CN109663601A - Load the application in the preparation method and its removal microcystic aeruginosa of nano material BiOBr/ fabric - Google Patents
Load the application in the preparation method and its removal microcystic aeruginosa of nano material BiOBr/ fabric Download PDFInfo
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- CN109663601A CN109663601A CN201910008874.4A CN201910008874A CN109663601A CN 109663601 A CN109663601 A CN 109663601A CN 201910008874 A CN201910008874 A CN 201910008874A CN 109663601 A CN109663601 A CN 109663601A
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- Prior art keywords
- fabric
- biobr
- nano material
- frustule
- microcystic aeruginosa
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- 239000004744 fabric Substances 0.000 title claims abstract description 137
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001963 growth medium Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 241000195493 Cryptophyta Species 0.000 claims description 47
- 230000034994 death Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 6
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 5
- 230000003698 anagen phase Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims 1
- 239000002775 capsule Substances 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 230000012010 growth Effects 0.000 abstract description 13
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- 239000000049 pigment Substances 0.000 abstract description 9
- 150000002632 lipids Chemical class 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 35
- 229930002868 chlorophyll a Natural products 0.000 description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 235000021466 carotenoid Nutrition 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 150000001747 carotenoids Chemical class 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 108010004469 allophycocyanin Proteins 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 10
- 241000894007 species Species 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 108010053210 Phycocyanin Proteins 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 108010004729 Phycoerythrin Proteins 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
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- 238000010672 photosynthesis Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 108090000623 proteins and genes Proteins 0.000 description 8
- 102000004169 proteins and genes Human genes 0.000 description 8
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- 230000008569 process Effects 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 241000192710 Microcystis aeruginosa Species 0.000 description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 108020004414 DNA Proteins 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 238000009395 breeding Methods 0.000 description 4
- 230000001488 breeding effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000004060 metabolic process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 230000004792 oxidative damage Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000006907 apoptotic process Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229930002875 chlorophyll Natural products 0.000 description 2
- 235000019804 chlorophyll Nutrition 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KBPHJBAIARWVSC-RGZFRNHPSA-N lutein Chemical compound C([C@H](O)CC=1C)C(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\[C@H]1C(C)=C[C@H](O)CC1(C)C KBPHJBAIARWVSC-RGZFRNHPSA-N 0.000 description 2
- 229960005375 lutein Drugs 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 108060006184 phycobiliprotein Proteins 0.000 description 2
- XJMOSONTPMZWPB-UHFFFAOYSA-M propidium iodide Chemical compound [I-].[I-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 XJMOSONTPMZWPB-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- FJHBOVDFOQMZRV-XQIHNALSSA-N xanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C=C(C)C(O)CC2(C)C FJHBOVDFOQMZRV-XQIHNALSSA-N 0.000 description 2
- 235000008210 xanthophylls Nutrition 0.000 description 2
- NNMALANKTSRILL-LXENMSTPSA-N 3-[(2z,5e)-2-[[3-(2-carboxyethyl)-5-[(z)-[(3e,4r)-3-ethylidene-4-methyl-5-oxopyrrolidin-2-ylidene]methyl]-4-methyl-1h-pyrrol-2-yl]methylidene]-5-[(4-ethyl-3-methyl-5-oxopyrrol-2-yl)methylidene]-4-methylpyrrol-3-yl]propanoic acid Chemical compound O=C1C(CC)=C(C)C(\C=C\2C(=C(CCC(O)=O)C(=C/C3=C(C(C)=C(\C=C/4\C(\[C@@H](C)C(=O)N\4)=C\C)N3)CCC(O)=O)/N/2)C)=N1 NNMALANKTSRILL-LXENMSTPSA-N 0.000 description 1
- 241000143060 Americamysis bahia Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000192700 Cyanobacteria Species 0.000 description 1
- 102000053602 DNA Human genes 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 244000071493 Iris tectorum Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 241000192701 Microcystis Species 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000003149 assay kit Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
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- 229910052564 epsomite Inorganic materials 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229960004642 ferric ammonium citrate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000003859 lipid peroxidation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229940118019 malondialdehyde Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
-
- 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
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention provides a kind of preparation method for loading nano material BiOBr/ fabric, is specifically dissolved in KBr, and fabric is added, and stirs to get mixed solution A；By Bi (NO3)3·5H2It in the aqueous acetic acid that O is dissolved in, then will be added in mixed solution A, stir at room temperature, ultrasound is stood, and load nano material BiOBr/ fabric can be prepared by taking out drying.Application of the load nano material BiOBr/ fabric being prepared on removal microcystic aeruginosa.Under conditions of illumination, BiOBr/ fabric passes through O in consumption culture medium2And the free radical of strong oxidizing property is generated in BiOBr particle surface, to polyunsaturated fatty acid depth degradation and oxidation on photosynthetic pigments, phycobniliprotein and cell membrane, photosynthetic function is caused to collapse, albumen biosynthesis block, Cell membrane lipids peroxidating, so that destroying frustule inhibits frustule growth.
Description
Technical field
The present invention relates in a kind of preparation method for loading nano material BiOBr/ fabric and its removal microcystic aeruginosa
Using belonging to technical field of water pollution control.
