CN115228309A - Preparation method and application of oil-water separation mineralization film with photocatalysis and antibacterial functions - Google Patents
Preparation method and application of oil-water separation mineralization film with photocatalysis and antibacterial functions Download PDFInfo
- Publication number
- CN115228309A CN115228309A CN202210986646.6A CN202210986646A CN115228309A CN 115228309 A CN115228309 A CN 115228309A CN 202210986646 A CN202210986646 A CN 202210986646A CN 115228309 A CN115228309 A CN 115228309A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- membrane
- mineralization
- separation
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 238000000926 separation method Methods 0.000 title claims abstract description 145
- 230000033558 biomineral tissue development Effects 0.000 title claims abstract description 91
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 54
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 48
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 138
- 210000004379 membrane Anatomy 0.000 claims abstract description 137
- 239000007864 aqueous solution Substances 0.000 claims abstract description 129
- 239000008367 deionised water Substances 0.000 claims abstract description 111
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 111
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 99
- 238000002791 soaking Methods 0.000 claims abstract description 81
- 239000000243 solution Substances 0.000 claims abstract description 69
- 238000005406 washing Methods 0.000 claims abstract description 59
- 239000001509 sodium citrate Substances 0.000 claims abstract description 57
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 57
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 53
- 238000001035 drying Methods 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 5
- PCIGTTWKYUNLEP-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;titanium;dihydrate Chemical compound N.N.O.O.[Ti].CC(O)C(O)=O.CC(O)C(O)=O PCIGTTWKYUNLEP-UHFFFAOYSA-N 0.000 claims description 43
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 17
- -1 bis (2-hydroxypropionic acid) diammonium dihydroxide titanium hydrate Chemical compound 0.000 claims description 16
- 230000003115 biocidal effect Effects 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 230000003373 anti-fouling effect Effects 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- DELALDBRGCSCBZ-UHFFFAOYSA-L 2-hydroxypropanoate;titanium(2+);dihydrate Chemical compound O.O.[Ti+2].CC(O)C([O-])=O.CC(O)C([O-])=O DELALDBRGCSCBZ-UHFFFAOYSA-L 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 3
- FAOZOTRMNZCRRW-UHFFFAOYSA-N C(C(O)C)(=O)O.C(C(O)C)(=O)O.[NH4+].[OH-].[OH-].[NH4+] Chemical compound C(C(O)C)(=O)O.C(C(O)C)(=O)O.[NH4+].[OH-].[OH-].[NH4+] FAOZOTRMNZCRRW-UHFFFAOYSA-N 0.000 abstract 1
- 101710134784 Agnoprotein Proteins 0.000 description 39
- 229910010413 TiO 2 Inorganic materials 0.000 description 26
- 238000005303 weighing Methods 0.000 description 25
- 230000001089 mineralizing effect Effects 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 11
- 230000004907 flux Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 235000019476 oil-water mixture Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 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 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 239000002585 base Substances 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
- 238000011109 contamination Methods 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- CPWZPANSGPSCFX-UHFFFAOYSA-N [NH4+].[NH4+].CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [NH4+].[NH4+].CC(O)C([O-])=O.CC(O)C([O-])=O CPWZPANSGPSCFX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- AGYAOGDEHQSPNF-UHFFFAOYSA-N [Ti].[OH-].[OH-].[NH4+].[NH4+] Chemical compound [Ti].[OH-].[OH-].[NH4+].[NH4+] AGYAOGDEHQSPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003501 co-culture Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/59—
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- 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
- C02F2305/10—Photocatalysts
Abstract
The invention discloses an oil-water separation mineralization film with photocatalysis and antibacterial functions, and a preparation method of the oil-water separation mineralization film comprises the following steps: (1) Soaking the hydrophilic basement membrane in a polyethyleneimine water solution, then soaking in a bis (2-hydroxypropionic acid) diammonium dihydroxide and titanium aqueous solution, repeating the alternate soaking process, washing with deionized water, and drying to obtain a titanium dioxide mineralized separation membrane; (2) Soaking the titanium dioxide mineralization separation membrane in a mixed solution of a silver nitrate aqueous solution and a sodium citrate aqueous solution, and reacting for 10-30min at the rotating speed of 300-500rpm and the reaction temperature of 60-80 ℃ to prepare the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions. The mineralized membrane prepared by the invention has photocatalysis and antibacterial properties, and the long-term durability and the application range of the separation membrane are improved.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to a preparation method and application of an oil-water separation mineralization film with photocatalysis and antibacterial functions.
