CN106824288A - Magnetic quinone amboceptor nano-functional material and its preparation method and application - Google Patents
Magnetic quinone amboceptor nano-functional material and its preparation method and application Download PDFInfo
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- CN106824288A CN106824288A CN201710066553.0A CN201710066553A CN106824288A CN 106824288 A CN106824288 A CN 106824288A CN 201710066553 A CN201710066553 A CN 201710066553A CN 106824288 A CN106824288 A CN 106824288A
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- Prior art keywords
- magnetic
- nano
- particle
- amboceptor
- quinone
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 35
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 35
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 35
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 15
- -1 aminopropyl Chemical group 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000006249 magnetic particle Substances 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000003344 environmental pollutant Substances 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 231100000719 pollutant Toxicity 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000006065 biodegradation reaction Methods 0.000 claims description 7
- 239000008236 heating water Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 4
- YRHBFXZMYZMWFO-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonyl chloride Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)Cl YRHBFXZMYZMWFO-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical group O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 claims 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-M 9,10-dioxoanthracene-1-sulfonate Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] JAJIPIAHCFBEPI-UHFFFAOYSA-M 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 241000255964 Pieridae Species 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 150000004056 anthraquinones Chemical class 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 125000004151 quinonyl group Chemical group 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- LPDMVSGUSCAZFD-UHFFFAOYSA-N [Cl].C1(=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O)S(=O)(=O)O Chemical compound [Cl].C1(=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O)S(=O)(=O)O LPDMVSGUSCAZFD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 19
- 210000002966 serum Anatomy 0.000 description 19
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 239000000987 azo dye Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 229940082569 selenite Drugs 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- 241000863430 Shewanella Species 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000011953 bioanalysis Methods 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229940091258 selenium supplement Drugs 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 2
- UDFCHANCMRCOQT-UHFFFAOYSA-N 9,10-dioxoanthracene-2-sulfonyl chloride Chemical class C1=CC=C2C(=O)C3=CC(S(=O)(=O)Cl)=CC=C3C(=O)C2=C1 UDFCHANCMRCOQT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002539 nanocarrier Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 229960001471 sodium selenite Drugs 0.000 description 2
- 239000011781 sodium selenite Substances 0.000 description 2
- 235000015921 sodium selenite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000037323 metabolic rate Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000010784 textile waste Substances 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J31/26—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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/106—Selenium compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of magnetic quinone amboceptor nano-functional material and its preparation method and application, with FeCl3、FeCl2It is raw material with ammoniacal liquor, the Fe of magnetic is prepared by coprecipitation3O4Particle；By adding tetraethoxysilane, make magnetic Fe3O4Particle surface covers silicon dioxide layer；The magnetic nano-particle of surface amino groups modification, Fe are prepared by using silane coupler aminopropyl triethoxy silica alkane3O4‑SiO2@NH2Reacted under conditions of triethylamine does acid binding agent with anthraquinone sulfonic acid chlorine and prepared.Quinone amboceptor magnetic Nano material prepared by the present invention can realize its extracting and developing and recovery by externally-applied magnetic field, effectively solve water-soluble quinonyl amboceptor and outflow with water and cause secondary pollution and continuously add the increased problem of cost；Anthraquinone amboceptor is fixed on magnetic nano-particle in the form of being chemically bonded, and because the surface area of nano-particle is big, can improve the load factor of anthraquinone amboceptor, and then realize its catalytic efficiency high.
Description
Technical field
The invention belongs to water environment treatment amboceptor field of functional materials, and in particular to a kind of magnetic quinone amboceptor nano functional
Material and preparation method thereof, can be used for the biodegradation of catalytic environment pollutant, such as azo dyes, perchlorate, selenite
Deng.
