CN114405552B - Difunctional fiber membrane for promoting Fenton reaction and preparation method thereof - Google Patents
Difunctional fiber membrane for promoting Fenton reaction and preparation method thereof Download PDFInfo
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- CN114405552B CN114405552B CN202210138528.XA CN202210138528A CN114405552B CN 114405552 B CN114405552 B CN 114405552B CN 202210138528 A CN202210138528 A CN 202210138528A CN 114405552 B CN114405552 B CN 114405552B
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- bismuth vanadate
- molybdenum sulfide
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- fenton reaction
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- 239000000835 fiber Substances 0.000 title claims abstract description 105
- 239000012528 membrane Substances 0.000 title claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 91
- 230000001737 promoting effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 14
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 103
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 103
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002033 PVDF binder Substances 0.000 claims abstract description 40
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 29
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 28
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims description 108
- 238000009987 spinning Methods 0.000 claims description 67
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 56
- 229940043267 rhodamine b Drugs 0.000 claims description 56
- 239000002351 wastewater Substances 0.000 claims description 46
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 230000001588 bifunctional effect Effects 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 13
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- 229920005594 polymer fiber Polymers 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 25
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 239000002121 nanofiber Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 238000002386 leaching Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 210000001170 unmyelinated nerve fiber Anatomy 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
- 238000001523 electrospinning Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001621 bismuth Chemical class 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
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- -1 transition metal sulfide Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000131 polyvinylidene Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a bi-functional fiber membrane for promoting Fenton reaction and a preparation method thereof, wherein molybdenum sulfide and bismuth vanadate are simultaneously introduced into a Fenton system, and Mo in the molybdenum sulfide 4+ Fe is added to 3+ Reduction to Fe 2+ ，Mo 4+ Itself is oxidized to Mo 6+ Bismuth vanadate generates photo-generated electrons under the irradiation of visible light, and the photo-generated electrons further add Mo 6+ Reduction to Mo 4+ Mo is realized on the basis of not consuming hydrogen peroxide additionally 6+ /Mo 4+ Is a normal cycle of (2); the simultaneous introduction of molybdenum sulfide and bismuth vanadate plays the dual functions of a reducing agent and a photocatalyst, and ensures considerable Fe in a Fenton system 2+ Thereby improving the utilization rate of hydrogen peroxide; the polymer fiber membrane carrying the bismuth vanadate is prepared from the raw materials of molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate by adopting an electrostatic spinning technology, is integral, has good flexibility and excellent mechanical properties, is difficult to leach and run off compared with the powder of the molybdenum sulfide and the bismuth vanadate, is easier to process and form, and has a wide application range.
Description
Technical Field
The invention relates to the technical field of a difunctional fiber membrane for promoting Fenton reaction and a preparation method thereof, in particular to a difunctional fiber membrane for promoting Fenton reaction and a preparation method thereof.
Background
The traditional Fenton oxidation technology has the advantages of mild reaction conditions, non-toxicity of reagents, simple equipment structure, convenient operation, small device investment and the like, and is widely concerned in organic wastewater treatment research, but the traditional Fenton oxidation technology also has some disadvantages, such as low hydrogen peroxide utilization rate, large Fenton reagent consumption, large iron mud production, high wastewater treatment cost and the like, and the popularization and application of the Fenton technology are greatly limited. From the Fenton reaction formula, the reaction rate of reducing ferric ions into ferrous ions is the slowest, and the method is a rate control step, and aims to solve the problems of large Fenton reagent consumption and large iron sludge production, and mainly aims to improve the reaction rate of the step of ferrous ion regeneration. In recent years, the literature has accelerated the rate of reduction of ferric ions to ferrous ions by adding organic substances having complexing functions and reducing properties. The addition of the organic matters can promote the reduction of ferric iron to a certain extent and improve Fe 3+ /Fe 2+ The cycle efficiency of the iron sludge is effectively reduced; however, these organic substances themselves also generate a certain TOC, so that the overall TOC removal rate is not high, and these organic substances are decomposed by hydrogen peroxide, so that this accelerating effect is difficult to keep stable as the reaction proceeds. Compared with organic matters, inorganic matters have better stability in Fenton systems, so that the search of inorganic matters for promoting the reduction of ferric iron and further improving Fenton oxidation efficiency is widely focused.
Molybdenum sulfide (MoS) 2 ) The semiconductor material is a graphene-like layered structure, the layers are connected by weak van der Waals force, and the layers are formed by covalent bonds of an S-Mo-S three-atomic-layer structure. The crystal structure of the molybdenum sulfide has three types of 1T, 2H and 3R, wherein the 1T and 3R are metastable, the 2H type is stable in normal state, and the unique physical properties are different from other materials, and the molybdenum sulfide has been applied to various fields such as catalysis, photovoltaics, lubricating oil and the like. The band gap of bulk molybdenum sulphide is only 1.17eV, the photo-generated electrons (e - ) And cavity (h) + ) Is easily composited and has limited application in photocatalytic processes. However, as a layered transition metal sulfide with various crystal structures, the edge structure of molybdenum sulfide is complex, and the molybdenum sulfide has the characteristics of high unsaturation, high reactivity and the like, and has application potential in the field of catalysis. There is literature on the use of molybdenum sulfide (MoS 2 ) As a cocatalyst to increase the efficiency of Fenton reaction, reduced Mo with exposed molybdenum sulfide surface 4+ Promote Fe 3+ /Fe 2+ Is excellent in iron ion cycle efficiency and lower in Fe 2+ The dosage effectively inhibits the generation of iron mud. In this process, mo in a reduced state 4+ Oxidized to Mo 6+ To hold Mo 6+ /Mo 4+ Is H in Fenton system 2 O 2 Mo is added with 6+ Reduction to Mo 4+ . It can be seen that promoting Fe 3+ /Fe 2+ Is to consume H 2 O 2 At the cost, the benefit of the iron ion circulation is offset to a certain extent, and the cost of treating wastewater by Fenton reaction is not reduced. Bismuth vanadate has been widely paid attention as a semiconductor type visible light catalyst because of its characteristics of non-toxicity, special physical and optical properties, excellent chemical and light stability, and the like. Bismuth vanadate mainly has 3 crystal forms: tetragonal zircon structure, monoclinic scheelite structure and tetragonal scheelite structure, wherein monoclinic bismuth vanadate (m-BiVO 4 ) The forbidden bandwidth is 2.3-2.4eV, has excellent response in a visible light region, can generate photo-generated electrons under the irradiation of visible light, and can be used for degrading organic pollutants. Bismuth vanadate is further introduced into the molybdenum sulfide-Fenton system, and the bismuth vanadate is utilized to react under the irradiation of light to generate