Background
The discharge of oil/water pollutants generated in the household or industrial fields of food, petroleum, manufacturing industry and the like, and the direct discharge of a large amount of oil spills and oily wastewater at sea destroy the balance of an ecological system and threaten the health of human beings. Membrane separation techniques are considered to be one of the most effective methods of treating oil/water mixtures. However, the separation membrane is inevitably polluted by oil stains in the long-term use process, so that the separation efficiency and the flux are obviously reduced. In addition, the oily sewage in daily life usually contains a large amount of bacteria or microorganisms, and when passing through the separation membrane, the bacteria and microorganisms on the separation membrane cause the blockage of pores, which also results in the reduction of the separation flux. The traditional method is to wash the membrane with a large amount of water after use or directly replace a new membrane, which causes waste of resources. Therefore, it is necessary to impart photocatalytic properties and antimicrobial properties to the separation membrane in order to improve the service life thereof.
Titanium dioxide (TiO) 2 ) The catalyst is a semiconductor material with excellent catalytic performance under ultraviolet irradiation, and is widely used due to the advantages of no toxicity, stability, low price and the like. When it exceeds TiO 2 When light with the band gap width irradiates the surface, electrons in a valence band absorb energy and jump to a conduction band, holes are generated at the corresponding position of the valence band, and the hole-electron pairs can induce the surface to generate a strong oxidant, so that TiO is degraded 2 Ambient organic contaminants.
At present, the crystal structures of titanium dioxide commonly used for photocatalysis mainly comprise anatase and rutile, but the preparation process of the titanium dioxide mostly needs high-temperature heat treatment, which is not beneficial to reducing the cost and being safe and environment-friendly; and TiO directly supported on the membrane 2 Easily fall off to lose the photocatalytic performance. Therefore, how to use the polymer to mineralize in situ under mild conditions to prepare the long-acting and high-efficiency photocatalytic titanium dioxide mineralized film has important significance for oil-water separation.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method and application of an oil-water separation mineralization film with both photocatalysis and antibacterial functions. The surface of the mineralized film of the invention is provided with Ag nano particles which are evenly attached to TiO 2 On the mineralized layer, the high-efficiency oil-water separation performance is achieved, the separation of photo-generated electron-hole pairs is promoted through the deposition of the noble metal Ag on the surface of the titanium dioxide, meanwhile, the energy band structure of the titanium dioxide is changed, absorption of energy photons is facilitated, the utilization rate of sunlight is increased, the prepared mineralized membrane has photocatalysis and antibacterial properties, and the long-term durability and the application range of the separation membrane are improved.
The technical scheme of the invention is as follows:
the preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Soaking a hydrophilic basement membrane in a Polyethyleneimine (PEI) aqueous solution, taking out the hydrophilic basement membrane, washing the hydrophilic basement membrane with deionized water, soaking the hydrophilic basement membrane in a di (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution, taking out the hydrophilic basement membrane, washing the hydrophilic basement membrane with deionized water, forming an alternate soaking cycle, repeating the alternate soaking process, washing the hydrophilic basement membrane with deionized water, and drying the hydrophilic basement membrane to obtain a titanium dioxide mineralized separation membrane;
(2) Soaking the titanium dioxide mineralization separation membrane prepared in the step (1) in a mixed solution of a silver nitrate aqueous solution and a sodium citrate aqueous solution, reacting for 10-30min at the rotating speed of 300-500rpm and the reaction temperature of 60-80 ℃, taking out the separation membrane, washing with deionized water, and drying in an oven to prepare the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
In the step (1), the hydrophilic base membrane is one of a polyvinylidene fluoride membrane subjected to hydrophilic treatment, a polytetrafluoroethylene membrane (PTFE) subjected to hydrophilic treatment and a stainless steel mesh subjected to hydrophilic treatment.
In the step (1), the concentration of the polyethyleneimine aqueous solution is 10-30g/L, and the pH of the polyethyleneimine solution is 6.8-7.4.
In the step (1), the concentration of the aqueous solution of the di (2-hydroxypropionic acid) diammonium dihydroxide titanium hydrate is 10-30g/L.
In the step (1), the volume of the polyethyleneimine solution and the bis (2-hydroxypropionic acid) diammonium dihydroxide titanium solution is 1.
In the step (1), the soaking time in the polyethyleneimine water solution or the soaking time in the di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution is 3-15min, the soaking time of each alternate soaking cycle is kept consistent, and the number of alternate soaking cycles is 1-10. Preferably, soaking for 10min, and circulating for 3 times;
in the step (2), the concentration of the silver nitrate aqueous solution is 0.85-3.4g/L.