Background technology
With maintaining sustained and rapid growth for China's economy, water resources consumption is increased considerably so that water environment pollution problem day
Become serious.For example：Azo dyes is typical pollutant in textile waste, after it enters river, not only influences the colourity of river
And turbidity, and carcinogenic aromatic amine can be changed into, and water environment pollution is caused, influence the health of the mankind；Perchlorate is that one kind is held
The inorganic pollution of long property, diffusion velocity is fast, stability is high, difficult degradation, and it can suppress the absorption of iodine and weaken thyroid gland work(
Energy；Agricultural irrigation, mining activities and industrial wastewater discharge, making the selenium slow poisoning of selenium contamination environment, animal can cause breeding
Deformity, mankind's intake soluble selenium can produce alkali disease etc..Therefore the removal or conversion of research water environment pollution has
Important meaning.The method of pollutant process can be divided into Physical, chemical method, bioanalysis in existing water environment.Wherein, physics
Method mainly has absorption method and membrane separation process etc., and chemical method mainly has Coagulation Method and oxidizing process etc., however, the method for these purifications
Operating cost is generally higher, and easily causes secondary pollution.Comparatively speaking, bioanalysis, not only low cost, and secondary dirt can be reduced
The generation of dye, bioanalysis is widely used as a kind of the most economic, effective method for treating water.
The biological treatment of waste water, general using anaerobic-aerobic disposal treatment, being processed by anaerobic stages can improve thereafter
Continue aerobic biodegradability.However, the microorganism fungus kind of most environmental contaminants is under anaerobic, metabolic rate is slow, treatment
The efficiency of pollutant is low.Therefore, the reaction rate of anaerobic stages turns into the speed limit of environmental contaminants complete biodegradable or removal
Step.The research of the chemistry and bioconversion of nearest redox mediators catalytic intensification Recalcitrant chemicals, difficult pollution degradation
The degraded of thing high-performance bio provides new Research Thinking.
The initial period of redox mediators research is that water-soluble amboceptor directly adds utilization, but water-soluble amboceptor is present easily
Loss causes secondary pollution and continuously adds cost increase problem, and research is concentrated mainly on laboratory stage.In order to solve water
The problem that soluble mediator is easy to run off, researcher have developed the immobilization technology of amboceptor, mainly with redox mediators with physical
The modes such as embedding, absorption or chemical bonding are fixed on carrier, carry out catalysis pollutant anaerobic biodegradation/changing effect and
Pilot reactor is studied.The amboceptor immobilization technology of existing report, from the size of immobilization carrier, can be divided into macro-size load
Body and microscopic dimensions carrier technique for fixing.The technique for fixing of macro-size carrier effectively avoids water-soluble amboceptor loss and causes
Secondary pollution and the continuous cost that adds increase problem.But the surface area of the carrier of macro-size is small, redox mediators are repaiied
Decorations rate is relatively low, have impact on amboceptor catalytic efficiency.Then, the amboceptor immobilization technology of micro-nano carrier is of concern.But often
The technique for fixing of the nano-carrier of rule there is also the problem for outflowing with water of amboceptor, cause the secondary pollution to environment.
The content of the invention
The technical problem to be solved in the present invention be to provide a kind of magnetic quinone amboceptor nano-functional material and preparation method thereof and
Using it modifies in magnetic Fe quinone amboceptor by way of chemical bonding3O4The surface of nano-particle, is obtained quinone mediator-modified
Magnetic particle, can be used for the biodegradation of catalytic environment pollutant.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of magnetic quinone amboceptor nano-functional material, it is with nanometer Fe3O4Particle be magnetic kernel, with amorphous Si O2For in
Between shell, in Fe3O4- SiO2Outer surface be modified with amino, the magnetic that anthraquinone -2- sulfonyls are grafted with the amino is received
Rice functional material.
