CN114405552A - Bifunctional fiber membrane for promoting catalytic Fenton reaction and preparation method thereof - Google Patents
Bifunctional fiber membrane for promoting catalytic Fenton reaction and preparation method thereof Download PDFInfo
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- CN114405552A CN114405552A CN202210138528.XA CN202210138528A CN114405552A CN 114405552 A CN114405552 A CN 114405552A CN 202210138528 A CN202210138528 A CN 202210138528A CN 114405552 A CN114405552 A CN 114405552A
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- fiber membrane
- bismuth vanadate
- molybdenum sulfide
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- 239000012528 membrane Substances 0.000 title claims abstract description 134
- 239000000835 fiber Substances 0.000 title claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 94
- 230000001737 promoting effect Effects 0.000 title claims abstract description 25
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 105
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 105
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 103
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002033 PVDF binder Substances 0.000 claims abstract description 41
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 34
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 117
- 238000009987 spinning Methods 0.000 claims description 73
- 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 47
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 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 20
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000003756 stirring Methods 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
- 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 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 19
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 13
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 11
- 239000011941 photocatalyst Substances 0.000 abstract description 7
- 229920005594 polymer fiber Polymers 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910017108 Fe—Fe Inorganic materials 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 26
- 230000000694 effects Effects 0.000 description 23
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 238000006555 catalytic reaction Methods 0.000 description 17
- 239000002121 nanofiber Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 238000002386 leaching Methods 0.000 description 11
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000011521 glass 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
- 238000005070 sampling Methods 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- 238000002474 experimental method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000593 degrading effect Effects 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
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 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
- 238000001523 electrospinning Methods 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
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 230000001603 reducing effect Effects 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
- 239000002904 solvent Substances 0.000 description 3
- -1 transition metal sulfide Chemical class 0.000 description 3
- 210000001170 unmyelinated nerve fiber Anatomy 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
- 229910003206 NH4VO3 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process 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
- 230000009977 dual effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 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
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 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
- 238000004064 recycling Methods 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 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
- 229910016002 MoS2a Inorganic materials 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
- 238000010521 absorption reaction Methods 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
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 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
- 238000003763 carbonization Methods 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
- 239000011248 coating agent Substances 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 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
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- 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 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
- 229920000131 polyvinylidene Polymers 0.000 description 1
- UAJUXJSXCLUTNU-UHFFFAOYSA-N pranlukast Chemical compound C=1C=C(OCCCCC=2C=CC=CC=2)C=CC=1C(=O)NC(C=1)=CC=C(C(C=2)=O)C=1OC=2C=1N=NNN=1 UAJUXJSXCLUTNU-UHFFFAOYSA-N 0.000 description 1
- 229960004583 pranlukast Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness 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
- 238000003786 synthesis reaction Methods 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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 bifunctional fiber membrane for promoting catalytic Fenton reaction and a preparation method thereof4+Mixing Fe3+Reduction to Fe2+，Mo4+Is oxidized into Mo6+Bismuth vanadate generates photoproduction electrons under the irradiation of visible light, and the photoproduction electrons further lead Mo6+Reduction to Mo4+Mo is realized on the basis of no extra consumption of hydrogen peroxide6+/Mo4+Normal cycle of (2); the same of molybdenum sulfide and bismuth vanadateThe double functions of a reducing agent and a photocatalyst are exerted by introducing the Fe-Fe alloy, and considerable Fe in a Fenton system is ensured2+The concentration of the hydrogen peroxide is reduced, so that the utilization rate of the hydrogen peroxide is improved; the polymer fiber membrane loaded with the bismuth vanadate is prepared by taking molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate as raw materials and adopting an electrostatic spinning technology, is integral, has good flexibility and excellent mechanical property, is not easy to leach and run off compared with molybdenum sulfide and bismuth vanadate powder, is easier to process and mold, and has a wide application range.
Description
Technical Field
The invention relates to the technical field of bifunctional fibrous membranes for promoting catalytic Fenton reactions and preparation methods thereof, in particular to a bifunctional fibrous membrane for promoting catalytic Fenton reactions and a preparation method thereof.
Background
The traditional Fenton oxidation technology has the advantages of mild reaction conditions, no toxicity of reagents, simple equipment structure, convenience in 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 defects, such as low hydrogen peroxide utilization rate, high 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 for the rate control step, the problems of large consumption of fenton reagent and large generation of iron mud are solved, and the reaction rate of the step of regenerating ferrous ions is mainly improved. In recent years, the literature has accelerated the rate of reduction of ferric ions to ferrous ions by adding organic substances with complexing functions and reducing properties. The addition of the organic matters can promote the reduction of the ferric iron to a certain extent and improve the Fe content3+/Fe2+The circulation efficiency of the method effectively reduces the generation amount of the iron mud; however, these organic substances themselves generate a certain amount of TOC, so that the overall TOC removal rate is not high, and these organic substances are also decomposed by hydrogen peroxide, so that the promoting effect is hardly exerted as the reaction proceedsAnd keeping stable. Compared with organic materials, inorganic materials have better stability in a fenton system, so that the search for the inorganic materials for promoting the reduction of ferric iron and further improving the fenton oxidation efficiency is widely concerned.