Background technique
Algal tufa is frequently broken out as the reservoir of potable water source district and lake in recent years, microcystic aeruginosa is many reservoirs and lake
Pool breaks out the advantage algae in algal tufa.Cyanobacteria algal tufa brings a series of serious influences, if low dissolved oxygen causes fishes and shrimps dead, produces
Raw toxic odor, destroys the normal circulation of the ecosystem, also will have a direct impact on drinking water treatment systems, not only cause serious warp
Ji loss, and the health of the mankind is seriously endangered, so there is an urgent need to find a kind of reliable method to remove nocuousness
Algae.Currently, common minimizing technology has mechanical salvaging, UF membrane, chemical algae removing agent, flocculation and photocatalysis.In these processing
In, photocatalysis is considered as one of most promising method, and at low cost, ecological risk is small.
As a kind of visible light-responded photochemical catalyst, BiOBr is because having unique layered structure and high chemical stability
It is attracted wide attention in environmental treatment field.Guo and Jiang etc. is by BiOBr and magnetic material Fe3O4Or CoFe2O4It is compound,
Wish to act on by external magnetic force and collect, but since little particle cannot rapidly make a response to magnetic field, when the later period being caused to be collected
Between it is long.The BiOBr of the preparations such as the Cao and Ag of the preparations such as the compound floating material of nitridation silicon foam and Hou3PO4/ZnFe2O4/ empty
Heart floating bead complex pretreatment, needs high-temperature process, time-consuming.
Summary of the invention
The present invention selects the visible light catalyst BiOBr of high activity, prepares the photocatalysis of float type using fabric as template
Agent BiOBr/ fabric, and BiOBr/ fabric is subjected to photocatalysis destruction to microcystic aeruginosa.Using the methods of XRD, SEM couple
BiOBr/ fabric is characterized, and research under visible light, removes verdigris to BiOBr/ fabric under the conditions of photochemical catalyst dosage, pH etc.
The influence of Microcystis aeruginosa effect is based on effect data, and obtaining BiOBr/ fabric has efficient application value on removal microcystic aeruginosa.
Based on this, the present invention provides the preparation method of load nano material BiOBr/ fabric, includes the following steps:
(1) in being dissolved in KBr, and fabric is added, stirs to get mixed solution；
(2) by Bi (NO3)3·5H2In the aqueous acetic acid that O is dissolved in, the mixed solution of step (1) then will be added to
In, it stirs at room temperature, ultrasound is stood, and load nano material BiOBr/ fabric can be prepared by taking out drying.
The KBr and Bi (NO3)3·5H2The concentration ratio of O is 1:0.8-1.2；And KBr and Bi (NO3)3·5H2O's is dense
Degree is 0.01mol/L-0.11mol/L.In preferred embodiment, KBr and the Bi (NO of addition3)3·5H2The concentration of O is respectively
0.09mol/L。
The fabric includes cotton fabric, burlap fabric, chemical & blended fabric, any one or more in blended fabric
Mixing.
The volumetric concentration of the aqueous acetic acid is 5-10%.
Another technical solution of the invention is to be applied to go by the load nano material BiOBr/ fabric being prepared
Except on microcystic aeruginosa.
Specific application method includes the following steps: that in pH value be 7-8, and 20-30 DEG C and illumination are 1500-2500Lx condition
Under, microcystic aeruginosa is added into the culture medium to sterilize respectively, adds load nano material BiOBr/ fabric, is put into illumination
Incubator 2-20d removes microcystic aeruginosa.
The density of the microcystic aeruginosa is 1.0 × 106-1.0×107Cells/mL, microcystic aeruginosa include in pair
The frustule in number growth period and death phase.The density of microcystic aeruginosa described in preferred embodiment is 2.0 × 106Cells/mL,
Microcystic aeruginosa includes the frustule in death phase.
The additive amount of the load nano material BiOBr/ fabric is 0.01mol/L-0.11mol/L.
Fabric is the most abundant natural resources on the earth, because it is with thermal stability, flexibility, light-weight, cheap
The advantages that and be concerned.The present invention will load microcystic aeruginosa in nano material BiOBr/ fabric degradation water body, as a result, it has been found that
Photocatalysis and fixed dual function may be implemented.
BiOBr/ fabric is removed the effect of microcystic aeruginosa by technical solution of the present invention under visible light.Work as reaction precursor
The BiOBr/ fabric that object concentration is prepared when being 0.09mol/L is best to the removal effect of microcystic aeruginosa, finds simultaneously, in algae
Locating period be death phase, illumination and reaction pH when being faintly acid BiOBr/ fabric it is maximum to Microcystis aeruginosa chlorophyll a removal rate.
Physical signs, dissolved oxygen and the active specy during microcystic aeruginosa, and association reaction are removed by measurement BiOBr/ fabric
The surface texture of front and back Microcystis aeruginosa Strains changes and the change of cell membrane integrity, is concluded that in illumination
Under the conditions of, BiOBr/ fabric passes through O in consumption culture medium2And the free radical of strong oxidizing property is generated in BiOBr particle surface, to light
Polyunsaturated fatty acid depth degradation and oxidation on conjunction pigment, phycobniliprotein and cell membrane, cause photosynthetic function to collapse, and albumen closes
At being obstructed, Cell membrane lipids peroxidating inhibits frustule to grow to destroy frustule.