photo-generated electrons (e - ) For Fe 3+ 、Mo 6+ Reduction is carried out, and is hopeful to solve the problem of Fe 3+ /Fe 2+ 、Mo 6+ /Mo 4+ The recycling problem is solved, thereby reducing the generation of iron mud and improving H 2 O 2 The utilization rate of the hydroxyl radical is improved, and the cost of wastewater treatment is reduced. Vulcanization in most studiesMolybdenum and bismuth vanadate exist in a system in a powder form, and although the catalytic effect is excellent, the catalyst is difficult to recover and is easy to run off, so that researchers have proposed to load bismuth vanadate on conductive glass to fix molybdenum sulfide or bismuth vanadate. The patent CN 201610002369.5 is prepared by dissolving molybdenum-containing salt (such as sodium molybdate and the like) in an alcohol solution of a sulfur-containing source (such as thiourea), adding a substrate material, loading the substrate material into a hydrothermal kettle, solvothermal for 6-24h at 180-230 ℃, and taking out, cleaning and drying the substrate to obtain the molybdenum sulfide in-situ electrode. Patent CN201811518486.2 synthesizes MoS by one-step hydrothermal method 2 CNTs composite and then applying a drop coating to MoS 2 the/CNTs composite is deposited on FTO conductive glass to make a counter electrode. Patent CN201310078273.3 uses Bi (NO) 3 ) 3 ·5H 2 Bismuth vanadate colloid prepared from O-acetic acid solution and vanadyl acetylacetonate-acetylacetone solution is spin-coated on clean ITO conductive glass, and is baked to obtain the nano bismuth vanadate film. Patent CN 201310033856.4 uses Bi (NO) 3 ) 3 ·5H 2 O and NH 4 VO 3 And (3) preparing a precursor solution by taking citric acid, acetic acid and ethanolamine as auxiliary solvents, and obtaining the bismuth vanadate film on the conductive glass substrate by adopting a chemical solution deposition method. Patent CN 201710203262.1 uses nitric acid and boric acid to regulate Bi (NO 3 ) 3 ·5H 2 O and NH 4 VO 3 The mixed solution forms amorphous BiVO on the substrate by electrostatic adsorption self-assembly and layer-by-layer assembly technology 4 A film. Molybdenum sulfide or bismuth vanadate is loaded on conductive glass, so that the molybdenum sulfide or bismuth vanadate is conveniently separated from a solution system, the problem that molybdenum sulfide and bismuth vanadate are difficult to recover can be solved, but the problem that the molybdenum sulfide and bismuth vanadate are leached out and lost in a water body due to weak binding force between the molybdenum sulfide and bismuth vanadate and the conductive glass can not be overcome. The electrostatic spinning is a spinning technology for stretching and solidifying a polymer solution or melt into nanofibers by utilizing high electrostatic field force, and is a reliable technology for preparing the nanofibers, and the prepared nanofibers have the characteristics of small diameter, large specific surface area, multiple holes, good flexibility, excellent mechanical strength and the like, and are simple in device and low in manufacturing cost, and have been applied to the fields of filter membranes, catalysis, sensors, tissue engineering and the like in recent years. Polyvinylidene fluorideEthylene has excellent chemical stability, is resistant to acid and alkali corrosion at room temperature, has good tolerance to organic solvents such as hydrocarbons, alcohols and aldehydes, has high mechanical strength, has piezoelectricity, dielectric property, thermoelectric property and the like, and is widely used as a film material. By adopting an electrostatic spinning technology, the combination of molybdenum sulfide, bismuth vanadate and polyvinylidene fluoride is one of the ways for solving the leaching loss problem of the molybdenum sulfide and the bismuth vanadate. The patent CN 202110275000.2 firstly adopts an electrostatic spinning method to prepare a PVDF nanofiber film, and then synthesizes in-situ grown MoS on the surface of the PVDF nanofiber film by a hydrothermal method 2 Nanometer flower, and AuNPs is modified in MoS by adopting in-situ reduction reaction 2 Obtaining PVDF/MoS 2 AuNPS material. The patent CN 201710978781.5 takes polyacrylonitrile as a raw material, N, N-dimethylformamide as a solvent to prepare spinning solution, an electrospinning nanofiber is prepared by adopting an electrospinning method, then the electrospinning nanofiber is taken as a template, ethylene glycol and ethanol are taken as mixed solvents, bismuth nitrate, copper sulfate and ammonium metavanadate are taken as reaction precursors, and the copper-doped bismuth vanadate porous nanotube photocatalyst is obtained through washing, drying and roasting by a solution heating method. It is reported that a polyvinylidene fluoride fiber film is prepared by an electrostatic spinning method, a Ni (shell)/PVDF (core) coaxial fiber film having a core-shell structure is prepared by a chemical deposition method, and then manganese dioxide nano-flakes can be grown on the Ni/PVDF coaxial fiber film by a simple hydrothermal treatment. The above document is that the polymer nanofiber is prepared by the electrostatic spinning technology, then the inorganic material is loaded on the polymer fiber, the binding force between the inorganic material and the polymer is still weak, and the problem of loss cannot be solved fundamentally. The patent CN 201510947452.5 is characterized in that a polyacrylonitrile nanofiber membrane is prepared through electrostatic spinning, graphene oxide is wrapped on the polyacrylonitrile nanofiber through a solution soaking method, then a graphene/carbon nanofiber composite membrane is prepared through high-temperature carbonization, and finally molybdenum disulfide nanosheets are grown on the graphene/carbon nanofiber in situ through a one-step hydrothermal method, so that the molybdenum disulfide/graphene/carbon nanofiber composite material is prepared. The patent CN 201810573295.X firstly utilizes the electrostatic spinning technology to synthesize the carbon nano-fiber, then uses the carbon nano-fiber as a precursor, and containsCarrying out hydrothermal reaction in aqueous solution with molybdenum source and sulfur source to obtain MoS 2 The CNFs compound is annealed at high temperature to obtain MoS 2 CNFs composite. The patent aims to prepare carbon fiber and molybdenum sulfide composite materials, firstly, preparing polymer nanofibers through electrostatic spinning, then, carrying out heat treatment on the polymer nanofibers under inert atmosphere to obtain carbon nanofibers, and then, loading molybdenum sulfide on the carbon fibers, wherein the product is in a powder form, is not easy to recover when being used in a water phase, and has the problem of loss. The patent CN201310257173.7 takes organic vanadium salt and organic bismuth salt with good alcohol solubility as precursor reactants, and is mixed with polyvinylpyrrolidone and ethanol to prepare spinning solution, and the spinning solution is electrospun into filaments by an electrostatic spinning device, and then the filaments are baked at high temperature to obtain the vanadate nano photocatalyst. The patent CN 201911280662.8 disperses bismuth source and vanadium source in a mixed solvent composed of N, N-dimethylformamide, acetic acid and ethanol, then polyvinylpyrrolidone is added, the mixture is uniformly mixed to prepare spinning solution, then electrostatic spinning is carried out to obtain spinning product, and bismuth vanadate nanofiber is obtained after drying and calcining. The above patents are to blend soluble bismuth salt, soluble vanadate and polymer to make yarn, when there is no roasting treatment, bismuth vanadate and polymer are compounded in the form of fiber film, although the problem of loss can be overcome, but the formation of bismuth vanadate can not be ensured, and the crystal form of bismuth vanadate can not be ensured to be monoclinic phase, so that these patents all carry out roasting treatment on electrostatic spinning products; after the roasting treatment, the polymer is completely removed in the roasting process, the integral fiber membrane loaded with bismuth vanadate is not needed, and the rest is bismuth vanadate in powder form, so that the leaching loss problem cannot be solved. Therefore, for the traditional Fenton system, the material which has the advantages of excellent catalysis assisting effect, easy recovery, recycling, difficult leaching loss, simple preparation process and suitability for large-scale production has wide application prospect.