Molybdenum sulfide (MoS)2) The graphene-like semiconductor material is a graphene-like semiconductor material, layers are connected by weak van der Waals force, and the layers are formed by covalent bonds of S-Mo-S three-atom layer structures. The crystal structure of molybdenum sulfide has three types of 1T, 2H and 3R, wherein the types of 1T and 3R are metastable states, the type of 2H is stable in a normal state, the unique physical property of the molybdenum sulfide is different from that of other materials, and the molybdenum sulfide is applied to the fields of catalysis, photovoltaics, lubricating oil and the like. The band gap of bulk molybdenum sulfide is only 1.17eV, and photo-generated electrons (e)-) And a cavity (h)+) Easy recombination and limited application in photocatalytic processes. However, as the layered transition metal sulfide with various crystal structures, molybdenum sulfide has the characteristics of complex edge structure, high unsaturation, high reaction activity and the like, and the application of the molybdenum sulfide in the field of catalysis still has application potential. The use of molybdenum sulfide (MoS) has been proposed in the literature2) Reduced Mo exposed on the surface of molybdenum sulfide as a promoter for improving efficiency of Fenton reaction4+Promote Fe3+/Fe2+Excellent iron ion cycle efficiency and low Fe2+The dosage is effective to inhibit the generation of iron mud. During this process, Mo in a reduced state4+Is oxidized into Mo6+To hold Mo6+/Mo4+Normal cycle of (1), H in Fenton System2O2Mo is mixed with6+Reduction to Mo4+. It can be seen that Fe is promoted3+/Fe2+Is circulated by consuming H2O2At the expense, the benefit brought by iron ion circulation is offset to a certain extent, and the cost of wastewater treatment by Fenton reaction is not reduced. Bismuth vanadate has been widely noticed as a semiconductor-type visible light catalyst because of its non-toxicity, special physical and optical properties, and excellent chemical and optical stability. Bismuth vanadate has mainly 3 crystal forms: a tetragonal zircon structure, a monoclinic scheelite-type structure and a tetragonal scheelite-type structure, whereinMonoclinic phase bismuth vanadate (m-BiVO)4) The forbidden band width is 2.3-2.4eV, the material has excellent responsiveness in a visible light region, can generate photogenerated electrons under the irradiation of visible light, and can be used for degrading organic pollutants. Bismuth vanadate is further introduced into a molybdenum sulfide-Fenton system, and photo-generated electrons are generated by the reaction of the bismuth vanadate under light irradiation (e)-) To Fe3+、Mo6+Reduction is carried out, and Fe is hopefully solved3+/Fe2+、Mo6+/Mo4+The problem of circulation is solved, thereby reducing the generation of iron mud and increasing H2O2The utilization rate of the method improves the generation amount of hydroxyl free radicals, and reduces the cost of wastewater treatment. In most studies, molybdenum sulfide and bismuth vanadate exist in a system in a powder form, and although the catalytic effect is excellent, the problems that the catalyst is difficult to recover and easy to run off exist, so that researchers propose that bismuth vanadate is supported on conductive glass to fix molybdenum sulfide or bismuth vanadate. In patent CN 201610002369.5, a molybdenum-containing salt (such as sodium molybdate and the like) is dissolved in an alcohol solution containing a sulfur source (such as thiourea), the solution is added into a substrate material and then is put into a hydrothermal kettle, the hydrothermal kettle is heated with a solvent at the temperature of 180 ℃ and 230 ℃ for 6-24h, and the substrate is taken out, cleaned and dried to obtain the molybdenum sulfide in-situ electrode. Patent CN201811518486.2 synthesis of MoS by one-step hydrothermal method2CNTs composite material, and then MoS is subjected to a drop coating method2the/CNTs composite was deposited on FTO conductive glass to make a counter electrode. Patent CN201310078273.3 uses Bi (NO)3)3·5H2And (3) coating bismuth vanadate colloid prepared from an O-acetic acid solution and an acetylacetonatovanadyl-acetylacetone solution on clean ITO conductive glass in a spinning way, and roasting to obtain the nano bismuth vanadate film. Patent CN 201310033856.4 uses Bi (NO)3)3·5H2O and NH4VO3And citric acid, acetic acid and ethanolamine are used as auxiliary solvents to prepare a precursor solution, and a chemical solution deposition method is adopted to obtain the bismuth vanadate film on the conductive glass substrate. Patent CN 201710203262.1 uses nitric acid and boric acid to regulate Bi (NO)3)3·5H2O and NH4VO3Mixed solution, amorphous BiVO is formed on the substrate by electrostatic adsorption self-assembly and layer-by-layer assembly technology4A film. Loading molybdenum sulfide or bismuth vanadate onOn the conductive glass, the conductive glass 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 molybdenum sulfide and bismuth vanadate are leached and lost in a water body can not be solved due to the fact that the binding force between the molybdenum sulfide and bismuth vanadate and the conductive glass is weak. Electrostatic spinning is a spinning technology for stretching and solidifying polymer solution or melt into nano-fiber by utilizing high electrostatic field force, is a reliable technology for preparing nano-fiber, and the prepared nano-fiber has the characteristics of small diameter, large specific surface area, porosity, good flexibility, excellent mechanical strength and the like, is simple in device and low in manufacturing cost, and has been applied to the fields of filter membranes, catalysis, sensors, tissue engineering and the like in recent years. Polyvinylidene fluoride 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, and also has piezoelectric property, dielectric property, thermoelectric property and the like, and is widely applied as a film material. The method combines molybdenum sulfide, bismuth vanadate and polyvinylidene fluoride by adopting an electrostatic spinning technology, and is one of