Present invention also offers the preparation method of above-mentioned magnetic quinone amboceptor nano-functional material, comprise the following steps：
A, preparation Fe3O4Magnetic nano-particle：With FeCl3And FeCl2For raw material is configured to solution, 40-80 DEG C is heated slowly to,
Add ammoniacal liquor, stirring 10min-2h, washing, then by the Fe of hygrometric state3O4It is transferred in sodium citrate solution, ultrasonic disperse, washs,
Fe is obtained3O4Magnetic nano-particle；
B, in Fe3O4Wrap up SiO in magnetic nano-particle outer surface2Layer：By Fe3O4Magnetic nano-particle is scattered in water and anhydrous second
In the mixed solution of alcohol, tetraethoxysilane and ammoniacal liquor are sequentially added, under nitrogen atmosphere after stirring reaction 1-8 h, washing is produced
Thing, drying, obtain Fe3O4- SiO2Magnetic particle；
C、Fe3O4- SiO2Particle modifies amino：By aminopropyl triethoxy silica alkane and Fe3O4- SiO2Magnetic particle disperses
In absolute ethyl alcohol, ultrasonic 10min-2h after reacting 3-24h under 30-70 DEG C of nitrogen atmosphere, products therefrom is separated, washing,
Dry, obtain amido modified Fe3O4- SiO2@ NH2Magnetic particle；
D, grafting anthraquinone sulfonyl：By the Fe3O4- SiO2@ NH2Magnetic particle is dispersed in the mixed of triethylamine and carbon dichloride
Close in solution, be subsequently adding the carbon dichloride solution of anthraquinone sulfonic acid chloride, react 3-24h, FeSi-AQS magnetic particles are obtained.
Preferably, the mol ratio of FeCl3 and FeCl2 is Fe in step A3O4Metering compare 2:1, sodium citrate solution it is dense
It is 0.1-1.0 mol/L to spend.
Aminopropyl triethoxy silica alkane and Fe in step C3O4- SiO2The mass ratio of particle is 1:1-3.
The synthetic method of anthraquinone sulfonic acid chloride is in step D：Weigh sodium anthraquinone sulfonate to be dissolved in dichloromethane, heating water bath is extremely
40-50 DEG C, condensing reflux measures chlorosulfonic acid and is placed in constant pressure funnel, dropwise completion of dropping, cold after the -7h of condensing reflux 6
But to room temperature, organic phase is distilled into water washing 3 times, after anhydrous magnesium sulfate dries organic phase, rotates dichloromethane, obtain anthraquinone sulphonyl
Chlorine.
In above-mentioned technical proposal, with FeCl3、FeCl2It is raw material with ammoniacal liquor, magnetic is prepared by coprecipitation
Fe3O4Nano-particle；By adding tetraethoxysilane, make magnetic Fe3O4Particle surface covers silicon dioxide layer；By using
Silane coupler aminopropyl triethoxy silica alkane（Abbreviation APTES）Prepare the Fe of surface amino groups modification3O4- SiO2 @
NH2Magnetic particle, Fe3O4- SiO2@ NH2With anthraquinone sulfonic acid chlorine（Abbreviation AQSCl）Reacted under conditions of triethylamine does acid binding agent
Prepare.Anthraquinone amboceptor is fixed on magnetic Fe by chemical bonding3O4On nano-particle, due to the particle diameter chi of nano-particle
It is very little small, it is fully contacted with microorganism beneficial to amboceptor, be conducive to the biodegradation of the more preferable catalytic environment pollutant of the functional material.
Magnetic functional material can make its displacement by externally-applied magnetic field, and then realize its separation and recovery and recycle, both effectively
Avoid secondary pollution, and recoverable, with good economy.
Using above-mentioned technical proposal produce beneficial effect be：（1）Quinone amboceptor magnetic Nano material prepared by the present invention
Its extracting and developing and recovery can be realized by externally-applied magnetic field, effectively solve water-soluble quinonyl amboceptor and outflow with water and make
Into secondary pollution and continuously add the increased problem of cost；（2）Anthraquinone amboceptor of the present invention is fixed on magnetic in the form of being chemically bonded
Property nano-particle on, because the surface area of nano-particle is big, the load factor of anthraquinone amboceptor can be improved, and then realize its height catalysis
Efficiency.