In the step (2), the concentration of the sodium citrate water solution is 5-15g/L.
In the step (2), the volume ratio of the sodium citrate aqueous solution to the silver nitrate aqueous solution in the mixed solution is 3 to 5, and is 18 to 25, preferably 3.
The application of the oil-water separation mineralization film with both photocatalysis and antibacterial functions, which is prepared by the preparation method, is used in the fields of oil-water separation, photocatalysis, antibacterial, antifouling coating and packaging.
The beneficial technical effects of the invention are as follows:
the surface of the mineralized membrane is attached with Ag nano particles with the particle size of about 80-100nm, and the mineralized membrane is closely attached to the base material and has super-hydrophilicity, photocatalysis and antibacterial property.
Based on a hydrophilic base film, in-situ mineralization of polyethyleneimine is used for generating titanium dioxide under mild conditions, multiple layers of titanium dioxide mineralization films are prepared by alternate deposition, and silver nanoparticles are loaded on the surfaces of the titanium dioxide mineralization films to obtain silver-loaded titanium dioxide oil-water separation mineralization films; the light absorption of titanium dioxide is enhanced through the plasma resonance effect (APR) of Ag, so that the separation membrane has a strong photocatalytic effect, and long-acting photocatalysis and antibacterial properties are realized.
The mineralized membrane prepared by the invention keeps chemical stability in acid, alkali and other solutions; the oil-water mixture containing bacteria can be efficiently classified; after ultraviolet irradiation, the oil stain on the surface can be degraded.
The invention utilizes the electrostatic and hydrogen bond interaction of polyethyleneimine and di (2-hydracrylic acid) diammonium dihydroxide titanium to prepare TiO on the base film 2 Mineralizing the film using TiO 2 The prepared separation membrane can be used for separating a plurality of common oil-water mixtures, the separation efficiency reaches 98 percent, and the separation flux of the oil-water mixture reaches 6238 L.m -2 ·h -1 . The separation flux of the emulsion prepared by using normal hexane as an oil phase is 663 L.m -2 ·h -1 . And after UV irradiation, the TiO is 2 The mineralized membrane can degrade residual oil stains on the surface and prolong the service life of the separation membrane. Meanwhile, ag nanoparticles attached to the surface of the composite material have broad-spectrum antibacterial property, the mineralized membrane can efficiently separate oil-water mixtures containing bacteria, and compared with a common separation membrane, the composite material has longer service life.
The invention introduces Ag into TiO 2 In the separation membrane, the photocatalysis performance of the separation membrane can be improved, and the antibacterial performance to bacteria or microorganisms can be realized, so that the separation membrane has long-acting and high-efficiency separation performance.
In the mineralization system of Ti-BALDH/PEI, PEI is used as TiO 2 After the growth inducer is soaked in a PEI solution, PEI molecules are firstly adsorbed on the surface of a basement membrane; then the positively charged PEI molecules adsorb and negatively charged titanium precursors (Ti-BALDH molecules) by electrostatic and hydrogen bonding interactions; when the PEI molecule and the Ti-BALDH molecule are very close, the hydrogen bond between the Ti-OH of the Ti-BALDH molecule and the N-H of the PEI molecule attacks the Ti-O bond on another adjacent titanium atom to generate nucleophilic substitution; with the progress of the mineralization reaction, the titanium dioxide and the basement membrane have polycondensation reaction to generate uniform TiO 2 And (4) mineralizing the membrane. With the increase of the alternate soaking times, the surface mineralized film can grow layer by layer. Therefore, tiO can be controlled by controlling the soaking time and the alternate soaking times 2 The mineralized membrane is uniformly and tightly attached to the PTFE fiber, so that the super-hydrophilicity is ensured, and the aperture of the separation membrane is not influenced.
Drawings
FIG. 1 shows PTFE-TiO prepared in example 1 2 Schematic water contact angle of Ag films before (a) and after (b) and after photocatalysis of stearic acid contamination (c); FIGS. d, e, f PTFE-TiO, respectively 2 Photos of Ag film and original film before (d) and after (e) stearic acid contamination, and photo after 5min photocatalysis after contamination (f);
FIG. 2 is a graph of separation-catalytic cycle number versus water flux;
FIG. 3 shows that no PTFE-TiO is added 2 Ag films (a, c) with addition of PTFE-TiO 2 Images of colonies of E.coli (a, b) and Staphylococcus aureus (c, d) after 24h incubation in the culture medium of Ag membrane (b, d).
