mixed liquor c, the amount ratio of the dehydrated alcohol in the modified coal ash being used and the mixed liquor a being used is 1g:36ml；Institute
The temperature stating closing stirring is 40 DEG C；The time of described closing stirring a is 15min；The time for adding of described ammonia second solution
For 10～15min；The time of described closing stirring b is 10min；The time of described closing stirring c is 30min；Described closing is stirred
The time mixing d is 6h.
7. the popd/tio of a kind of three-dimensional single-minded identification according to claim 22/sio2@fe3o4/ fac trace nanometer is reacted
The preparation method of device it is characterised in that in step 4, when preparing mixed liquor d, the dehydrated alcohol being used and tetra-n-butyl titanate
Volume ratio be 3.6:1；When preparing mixed liquor e, the sio that used2@fe3o4The use of the dehydrated alcohol in/fac and mixed liquor d
Amount ratio is 1g:36ml；In described hydrochloric acid second solution, the volume ratio of dehydrated alcohol, deionized water and hydrochloric acid is 36:3:0.2, hydrochloric acid
The volume ratio of the dehydrated alcohol in second solution and the dehydrated alcohol in mixed liquor d is 1:1；The concentration of described hydrochloric acid is 1mol/
l；The temperature of described closing stirring is 40 DEG C；Preparing closing mixing time during mixed liquor d is 15min；Described hydrochloric acid second is molten
The time for adding of liquid is 10～15min；After described formation gel, digestion time is 2h；Calcining heat in described tube furnace is
500 DEG C, calcination time is 4h, and heating rate is 5 DEG C/min.
8. the popd/tio of a kind of three-dimensional single-minded identification according to claim 22/sio2@fe3o4/ fac trace nanometer is reacted
The preparation method of device it is characterised in that in step 5, in modified tio2/sio2@fe3o4In/fac preparation process, tio2/
sio2@fe3o4The amount ratio of/fac, Macrogol 4000 and distilled water is 0.5g:2.5g:15ml；Described ultrasonic time is
0.5h；When preparing mixed liquor f, the Enrofloxacin HCL that used, o-phenylenediamine, toluene, trimethylol propane trimethyl propylene
The amount ratio of acid esters and double (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes is 0.05g:1～10mmol:15ml:
0.7ml:0.005g；The tio of described modification2/sio2@fe3o4Distilled water in/fac and the volume of the toluene in mixed liquor f
Than for 1:1；Distilled water in mixed liquor g and modified tio2/sio2@fe3o4The volume ratio of the distilled water in/fac is 40:3；
The rotating speed of described magnetic agitation is 600rpm/min, uses radiation of visible light reaction temperature to be 30 DEG C, nitrogen under nitrogen atmosphere
The radiation of visible light response time is used to be 5～30min under atmosphere；The reaction temperature using radiation of visible light under air atmosphere is 30 DEG C,
The response time of air atmosphere radiation of visible light is 2h.
9. the popd/tio of a kind of three-dimensional single-minded identification according to claim 22/sio2@fe3o4/ fac trace nanometer is reacted
The preparation method of device is it is characterised in that in step 1～5, the temperature being dried is 50 DEG C, and drying time is 12h；Step 1～
In 5, vacuum drying temperature is 30 DEG C, and drying time is 12h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837799A (en) * | 2017-11-16 | 2018-03-27 | 河南永泽环境科技有限公司 | A kind of magnetic for phenol wastewater of degrading strengthens flyash trace photochemical catalyst |
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| US8158005B1 (en) * | 2007-11-02 | 2012-04-17 | University Of South Florida | Functional composites formed from colloidal polymer particles with photocatalytic metal oxide (MOx) nanoparticles |
| CN103223352A (en) * | 2013-04-02 | 2013-07-31 | 江苏大学 | Preparation method of magnetic imprinting composite photocatalyst with good light transmission |
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| US8158005B1 (en) * | 2007-11-02 | 2012-04-17 | University Of South Florida | Functional composites formed from colloidal polymer particles with photocatalytic metal oxide (MOx) nanoparticles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107837799A (en) * | 2017-11-16 | 2018-03-27 | 河南永泽环境科技有限公司 | A kind of magnetic for phenol wastewater of degrading strengthens flyash trace photochemical catalyst |
| CN107837799B (en) * | 2017-11-16 | 2020-06-23 | 河南永泽环境科技有限公司 | Magnetic reinforced fly ash imprinted photocatalyst for degrading phenol-containing wastewater |
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