Disclosure of Invention
In order to achieve the above purpose, the present invention provides the following technical solutions: the double-function fiber membrane for promoting Fenton reaction consists of molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate; the mass content of the molybdenum sulfide is 5-10%, the mass content of the bismuth vanadate is 10-15%, the mass content of the polyvinylidene fluoride is 60-80%, and the mass content of the polymethyl methacrylate is 10-20%.
Preferably, the mass content of molybdenum sulfide is 8%, the mass content of bismuth vanadate is 12%, the mass content of polyvinylidene fluoride is 70%, and the mass content of polymethyl methacrylate is 10%.
Preferably, the molybdenum sulfide crystal structure is 2H type, and bismuth vanadate is monoclinic phase.
Preferably, the polyvinylidene fluoride is present in an amount of 20 to 60 g/mol.
A method for preparing a bifunctional fibrous membrane for promoting a Fenton reaction, comprising the steps of:
1) Ball milling is carried out on the molybdenum sulfide powder, and the particle size of the molybdenum sulfide powder after the ball milling is below 200 nm;
2) Ball milling is carried out on bismuth vanadate powder, and the particle size of the bismuth vanadate powder after the ball milling is below 200 nm;
3) Mixing the molybdenum sulfide powder obtained in the step 1 with the bismuth vanadate powder obtained in the step 2, and continuing ball milling for 2-6 hours;
4) Adding molybdenum sulfide and bismuth vanadate subjected to ball milling treatment in the step 3 into a mixed solution of N, N-dimethylacetamide and acetone according to a metering ratio, and performing ultrasonic treatment for 1 hour to form a solution A;
5) Adding polyvinylidene fluoride and polymethyl methacrylate into a mixed solution of N, N-dimethylacetamide and acetone according to a metering ratio, and performing ultrasonic treatment at 50 ℃ for 1 hour to form a solution B;
6) Slowly dripping the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain spinning solution;
7) And carrying out electrostatic spinning on the spinning solution to obtain a spinning product, and then drying the spinning product at the temperature of 4kPa and 90 ℃ for 12 hours to obtain a fibrous membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate.
Preferably, in the steps 4 and 5, the mass ratio of the N, N-dimethylacetamide to the acetone is 2:3, in the step 4, the mass content of the molybdenum sulfide in the solution A is 6%, the mass content of the bismuth vanadate is 9%, and in the step 5, the mass content of the polyvinylidene fluoride in the solution B is 12%.
Preferably, in step 7, the specific process of electrospinning is as follows:
adding spinning solution into an injector, wherein a needle of the injector is obliquely downward and connected with a high-voltage power supply anode, a low-speed roller wrapping release paper is used for collecting spinning products, the spinning products are placed under the injector obliquely, the low-speed roller is horizontally placed and grounded, the distance between the needle and a collecting plate is 10cm-20cm, the spinning voltage is set to 15kV-25kV in an environment with the relative humidity of 25% -45% at 20 ℃ -30 ℃, a constant-flow pump is started to control the flow rate of the spinning solution in the injector to be 1ml/h, and the spinning products can be collected, wherein the specific process of assisting the Fenton reaction is as follows: under the stirring state, ferrous sulfate heptahydrate is added into the wastewater solution, then dilute sulfuric acid is used for regulating the pH value of the solution, a bifunctional fiber membrane is added into the wastewater solution, after standing and adsorption balancing, hydrogen peroxide is added, fenton reaction is carried out under the irradiation of visible light, and organic pollutants in the wastewater are degraded.
The invention relates to a bi-functional fiber membrane for promoting Fenton reaction, which comprises the following specific processes: under the stirring state, ferrous sulfate heptahydrate is added into the wastewater solution, then dilute sulfuric acid is used for regulating the pH value of the solution, a bifunctional fiber membrane is added into the wastewater solution, after standing and adsorption balancing, hydrogen peroxide is added, fenton reaction is carried out under the irradiation of visible light, and organic pollutants in the wastewater are degraded.
Preferably, the dosage of the ferrous sulfate heptahydrate is 0.05-0.50mmol/L; the ratio of the hydrogen peroxide to the ferrous sulfate heptahydrate is 1.0-10.0; the dosage of the difunctional fiber film is 0.25-5.0g/L; the pH value of the solution is 2.0-6.0, and the concentration of the organic pollutants is 10-40mg/L; the organic pollutant is one or more of rhodamine B, phenol and N, N-dimethylformamide; the reaction time is 5-20 minutes.