Detailed description of the invention
Fig. 1 is the XRD diagram of fabric, BiOBr/ fabric and BiOBr.
Fig. 2 is the XRD diagram of fabric (a) and BiOBr/ fabric (b).
Fig. 3 is the Uv-Vis DRS spectrum (a) and (α h ν) of sample2- h ν schemes (b).
(a) BiOBr/ fabric load amount variation diagram in Fig. 4；(b) shadow of the difference BiOBr load capacity to chlorophyll a removal rate
It rings.
Fig. 5 is influence of the BiOBr/ fabric in different algal species growth period to chlorophyll a removal rate.
Fig. 6 is BiOBr/ fabric in dark and influence of the illumination to chlorophyll a removal rate.
Fig. 7 is the influence that water body pH removes chlorophyll a to BiOBr/ fabric.
Fig. 8 is influence of the BiOBr/ fabric to chlorophyll a and carotenoid removal rate；(Chla- chlorophyll a；Caro-
Carotenoid).
Fig. 9 is influence of the BiOBr/ fabric to phycobniliprotein removal rate；(PC- phycocyanin；APC- allophycocyanin；PE-
Phycoerythrin).
Figure 10 is influence of the BiOBr/ fabric to soluble protein removal rate.
Figure 11 is influence of the BiOBr/ fabric to MDA removal rate.
Figure 12 is BiOBr/ fabric except dissolved oxygen variation during algae.
Figure 13 is BiOBr/ fabric except the active specy during algae captures experiment.
Figure 14 is microcystic aeruginosa frustule SEM figure；(a)-(b) before BiOBr/ fabric treating；(c)-(d) BiOBr/ fabric
After processing.
Figure 15 is microcystic aeruginosa flow cytometer measurement chart；(a) before BiOBr/ fabric treating；(b) at BiOBr/ fabric
After reason.
Specific embodiment
Embodiment 1
Realize that reagent used in technical solution of the present invention and instrument are as follows:
Major experimental reagent: Bi (NO3)3·5H2O (northern joint-trial agent, AR)；KBr (three factory of Henan Jiaozuo city chemical industry, AR)；
NaOH (Ke Miou reagent, AR)；HCl (Xinyang chemical reagent factory, AR)；Glacial acetic acid (the sharp chemical reagent in Tianjin day, AR)；Iodine
Change the third pyridine (Propidium Iodide, PI) (Sigma Aldrich, AR).
Major experimental instrument: superclean bench (SW-CJ-1F, Wujiang Wei Feng cleaning equipment Co., Ltd)；High pressure sterilization
Pot (SYQ-DSY-280B, Shenan Medical Appliances Factory, Shanghai)；(PGX-250B, Ningbo sea daybreak match Buddhist laboratory apparatus to illumination box
Factory)；Ultraviolet-visible spectrophotometer (UV-Vis DRS, Lambda25, the U.S.)；PH meter (Delta 320, Mettler-
Toledo, Shanghai Co., Ltd)；X-ray diffractometer (XRD, D/max2500, Rigaku, Japan)；Awkward silence at a meeting scanning electron microscopy
Mirror (SEM, JSM-7500F, JEOL, Japan)；Flow cytometer (BD FACSVerse, USA)；Portable dissolved oxygen instrument (HACH
HQ30d5330100,USA)。
The preparation of BiOBr/ fabric
The synthesis of BiOBr/ fabric uses Hydrolyze method, weighs concentration respectively first than KBr and the Bi (NO for 1:13)3·
5H2O, KBr are dissolved in the water of 20mL and are added thereto the fabric of 2 × 2cm (0.07g), Bi (NO3)3·5H2O is dissolved in
In aqueous acetic acid of the 20mL containing 9% volume, then the latter is added in the former, stirs 4h, ultrasonic 30min at room temperature, stood
1h takes out dry at 60 DEG C.
The crystalline form of BiOBr/ fabric is measured using X-ray diffractometer, and 2 θ ranges of scanning are 20 ° -60 °；Awkward silence at a meeting scanning electron
The pattern of measurement microscope BiOBr/ fabric；Ultraviolet-visual spectrometer measures UV-vis DRS spectrum at room temperature.
Algae and culture
Microcystic aeruginosa (FACHB-905) is purchased from Chinese Academy of Sciences Wuhan aquatile research institute, using BG-11 culture medium in light
According to being expanded culture in incubator.Timing shakes 4-5 times and exchanges the placement position in illumination box daily in the training period
It sets, to reduce the even influence of uneven illumination.Cultivation temperature is 25 ± 1 DEG C, illumination 2000Lx, Light To Dark Ratio 12h:12h, entire to test
Operating process keeps sterile working.When algal grown to logarithmic phase (2 × 106Cells/mL it) takes out, 3000r/min's
It is centrifuged 10min under revolving speed, for the activity for guaranteeing frustule, the frustule being collected into is resuspended in the culture medium of BG-11
It is tested.
Include in the BG-11 culture medium of 1L: NaNO3(1.5g), K2HPO4(0.04g), Ferric ammonium
Citrate (0.006g), MgSO4·7H2O (0.075g), CaCl2·2H2O (0.036g), Citric acid (0.006g),
EDTA (0.001g), Na2CO3The A of (0.02g) and 1mL5Solution (H3BO4(2.86g),MnCl2·4H2O(1.81g),ZnSO4·
7H2O(0.222g),CuSO4·5H2O(0.079g),Na2MoO4·2H2O(0.39g),Co(NO3)2·6H2O(0.0494g)。
BiOBr/ fabric is except algae experiment under different physico chemical factors
The influence of different BiOBr load capacity: during preparing BiOBr/ fabric, guarantee KBr and Bi (NO3)3·5H2O
The concentration ratio 1:1 of addition is constant, so that the KBr and Bi (NO that are added3)3·5H2The concentration of O be respectively 0.01mol/L,
0.03mol/L, 0.05mol/L, 0.07mol/L, 0.09mol/L and 0.11mol/L, material prepared are named as BiOBri/
Fabric, i=1,3,5,7,9,11.
It is 7.5 that pH value is controlled in experiment, and temperature is 25 DEG C, illumination 2000Lx.The culture medium to sterilize respectively to 200mL
The middle frustule in logarithmic growth phase that equivalent is added, so that initial algae density is 2.0 × 106Cells/mL is put into illumination
Incubator tests 3d, and using the removal rate of chlorophyll a as evaluation criterion, 2 repetitions are arranged in each experimental group.
The influence of different algal species growth period: the culture medium after taking 200mL to sterilize is added raw in logarithm into culture medium
Long-term and death phase frustule, initial pH value 7.5, temperature are 25 DEG C, light intensity 2000Lx, BiOBr/ fabric dosage one
It is fixed, it is put into illumination box experiment 3d, using the removal rate of chlorophyll a as evaluation criterion, 2 repetitions are arranged in each experimental group.
The influence of illumination: it is thin that the algae in logarithmic growth phase is added into culture medium for the culture medium after taking 200mL to sterilize
Born of the same parents, so that initial algae density is 2.0 × 106Cells/mL, initial pH value 7.5, temperature are 25 DEG C, BiOBr/ fabric dosage
Centainly, illumination box experiment 18d, setting dark and two groups of experiments of illumination are put into, are evaluation mark with the removal rate of chlorophyll a
2 repetitions are arranged in standard, each experimental group.
The influence of pH: the initial algae density 2.0 × 10 of algae solution is kept6Cells/mL is constant, and temperature is 25 DEG C, light intensity
2000Lx, BiOBr/ fabric dosage are certain.Four processing group initial pH values are adjusted to 1mol/LHCl and 1mol/LNaOH
PH=5.5,6.5,7.5,8.5,9.5,10.5 no longer adjust the pH value of culture solution in experimentation.Experimental period is 3d, with leaf
The removal rate of green element a is evaluation criterion, and 2 repetitions are arranged in each experimental group.
BiOBr/ fabric is influenced on frustule physical signs and removal mechanisms at work
Culture medium after taking 200mL to sterilize the frustule for being in logarithmic growth phase is added into culture medium, so that initial algae
Density is 2.0 × 106Cells/mL, initial pH value 7.5, temperature are 25 DEG C, and BiOBr/ fabric dosage is certain, is put into illumination
Incubator tests 18d.By the chlorophyll a, carotenoid, phycobniliprotein, soluble protein and the malonaldehyde that measure frustule
The variation of content reflects BiOBr/ fabric to the shadow of frustule biomass, photosynthesis, physiological metabolism and oxidative damage respectively
It rings.
By monitoring except the type of the dissolved oxygen variation and active specy of culture medium during algae, and except frustule after algae
Pattern variation discloses BiOBr/ fabric to the removal mechanisms at work of frustule with cell membrane integrity.
The measuring method of index
The measurement of chlorophyll a and carotenoid content: taking 10mL algae solution 5000r/min to be centrifuged 5min, remove supernatant,
95% isometric ethyl alcohol is added into precipitating, is stayed overnight at 4 DEG C, then 5000r/min is centrifuged 5min, takes supernatant spectrophotometric
Value at 665,649 and 470nm of meter measurement.The calculation formula of chlorophyll a and carotenoid content is as follows:
Chla (mg/L)=13.7 × A665-5.76×A649
Caro (mg/L)=(1000 × A470-2.05×Chla)/245
The measurement of Phycobiliprotein Content: taking 5mL algae solution, and 10000r/min is centrifuged 10min, removes supernatant, and 5mL phosphorus is added
Acid buffer (0.05mol/L, pH value 7.0).The ultrasound 120s (working time 3s, off time 2s) on Ultrasonic Cell Disruptor, 4
At DEG C overnight, then 12000r/min is centrifuged 10min.Take the value at 650,620 and 565nm of supernatant spectrophotometric determination.