Brief description of the drawings
Fig. 1 is the infrared spectrum of quinone amboceptor functional material prepared by embodiment 1, and wherein A represents Fe3O4- SiO2@ NH2, B
Anthraquinone sulfonic acid chlorine is represented, C represents the infrared spectrum of FeSi-AQS；
Fig. 2 is the comparison chart of the quinone amboceptor functional material catalysis acceleration Azo dye decol of preparation in embodiment 1, wherein ■ generations
The data of table blank group a1, ● the data of control group b1 are represented, ▲ represent the data of experimental group c1；
Fig. 3 a and 3b are respectively the Fe of preparation in embodiment 13O4The transmission electricity of magnetic nano-particle and FeSi-AQS magnetic particles
Mirror figure.
Specific embodiment
Embodiment 1
A, Fe is prepared by chemical precipitation method3O4Magnetic nano-particle
FeCl is added in 250mL four-hole bottles3·6H2O（4.70g, 17.4mmol）、FeCl2·4H2O（1.72g, 8.7mmol）
With 80mL redistilled waters, 80 DEG C are slowly heated to after ultrasonic 30min, dissolve to obtain orange solution；Then 10mL ammonia is added
Water, solution is changed into black, and stirring reaction 30min at once.After reaction terminates, neutrality, magnetic are washed till with distilled water and absolute ethyl alcohol
Directly by gained hygrometric state Fe after separation3O4Nano-particle is transferred in the sodium citrate solution of 200mL 0.3mol/L, ultrasonic disperse
Open, and 12h is stirred at room temperature, washed solid product three times using redistilled water.Freeze-drying prepares black powder
Last Fe3O4Magnetic particle.
B, in Fe3O4Wrap up SiO in magnetic nano-particle outer surface2Layer
By 60mg Fe3O4It is scattered in the mixed solvent of water and absolute ethyl alcohol, sequentially adds 1mL tetraethoxysilanes
（TEOS）With 7mL ammoniacal liquor, under room temperature under nitrogen atmosphere after stirring reaction 5h, product Magneto separate, absolute ethyl alcohol and redistilled water
Washing three times is simultaneously vacuum dried, and obtains the magnetic nano-particle Fe of Silica-coated3O4- SiO2.Mixed solvent reclaimed water and nothing
The volume ratio of water-ethanol is 1:4.
C、Fe3O4- SiO2Amino is modified in magnetic particle outer surface
6mL APTES, 1.5mL ammoniacal liquor is dissolved in absolute ethyl alcohol, and in Fe3O4Disperse 100mg Fe in the absolute ethyl alcohol3O4-
SiO2Magnetic particle, ultrasonic 30min is 1 after 12h, products therefrom volume ratio is reacted under 70 DEG C of nitrogen atmospheres:4 water and ethanol
Mixed solvent washing, Magneto separate, vacuum drying obtain Fe3O4- SiO2@ NH2Magnetic particle.
D, grafting anthraquinone -2- sulfonyls
Anthraquinone -2- sulfonic acid chlorides are prepared first：By 2.5g anthraquinone-2-sodiums（AQS）It is dissolved in 150mL dichloromethane, ultrasound
30min, to 40 DEG C, rotor is at the uniform velocity stirred down heating water bath, condensing reflux, after reaching design temperature, is measured 4 mL chlorosulfonic acids and is put
In constant pressure funnel, dropwise it is added dropwise, continues to stir, after condensing reflux 6h, be cooled to room temperature, mixed liquor is poured slowly into steaming
In distilled water, point liquid goes water phase, then by organic phase distillation water washing 3 times is last dry organic phase 12h with anhydrous magnesium sulfate after, revolve
Dichloromethane is steamed, yellow solid AQSCl is obtained.
Then, 5mL triethylamines are placed in there-necked flask, uniform stirring, heating water bath adds 0.118g to 30 DEG C
Fe3O4- SiO2@ NH2, weigh 0.9200gAQSCl and be dissolved in 130mL chloroforms, constant pressure funnel fully is poured into after dissolving, by
In dropping to flask（In 30min）, clock reaction 4h.Product dichloromethane and distilled water respectively washing 3 times, drying obtain anthracene
The magnetic particle of quinone modification（FeSi-AQS）.