approaches for solving the problem of leaching loss of the molybdenum sulfide and the bismuth vanadate. In patent CN 202110275000.2, PVDF nanofiber membrane is prepared by electrostatic spinning method, and then in-situ grown MoS is synthesized on the surface of the PVDF nanofiber membrane by hydrothermal method2Nano flower, and modifying AuNPs in MoS by in-situ reduction reaction2Thus obtaining a PVDF/MoS2AuNPS material. The patent CN 201710978781.5 takes polyacrylonitrile as a raw material, N, N-dimethylformamide as a solvent to prepare a spinning solution, an electrospinning method is adopted to prepare electrospinning nanofibers, then the electrospinning nanofibers are 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 a solution heating method is adopted to obtain the copper-doped bismuth vanadate porous nanotube photocatalyst after washing, drying and roasting. It is reported that a polyvinylidene fluoride fiber membrane is prepared by an electrostatic spinning method, a Ni (shell)/PVDF (core) coaxial fiber membrane with a core-shell structure is prepared by a chemical deposition method, and then manganese dioxide nano sheets can be grown on the Ni/PVDF coaxial fiber membrane by simple hydrothermal treatment. The above documents describe the production of polymeric nanofibers by electrospinningThen, 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 fundamentally solved. According to the patent CN 201510947452.5, a polyacrylonitrile nanofiber membrane is prepared through electrostatic spinning, graphene oxide is wrapped on polyacrylonitrile nanofibers through a solution soaking method, a graphene/carbon nanofiber composite membrane is prepared through high-temperature carbonization, and finally molybdenum disulfide nanosheets are grown in situ on the graphene/carbon nanofibers through a one-step hydrothermal method to prepare a molybdenum disulfide/graphene/carbon nanofiber composite material. Patent CN 201810573295.X firstly synthesizes carbon nanofiber by utilizing an electrostatic spinning technology, then takes the carbon nanofiber as a precursor, and carries out hydrothermal reaction in an aqueous solution containing a molybdenum source and a sulfur source to obtain MoS2the/CNFs compound is annealed at high temperature to obtain MoS2a/CNFs composite material. The above patents aim at preparing carbon fiber and molybdenum sulfide composite materials, firstly preparing polymer nanofibers through electrostatic spinning, then carrying out heat treatment on the polymer nanofibers in an inert atmosphere to obtain carbon nanofibers, and then loading molybdenum sulfide on the carbon fibers, wherein the product is in a powder shape, is not easy to recover when used in a water phase, and has the problem of loss. In patent CN201310257173.7, organic vanadium salt and organic bismuth salt with good alcohol solubility are used as precursor reactants, and mixed with polyvinylpyrrolidone and ethanol to prepare spinning solution, and the spinning solution is electrospun into filaments by an electrostatic spinning device, and then calcined at high temperature to obtain the vanadate nano photocatalyst. Patent CN 201911280662.8 disperses a bismuth source and a vanadium source in a mixed solvent composed of N, N-dimethylformamide, acetic acid and ethanol, then adds polyvinylpyrrolidone, uniformly mixes to prepare a spinning solution, then carries out electrostatic spinning to obtain a spinning product, and obtains bismuth vanadate nanofibers after drying and calcining. In the patents, soluble bismuth salt, soluble vanadate and polymer are mixed to imitate silk, and when the roasting treatment is not carried out, bismuth vanadate and the polymer exist in a fiber film form in a compounding way, so that although the loss problem can be solved, the formation of bismuth vanadate cannot be ensured, and the monoclinic phase of the crystal form of bismuth vanadate cannot be ensured, so that the electrostatic spinning products are roasted in the patents; after being subjected to a baking treatmentAnd then, the polymer can be completely removed in the roasting process, the polymer is no longer an integral fiber membrane loaded with bismuth vanadate, and the rest is the powder form bismuth vanadate, so that the problem of leaching loss cannot be solved. Therefore, for the traditional Fenton system, the material which is good in cocatalyst effect, easy to recover, recyclable, not easy to leach and run off, simple in preparation process and suitable for large-scale production is developed, and has a wide application prospect.
Disclosure of Invention
In order to achieve the purpose, the invention provides the following technical scheme: a difunctional fiber membrane for promoting catalytic Fenton reaction is composed 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 crystal structure of the molybdenum sulfide is 2H type, and the bismuth vanadate is monoclinic phase.
Preferably, the polyvinylidene fluoride has a content of 20 to 60 ten thousand g/mol.
A preparation method of a bifunctional fiber membrane for promoting a Fenton reaction comprises the following steps:
1) performing ball milling treatment on molybdenum sulfide powder, wherein the particle size of the treated molybdenum sulfide powder is less than 200 nm;
2) performing ball milling treatment on bismuth vanadate powder, wherein the particle size of the treated bismuth vanadate powder is less than 200 nm;
3) mixing the molybdenum sulfide powder obtained in the step (1) and the bismuth vanadate powder obtained in the step (2), and continuing ball milling for 2-6 hours;
4) adding the molybdenum sulfide and the bismuth vanadate subjected to the 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 carrying out ultrasonic treatment for 1 hour at 50 ℃ to form a solution B;
6) slowly dropwise adding the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain a spinning solution;
7) and (3) carrying out electrostatic spinning on the spinning solution to obtain a spinning product, and then drying the spinning product at 4kPa and 90 ℃ for 12 hours to obtain the fiber membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate.