The calculation formula of phycocyanin (PC), allophycocyanin (APC) and phycoerythrin (PE) content is as follows:
PC=(A620-0.7×A650)/7.38
APC=(A650-0.19×A620)/5.65
PE=(A565-2.8×PC-1.34×APC)/1.27
The measurement of soluble protein and mda content: taking 20mL algae solution, and 10min is centrifuged under 5000r/min, and it is thin to collect algae
Born of the same parents are added the phosphate buffer 1mL (pH=7.8) of 0.05mol/L, utilize ultrasonic cell disruption instrument ice bath smudge cells
10min (work 5s, gap 20s therebetween), microscopy are without 10min, supernatant is centrifuged after intact cell under 12000r/min
Crude enzyme liquid.The protein content of Bioengineering Research Institute is built up in the measurement of soluble protein content and mda content referring to Nanjing
Assay kit (article No.: A045-2) and Malondialdehyde Kit (article No.: A003-1) specification carry out.
The measurement of dissolved oxygen: by BiBOr9/ fabric is added to the 2.0 × 10 of 200mL6It, will every 3d in cells/mL algae solution
Dissolved oxygen instrument probe, which is inserted into the algae solution of control group and processing group, measures dissolved oxygen content, measures 3 times, is averaged.
The detection of active specy: four conical flasks are taken, are added the 2.0 × 10 of 200mL in each conical flask6cells/mL
Algae solution and BiBOr9/ fabric.It is separately added into benzoquinones (BQ 1mM), isopropanol (IPA1mM) and second in three conical flasks thereto again
Ethylenediamine tetraacetic acid (EDTA) (EDTA1mM) reacts 18d, takes a sample every 3d, measures chlorophyll a value.
Frustule surface texture observation: untreated blank algae solution and addition BiOBr/ fabric treating after taking 100mL to react
Algae solution be centrifuged 10min at 4000r/min, discard supernatant liquid, the glutaraldehyde that 1mL2% is added into the frustule of collection is solid
Determine frustule 2h, is then cleaned 3 times with the phosphate buffer of 1mL0.1mol/L (pH=6.8), each 10min.Then 1mL is used
50%, 70%, 90% Gradient elution using ethanol 15min, 100% ethanol dehydration 2 times, each 30min, drying sample.Test sample
When sample is glued on sample stage with two-sided, observed and clapped under scanning electron microscope to after sample gold-plated film with ion sputtering instrument
According to.
The test of frustule film integrality: propidium iodide is a kind of nuclei dyeing color reagent that can be dyed to DNA.It is a kind of
The analog of Ethidum Eremide discharges red fluorescence after being embedded in double-stranded DNA.PI cannot penetrate intact cell film, but dead cell and
Damaged state is presented in its cell membrane of cell in apoptosis advanced stage, and PI molecule can penetrate, and incarnadine nucleus.It takes
Microcystic aeruginosa liquid each 1mL, 4000r/min the centrifugation 5min of after BiOBr/ fabric treating and normal growth breeding, discards
Clear liquid is added ultrapure water and cleans 2 times, and centrifugation discards supernatant liquid, and 1mL ultrapure water is added to be uniformly mixed.Add the PI solution of 61L
(1mg/mL), so that the ultimate density being added is 65.2mg/L.15min is dyed in dark, flow cytometer is detected using FL2
Device detection, data are analyzed using BD FACSuite Software software.
Fig. 1 is the XRD spectrum of fabric, BiOBr/ fabric and BiOBr.From Fig. 1 it can be found that BiOBr XRD spectrum with
Standard card PDF#09-0393 is corresponding, goes out at 25.19 °, 32.33 °, 39.78 °, 46.36 °, 57.26 °, 67.89 ° and 77.13 °
Existing characteristic peak, respectively corresponds (101), (110), (112), (200), (212), (220) and (310) crystal face.After load
BiOBr/ fabric has BiOBr characteristic diffraction peak compared with the XRD spectrum of BiOBr, illustrates successfully to incite somebody to action according to the method for the present invention
BiOBr is carried on fabric.
Fig. 2 is the SEM figure of fabric and BiOBr/ Fabric composites.It can be seen that unsupported BiOBr's from Fig. 2 (a)
The structure of three dimensional intersection circular tube shaped is presented in fabric, exists without apparent cake mass, and surface is smooth.It is load in Fig. 2 (b)
SEM after BiOBr schemes, and distributed the BiOBr nano particles of many whites on smooth fibre pipe, and the adsorbance of fabric depends on
The concentration of BiOBr precursor solution.Fabric has loose porous structure, can not only increase the contact surface of BiOBr and algae
Product, while absorption and removal ability can be enhanced, reach fabric and the synergistic effect of BiOBr, is conducive to the removal of algae.
UV-Vis DRS analysis
Fig. 3 is the UV-vis DRS figure of fabric and BiOBr/ fabric, is known by Fig. 3 a in 200-700nm wave band,
There is not characteristic absorption peak in the uv-vis spectra of fabric, but loads the fabric after BiOBr and increase in 500nm or less absorption intensity
Greatly.Compared with fabric, the absorption edge of BiOBr/ fabric has apparent red shift, and absorption edge 450nm illustrates that BiOBr/ is knitted
Visible light can be absorbed in object.It is reported that BiOBr has narrow forbidden bandwidth, can be calculated forbidden bandwidth by Fig. 3 b is
2.76eV。
The influence of different BiOBr load capacity
As shown in fig. 4 a, in the BiOBr presoma of various concentration, fabric is knitted with the increase of BiOBr precursor concentration
The adsorbance of BiOBr is gradually increased on object, and when the concentration of BiOBr presoma is 0.09mol/L, the adsorbance on fabric is gradually
Reach adsorption equilibrium.
The BiOBr/ fabric synthesized under different BiOBr precursor concentrations test except algae.As a result as shown in Figure 4 b, when
The precursor concentration of BiOBr is synthesized in 0.09mol/L or less, with the increase of BiOBr precursor concentration, microcystic aeruginosa
Chlorophyll a removal efficiency is constantly accelerated, this is because making to participate in reaction with the increase of BiOBr precursor concentration when synthesis
Effective catalyst concentration constantly increases, to improve reaction rate.When the precursor concentration of synthesis BiOBr is greater than 0.09mol/
When L, cluster is excessive on the fabric for BiOBr particle when causing to load, and the penetrability for not only reducing visible light leads to the scattering of light,
Also resulting in BiOBr particle, bad dispersibility influences photocatalytic activity on the fabric, so that not increasing removal efficiency tends to be flat
It is slow, therefore, select BiOBr9/ fabric carries out subsequent except algae is studied.
The influence of algae different growing stage
The growth of microcystic aeruginosa can be simulated with four different phases: lag period, logarithmic phase, stationary phase and death
Phase, due to the influence that the great variety and organic matter of cell number dissolve, this experiment only studies BiOBr/ fabric to algal grown
The effect of logarithmic phase and death phase.From Fig. 5 it can be found that the microcystic aeruginosa chlorophyll a removal rate of death phase during the reaction
It is consistently higher than logarithmic phase, respectively 43.55% and 30.12%.The chlorophyll a of frustule is easier in death phase than logarithmic phase
It removes, mainly due to the bioactivity of the frustule of different stages of growth, extracellular metabolism organic matter (Extracellular
Organic matters, EOM) component and morphologic difference.Furthermore the frustule of death phase leads to portion due to aqtocytolysis
Divide frustule natural death, the process of frustule death is promoted after addition BiOBr/ fabric.And the frustule growth of logarithmic phase
It flushes, metabolism is fast, and the secretion of frustule release is to BiOBr/ fabric except algae generates certain side effect.
The influence of illumination
Absorption and photocatalysis are two main process for realizing microcystic aeruginosa inactivation.Before photocatalysis, catalysis
Agent should complete the capture to frustule, this is determined by the characterization of adsorption of catalyst.Fig. 6 gives in dark reaction and illumination item
Removal effect of the BiOBr/ fabric to microcystic aeruginosa under part.Under the conditions of dark reaction, BiOBr/ fabric is reached by suction-operated
To a small amount of removal, the removal rate of chlorophyll a is 9.96%.And when illumination, the removal rate of chlorophyll a has reached 70.05%, says
Mingguang City influenced according to the removal rate on chlorophyll a it is significant, this is because BiOBr/ fabric relies solely on absorption and reaches under the conditions of dark reaction
To a small amount of removal, and under illumination condition, the active specy that photochemical catalyst BiOBr/ fabric generates can be with attack verdigris micro-capsule
The cell of algae accelerates the death of cell.
The influence of pH
The pH in China major part lake is generally in alkalinity, and in lake eutrophication development process, lake water pH present with
Algal grown and the trend significantly increased, this is because the CO in algae photosynthesis consumption water body2Hydrogen ion in water is caused to subtract
Few, pH is increased.
Different pH (5.5-10.5) conditions are set in experiment, investigate water body pH to BiOBr/ fabric removal microcystic aeruginosa
It influences, as a result as shown in fig. 7, BiOBr/ fabric has inhibiting effect to the growth of microcystic aeruginosa under difference pH.Wherein pH=
Inhibiting effect is maximum under the conditions of 5.5, and as pH > 5.5, chlorophyll a removal rate is successively reduced.It is primarily due to BiOBr/ fabric
Zero potential be 5.83, algae solution pH value size directly affects the electrically charged distribution of BiOBr/ fabric surface, to influence
To the removal effect of microcystic aeruginosa under different pH condition.When pH value is 5.5, the surface BiOBr is positively charged, verdigris micro-capsule
Algae surface is negatively charged, since electrostatic interaction facilitates absorption of the BiOBr/ fabric to microcystic aeruginosa, thus improves removal rate.
When pH value is in 5.5-10.5 range, the interface between the negatively charged influence of one side BiOBr/ fabric surface and microcystic aeruginosa is electric
Lotus reaction, to influence the removal efficiency of microcystic aeruginosa.On the other hand, the alkalescent frustule fitted closer to algal grown
Activity is higher, bigger with BiOBr collision rate, injures caused by frustule itself stronger.