Compared with the prior art, the invention provides the difunctional fiber membrane for promoting the Fenton reaction and the preparation method thereof, and the difunctional fiber membrane has the following beneficial effects:
1. the bi-functional fiber membrane for promoting Fenton reaction and the preparation method thereof are characterized in that molybdenum sulfide and bismuth vanadate are simultaneously introduced into a Fenton system, and Mo in the molybdenum sulfide 4+ Fe is added to 3+ Reduction to Fe 2+ Molybdenum sulfide plays a role of a reducing agent, and Mo 4+ Itself is oxidized to Mo 6+ Bismuth vanadate generates photo-generated electrons under the irradiation of visible light, and the photo-generated electrons further add Mo 6+ Reduction to Mo 4+ Mo is realized on the basis of not consuming hydrogen peroxide additionally 6+ /Mo 4+ At the same time, the photo-generated electrons can also generate Fe 3+ Reduction to Fe 2+ Remarkably promote Fe in Fenton system 3+ /Fe 2+ The bismuth vanadate plays a role of a photocatalyst; the simultaneous introduction of molybdenum sulfide and bismuth vanadate plays the dual functions of a reducing agent and a photocatalyst, and ensures considerable Fe in a Fenton system 2+ Thereby improving the utilization rate of hydrogen peroxide and effectively reducing the treatment cost of wastewater.
2. According to the bi-functional fiber membrane for promoting the Fenton reaction and the preparation method thereof, molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate are used as raw materials, and an electrostatic spinning technology is adopted to prepare the polymer fiber membrane loaded with the molybdenum sulfide and the bismuth vanadate.
3. According to the bi-functional fiber membrane for promoting the Fenton reaction and the preparation method thereof, the prepared polymer fiber membrane loaded with the molybdenum sulfide and the bismuth vanadate is embedded and anchored in the polymer nanofiber, the nanofiber is crosslinked and associated to form the fiber membrane, the binding force between the bismuth vanadate and the polymer is strong, the anti-scouring performance in water is obviously superior to that of the molybdenum sulfide or bismuth vanadate-based material prepared by the traditional technology, the problem that the molybdenum sulfide and the bismuth vanadate are easy to run off in the application process is solved, the polymer fiber membrane can be recycled, and the cost for treating wastewater by promoting the Fenton reaction is effectively reduced.
4. According to the bi-functional fiber membrane for promoting the Fenton reaction and the preparation method thereof, the polymethyl methacrylate is added into the polyvinylidene fluoride, so that the transparency of the polymer membrane is improved, the absorption rate of the fiber membrane to visible light is further promoted, and the Fenton reaction promoting effect is effectively improved.
Drawings
FIG. 1 shows the co-catalytic effect of the fiber membrane of sample A prepared in example 1, the fiber membrane of sample B prepared in comparative example 1, the fiber membrane of sample C prepared in comparative example 2 and the non-fibrous membrane on the treatment of rhodamine B wastewater by Fenton reaction;
FIG. 2 shows the Fe content of the fiber film of sample A, sample B, sample C and P-Fenton reaction system according to the present invention, wherein the fiber film is prepared in example 1, comparative example 2, and the P-Fenton reaction system is prepared without adding a fiber film 2+ Influence of concentration;
FIG. 3 shows leaching conditions of molybdenum sulfide and bismuth vanadate in a process of treating rhodamine B wastewater by promoting Fenton reaction in a sample A prepared in the embodiment 1 and a sample D prepared in the comparative example 3;
FIG. 4 shows the co-catalytic effect of the sample A fiber membrane prepared in example 1, the sample E fiber membrane prepared in comparative example 4, and no fiber membrane added on the treatment of rhodamine B wastewater by Fenton reaction;
FIG. 5 shows the co-catalytic effect of the fiber membrane of sample A prepared in example 1, the fiber membrane of sample F prepared in comparative example 5, and no fiber membrane added on the treatment of rhodamine B wastewater by Fenton reaction;
FIG. 6 shows the stability of the sample A fiber membrane prepared in example 1 of the present invention in the Fenton reaction treatment of rhodamine B wastewater.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to fig. 1-6, a first embodiment is presented:
(1) Ball milling is carried out on the molybdenum sulfide powder, and the particle size of the molybdenum sulfide powder after the ball milling is below 200 nm;
(2) Ball milling is carried out on bismuth vanadate powder, and the particle size of the bismuth vanadate powder after the ball milling is below 200 nm;
(3) Mixing 0.24g of molybdenum sulfide powder obtained in the step (1) with 0.36g of bismuth vanadate powder obtained in the step (2), and continuing ball milling for 5 hours;
(4) Adding molybdenum sulfide and bismuth vanadate subjected to ball milling treatment in the step (3) into a mixed solution of 1.6g of N, N-dimethylacetamide and 2.4g of acetone, and performing ultrasonic treatment for 1 hour to form a solution A;
(5) 2.1g of polyvinylidene fluoride and 0.3g of polymethyl methacrylate are added into a mixed solution of 7.0g of N, N-dimethylacetamide and 10.5g of acetone, and ultrasonic treatment is carried out for 1 hour at 50 ℃ to form a solution B;
(6) Slowly dripping the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain spinning solution;
(7) Carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding spinning solution into a syringe, connecting a syringe needle with a high-voltage power supply anode in a downward inclined manner, placing a low-speed roller wrapping release paper under the syringe in an inclined manner, horizontally placing the syringe and grounding the syringe, keeping the distance between the needle and a collecting plate at 15cm, setting the spinning voltage at 20kV in an environment with 25% of relative humidity, and starting a constant-current pump to control the flow rate of the spinning solution in the syringe to be 1 ml/hour to obtain the spinning product.
(8) The spinning product was dried at 90℃for 12 hours at 4kPa to give a fibrous membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate, labeled sample A.
Comparative example 1:
(1) Ball milling is carried out on the molybdenum sulfide powder, and the particle size of the molybdenum sulfide powder after the ball milling is below 200 nm;
(2) Adding 0.6g of molybdenum sulfide subjected to ball milling treatment into a mixed solution of 1.6g of N, N-dimethylacetamide and 2.4g of acetone, and performing ultrasonic treatment for 1 hour to form a solution A;
(3) 2.1g of polyvinylidene fluoride and 0.3g of polymethyl methacrylate are added into a mixed solution of 7.0g of N, N-dimethylacetamide and 10.5g of acetone, and ultrasonic treatment is carried out for 1 hour at 50 ℃ to form a solution B;
(4) Slowly dripping the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain spinning solution;
(5) Carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding spinning solution into a syringe, connecting a syringe needle with a high-voltage power supply anode in a downward inclined manner, placing a low-speed roller wrapping release paper under the syringe in an inclined manner, horizontally placing the syringe and grounding the syringe, keeping the distance between the needle and a collecting plate at 15cm, setting the spinning voltage at 20kV in an environment with 25% of relative humidity, and starting a constant-current pump to control the flow rate of the spinning solution in the syringe to be 1 ml/hour to obtain the spinning product.