Preferably, in steps 4 and 5, the mass ratio of N, N-dimethylacetamide to 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 electrostatic spinning is as follows:
adding the spinning solution into an injector, enabling a needle head of the injector to be obliquely downward and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector in an oblique mode, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 10cm-20cm, setting the spinning voltage to be 15kV-25kV in an environment with the relative humidity of 25% -45% at 20 ℃ -30 ℃, starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/hour, collecting the spinning products, and carrying out a catalytic Fenton reaction: adding ferrous sulfate heptahydrate into the wastewater solution under the stirring state, then adjusting the pH value of the solution by using dilute sulfuric acid, adding the bifunctional fiber membrane into the wastewater solution, standing for adsorption balance, adding hydrogen peroxide, and performing Fenton reaction under the irradiation of visible light to degrade organic pollutants in the wastewater.
The invention relates to a bifunctional fibrous membrane for promoting catalytic Fenton reaction, which comprises the following specific processes: adding ferrous sulfate heptahydrate into the wastewater solution under the stirring state, then adjusting the pH value of the solution by using dilute sulfuric acid, adding the bifunctional fiber membrane into the wastewater solution, standing for adsorption balance, adding hydrogen peroxide, and performing Fenton reaction under the irradiation of visible light to degrade organic pollutants in the wastewater.
Preferably, the dosage of the ferrous sulfate heptahydrate is 0.05-0.50 mmol/L; the ratio of the hydrogen peroxide to the ferrous sulfate heptahydrate is 1.0-10.0; the dosage of the difunctional fiber membrane is 0.25-5.0 g/L; the pH value of the solution is 2.0-6.0, and the concentration of organic pollutants is 10-40 mg/L; the organic pollutants are 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 bifunctional fiber membrane for promoting the catalytic Fenton reaction and the preparation method thereof, and the bifunctional fiber membrane has the following beneficial effects:
1. according to the bifunctional fiber membrane for promoting the catalytic Fenton reaction and the preparation method thereof, molybdenum sulfide and bismuth vanadate are simultaneously introduced into a Fenton system, and Mo in the molybdenum sulfide4+Mixing Fe3+Reduction to Fe2+Molybdenum sulfide acting as a reducing agent, Mo4+Is oxidized into Mo6+Bismuth vanadate generates photoproduction electrons under the irradiation of visible light, and the photoproduction electrons further lead Mo6+Reduction to Mo4+Mo is realized on the basis of no extra consumption of hydrogen peroxide6+/Mo4+Normal cycle of (1), and at the same time, the photo-generated electrons can also convert Fe3+Reduction to Fe2+Remarkably promotes Fe in a Fenton system3+/Fe2+The bismuth vanadate plays a role of a photocatalyst; the molybdenum sulfide and the bismuth vanadate are introduced simultaneously, so that the dual functions of a reducing agent and a photocatalyst are exerted, and considerable Fe in a Fenton system is ensured2+The concentration of the hydrogen peroxide is reduced, so that the utilization rate of the hydrogen peroxide is improved, and the treatment cost of the wastewater is effectively reduced.
2. According to the bifunctional fiber membrane for promoting catalytic Fenton reaction and the preparation method thereof, molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate are used as raw materials, and the polymer fiber membrane loaded with the molybdenum sulfide and the bismuth vanadate is prepared by adopting an electrostatic spinning technology, is integral, has good flexibility and excellent mechanical properties, is easier to process and form compared with a powder material, and has a wider application field.
3. According to the prepared polymer fiber membrane loaded with molybdenum sulfide and bismuth vanadate, the molybdenum sulfide and the bismuth vanadate are 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 a polymer is strong, the scouring resistance in a water body is obviously superior to that of a 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 fiber membrane can be recycled, and the cost for treating wastewater by the co-catalysis fenton reaction is effectively reduced.
4. According to the bifunctional fiber membrane for the co-catalysis 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 effect of the co-catalysis Fenton reaction is effectively promoted.
Drawings
FIG. 1 shows the 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 no fiber membrane on the catalysis of Fenton reaction for treating rhodamine B wastewater;
FIG. 2 shows Fe in the P-Fenton reaction system without using the fiber membrane of sample A obtained in example 1 of the present invention, the fiber membrane of sample B obtained in comparative example 1, the fiber membrane of sample C obtained in comparative example 2, and the fiber membrane2+The effect of concentration;
FIG. 3 shows the leaching conditions of molybdenum sulfide and bismuth vanadate in the process of treating rhodamine B wastewater by a catalytic Fenton reaction of the fiber membranes of the sample A prepared in example 1 and the sample D prepared in the comparative example 3;
FIG. 4 shows the effect of the fiber membrane of sample A prepared in example 1, the fiber membrane of sample E prepared in comparative example 4 and no fiber membrane in promoting the Fenton reaction for treating rhodamine B wastewater;
FIG. 5 shows the 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 in promoting the Fenton reaction for treating rhodamine B wastewater;
FIG. 6 shows the stability of the sample A fiber membrane prepared in example 1 of the present invention in the process of treating rhodamine B wastewater by Fenton reaction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to the attached figures 1-6, the first embodiment is proposed:
(1) performing ball milling treatment on molybdenum sulfide powder, wherein the particle size of the treated molybdenum sulfide powder is less than 200 nm;
(2) performing ball milling treatment on bismuth vanadate powder, wherein the particle size of the treated bismuth vanadate powder is less than 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 the molybdenum sulfide and bismuth vanadate subjected to ball milling treatment in the step (3) into a mixed solution of 1.6g 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 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 dropwise adding the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain a spinning solution;
(7) carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding the spinning solution into an injector, enabling a needle head of the injector to be downwards inclined and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector obliquely, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 15cm, setting the spinning voltage to be 20kV in an environment with the relative humidity of 25%, and starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/h to obtain the spinning products.