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
The purchased PTFE membrane does not need to be cut, and is respectively cleaned by acetone, ethanol and water for 5min by ultrasonic waves and then soaked in distilled water for standby;
example 1
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 3 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 2
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring evenly in the water solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 3
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 5min, and takingWashing with deionized water after the reaction, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium bihydrogen oxide titanium (Ti-BALDH) aqueous solution for 5min, taking out, washing with deionized water, repeating the alternate soaking process for 3 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 4
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibiosis functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) water solution for 5min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) water solution for reaction for 5min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized waterAnd drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL of deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring evenly in the water solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 5
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 3min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 3min, taking out, washing with deionized water, repeating the alternate soaking process for 3 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL deionized water to prepare AgNO 3 An aqueous solution; citric acid was prepared by weighing 1g of sodium citrate and dissolving in 100mL of deionized waterAn aqueous sodium solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 6
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a bis (2-hydroxypropionic acid) diammonium dihydroxide titanium water solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 3min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 3min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 Soaking the mineralized separation membrane in the mixed solution prepared in the step (3)And (3) reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralized membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the silver nanoparticle-loaded titanium dioxide mineralized separation membrane, namely the oil-water separation mineralized membrane with both photocatalysis and antibacterial functions.
Example 7
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized water and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.17g AgNO 3 Dissolving in 100mL deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 Soaking the mineralized separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotating speed of 450rpm and the temperature of 60 ℃, taking out the mineralized separation membrane to be washed by deionized water after the reaction is finished, and putting the mineralized separation membrane into an oven for drying to prepare the titanium dioxide mineralized separation membrane loaded with silver nanoparticles, namely the titanium dioxide mineralized separation membrane with both photocatalysis and antibacterial functionsThe oil-water separation mineralization film.
Example 8
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) 0.34g of AgNO was weighed 3 Dissolving in 100mL of deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 9
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized water and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL of deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring evenly in the water solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 70 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 10
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of bis (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a bis (2-hydroxypropionic acid) diammonium titanium dihydroxide aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL of deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 80 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 11
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 5 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL of deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring evenly in the water solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (4) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 15min at the rotation speed of 450rpm and the temperature of 80 ℃, taking out the mineralization separation membrane after the reaction is finished, washing the mineralization separation membrane with deionized water, and drying the mineralization separation membrane in an oven to prepare the titanium dioxide mineralization separation membrane loaded with the silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 12
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated PTFE membrane in 20mL of Polyethyleneimine (PEI) water solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium bihydrogen oxide titanium (Ti-BALDH) water solution for reaction for 10min, taking out, and then adding deionized waterWashing, repeating the alternate soaking process for 5 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolving in 100mL of deionized water to prepare AgNO 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring uniformly in the aqueous solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (3) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 10min at the rotation speed of 450rpm and the temperature of 80 ℃, taking out the mineralization membrane and washing with deionized water after the reaction is finished, and drying in an oven to obtain the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
Example 13
The preparation method of the oil-water separation mineralization film with both photocatalysis and antibacterial functions comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 100mL of deionized water, and adjusting the pH of the polyethyleneimine solution to 7 by using 1mol/L of HCl solution to prepare a polyethyleneimine aqueous solution; dissolving 4g of di (2-hydroxypropionic acid) diammonium titanium dihydroxide into 100mL of deionized water to prepare a di (2-hydroxypropionic acid) diammonium titanium dihydroxide titanium aqueous solution; placing a beaker filled with a polyethyleneimine water solution and a di (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution on a magnetic stirrer with the rotating speed of 400rpm for later use;
(2) Soaking the pretreated stainless steel mesh membrane in 20mL of Polyethyleneimine (PEI) aqueous solution for 10min, taking out, washing with deionized water, soaking in 20mL of bis (2-hydroxypropionic acid) diammonium dihydroxide titanium (Ti-BALDH) aqueous solution for reaction for 10min, taking out, washing with deionized water, repeating the alternate soaking process for 3 times, taking out, washing with deionized water, and drying to obtain TiO 2 Mineralizing the separation membrane;
(3) Weighing 0.085g AgNO 3 Dissolved in 100mL of deionized waterIn water, agNO was prepared 3 An aqueous solution; weighing 1g of sodium citrate, and dissolving the sodium citrate in 100mL of deionized water to prepare a sodium citrate aqueous solution; adding 3mL of the sodium citrate aqueous solution into 20mL of AgNO 3 Stirring evenly in the water solution to prepare a mixed solution;
(4) TiO prepared in the step (2) 2 And (4) soaking the mineralization separation membrane in the mixed solution prepared in the step (3), reacting for 20min at the rotation speed of 450rpm and the temperature of 60 ℃, taking out the mineralization separation membrane after the reaction is finished, washing the mineralization separation membrane with deionized water, and drying the mineralization separation membrane in an oven to prepare the titanium dioxide mineralization separation membrane loaded with the silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
The above embodiments are only for embodying the inventive concept of the inventor, and any type of evolution and improvement based on the inventive concept of the invention are within the protection scope of the invention.