(6) The spinning product was dried at 90℃for 12 hours at 4kPa to give a fibrous membrane containing molybdenum sulfide, polyvinylidene fluoride and polymethyl methacrylate, which was labeled as sample B.
Comparative example 2:
(1) Ball milling is carried out on bismuth vanadate powder, and the particle size of the bismuth vanadate powder after the ball milling is below 200 nm;
(2) Adding 0.6g of bismuth vanadate subjected to ball milling treatment into a mixed solution of 1.6g of N, N-dimethylacetamide and 2.4g of acetone, and performing ultrasonic treatment for 1 hour to form a solution A;
(3) 2.1g of polyvinylidene fluoride and 0.3g of polymethyl methacrylate are added into a mixed solution of 7.0g of N, N-dimethylacetamide and 10.5g of acetone, and ultrasonic treatment is carried out for 1 hour at 50 ℃ to form a solution B;
(4) Slowly dripping the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain spinning solution;
(5) Carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding spinning solution into a syringe, connecting a syringe needle with a high-voltage power supply anode in a downward inclined manner, placing a low-speed roller wrapping release paper under the syringe in an inclined manner, horizontally placing the syringe and grounding the syringe, keeping the distance between the needle and a collecting plate at 15cm, setting the spinning voltage at 20kV in an environment with 25% of relative humidity, and starting a constant-current pump to control the flow rate of the spinning solution in the syringe to be 1 ml/hour to obtain the spinning product.
(6) The spinning product was dried at 90℃for 12 hours at 4kPa to give a fibrous membrane containing bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate, labeled sample C.
Comparative example 3:
(1) Adding 2.1g of polyvinylidene fluoride and 0.3g of polymethyl methacrylate into a mixed solution of 7.0g of N, N-dimethylacetamide and 10.5g of acetone, and performing ultrasonic treatment at 50 ℃ for 1 hour to form a spinning solution;
(2) Carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding spinning solution into a syringe, connecting a syringe needle with a high-voltage power supply anode in a downward inclined manner, placing a low-speed roller wrapping release paper under the syringe in an inclined manner, horizontally placing the syringe and grounding the syringe, keeping the distance between the needle and a collecting plate at 15cm, setting the spinning voltage at 20kV in an environment with 25% of relative humidity, and starting a constant-current pump to control the flow rate of the spinning solution in the syringe to be 1 ml/hour to obtain the spinning product.
(3) And drying the spinning product at the temperature of 4kPa and 90 ℃ for 12 hours to obtain the polyvinylidene fluoride-polymethyl methacrylate composite fiber membrane.
(4) Dissolving 0.77g of anhydrous sodium molybdate, 0.29g of thiourea, 0.90g of bismuth nitrate pentahydrate and 0.22g of ammonium metavanadate in 40mL of deionized water, stirring and dissolving, continuing ultrasonic treatment for 0.5 hour, and transferring to a polytetrafluoroethylene-lined hydrothermal kettle;
(5) And (3) placing the fiber membrane prepared in the step (3) into a hydrothermal kettle, aging for 6 hours at 120 ℃, cooling, washing with deionized water for 3 times, and drying at 20kPa and 80 ℃ for 12 hours to obtain the molybdenum sulfide and bismuth vanadate deposited polyvinylidene fluoride and polymethyl methacrylate fiber membrane, wherein the sample is marked as a sample D.
Comparative example 4:
(1) Adding 0.77g of anhydrous sodium molybdate, 0.29g of thiourea, 0.90g of bismuth nitrate pentahydrate and 0.22g of ammonium metavanadate into a mixed solution of 1.6g of N, N-dimethylacetamide and 2.4g of acetone, and performing ultrasonic treatment for 1 hour to form a solution A;
(2) 2.1g of polyvinylidene fluoride and 0.3g of polymethyl methacrylate are added into a mixed solution of 7.0g of N, N-dimethylacetamide and 10.5g of acetone, and ultrasonic treatment is carried out for 1 hour at 50 ℃ to form a solution B;
(3) Slowly dripping the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain spinning solution;
(4) Carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding spinning solution into a syringe, connecting a syringe needle with a high-voltage power supply anode in a downward inclined manner, placing a low-speed roller wrapping release paper under the syringe in an inclined manner, horizontally placing the syringe and grounding the syringe, keeping the distance between the needle and a collecting plate at 15cm, setting the spinning voltage at 20kV in an environment with 25% of relative humidity, and starting a constant-current pump to control the flow rate of the spinning solution in the syringe to be 1 ml/hour to obtain the spinning product.
(5) The spinning product was dried at 90℃for 12 hours at 4kPa to give a fibrous membrane containing molybdenum salt, vanadium salt, bismuth salt, polyvinylidene fluoride and polymethyl methacrylate, which was labeled as sample E.
Comparative example 5:
(1) Ball milling is carried out on the molybdenum sulfide powder, and the particle size of the molybdenum sulfide powder after the ball milling is below 200 nm;
(2) Ball milling is carried out on bismuth vanadate powder, and the particle size of the bismuth vanadate powder after the ball milling is below 200 nm;
(3) Mixing 0.24g of molybdenum sulfide powder obtained in the step (1) with 0.36g of bismuth vanadate powder obtained in the step (2), and continuing ball milling for 5 hours;
(4) Adding molybdenum sulfide and bismuth vanadate subjected to ball milling treatment in the step (3) into a mixed solution of 1.6g of N, N-dimethylacetamide and 2.4g of acetone, and performing ultrasonic treatment for 1 hour to form a solution A;
(5) Adding 2.4g of polyvinylidene fluoride into a mixed solution of 7.0g of N, N-dimethylacetamide and 10.5g of acetone, and performing ultrasonic treatment at 50 ℃ for 1 hour to form a solution B;
(6) Slowly dripping the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain spinning solution;
(7) Carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding spinning solution into a syringe, connecting a syringe needle with a high-voltage power supply anode in a downward inclined manner, placing a low-speed roller wrapping release paper under the syringe in an inclined manner, horizontally placing the syringe and grounding the syringe, keeping the distance between the needle and a collecting plate at 15cm, setting the spinning voltage at 20kV in an environment with 25% of relative humidity, and starting a constant-current pump to control the flow rate of the spinning solution in the syringe to be 1 ml/hour to obtain the spinning product.
(8) The spinning product was dried at 90℃for 12 hours at 4kPa to give a fiber membrane containing molybdenum sulfide, bismuth vanadate and polyvinylidene fluoride, which was labeled as sample F.
Embodiment two:
the fiber membranes prepared in example 1, comparative example 2 and comparative example 3 were examined for their co-catalytic effect on the Fenton reaction treatment of rhodamine B wastewater.
Respectively weighing 0.5g of the sample A fiber membrane prepared in example 1, the sample B fiber membrane prepared in comparative example 1 and the sample C fiber membrane prepared in comparative example 2, putting the sample A fiber membrane and the sample B fiber membrane into a 150ml beaker, adding 100ml of rhodamine B wastewater solution with the concentration of 40mg/L, adding 0.006g of ferrous sulfate heptahydrate into the wastewater solution under stirring, regulating the pH value of the solution to 3.0 by dilute sulfuric acid, standing to reach adsorption equilibrium, adding 0.003ml of 30% hydrogen peroxide, carrying out Fenton reaction under the irradiation of an LED lamp (lambda >420 nm) to degrade rhodamine B in the wastewater, sampling the reaction time for 12min, measuring the concentration of rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer in the reaction process, and calculating the removal rate of rhodamine B.
The sample A fiber membrane, the sample B fiber membrane, the sample C fiber membrane and the non-fiber membrane are applied to assist in catalyzing Fenton reaction to treat rhodamine B wastewater, and the degradation rate of rhodamine B changes with time as shown in figure 1. The Fenton reaction has certain oxidizing property and the function of degrading organic matters, and when a fiber film is not added, the degradation rate of rhodamine B is 81.0% after 12 minutes of reaction under the irradiation of an LED lamp; after the sample B fiber film and the sample C fiber film are respectively added, the degradation rate of rhodamine B is improved to a certain extent, and the degradation rate of rhodamine B is respectively increased to 90.8 percent and 88.0 percent after the rhodamine B reacts for 12 minutes; after the sample A fiber membrane is added, the degradation rate of rhodamine B is obviously improved, and the degradation rate of rhodamine B is improved to 99.1% after 12 minutes of reaction. The experimental results show that the independent addition of molybdenum sulfide or bismuth vanadate has a promoting effect on Fenton reaction, and the promoting effect of the molybdenum sulfide is slightly better than that of bismuth vanadate; when molybdenum sulfide and bismuth vanadate are added into a Fenton system at the same time, the molybdenum sulfide and the bismuth vanadate have synergistic promotion effect, and the auxiliary catalysis effect is superior to that of independently adding molybdenum sulfide or bismuth vanadate. The fiber membrane prepared by the method has excellent catalysis-assisting effect on a Fenton reaction system under the irradiation of visible light.
Embodiment III:
examine Fe in the fiber membrane to Fenton reaction system prepared in example 1, comparative example 2 and comparative example 3 2+ Influence of concentration.
Respectively weighing 0.5g of the sample A fiber membrane prepared in example 1, the sample B fiber membrane prepared in comparative example 1 and the sample C fiber membrane prepared in comparative example 2, putting into a 150ml beaker, adding 100ml deionized water, adding 0.006g of ferrous sulfate heptahydrate into a wastewater solution under stirring, regulating the pH of the solution to 3.0 with dilute sulfuric acid, standing to reach adsorption equilibrium, adding 0.003ml of hydrogen peroxide with mass concentration of 30%, and placing the mixture into an LED lamp (lambda)>420 nm) for 12min, sampling at 0.5min, 2min, 4min, 8min and 12min, adding phenanthroline solution and sodium acetate solution into the sample to be detected, and measuring Fe at 510nm by ultraviolet-visible spectrophotometer 2+ Concentration.
Sample A fiber film, sample B fiber film, sample C fiber film and Fe in Fenton reaction system without fiber film 2+ The effect of concentration is shown in FIG. 2. As can be seen from FIG. 2, the Fenton system without fibrous membrane promoter reacts for 2 minutes to obtain Fe 2+ The concentration was only 11.5% of the initial concentration, and after 4 minutes of reaction, the Fe of the system was 2+ The concentration is reduced to 5.3% of the initial concentration, and Fe is reacted for 12min 2+ The concentration was reduced to 4.5% of the initial concentration; after the sample B fiber film and the sample C fiber film are respectively added, fe in a reaction system 2+ The concentration is improved to a certain extent, and after 12 minutes of reaction, fe 2+ The concentration is respectively increased to 33.0 percent and 29.0 percent; after adding the sample A fiber film, fe in the reaction system 2+ The concentration is obviously improved, and Fe is reacted for 12 minutes 2+ The concentration was raised to 60.2%. The experimental results show that, when molybdenum sulfide or bismuth vanadate is added separately, fe is added with 3+ /Fe 2+ The circulation of the molybdenum sulfide has a certain promoting effect, and the promoting effect of the molybdenum sulfide is slightly better than that of bismuth vanadate; when molybdenum sulfide and bismuth vanadate are added into Fenton system, the two have synergistic effect on Fe 3+ /Fe 2+ The promoting effect of circulation is superior to that of adding molybdenum sulfide or bismuth vanadate alone, which is consistent with the law of rhodamine B degradation rate data in example 2. The fiber membrane prepared by the method of the invention has the following characteristics of Fe under the irradiation of visible light 3+ /Fe 2+ Has remarkable promoting effect on circulation and has excellent promoting effect on Fenton reaction systems.
Experimental example four:
the leaching conditions of molybdenum sulfide and bismuth vanadate in the processes of treating rhodamine B wastewater by promoting Fenton reaction of the fiber membranes prepared in the example 1 and the comparative example 3 are examined.
Respectively weighing 0.5g of the sample A fiber film prepared in the example 1 and the sample D fiber film prepared in the comparative example 3, putting the sample A fiber film into a 150ml beaker, adding 100ml of rhodamine B wastewater solution with the concentration of 40mg/L, adding 0.006g of ferrous sulfate heptahydrate into the wastewater solution under the stirring state, regulating the pH value of the solution to 3.0 by dilute sulfuric acid, standing to reach adsorption equilibrium, adding 0.003ml of hydrogen peroxide with the mass concentration of 30%, and carrying out Fenton reaction under the irradiation of an LED lamp (lambda >420 nm) to degrade rhodamine B in wastewater, wherein the reaction time is 12min, and no sample is taken in the reaction process. After the experiment is completed, the fiber membrane is taken out, washed by deionized water, weighed after being dried, the weight is recorded, the leaching rate is calculated, and then the next experiment is carried out, and the process is repeated for 5 times.
Under the irradiation of visible light, the leaching conditions of the sample A and the sample D fiber membranes in the process of treating rhodamine B wastewater by promoting Fenton reaction are shown in figure 3. As can be seen from fig. 3, in the process of treating rhodamine B wastewater by promoting the Fenton reaction under the irradiation of visible light, the leaching rate of molybdenum sulfide and bismuth vanadate is basically unchanged after 5 times of cyclic use of the sample a fiber membrane, and is less than 0.13%; and for the sample D fibrous membrane, the leaching rate is 3.2% after the first use, and is as high as 6.0% after 5 times of recycling, which shows that the preparation method has remarkable influence on the leaching rate of molybdenum sulfide and bismuth vanadate.
Experimental example five:
the fiber membranes prepared in example 1 and comparative example 4 were examined for their co-catalytic effect on the Fenton reaction treatment of rhodamine B wastewater.
Respectively weighing 0.5g of the sample A fiber film prepared in the example 1 and the sample E fiber film prepared in the comparative example 4, putting into a 150ml beaker, adding 100ml of rhodamine B wastewater solution with the concentration of 40mg/L, adding 0.006g of ferrous sulfate heptahydrate into the wastewater solution under stirring, regulating the pH of the solution to 3.0 by dilute sulfuric acid, standing to reach adsorption equilibrium, adding 0.003ml of hydrogen peroxide with the mass concentration of 30%, carrying out Fenton reaction under the irradiation of an LED lamp (lambda >420 nm) to degrade rhodamine B in the wastewater, wherein the reaction time is 12min, sampling at 0.5min, 2min, 4min, 8min and 12min in the reaction process, measuring the concentration of rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer, and calculating the removal rate of rhodamine B.
The sample A fiber membrane, the sample E fiber membrane and the non-added fiber membrane are applied to assist in catalyzing Fenton reaction to treat rhodamine B wastewater, and the degradation rate of rhodamine B changes with time as shown in figure 4. The Fenton reaction has certain oxidizing property and the function of degrading organic matters, and when a fiber film is not added, the degradation rate of rhodamine B is 81.0% after 12 minutes of reaction under the irradiation of an LED lamp; after the sample E fiber membrane is added, the degradation rate of rhodamine B is slightly improved, and the degradation rate of rhodamine B is improved to 82.9% after 12 minutes of reaction; after the sample A fiber membrane is added, the degradation rate of rhodamine B is obviously improved, the degradation rate of rhodamine B is improved to 99.1% after 12 minutes of reaction, and the preparation method has obvious influence on the catalysis aiding effect of Fenton reaction.
Experimental example six:
the fiber membranes prepared in example 1 and comparative example 5 were examined for their co-catalytic effect on the Fenton reaction treatment of rhodamine B wastewater.
Respectively weighing 0.5g of the sample A fiber membrane prepared in the example 1 and the sample F fiber membrane prepared in the comparative example 5, putting the sample A fiber membrane and the sample F fiber membrane into a 150ml beaker, adding 100ml of rhodamine B wastewater solution with the concentration of 40mg/L, adding 0.006g of ferrous sulfate heptahydrate into the wastewater solution under the stirring state, regulating the pH value of the solution to 3.0 by dilute sulfuric acid, standing to reach adsorption equilibrium, adding 0.003ml of hydrogen peroxide with the mass concentration of 30%, carrying out Fenton reaction under the irradiation of an LED lamp (lambda >420 nm) to degrade rhodamine B in the wastewater, wherein the reaction time is 12min, sampling at 0.5min, 2min, 4min, 8min and 12min respectively during the reaction, measuring the concentration of rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer, and calculating the removal rate of rhodamine B.
The sample A fiber membrane, the sample F fiber membrane and the non-added fiber membrane are applied to assist in catalyzing Fenton reaction to treat rhodamine B wastewater, and the degradation rate of rhodamine B changes with time as shown in figure 5. The Fenton reaction has certain oxidizing property and the function of degrading organic matters, and when a fiber film is not added, the degradation rate of rhodamine B is 81.0% after 12 minutes of reaction under the irradiation of an LED lamp; after the sample A fiber membrane is added, the degradation rate of rhodamine B is obviously improved, and the degradation rate of rhodamine B is improved to 99.1% after 12 minutes of reaction; after the sample F fiber film is added, the degradation rate of rhodamine B after reaction for 12 minutes is 82.9 percent, which is obviously lower than the effect of adding the sample A fiber film, so that the transparency of the fiber film has a larger influence on the catalysis assisting effect of Fenton reaction.
Experimental example seven:
the stability of the fiber membrane prepared in example 1 in the Fenton reaction treatment of rhodamine B wastewater was examined.
Weighing 0.5g of the sample A fiber membrane prepared in the embodiment 1, putting the sample A fiber membrane into a 150ml beaker, adding 100ml of rhodamine B wastewater solution with the concentration of 40mg/L, adding 0.006g of ferrous sulfate heptahydrate into the wastewater solution under the stirring state, regulating the pH of the solution to 3.0 by dilute sulfuric acid, standing to reach adsorption balance, adding 0.003ml of hydrogen peroxide with the mass concentration of 30%, carrying out Fenton reaction under the irradiation of an LED lamp (lambda >420 nm) to degrade rhodamine B in the wastewater, sampling at 0.5min, 2min, 4min, 8min and 12min in the reaction process, measuring the concentration of rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer, and calculating the removal rate of rhodamine B. After the experiment is completed, the fiber membrane is taken out, washed by deionized water, dried and subjected to the next experiment, and repeated for 5 times.
The stability of sample A in the Fenton reaction treatment of rhodamine B wastewater under visible light irradiation is shown in FIG. 6. As shown in FIG. 6, after the fiber membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate prepared by the invention is recycled for 5 times, the removal rate of rhodamine B is basically unchanged under the condition of visible light, and the removal rate is over 99.0 percent, which indicates that the fiber membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate synthesized by the invention has stable catalysis-assisting effect on a Fenton reaction system and can be reused.
The beneficial effects of the invention are as follows: the bi-functional fiber membrane for promoting Fenton reaction and the preparation method thereof are characterized in that molybdenum sulfide and bismuth vanadate are simultaneously introduced into a Fenton system, and Mo in the molybdenum sulfide 4+ Fe is added to 3+ Reduction to Fe 2+ Molybdenum sulfide plays a role of a reducing agent, and Mo 4+ Itself is oxidized to Mo 6+ Bismuth vanadate generates photo-generated electrons under the irradiation of visible light, and the photo-generated electrons further add Mo 6+ Reduction to Mo 4+ Mo is realized on the basis of not consuming hydrogen peroxide additionally 6+ /Mo 4+ At the same time, the photo-generated electrons can also generate Fe 3+ Reduction to Fe 2+ Remarkably promote Fe in Fenton system 3+ /Fe 2+ The bismuth vanadate plays a role of a photocatalyst; the simultaneous introduction of molybdenum sulfide and bismuth vanadate plays the dual functions of a reducing agent and a photocatalyst, and ensures considerable Fe in a Fenton system 2+ Thereby improving the utilization rate of hydrogen peroxide and effectively reducing the treatment cost of wastewater; the polymer fiber membrane loaded with the molybdenum sulfide and the bismuth vanadate is prepared by taking the molybdenum sulfide, the bismuth vanadate, the polyvinylidene fluoride and the polymethyl methacrylate as raw materials and adopting an electrostatic spinning technology, and the fiber membrane is integral, good in flexibility and excellent in mechanical property, and is easier to process and form and wider in application field compared with a powder material; the prepared polymer fiber membrane loaded with the molybdenum sulfide and the bismuth vanadate is embedded and anchored in polymer nanofibers, the nanofibers are crosslinked and associated to form the fiber membrane, the binding force between the bismuth vanadate and the polymer is strong, the scouring resistance in water is obviously superior to that of molybdenum sulfide or bismuth vanadate-based materials prepared by the traditional technology, the problem that the molybdenum sulfide and the bismuth vanadate are easy to run off in the application process is solved, the molybdenum sulfide and the bismuth vanadate can be recycled, and the cost for promoting Fenton reaction to treat wastewater is effectively reduced; by adding polymethyl methacrylate into polyvinylidene fluoride, the transparency of the polymer film is improved, the absorption rate of the fiber film to visible light is further promoted, and the effect of promoting Fenton reaction is effectively improved.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A method for preparing a bifunctional fibrous membrane for promoting a Fenton reaction, comprising the steps of:
s1, performing ball milling treatment on molybdenum sulfide powder, wherein the particle size of the treated molybdenum sulfide powder is below 200 nm;
s2, performing ball milling treatment on bismuth vanadate powder, wherein the particle size of the treated bismuth vanadate powder is below 200 nm;
s3, mixing the molybdenum sulfide powder obtained in the step 1 with the bismuth vanadate powder obtained in the step 2, and continuing ball milling for 2-6 hours;
s4, adding the molybdenum sulfide and bismuth vanadate subjected to ball milling treatment in the step 3 into a mixed solution of N, N-dimethylacetamide and acetone according to a metering ratio, and performing ultrasonic treatment for 1 hour to form a solution A;
s5, adding polyvinylidene fluoride and polymethyl methacrylate into a mixed solution of N, N-dimethylacetamide and acetone according to a metering ratio, and performing ultrasonic treatment at 50 ℃ for 1 hour to form a solution B;
s6, slowly dripping the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain spinning solution;
s7, carrying out electrostatic spinning on the spinning solution to obtain a spinning product, and then drying the spinning product at the temperature of 4kPa and 90 ℃ for 12 hours to obtain a fibrous membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate;
in the step S1, the crystal structure of the molybdenum sulfide is of a 2H type, and bismuth vanadate is of a monoclinic phase; in step S7, the specific process of electrostatic spinning is as follows: adding spinning solution into an injector, connecting a needle of the injector with a high-voltage power supply anode in a downward inclined manner, wrapping a low-speed roller of release paper for collecting spinning products, placing the low-speed roller under the injector in an inclined manner, horizontally placing the low-speed roller and grounding the low-speed roller, wherein the distance between the needle and a collecting plate is 10cm-20cm, setting the spinning voltage to 15kV-25kV in an environment with the relative humidity of 25% -45% at 20 ℃ -30 ℃, and starting a constant-current pump to control the flow rate of the spinning solution in the injector to be 1ml/h, so that the spinning products can be collected.
2. The method for preparing a bifunctional fibrous membrane for promoting Fenton reaction according to claim 1, wherein in the steps S4 and S5, the mass ratio of N, N-dimethylacetamide to acetone is 2:3, in the step S4, the mass content of the molybdenum sulfide in the solution A is 6%, the mass content of the bismuth vanadate is 9%, and in the step S5, the mass content of the polyvinylidene fluoride in the solution B is 12%.
3. The method for preparing the bi-functional fiber membrane for promoting Fenton reaction according to claim 1, wherein the fiber membrane consists of four substances of molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate; the mass content of the molybdenum sulfide is 5-10%, the mass content of the bismuth vanadate is 10-15%, the mass content of the polyvinylidene fluoride is 60-80%, and the mass content of the polymethyl methacrylate is 10-20%.
4. A method for preparing a bifunctional fibrous membrane for promoting a Fenton reaction according to claim 3, wherein the mass content of molybdenum sulfide is 8%, the mass content of bismuth vanadate is 12%, the mass content of polyvinylidene fluoride is 70%, and the mass content of polymethyl methacrylate is 10%.
5. The method of preparing a bifunctional fibrous membrane for facilitating a Fenton reaction as recited in claim 4, wherein the polyvinylidene fluoride has a weight of 20-60 g/mol.
6. The method for preparing the bi-functional fiber membrane for promoting the Fenton reaction according to claim 1, wherein the specific process for promoting the Fenton reaction is as follows: under the stirring state, ferrous sulfate heptahydrate is added into the wastewater solution containing organic pollutants, then dilute sulfuric acid is used for adjusting the pH value of the solution, a bifunctional fiber membrane is added into the wastewater solution, after standing, adsorption and balancing, hydrogen peroxide is added, fenton reaction is carried out under the irradiation of visible light, and the organic pollutants in the wastewater are degraded.
7. The method for preparing a bifunctional fibrous membrane for promoting Fenton reaction according to claim 6, wherein the dosage of ferrous sulfate heptahydrate in the specific process of promoting Fenton reaction is 0.05-0.50mmol/L; the ratio of the hydrogen peroxide to the ferrous sulfate heptahydrate is 1.0-10.0g/mL; the dosage of the difunctional fiber film is 0.25-5.0g/L; the pH value of the solution is 2.0-6.0; the concentration of the organic pollutant is 10-40mg/L; the organic pollutant is one or more of rhodamine B, phenol and N, N-dimethylformamide; the reaction time of the catalysis-assisted Fenton reaction is 5-20 minutes.
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