By anthraquinone-modified magnetic particle manufactured in the present embodiment, Fe3O4- SiO2@ NH2Particle and anthraquinone-2-sodium
Infrared spectrum analysis is carried out respectively, referring to Fig. 1.The infrared spectrum of the front and rear magnetic particle of AQS modifications can be contrasted from figure,
The characteristic absorption peak of AQS is increased in the infrared spectrum of FeSi-AQS, it was demonstrated that AQS has successfully been grafted to Fe3O4- SiO2@
NH2On magnetic particle.
To the Fe prepared in step A3O4The FeSi-AQS magnetic particles prepared in magnetic particle and step D carry out pattern
Analysis, participates in Fig. 3, Fe3O4The particle diameter of magnetic particle is about 10nm, is still nano material through anthraquinone-modified FeSi-AQS.
Application Example 1
In order to verify the catalysis efficiency of FeSi-AQS, Setup Experiments blank group, control group and experimental group verify FeSi-AQS antithesis
The influence of nitrogen biodegradation behavior.
First, using the acclimation method for stepping up dye strength, the azo dye that can degrade is tamed out from mud sample
Expect the mixed bacterial of Reactive Brilliant Red K-2BP.Take thalline of the 10mL in exponential phase and be inoculated into 200mL LB degraded culture mediums
In, at 35 DEG C, shaking speed treats that bacterium solution reaches 0.8A in 600nm absorbances to cultivate 12h under conditions of 140 r/min
The research that microorganism biological reduces Azo dye decol is carried out during left and right.
Design three groups of experiments：Take three numbering be a1, b1 and c1 300mL serum bottles.1. to the serum bottle that numbering is a1
Add LB degraded culture mediums（Without inoculated bacteria）The FeSi-AQS magnetic ions prepared with 18mg embodiments 1 are used as blank group；②
To numbering be above-mentioned culture is added in the serum bottle of b1 bacterium solution as a control group；3. it is to be added in the serum bottle of c1 to numbering
The FeSi-AQS magnetic ions of bacterium solution and 18mg embodiments 1 preparation of culture are stated as experimental group.Active red dye in three groups of experiments
The initial concentration of material is 200 mg/L.All serum bottles are sealed into bottle with serum cap and aluminium-plastic cap, it is ensured that maintained in serum bottle
Anaerobic environment.
3mL is sampled every 2h, the dilution of centrifuging and taking supernatant is bent by standard after its absorbance is determined under 540nm wavelength
The concentration of line computation dyestuff, and then obtain dyestuff degradation rate situation.Numbering is the biology of the corresponding azo dyes of a1, b1 and c1 group
The percent of decolourization situation that changes with time is as shown in Figure 2.As can be seen from the figure because the addition of FeSi-AQS magnetic particles is catalyzed
Accelerate the biological decolouring efficiency of azo dyes.
Embodiment 2
A, Fe is prepared by chemical precipitation method3O4Magnetic nano-particle
FeCl is added in 250mL four-hole bottles3·6H2O（2.70g, 10mmol）、FeCl2·4H2O（0.99g, 5mmol）With
80mL redistilled waters, are slowly heated to 70 DEG C after ultrasonic 30min, dissolve to obtain orange solution；Then 8mL ammoniacal liquor is added simultaneously
Stirring reaction 30min.After reaction terminates, neutrality is washed till with distilled water and absolute ethyl alcohol, directly by gained hygrometric state after Magneto separate
Fe3O4Nano-particle is transferred in the sodium citrate solution that 200mL concentration is 0.3mol/L, and ultrasonic disperse is opened, and is stirred at room temperature
Reaction 10h is mixed, solid product is washed three times using redistilled water.Freeze-drying prepares black powder Fe3O4Magnetic grain
Son.