Test example:
(1) The measurement results of the oil-water separation efficiency are as follows: completely performing oil-water separation by gravity self-driving, mixing 100mL of deionized water and 100mL of n-hexane, and separating with a separation efficiency of eta = (m) 1 /m 0 ) X 100% where m 0 And m 1 Respectively the quality of the water before and after the separation process.
(2) The measurement results of the oil-water separation flux involved: the effective test membrane area is 9.62cm by adopting a laboratory oil-water separation device 2 100mL of the aqueous phase was continuously poured from above the apparatus onto the surface of a stainless steel mesh. The oil-water separation flux is calculated by the formula:
wherein v is the volume of water permeating the membrane; a is the effective filtration area of the membrane; Δ t is the permeation time.
(3) The method for measuring the mechanical stability comprises the following steps: the method comprises the steps of selecting sand paper with the model of 1000 meshes, sliding an oil-water separation mineralization film on the sand paper for 10cm, sequentially washing away powder generated on the surface of the film by deionized water and nitrogen, testing the stability of the oil-water separation mineralization film after the sand paper is rubbed, and testing each sample for 3 times to calculate an average value.
(4) The related chemical stability determination method comprises the following steps: the prepared oil-water separation mineralization film is soaked in 0.1mol of HCl, naOH and NaCl solution for 30min, and the water contact angle of the film is measured.
(5) Measurement results of the photocatalytic performance involved:
mixing PTFE-TiO 2 Membrane and PTFE-TiO 2 Soaking the Ag film in 1g/L stearic acid solution for 20min, taking out, drying, and measuring the contact angle. Placing under a xenon lamp parallel light source with a height of 7cm, and illuminating in dark for 10min as a group of cycles for multiple cycles. Preparing 5mg/L rhodamine B solution, soaking the mineralized membrane in a surface dish filled with 10mL of rhodamine B solution, placing the surface dish under a xenon lamp parallel light source for irradiation, wherein the height is 7cm, and the irradiation is performed for 10min in a dark environment to form a group of circulation, and multiple circulation is performed. And the method can prevent the evaporation of rhodamine B from causing the reduction of the volume of the solution to influence the measurement result, calculate the concentration of the residual rhodamine B through ultraviolet measurement after each measurement, and supplement the rhodamine B solution with the same concentration to 10mL.
(6) The measurement results of the antibacterial properties are as follows:
culturing gram-positive Staphylococcus aureus (S.aureus) and gram-negative Escherichia coli (E.coli) in nutrient broth at 37 deg.C in water bath constant temperature oscillator for 12 hr to reach bacteria concentration of 10 8 cfu·mL -1 Diluting to a certain concentration, adding ultraviolet sterilized 1cm 2 Of PTFE-TiO 2 Ag film, blank without PTFE-TiO 2 Ag film, after further culturing for 3 h. And uniformly coating 100 mu L of cultured bacterial liquid on a solid culture medium, culturing at 37 ℃ for 24h, and counting the number of colonies on the culture medium.
10mL of 10-concentrated oil-water mixture (n-hexane as oil phase) was added to 200mL of the oil-water mixture 8 cfu·mL -1 The suspension of Escherichia coli and Staphylococcus aureus is prepared by using PTFE-TiO 2 The Ag membrane is subjected to an oil-water separation cycle separation test.