(8) And drying the spinning product at 4kPa and 90 ℃ for 12 hours to obtain a fiber membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate, and marking as a sample A.
Comparative example 1:
(1) performing ball milling treatment on molybdenum sulfide powder, wherein the particle size of the treated molybdenum sulfide powder is less than 200 nm;
(2) adding 0.6g of molybdenum sulfide subjected to ball milling into a mixed solution of 1.6g 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 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 dropwise adding the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain a spinning solution;
(5) carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding the spinning solution into an injector, enabling a needle head of the injector to be downwards inclined and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector obliquely, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 15cm, setting the spinning voltage to be 20kV in an environment with the relative humidity of 25%, and starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/h to obtain the spinning products.
(6) The spinning product was dried at 4kPa, 90 ℃ for 12 hours to obtain a fibrous membrane containing molybdenum sulfide, polyvinylidene fluoride and polymethyl methacrylate, which was labeled as sample B.
Comparative example 2:
(1) performing ball milling treatment on bismuth vanadate powder, wherein the particle size of the treated bismuth vanadate powder is less than 200 nm;
(2) adding 0.6g of bismuth vanadate subjected to ball milling treatment into a mixed solution of 1.6g N, N-dimethylacetamide and 2.4g of acetone, and carrying out 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 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 dropwise adding the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain a spinning solution;
(5) carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding the spinning solution into an injector, enabling a needle head of the injector to be downwards inclined and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector obliquely, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 15cm, setting the spinning voltage to be 20kV in an environment with the relative humidity of 25%, and starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/h to obtain the spinning products.
(6) And drying the spinning product at 4kPa and 90 ℃ for 12 hours to obtain a fiber membrane containing bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate, and marking as a 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 N, N-dimethylacetamide and 10.5g of acetone, and carrying out 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 the spinning solution into an injector, enabling a needle head of the injector to be downwards inclined and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector obliquely, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 15cm, setting the spinning voltage to be 20kV in an environment with the relative humidity of 25%, and starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/h to obtain the spinning products.
(3) And drying the spinning product at the temperature of 90 ℃ for 12 hours under the condition of 4kPa 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 then transferring to a polytetrafluoroethylene-lined hydrothermal kettle;
(5) and (3) putting the fiber membrane prepared in the step (3) into a hydrothermal kettle, aging for 6 hours at 120 ℃, cooling, washing for 3 times by using deionized water, and drying for 12 hours at 20kPa and 80 ℃ to obtain the polyvinylidene fluoride and polymethyl methacrylate fiber membrane deposited by molybdenum sulfide and bismuth vanadate, wherein the label is 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 N, N-dimethylacetamide and 2.4g of acetone, and carrying out 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 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 dropwise adding the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain a spinning solution;
(4) carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding the spinning solution into an injector, enabling a needle head of the injector to be downwards inclined and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector obliquely, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 15cm, setting the spinning voltage to be 20kV in an environment with the relative humidity of 25%, and starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/h to obtain the spinning products.
(5) And drying the spinning product at 4kPa and 90 ℃ for 12 hours to obtain a fiber film containing molybdenum salt, vanadium salt, bismuth salt, polyvinylidene fluoride and polymethyl methacrylate, and marking as a sample E.
Comparative example 5:
(1) performing ball milling treatment on molybdenum sulfide powder, wherein the particle size of the treated molybdenum sulfide powder is less than 200 nm;
(2) performing ball milling treatment on bismuth vanadate powder, wherein the particle size of the treated bismuth vanadate powder is less than 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 the molybdenum sulfide and bismuth vanadate subjected to ball milling treatment in the step (3) into a mixed solution of 1.6g 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 N, N-dimethylacetamide and 10.5g of acetone, and carrying out ultrasonic treatment at 50 ℃ for 1 hour to form a solution B;
(6) slowly dropwise adding the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain a spinning solution;
(7) carrying out electrostatic spinning on the spinning solution, wherein the specific process of the electrostatic spinning is as follows: adding the spinning solution into an injector, enabling a needle head of the injector to be downwards inclined and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector obliquely, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 15cm, setting the spinning voltage to be 20kV in an environment with the relative humidity of 25%, and starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/h to obtain the spinning products.
(8) And drying the spinning product at 4kPa and 90 ℃ for 12 hours to obtain a fiber membrane containing molybdenum sulfide, bismuth vanadate and polyvinylidene fluoride, and marking as a sample F.
Example two:
the auxiliary effects of the fiber membranes prepared in example 1, comparative example 2 and comparative example 3 on the treatment of rhodamine B wastewater by Fenton reaction are considered.
Respectively weighing 0.5g of the fiber membrane of the sample A prepared in the example 1, the fiber membrane of the sample B prepared in the comparative example 1 and the fiber membrane of the sample C prepared in the comparative example 2, putting the fiber membranes into a beaker of 150ml, 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, then adjusting the pH of the solution to 3.0 by using dilute sulfuric acid, standing to reach adsorption balance, adding 0.003ml of hydrogen peroxide with the mass concentration of 30 percent, performing a fenton reaction under the irradiation of an LED lamp (lambda is more than 420nm) to degrade the rhodamine B in the wastewater, wherein the reaction time is 12min, sampling is respectively performed at 0.5min, 2min, 4min, 8min and 12min in the reaction process, measuring the concentration of the rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer, and calculating the removal rate of the rhodamine B.