B, in Fe3O4Wrap up SiO in magnetic nano-particle outer surface2Layer
By 100mg Fe3O4It is scattered in the mixed solvent of water and absolute ethyl alcohol, sequentially adds 1mLTEOS and 6mL ammoniacal liquor, room
Under warm nitrogen atmosphere after stirring reaction 6h, product Magneto separate, absolute ethyl alcohol and second distillation water washing three times are simultaneously vacuum dried,
Obtain the magnetic nano-particle Fe of Silica-coated3O4- SiO2.The volume ratio of mixed solvent reclaimed water and absolute ethyl alcohol is 1:1.
C、Fe3O4- SiO2Amino is modified in magnetic particle outer surface
6 mLAPTES and 1.5mL ammoniacal liquor are dissolved in absolute ethyl alcohol, 100mg Fe3O4- SiO2Magnetic particle is scattered in dissolving
In the ethanol solution of APTES and ammoniacal liquor, ultrasonic 30min is after reacting 12 h, products therefrom water under 70 DEG C of nitrogen atmospheres
And ethanol（Volume ratio 1:3）Mixed solvent washing, Magneto separate, vacuum drying obtain Fe3O4- SiO2@ NH2Magnetic particle.
D, grafting anthraquinone -2- sulfonyls
Anthraquinone -2- sulfonic acid chlorides are prepared first：It is identical with the method in embodiment 1, unlike：The amount of chlorosulfonic acid is 4mL.
Then, 5mL triethylamines are placed in there-necked flask, uniform stirring, heating water bath adds 118mg to 30 DEG C
Fe3O4- SiO2@ NH2, weigh 920mgAQSCl and be dissolved in 100mL chloroforms, constant pressure funnel fully is poured into after dissolving, dropwise
In dropping to flask（In 30min）, react 5h.Product dichloromethane and distilled water respectively washing 3 times, drying obtain FeSi-AQS
Magnetic particle.
Application Example 2
Using the acclimation method for stepping up perchlorate concentration, the mixed of the perchlorate that can degrade is tamed out from mud sample
Close flora.Take thalline of the 10mL in exponential phase to be inoculated into 200mL perchlorate degraded culture medium, at 35 DEG C, shake
Bed rotating speed treats that bacterium solution absorbance reaches 0.3 to cultivate 12h under conditions of 140r/min（λ=600nm）During left and right, chlorine high is added
Sour sodium simultaneously makes its initial concentration be 50mg/L.
3 300 mL serum bottles are taken, numbering is a2, b2 and c2 respectively.By above-mentioned flora and the mixed solution of perchlorate
It is dispensed into the serum bottle that numbering is b2, c2, the FeSi-AQS magnetic grain of the preparation of 20mg embodiments 2 is additionally added in wherein c2 bottles
Son, numbering be a2 serum bottle in add perchlorate degraded culture medium（Without inoculated bacteria）With the FeSi-AQS magnetic of 20mg
Particle and sodium perchlorate, and make sodium perchlorate initial concentration be 50mg/L.All serum bottles are sealed with serum cap and aluminium-plastic cap
Bottle, it is ensured that anaerobic environment is maintained in serum bottle.
Sample at regular intervals, using ion chromatography ClO4- concentration, calculate perchlorate degradation rate.By than
Compared with experimental group and control group, as a result show FeSi-AQS magnetic materials in itself to the perchlorate no degradation of drop, but its
Catalysis significantly accelerates ClO4 -Biological reducing.
Embodiment 3
Fe is prepared by chemical precipitation method3O4Magnetic nano-particle.FeCl is added in 250mL four-hole bottles3·6H2O（2.70g,
10mmol）、FeCl2·4H2O（0.99g, 5mmol）With 80mL redistilled waters, 70 °C are slowly heated to after ultrasonic 30min, so
After add 8mL ammoniacal liquor and stirring reaction 30min.After reaction terminates, neutrality is washed till with distilled water and absolute ethyl alcohol, after Magneto separate
Directly by gained hygrometric state Fe3O4Nano-particle is transferred in the sodium citrate solution that 200mL concentration is 0.3mol/L, ultrasonic disperse
Open, and reaction 10h is stirred at room temperature, washed solid product three times using redistilled water.Freeze-drying prepares black
Color powder Fe3O4Magnetic particle.