The results of the performance tests on the oil-water separation mineralization films obtained in examples 1, 5, 7, 9 and 11 are shown in table 1:
TABLE 1
The separation membrane prepared in example 1 was subjected to oil-water separation performance test, photocatalytic test, and antibacterial test. The normal hexane is used as an oil phase, the separation efficiency of an oil-water mixture reaches 98%, and the separation flux reaches 6238 L.m -2 ·h -1 . The separation flux of the emulsion prepared by using normal hexane as an oil phase is 663 L.m -2 ·h -1 . Meanwhile, the stearic acid is used as a pollutant model to test the photodegradable performance of the film, the separating film loses the super-hydrophilic performance after the stearic acid is polluted, the separating film recovers the super-hydrophilic performance after the ultraviolet light is irradiated, the stearic acid dyed with red oil on the mineralized film is gradually degraded, the mineralized film recovers the white color, and the original film is still red even after the original film is irradiated by the light. (FIG. 1) the separation-catalysis can be circulated for more than 5 times (FIG. 2), which shows that the prepared separation membrane has long-acting separation performance and reusability. By means of Escherichia coli and Staphylococcus aureus with PTFE-TiO 2 Co-culture experiments of-Ag films demonstrated excellent antibacterial properties (FIG. 3).
Claims (10)
1. The oil-water separation mineralization film with both photocatalysis and antibiosis functions is characterized in that the preparation method of the oil-water separation mineralization film comprises the following steps:
(1) Soaking the hydrophilic basement membrane in a polyethyleneimine water solution, taking out the basement membrane, washing the basement membrane by using deionized water, soaking the basement membrane in a bis (2-hydroxypropionic acid) diammonium dihydroxide titanium hydrate water solution, taking out the basement membrane, washing the basement membrane by using deionized water, performing an alternate soaking cycle, repeating the alternate soaking process, washing the basement membrane by using the deionized water, and drying the basement membrane to obtain the titanium dioxide mineralized separation membrane;
(2) Soaking the titanium dioxide mineralization separation membrane prepared in the step (1) in a mixed solution of a silver nitrate aqueous solution and a sodium citrate aqueous solution, reacting for 10-30min at the rotating speed of 300-500rpm and the reaction temperature of 60-80 ℃, taking out the separation membrane, washing with deionized water, and drying in an oven to prepare the titanium dioxide mineralization separation membrane loaded with silver nanoparticles, namely the oil-water separation mineralization membrane with both photocatalysis and antibacterial functions.
2. The method according to claim 1, wherein in the step (1), the hydrophilic base film is one of a hydrophilic-treated polyvinylidene fluoride film, a hydrophilic-treated polytetrafluoroethylene film, and a hydrophilic-treated stainless steel mesh.
3. The method according to claim 1, wherein in the step (1), the concentration of the polyethyleneimine aqueous solution is 10 to 30g/L, and the pH of the polyethyleneimine solution is 6.8 to 7.4.
4. The method according to claim 1, wherein in the step (1), the concentration of the aqueous solution of bis (2-hydroxypropionic acid) diammonium titanium dihydroxide and titanium is 10 to 30g/L.
5. The method according to claim 1, wherein in step (1), the volume of the polyethyleneimine solution and the solution of bis (2-hydroxypropionic acid) titanium dihydroxide is 1.
6. The preparation method according to claim 1, wherein in the step (1), the soaking time in the polyethyleneimine aqueous solution or in the bis (2-hydroxypropionic acid) diammonium dihydroxide titanium aqueous solution is 3-15min, the soaking time in each alternate soaking cycle is consistent, and the number of alternate soaking cycles is 1-10.
7. The method according to claim 1, wherein in the step (2), the concentration of the silver nitrate aqueous solution is 0.85 to 3.4g/L.
8. The method according to claim 1, wherein in the step (2), the concentration of the aqueous solution of sodium citrate is 5 to 15g/L.
9. The method according to claim 1, wherein in the step (2), the volume ratio of the aqueous solution of sodium citrate to the aqueous solution of silver nitrate in the mixed solution is 3 to 5.