Chlorophyll a and carotenoid
Chlorophyll a and carotenoid are main photosynthetic pigments in Microcystis aeruginosa Strains, chlorophyll-a concentration can between
The biomass of the reflection microcystic aeruginosa connect.Fig. 8 is BiOBr/ fabric to chlorophyll a and carotenoid removal rate figure, from Fig. 8
In it can be found that with reaction progress, the microcystic aeruginosa Determination of Chlorophyll a of BiOBr/ fabric treating and containing for carotenoid
Amount is substantially reduced, and to when reacting 18d, the removal rate of chlorophyll a is 70.05%, the removal rate 57.34% of carotenoid.This
As a result illustrate that the photosynthesis of microcystic aeruginosa is severely impacted, and BiOBr/ fabric is big to the coercion of chlorophyll a
In carotenoid.This is mainly due to carotenoid not only to have outside certain function in photosynthesis, can also absorb
Extra luminous energy, quenching activity oxygen prevent frustule membrane lipid peroxidatio, protect chlorophyll and photosynthetic function, and verdigris micro-capsule
Photosynthetic pigments in algae have different sensibility, the class Hu trailing plants of sensibility difference in photosynthesis to the stress of BiOBr/ fabric
Bu Su can compensate the loss as caused by sensitive pigment, chlorophyll a.
Phycobniliprotein
Phycobilin is a kind of important photosynthesis accessory pigments, it forms phycoerythrin in conjunction with soluble protein
(PE), the Light energy transfer absorbed is used for light to chlorophyll by phycocyanin (PC), allophycocyanin (APC), this 3 kinds of albumen
Cooperation is used.Fig. 9 has reacted influence of the BiOBr/ fabric to frustule Phycobiliprotein Content, during reaction, although algae red
Albumen, phycocyanin, allophycocyanin are affected, but allophycocyanin, by maximum is influenced, phycocyanin is secondary
It, influences phycoerythrin minimum.Wherein, when reacting 18d, allophycocyanin removal rate reaches 90.33%, phycocyanin removal
Rate reaches 83.56%, and phycoerythrin removal rate reaches 60.55%.
Soluble protein
Other than these photosynthetic pigments of chlorophyll a, carotenoid and phycobniliprotein, what is contained in microcystic aeruginosa body can
Dissolubility albumen is also the index for maintaining the metabolism of frustule normal physiological, and the variation of content also can reflect the growth shape of frustule
Condition.As shown in Figure 10, consistent with the variation of chlorophyll a, with the progress of reaction, the intracorporal soluble protein removal rate of frustule
Lasting to rise, to when reacting 18d, removal rate has reached 59.8%.This is because the active specy generated during the reaction is such as
OH and superoxide radical lead to cell inclusion soluble protein depth degradation, inhibit frustule survival.
Malonaldehyde
Malonaldehyde is the final product of frustule lipid peroxidation, generate quantity number represent cell membrane lipid
The degree of matter peroxidating also reflects membranous system oxidative damage degree indirectly.
Figure 11 is influence of the BiOBr/ fabric to frustule cell membrane, it can be found that the content of malonaldehyde is presented from Figure 11
The trend fallen after rising.The 12d from starting to reacting, MDA content rise to 16.2nmol.mg/TSP by 8.3nmol.mg/TSP,
13.5nmol.mg/TSP is reduced to by 16.2nmol.mg/TSP from 12d to 18d, MDA content is reacted.This be primarily due to
Oxidative degradation of the polyunsaturated fatty acid in cell membrane of the progress frustule of reaction, cause mda content to increase.Instead
It should terminate, it is the cell dead since frustule film has disintegrated at this time that mda content, which reduces,.
Variation of the BiOBr/ fabric to the research dissolved oxygen of frustule removal mechanisms at work
Microcystic aeruginosa, which carries out photosynthesis on daytime, can release oxygen, so that content of oxygen dissolved in water be made to increase.It is logical
Cross measurement blank algae solution and BiOBr/ fabric treating algae solution Oxygen releasing, the survival state of indirect observation algae, as a result
As shown in figure 12.Plus in the algae solution of BiOBr/ fabric dissolved oxygen does not gradually rise with the extension of time as seen from Figure 12,
The content of the processing group dissolved oxygen of BiOBr/ fabric is added as the time continues to decline, photosynthetic oxygen evolution ability reduces 81.5%.
It could therefore be concluded that BiOBr/ fabric inhibits the photosynthesis of microcystic aeruginosa, to inhibit the growth and breeding of algae.
Except the active specy measurement during algae
The chief active species generated during microcystic aeruginosa are removed under light illumination in order to inquire into BiOBr/ fabric, are being removed
It is separately added into EDTA, BQ, IPA capturing agent during algae, to the photohole (h generated in reaction process+), superoxide radical
It is captured with OH.As shown in figure 13, it is added after different capturing agents and affects removing for BiOBr/ fabric to a certain extent
Algae effect.The algae chlorophyll a removal rate that any capturing agent is not added wherein is 70.06%, EDTA and IPA capturing agent pair is added
BiOBr/ fabric photocatalysis process of inhibition only generates minimal effect, and influences significant, removal rate 42.23% after BQ is added.It says
The bright species of chief active during the reaction are superoxide radical, are made after BQ is added due to its capture to superoxide radical
Chlorophyll a removal rate reduces.It secondly is EDTA, chlorophyll a removal rate is 51.97%, and removal rate 62.54% after IPA is added.
A large amount of free radicals are generated by redox mode when BiOBr/ fabric and frustule act on, into frustule after break
Its bad ordered structure and normal metabolic function cause function impaired.Wherein superoxide radical has occurs instead with large biological molecule
It answers, so that inducing cell damages, and superoxide radical can form other reactive oxygen compounds during the reaction, these changes
The oxidative damage of lipid, protein and DNA can be promoted by closing object.
Structure of cell surface observation
The metamorphosis of frustule is as shown in figure 14 in photocatalytic process.Figure 14 a and Figure 14 b are the copper of normal growth breeding
Green microcystis, cell surface are full, smooth.Figure 14 c and Figure 14 d are that the microcystic aeruginosa after BiOBr/ fabric treating is thin
Born of the same parents, after reaction 18d is shown in Figure 14 c, part BiOBr granular absorption is on frustule surface.Find that a large amount of patterns are endless in Figure 14 d
Whole frustule, some cell walls are cracked, badly broken.
Frustule pattern, which is badly damaged mainly, has two parts reason to cause, and one side photon intensity is excessive, on the other hand
BiOBr/ fabric generated during light-catalyzed reaction Strong oxdiative ability active oxygen (Reactive Oxygen Species,
ROS).Excessive photon intensity can quickly enhance the generation of ROS in frustule chloroplaset, so as to cause photosynthetical system by light
Inhibit the photooxidation with pigment.When ROS increases to a certain extent, water-water circulation will be triggered, and activate the anti-oxidant of frustule
System.By the way that extra electronics is transferred to photosynthetical system I (PSI) from photosyntheticsystemⅱ (PS II), active oxygen is reduced into water,
Realize the purpose for preventing Xanthophyll cycle and removing ROS.However, with photocatalysis generate active oxygen increase, electron-transport by
Inhibit.To sum up, after frustule wall is impaired, frustule can in high oxidation stress in environment, to accelerate the destruction of cell, and
And under Xanthophyll cycle and photocatalysis, the photosynthetic pigments in frustule are aoxidized by active oxygen, ineffective.
Frustule apoptosis situation
Using the integrality of Microcystis aeruginosa Strains film after flow cytomery BiOBr/ fabric treating, as a result such as Figure 15
It is shown.Figure 15 a is the microcystic aeruginosa of normal growth breeding, since the cell membrane of normal frustule is not destroyed, PI points
Son cannot be introduced into the cell, so negative status is presented in PI molecule, having 98.03% frustule is living cells.Figure 15 b is
Microcystis aeruginosa Strains after BiOBr/ fabric treating, PI molecule almost all are in positive, i.e. PI molecule enters frustule
Interior and incarnadine in conjunction with the base-pair of intracellular DNA, dead frustule reaches 99.91%.The result illustrates BiOBr/ fabric
There is very strong destruction to frustule film, so as to cause its death.
Claims (8)
1. loading the preparation method of nano material BiOBr/ fabric, which comprises the steps of:
(1) in being dissolved in KBr, and fabric is added, stirs to get mixed solution；
(2) by Bi (NO3)3·5H2In the aqueous acetic acid that O is dissolved in, then it will be added in the mixed solution of step (1), room
The lower stirring of temperature, ultrasound are stood, and load nano material BiOBr/ fabric can be prepared by taking out drying.
2. the preparation method of load nano material BiOBr/ fabric according to claim 1, which is characterized in that described
KBr and Bi (NO3)3·5H2The concentration ratio of O is 1:0.8-1.2；And KBr and Bi (NO3)3·5H2The concentration of O is 0.01 mol/L-
0.11 mol/L。
3. the preparation method of load nano material BiOBr/ fabric according to claim 1, which is characterized in that described knits
Object includes cotton fabric, burlap fabric, chemical & blended fabric, the mixing of any one or more in blended fabric.
4. the preparation method of load nano material BiOBr/ fabric according to claim 1, which is characterized in that the vinegar
The volumetric concentration of aqueous acid is 5-10%.
5. the load nano material BiOBr/ fabric being prepared described in -4 any one according to claim 1 is micro- in removal verdigris
Application on capsule algae.
6. application according to claim 5, which comprises the steps of: pH value be 7-8,20-30 DEG C and light
Under the conditions of for 1500-2500 Lx, microcystic aeruginosa is added into the culture medium to sterilize respectively, adds load nanometer material
Expect BiOBr/ fabric, be put into illumination box 2-20d, removes microcystic aeruginosa.
7. application according to claim 6, which is characterized in that it is characterized in that, the density of the microcystic aeruginosa is
1.0×106 -1.0×107Cells/mL, microcystic aeruginosa include the frustule in logarithmic growth phase and death phase.
8. application according to claim 6, which is characterized in that it is characterized in that, the load nano material BiOBr/
The additive amount of fabric is 0.01 mol/L-0.11 mol/L.
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| CN112588306A (en) * | 2020-11-30 | 2021-04-02 | 山东理工大学 | Magnetically separable composite photocatalyst BiOBr/CoFe2O4And preparation method and application thereof |
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