The sample A fiber membrane, the sample B fiber membrane, the sample C fiber membrane and the fiber membrane which is not added are applied to the catalysis-assisted Fenton reaction for treating rhodamine B wastewater, and the degradation rate of rhodamine B changes along with time as shown in figure 1. Because the Fenton reaction has certain oxidability and has the function of degrading organic matters, the degradation rate of rhodamine B in 12 minutes of reaction is 81.0 percent under the irradiation of an LED lamp when a fiber membrane is not added; after the sample B fiber membrane and the sample C fiber membrane 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 reaction is carried out 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 the reaction is carried out for 12 minutes. The experimental results show that the molybdenum sulfide or the bismuth vanadate which is independently added can promote the Fenton reaction, and the catalysis promoting effect of the molybdenum sulfide is slightly better than that of the 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 a synergistic promotion effect, and the catalysis promotion effect is superior to that of the molybdenum sulfide or the bismuth vanadate which is added independently. The fiber membrane prepared by the method has excellent catalysis assisting effect on a Fenton reaction system under the irradiation of visible light.
Example three:
investigating Fe in the fiber membrane pair Fenton reaction system prepared in example 1, comparative example 2 and comparative example 32+The effect of concentration.
Respectively weighing 0.5g of the fiber membrane of the sample A prepared in example 1, the fiber membrane of the sample B prepared in comparative example 1 and the fiber membrane of the sample C prepared in comparative example 2, placing the materials into a beaker of 150ml, adding 100ml of deionized water, adding 0.006g of ferrous sulfate heptahydrate into a wastewater solution under the stirring state, then adjusting the pH of the solution to 3.0 by using dilute sulfuric acid, standing the solution until adsorption balance is achieved, adding 0.003ml of hydrogen peroxide with the mass concentration of 30 percent, and placing the solution in an LED lamp (lambda)>420nm), sampling at 0.5min, 2min, 4min, 8min and 12min, adding phenanthroline solution and sodium acetate solution into the sample to be tested, and using ultraviolet-visible spectrophotometerDetermination of Fe at 510nm2+And (4) concentration.
Sample A fiber membrane, sample B fiber membrane, sample C fiber membrane and Fe in p-Fenton reaction system without fiber membrane2+The effect of concentration is shown in FIG. 2. As can be seen from FIG. 2, Fe was obtained after 2 minutes of reaction in the Fenton system without the addition of the fibrous membrane promoter2+The concentration was only 11.5% of the initial concentration, while after 4 minutes of reaction, the Fe of the system2+The concentration is reduced to 5.3 percent of the initial concentration, and the Fe of the system is reacted for 12 minutes2+The concentration is reduced to 4.5% of the initial concentration; after the fiber film of the sample B and the fiber film of the sample C are respectively added, Fe in the reaction system2+The concentration is increased to a certain extent, and after 12 minutes of reaction, Fe2+The concentration is respectively increased to 33.0 percent and 29.0 percent; after adding the sample A fiber film, Fe in the reaction system2+The concentration is obviously improved, and Fe is reacted for 12 minutes2+The concentration is increased to 60.2%. The above experimental results show that the addition of molybdenum sulfide or bismuth vanadate alone to Fe3+/Fe2+The circulation of the molybdenum sulfide has a certain promotion effect, and the promotion effect of the molybdenum sulfide is slightly superior to 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 a synergistic promotion effect on Fe3+/Fe2+The promotion effect of the circulation is better than that of the molybdenum sulfide or the bismuth vanadate which is added independently, and the promotion effect is consistent with the data rule of the degradation rate of the rhodamine B in the example 2. The fiber membrane prepared by the method can be used for treating Fe under the irradiation of visible light3+/Fe2+The cycle of the method has obvious promotion effect and has excellent promoting effect on a Fenton reaction system.
Experimental example four:
the leaching conditions of molybdenum sulfide and bismuth vanadate in the process of treating rhodamine B wastewater by using the fiber membranes prepared in the example 1 and the comparative example 3 through the catalytic Fenton reaction are examined.
Respectively weighing 0.5g of the fiber membrane of the sample A prepared in the example 1 and the fiber membrane of the sample D prepared in the comparative example 3, placing the fiber membranes into a beaker of 150ml, 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, then adjusting the pH of the solution to 3.0 by using dilute sulfuric acid, standing the solution to achieve adsorption balance, adding 0.003ml of hydrogen peroxide with the mass concentration of 30 percent, and performing a fenton reaction under the irradiation of an LED lamp (lambda is more than 420nm) to degrade the rhodamine B in the wastewater, wherein the reaction time is 12min, and no sampling is performed in the reaction process. After one experiment, the fiber membrane was taken out, washed with deionized water, dried, weighed, recorded for weight, and the leaching rate was calculated, and then the next experiment was performed, and repeated 5 times.
Under the irradiation of visible light, the leaching conditions of molybdenum sulfide and bismuth vanadate in the process of treating rhodamine B wastewater by the fiber membranes of the sample A and the sample D through the catalytic Fenton reaction are shown in figure 3. As can be seen from fig. 3, in the process of treating rhodamine B wastewater by a co-catalytic fenton reaction under the irradiation of visible light, the leaching rates of molybdenum sulfide and bismuth vanadate of the sample a fiber membrane are basically kept unchanged after 5 times of recycling, and the leaching rate is less than 0.13%; for the fiber membrane of sample D, the leaching rate is 3.2% after the first use, and after 5 times of recycling, the leaching rate is as high as 6.0%, which shows that the preparation method has obvious influence on the leaching rates of molybdenum sulfide and bismuth vanadate.
Experimental example five:
the catalysis of the fiber membranes prepared in example 1 and comparative example 4 on the treatment of rhodamine B wastewater by Fenton reaction is examined.
Respectively weighing 0.5g of the fiber membrane of the sample A prepared in the example 1 and the fiber membrane of the sample E prepared in the comparative example 4, placing the fiber membranes into a beaker of 150ml, 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, then adjusting the pH of the solution to 3.0 by using dilute sulfuric acid, standing the solution to reach adsorption balance, adding 0.003ml of hydrogen peroxide with the mass concentration of 30%, performing Fenton reaction under the irradiation of an LED lamp (lambda is more than 420nm) to degrade the rhodamine B in the wastewater, wherein the reaction time is 12min, sampling is performed at 0.5min, 2min, 4min, 8min and 12min in the reaction process, measuring the concentration of the rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer, and calculating the removal rate of the rhodamine B.
The sample A fiber membrane, the sample E fiber membrane and the fiber-free membrane are applied to the treatment of rhodamine B wastewater by the catalytic Fenton reaction, and the degradation rate of rhodamine B changes along with time as shown in figure 4. Because the Fenton reaction has certain oxidability and has the function of degrading organic matters, the degradation rate of rhodamine B in 12 minutes of reaction is 81.0 percent under the irradiation of an LED lamp when a fiber membrane is not added; 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 percent after the reaction is carried out for 12 minutes; after the fiber membrane of the sample A is added, the degradation rate of rhodamine B is obviously improved, the degradation rate of rhodamine B is improved to 99.1% after the rhodamine B reacts for 12 minutes, and the preparation method shows that the preparation method has obvious influence on the catalysis assisting effect of the Fenton reaction.
Experimental example six:
the catalysis of the fiber membranes prepared in example 1 and comparative example 5 on the treatment of rhodamine B wastewater by Fenton reaction is examined.
Respectively weighing 0.5g of the fiber membrane of the sample A prepared in the example 1 and the fiber membrane of the sample F prepared in the comparative example 5, placing the fiber membranes into a beaker of 150ml, 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, then adjusting the pH of the solution to 3.0 by using dilute sulfuric acid, standing the solution to reach adsorption balance, adding 0.003ml of hydrogen peroxide with the mass concentration of 30 percent, performing Fenton reaction under the irradiation of an LED lamp (lambda is more than 420nm) to degrade the rhodamine B in the wastewater, wherein the reaction time is 12min, sampling is respectively performed at 0.5min, 2min, 4min, 8min and 12min in the reaction process, measuring the concentration of the rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer, and calculating the removal rate of the rhodamine B.
The sample A fiber membrane, the sample F fiber membrane and the fiber membrane which is not added are applied to the treatment of rhodamine B wastewater by the catalytic Fenton reaction, and the degradation rate of rhodamine B changes along with time as shown in figure 5. Because the Fenton reaction has certain oxidability and has the function of degrading organic matters, the degradation rate of rhodamine B in 12 minutes of reaction is 81.0 percent under the irradiation of an LED lamp when a fiber membrane is not added; 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 percent after the reaction is carried out for 12 minutes; after the fiber membrane of the sample F is added, the degradation rate of rhodamine B in 12 minutes of reaction is 82.9 percent, which is obviously lower than the effect of adding the fiber membrane of the sample A, and the transparency of the fiber membrane has larger influence on the co-catalysis of the Fenton reaction.
Example seven:
the stability of the fiber membrane prepared in example 1 in the treatment of rhodamine B wastewater by Fenton reaction is examined.
Weighing 0.5g of the fiber membrane of the sample A prepared in the example 1, placing the fiber membrane into a beaker of 150ml, 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, adjusting the pH value of the solution to 3.0 by using dilute sulfuric acid, standing the solution until the adsorption balance is achieved, adding 0.003ml of hydrogen peroxide with the mass concentration of 30%, performing Fenton reaction under the irradiation of an LED lamp (lambda is more than 420nm) to degrade the rhodamine B in the wastewater, wherein the reaction time is 12min, sampling the reaction process at 0.5min, 2min, 4min, 8min and 12min respectively, measuring the concentration of the rhodamine B at 554nm by using an ultraviolet-visible spectrophotometer, and calculating the removal rate of the rhodamine B. After one experiment is finished, the fiber membrane is taken out, washed by deionized water, dried and then subjected to the next experiment, and the experiment is repeated for 5 times.
The stability of sample A in the process of treating rhodamine B wastewater by the Fenton reaction under the irradiation of visible light is shown in figure 6. As can be seen from fig. 6, after the fiber membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate prepared by the present invention is recycled for 5 times, the removal rate of rhodamine B under visible light conditions remains substantially unchanged, and the removal rate is all above 99.0%, which indicates that the fiber membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate synthesized by the present invention has a stable co-catalysis effect on a fenton reaction system, and can be reused.
The invention has the beneficial effects that: according to the bifunctional fiber membrane for promoting the catalytic Fenton reaction and the preparation method thereof, molybdenum sulfide and bismuth vanadate are simultaneously introduced into a Fenton system, and Mo in the molybdenum sulfide4+Mixing Fe3+Reduction to Fe2+Molybdenum sulfide acting as a reducing agent, Mo4+Is oxidized into Mo6+Bismuth vanadate generates photoproduction electrons under the irradiation of visible light, and the photoproduction electrons further lead Mo6+Reduction to Mo4+Mo is realized on the basis of no extra consumption of hydrogen peroxide6+/Mo4+Normal cycle of (1), and at the same time, the photo-generated electrons can also convert Fe3+Reduction to Fe2+Remarkably promotes Fe in a Fenton system3+/Fe2+The bismuth vanadate plays a role of a photocatalyst; the molybdenum sulfide and the bismuth vanadate are introduced simultaneously, so that the dual functions of a reducing agent and a photocatalyst are exerted, and considerable Fe in a Fenton system is ensured2+The concentration of the hydrogen peroxide is reduced, so that the utilization rate of the hydrogen peroxide is improved, and the treatment cost of the wastewater is effectively reduced; 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, has good flexibility and excellent mechanical property, is easier to process and mold compared with a powder material, and has wider application field; according to the prepared molybdenum sulfide and bismuth vanadate loaded polymer fiber membrane, the molybdenum sulfide and bismuth vanadate are 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 a water body is obviously superior to that of a molybdenum sulfide or bismuth vanadate-based material prepared by the traditional technology, the problem that the molybdenum sulfide and bismuth vanadate are easy to run off in the application process is solved, the molybdenum sulfide and bismuth vanadate-based material can be recycled, and the cost of wastewater treatment by a co-catalysis Fenton reaction is effectively reduced; through adding polymethyl methacrylate in polyvinylidene fluoride, improved the transparency of polymer film, further promoted the absorptivity of fibre membrane to visible light, effectual promotion fenton reaction's effect.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A difunctional fiber membrane for promoting catalytic Fenton reaction is characterized in that the fiber membrane is composed 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%.
2. The bifunctional fiber membrane for promoting a Fenton reaction according to claim 1, 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%.
3. The bifunctional fibrous membrane for promoting a Fenton's reaction according to claim 2, wherein the molybdenum sulfide crystal structure is 2H type, and bismuth vanadate is monoclinic phase.
4. The bifunctional fibrous membrane for promoting a Fenton's reaction according to claim 3, wherein the polyvinylidene fluoride has a content of 20 to 60 ten thousand g/mol.
5. The method for preparing a bifunctional fibrous membrane for a promoted fenton reaction according to claim 4, comprising the steps of:
1) performing ball milling treatment on molybdenum sulfide powder, wherein the particle size of the treated molybdenum sulfide powder is less than 200 nm;
2) performing ball milling treatment on bismuth vanadate powder, wherein the particle size of the treated bismuth vanadate powder is less than 200 nm;
3) mixing the molybdenum sulfide powder obtained in the step (1) and the bismuth vanadate powder obtained in the step (2), and continuing ball milling for 2-6 hours;
4) adding the molybdenum sulfide and the bismuth vanadate subjected to the 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 carrying out ultrasonic treatment for 1 hour at 50 ℃ to form a solution B;
6) slowly dropwise adding the solution A into the solution B, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour to obtain a spinning solution;
7) and (3) carrying out electrostatic spinning on the spinning solution to obtain a spinning product, and then drying the spinning product at 4kPa and 90 ℃ for 12 hours to obtain the fiber membrane containing molybdenum sulfide, bismuth vanadate, polyvinylidene fluoride and polymethyl methacrylate.
6. The method for preparing a bifunctional fibrous membrane for a promoted fenton reaction according to claim 5, wherein 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%.
7. The method for preparing a bifunctional fiber membrane for promoting a Fenton reaction according to claim 6, wherein in the step 7, the specific process of electrostatic spinning is as follows:
adding the spinning solution into an injector, enabling a needle head of the injector to be obliquely downward and connected with a positive electrode of a high-voltage power supply, enabling a low-speed roller wrapped by release paper to be used for collecting spinning products, placing the low-speed roller below the injector in an oblique mode, horizontally placing the low-speed roller and grounding the injector, enabling the distance between the needle head and a collecting plate to be 10cm-20cm, setting the spinning voltage to be 15kV-25kV in an environment with the relative humidity of 25% -45% at 20 ℃ -30 ℃, starting a constant-current pump to control the flow of the spinning solution in the injector to be 1 ml/hour, collecting the spinning products, and carrying out a catalytic Fenton reaction: adding ferrous sulfate heptahydrate into the wastewater solution under the stirring state, then adjusting the pH value of the solution by using dilute sulfuric acid, adding the bifunctional fiber membrane into the wastewater solution, standing for adsorption balance, adding hydrogen peroxide, and performing Fenton reaction under the irradiation of visible light to degrade organic pollutants in the wastewater.
8. The bifunctional fiber membrane for promoting the Fenton reaction according to claim 1, wherein the specific process of the promoting Fenton reaction is as follows: adding ferrous sulfate heptahydrate into a wastewater solution containing organic pollutants under a stirring state, adjusting the pH value of the solution by using dilute sulfuric acid, adding the bifunctional fiber membrane into the wastewater solution, standing for adsorption balance, adding hydrogen peroxide, and performing a Fenton reaction under the irradiation of visible light to degrade the organic pollutants in the wastewater.
9. The catalytic Fenton's reaction process according to claim 8, wherein the amount of ferrous sulfate heptahydrate is 0.05-0.50 mmol/L; the ratio of the hydrogen peroxide to the ferrous sulfate heptahydrate is 1.0-10.0; the dosage of the difunctional fiber membrane is 0.25-5.0 g/L; the pH value of the solution is 2.0-6.0; the concentration of the organic pollutants is 10-40 mg/L; the organic pollutants are one or more of rhodamine B, phenol and N, N-dimethylformamide; the reaction time is 5-20 minutes.
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