10. The application of the oil-water separation mineralized membrane prepared by the preparation method of claim 1 and having the functions of photocatalysis and antibiosis is characterized by being used in the fields of oil-water separation, photocatalysis, antibiosis, antifouling coating and packaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210986646.6A CN115228309A (en) | 2022-08-17 | 2022-08-17 | Preparation method and application of oil-water separation mineralization film with photocatalysis and antibacterial functions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210986646.6A CN115228309A (en) | 2022-08-17 | 2022-08-17 | Preparation method and application of oil-water separation mineralization film with photocatalysis and antibacterial functions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115228309A true CN115228309A (en) | 2022-10-25 |
Family
ID=83678416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210986646.6A Pending CN115228309A (en) | 2022-08-17 | 2022-08-17 | Preparation method and application of oil-water separation mineralization film with photocatalysis and antibacterial functions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115228309A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497003A (en) * | 2009-01-24 | 2009-08-05 | 大连理工大学 | Multifunctional photocatalysis composite ceramic separation membrane as well as preparation method and use thereof |
| CN102580566A (en) * | 2012-03-16 | 2012-07-18 | 北京工业大学 | Method for in situ generating inorganic nano particles-polyelectrolyte hybrid membrane |
| CN102895888A (en) * | 2012-10-12 | 2013-01-30 | 福州大学 | Polyvinylidene fluoride film capable of responding to visible light and preparation method of polyvinylidene fluoride film |
| CN103394294A (en) * | 2013-08-08 | 2013-11-20 | 哈尔滨工业大学 | Preparation method of high-performance PVDF composite ultrafiltration membrane with surface loaded with TiO2 thin membrane |
| CN106512553A (en) * | 2016-11-14 | 2017-03-22 | 安徽名杰净化科技有限公司 | Electrostatic spun/electret composite fiber filter material comprising sodium tartrate intercalated hydrotalcite and preparation method of filter material |
| CN108176255A (en) * | 2017-12-30 | 2018-06-19 | 浙江工业大学 | A kind of Kynoar-titania hybrid film and its preparation method and application |
| CN108380063A (en) * | 2018-02-27 | 2018-08-10 | 天津大学 | A kind of preparation method of nano titanium dioxide hybrid composite nanometer filtering film |
| CN108744990A (en) * | 2018-06-01 | 2018-11-06 | 徐州医科大学 | A kind of titanium dioxide nanofiber membrane material of modified by silver nanoparticles and its preparation method and application |
| CN108889145A (en) * | 2018-07-16 | 2018-11-27 | 山东大学 | A kind of Ag and TiO2Pass through the co-modified PES microfiltration membranes and the preparation method and application thereof of dopamine |
| CN109433029A (en) * | 2018-11-15 | 2019-03-08 | 山东大学 | A kind of preparation method of the reverse osmosis membrane of anti-pollution type doped cerium oxide and silver nano-grain |
| WO2019137054A1 (en) * | 2018-01-09 | 2019-07-18 | 时代沃顿科技有限公司 | Preparation method for super-hydrophilic ultrafiltration membrane having photocatalytic properties |
| US20210046431A1 (en) * | 2019-08-14 | 2021-02-18 | King Fahd University Of Petroleum And Minerals | Simultaneous sorption of dyes and toxic metals from waters using titania-incorporated polyamide |
-
2022
- 2022-08-17 CN CN202210986646.6A patent/CN115228309A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497003A (en) * | 2009-01-24 | 2009-08-05 | 大连理工大学 | Multifunctional photocatalysis composite ceramic separation membrane as well as preparation method and use thereof |
| CN102580566A (en) * | 2012-03-16 | 2012-07-18 | 北京工业大学 | Method for in situ generating inorganic nano particles-polyelectrolyte hybrid membrane |
| CN102895888A (en) * | 2012-10-12 | 2013-01-30 | 福州大学 | Polyvinylidene fluoride film capable of responding to visible light and preparation method of polyvinylidene fluoride film |
| CN103394294A (en) * | 2013-08-08 | 2013-11-20 | 哈尔滨工业大学 | Preparation method of high-performance PVDF composite ultrafiltration membrane with surface loaded with TiO2 thin membrane |
| CN106512553A (en) * | 2016-11-14 | 2017-03-22 | 安徽名杰净化科技有限公司 | Electrostatic spun/electret composite fiber filter material comprising sodium tartrate intercalated hydrotalcite and preparation method of filter material |
| CN108176255A (en) * | 2017-12-30 | 2018-06-19 | 浙江工业大学 | A kind of Kynoar-titania hybrid film and its preparation method and application |
| WO2019137054A1 (en) * | 2018-01-09 | 2019-07-18 | 时代沃顿科技有限公司 | Preparation method for super-hydrophilic ultrafiltration membrane having photocatalytic properties |
| CN108380063A (en) * | 2018-02-27 | 2018-08-10 | 天津大学 | A kind of preparation method of nano titanium dioxide hybrid composite nanometer filtering film |