By 100mg Fe3O4It is scattered in the mixed solvent of water and absolute ethyl alcohol, sequentially adds 1.5mLTEOS and 8mL ammonia
Water, under room temperature under nitrogen atmosphere after stirring reaction 6h, product Magneto separate, absolute ethyl alcohol and second distillation water washing three times and vacuum
Dry, obtain the magnetic particle Fe of Silica-coated3O4- SiO2。
By 6mLAPTES, 1.5mL ammoniacal liquor and 100mg Fe3O4- SiO2Be scattered in absolute ethyl alcohol, ultrasonic 30min after
12h, products therefrom water and ethanol are reacted under 70 DEG C of nitrogen atmospheres（1:4）Mixed solvent washing, Magneto separate is vacuum dried
To Fe3O4- SiO2@ NH2。
By 2.5g anthraquinone-2-sodiums（AQS）Be dissolved in 150mL dichloromethane, ultrasonic 30min, heating water bath to 40 DEG C,
Rotor is at the uniform velocity stirred down, condensing reflux, after reaching design temperature, is measured 6mL chlorosulfonic acids and is placed in constant pressure funnel, is dropwise dripped
Plus, continue to stir, after condensing reflux 6h, room temperature is cooled to, mixed liquor is poured slowly into distilled water, point liquid water phase, organic phase
With water washing is distilled 3 times, after drying organic phase 12h with anhydrous magnesium sulfate, dichloromethane is rotated, obtain yellow solid AQSCl.
5mL triethylamines are placed in there-necked flask, uniform stirring, heating water bath adds 100mg Fe to 30 DEG C3O4-
SiO2@ NH2, weigh 900mg AQSCl and be dissolved in 100mL chloroforms, constant pressure funnel fully is poured into after dissolving, dropwise drop to
In flask（In 30min）, react 5h.Product dichloromethane and distilled water respectively washing 3 times, drying obtain FeSi-AQS magnetic grain
Son.
Application Example 3
Take and be inoculated into 200mL Shewanella culture mediums in 10mL Shewanella liquid, at 35 DEG C, shaking speed is 140r/
12h is cultivated under conditions of min, sodium selenite is added and is made its initial concentration be 1mmol/L.
3 300mL serum bottles are taken, numbering is a3, b3 and c3 respectively.Above-mentioned flora is equal with the mixed solution of selenite
It is even to be dispensed into during numbering is b3 and c3 serum bottles, the FeSi-AQS magnetic particles of 20mg are added in wherein c3 bottles.In serum bottle a3
Add Shewanella culture medium（Without inoculated bacteria）The 20mgFeSi-AQSS magnetic particles and selenous acid prepared with embodiment 3
Sodium, makes the concentration of sodium selenite for 1mmol/L, as blank group；B2 is control group, and c3 is experimental group.All serum bottles are used
Serum cap and aluminium-plastic cap envelope bottle, it is ensured that anaerobic environment is maintained in serum bottle.
Sample at regular intervals, by inductivity coupled plasma mass spectrometry（ICP-MS）The concentration of selenite radical is determined,
Calculate the degradation rate of selenite radical.By comparative experiments group c3 and control group b2 and blank group, as a result show FeSi-AQS functions
The addition of material catalysis significantly accelerates the biological reducing of selenite radical.
In sum, FeSi-AQS magnetic particles can realize its extracting and developing and recovery by externally-applied magnetic field, effectively
Water-soluble quinonyl amboceptor is solved to outflow with water and cause secondary pollution and continuously add the increased problem of cost.FeSi-AQS magnetic
Property particle has effectively been catalyzed bio-degradation reactions.
Claims (10)
1. a kind of magnetic quinone amboceptor nano-functional material, it is characterised in that it is with nanometer Fe3O4Particle be magnetic kernel, with non-
Crystalline state SiO2It is subshell, in Fe3O4- SiO2Outer surface be modified with amino, anthraquinone -2- sulphurs are grafted with the amino
The magnetic Nano functional material of acyl group.
2. the preparation method of magnetic quinone amboceptor nano-functional material described in a kind of claim 1, it is characterised in that including following step
Suddenly：
A, preparation Fe3O4Magnetic nano-particle：With FeCl3And FeCl2For raw material is configured to solution, 40-80 DEG C is heated slowly to, plus
Enter ammoniacal liquor, stirring 10min-2h, washing, then by the Fe of hygrometric state3O4It is transferred in sodium citrate solution, ultrasonic disperse, washs, system
Obtain Fe3O4Magnetic nano-particle；
B, in Fe3O4Wrap up SiO in magnetic nano-particle outer surface2Layer：By Fe3O4Magnetic nano-particle is scattered in water and absolute ethyl alcohol
Mixed solution in, sequentially add tetraethoxysilane and ammoniacal liquor, under nitrogen atmosphere after stirring reaction 1-8h, washed product,
Dry, obtain Fe3O4-SiO2Magnetic particle；
C, amido modified Fe3O4-SiO2Particle：By aminopropyl triethoxy silica alkane and Fe3O4-SiO2Magnetic particle is scattered in
In absolute ethyl alcohol, products therefrom is separated, washed, done by ultrasonic 10min-2h after 3-24h is reacted under 30-70 DEG C of nitrogen atmosphere
It is dry, obtain amido modified Fe3O4-SiO2@NH2Magnetic particle；
D, grafting anthraquinone sulfonyl：By the Fe3O4-SiO2@NH2Magnetic particle is dispersed in triethylamine and the mixing of carbon dichloride is molten
In liquid, the carbon dichloride solution of anthraquinone sulfonic acid chloride is subsequently adding, reacts 3-24h, FeSi-AQS magnetic particles are obtained.
3. the preparation method of magnetic quinone amboceptor nano-functional material according to claim 2, it is characterised in that in step A
FeCl3And FeCl2Mol ratio be 2:1, the concentration of sodium citrate solution is 0.1-1.0 mol/L.
4. the preparation method of magnetic quinone amboceptor nano-functional material according to claim 2, it is characterised in that institute in step B
It is 1 that mixed solution reclaimed water is stated with the volume ratio of absolute ethyl alcohol:1-10.
5. the preparation method of magnetic quinone amboceptor nano-functional material according to claim 4, it is characterised in that step B reclaimed waters
It is 1 with the volume ratio of absolute ethyl alcohol:4-10.
6. the preparation method of magnetic quinone amboceptor nano-functional material according to claim 2, it is characterised in that ammonia in step C
Base propyl-triethoxysilicane oxygen alkane and Fe3O4-SiO2The mass ratio of magnetic particle is 1:1-3.
7. the preparation method of magnetic quinone amboceptor nano-functional material according to claim 2, it is characterised in that step B and C
Middle washing volume ratio is 1:The water of 1-10 and the mixed liquor of absolute ethyl alcohol.
8. the preparation method of magnetic quinone amboceptor nano-functional material according to claim 2, it is characterised in that anthracene in step D
The synthetic method of quinone sulfonic acid chloride is：Sodium anthraquinone sulfonate is weighed to be dissolved in dichloromethane, heating water bath to 40-50 DEG C, condensing reflux,
Measure chlorosulfonic acid to be placed in constant pressure funnel, dropwise completion of dropping, after condensing reflux 6-7h, be cooled to room temperature, by organic phase
Distillation water washing 3 times, after anhydrous magnesium sulfate dries organic phase, rotates dichloromethane, obtains anthraquinone sulfonic acid chloride.
9. the preparation method of magnetic quinone amboceptor nano-functional material according to claim 8, it is characterised in that chlorosulfonic acid with
The mol ratio of sodium anthraquinone sulfonate is 2-10:1.
10. application of the magnetic quinone amboceptor nano-functional material described in claim 1 in the biodegradation of catalytic environment pollutant.
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