| CN108744990A (en) * | 2018-06-01 | 2018-11-06 | 徐州医科大学 | A kind of titanium dioxide nanofiber membrane material of modified by silver nanoparticles and its preparation method and application |
| CN108889145A (en) * | 2018-07-16 | 2018-11-27 | 山东大学 | A kind of Ag and TiO2Pass through the co-modified PES microfiltration membranes and the preparation method and application thereof of dopamine |
| CN109433029A (en) * | 2018-11-15 | 2019-03-08 | 山东大学 | A kind of preparation method of the reverse osmosis membrane of anti-pollution type doped cerium oxide and silver nano-grain |
| US20210046431A1 (en) * | 2019-08-14 | 2021-02-18 | King Fahd University Of Petroleum And Minerals | Simultaneous sorption of dyes and toxic metals from waters using titania-incorporated polyamide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Abdelhaleem et al. | Photodegradation of 4-chlorophenoxyacetic acid under visible LED activated N-doped TiO2 and the mechanism of stepwise rate increment of the reused catalyst | |
| Baruah et al. | Nanostructured zinc oxide for water treatment | |
| Ahmadpour et al. | A hierarchical Ca/TiO 2/NH 2-MIL-125 nanocomposite photocatalyst for solar visible light induced photodegradation of organic dye pollutants in water | |
| Lin et al. | Iodine-modified nanocrystalline titania for photo-catalytic antibacterial application under visible light illumination | |
| Fischer et al. | Photoactive microfiltration membranes via directed synthesis of TiO2 nanoparticles on the polymer surface for removal of drugs from water | |
| CN101961662B (en) | Method for preparing ion imprinting supported composite photocatalyst | |
| Chauhan et al. | Immobilization of titania nanoparticles on the surface of cellulose fibres by a facile single step hydrothermal method and study of their photocatalytic and antibacterial activities | |
| Pinho et al. | Oxidation of microcystin-LR and cylindrospermopsin by heterogeneous photocatalysis using a tubular photoreactor packed with different TiO2 coated supports | |
| Matoh et al. | Photocatalytic water treatment | |
| Cui et al. | Fabrication of silver vanadate quantum dots/reduced graphene oxide/graphitic carbon nitride Z-scheme heterostructure modified polyvinylidene fluoride self-cleaning membrane for enhancing photocatalysis and mechanism insight | |
| Yue et al. | Ag/AgBr/AgVO3 photocatalyst-embedded polyacrylonitrile/polyamide/chitosan nanofiltration membrane for integrated filtration and degradation of RhB | |
| CN108654586A (en) | A kind of graphitization mesoporous carbon-TiO2Composite photocatalyst material and the preparation method and application thereof | |
| Rengifo-Herrera et al. | Why five decades of massive research on heterogeneous photocatalysis, especially on TiO2, has not yet driven to water disinfection and detoxification applications? Critical review of drawbacks and challenges | |
| Wan et al. | PDA/PEI-induced in-situ growth of a lotus leaf-like TiO2 nanoparticle film on N-halamine cotton fabric for photocatalytic, self-cleaning and efficient antibacterial performance | |
| Li et al. | Polyethylene imine-grafted ACF@ BiOI0. 5Cl0. 5 as a recyclable photocatalyst for high-efficient dye removal by adsorption-combined degradation | |
| CN111632618A (en) | Preparation method and application of supported double-doped modified titanium dioxide photocatalyst | |
| Arif et al. | Development of eco-friendly, self-cleaning, antibacterial membrane for the elimination of chromium (VI) from tannery wastewater | |
| Hernández-Del Castillo et al. | An eco-friendly and sustainable support of agave-fibers functionalized with graphene/TiO2: SnO2 for the photocatalytic degradation of the 2, 4-D herbicide from the drinking water | |
| Liu et al. | Removal of antibiotics from black water by a membrane filtration-visible light photocatalytic system | |
| Zhang et al. | In situ recombination for durable photoelectrocatalytic degradation of organic dye in wastewater | |
| Zhang et al. | A multifunctional composite membrane with photocatalytic, self-cleaning, oil/water separation and antibacterial properties | |
| Almasi et al. | Photocatalytic activity and water purification performance of in situ and ex situ synthesized bacterial cellulose‐CuO nanohybrids | |
| Safari et al. | Construction of recoverable Ag2SeO3/Ag3PO4/MWCNT/PVDF porous film photocatalyst with enhanced photocatalytic performance for degrading Indigo carmine dye in continuous flow-loop photoreactor | |
| CN115228309A (en) | Preparation method and application of oil-water separation mineralization film with photocatalysis and antibacterial functions | |
| Baig et al. | Fabrication of polypyrrole-graphitic carbon nitride nanocomposite containing hyper-cross-linked polyamide photoresponsive membrane with self-cleaning properties for water decontamination and desalination applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |