CN110787645A - Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof - Google Patents
Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN110787645A CN110787645A CN201910978918.6A CN201910978918A CN110787645A CN 110787645 A CN110787645 A CN 110787645A CN 201910978918 A CN201910978918 A CN 201910978918A CN 110787645 A CN110787645 A CN 110787645A
- Authority
- CN
- China
- Prior art keywords
- cds
- photocatalyst
- membrane
- ultrafiltration membrane
- rgo
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 197
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 137
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 134
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 121
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 229910001868 water Inorganic materials 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 37
- 238000005266 casting Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000007790 scraping Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000002073 nanorod Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000002135 nanosheet Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 239000000356 contaminant Substances 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 16
- 241000588724 Escherichia coli Species 0.000 abstract description 16
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 15
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 241000192125 Firmicutes Species 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 230000002147 killing effect Effects 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 230000036619 pore blockages Effects 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 162
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 158
- 239000000243 solution Substances 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 10
- 239000004021 humic acid Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 9
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 9
- 229940098773 bovine serum albumin Drugs 0.000 description 9
- 230000002779 inactivation Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 235000010413 sodium alginate Nutrition 0.000 description 9
- 229940005550 sodium alginate Drugs 0.000 description 9
- 239000000661 sodium alginate Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/022—Membrane sterilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- 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
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- 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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/34—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention relates to a visible light photocatalyst modified PVDF ultrafiltration membrane, a preparation method and application thereof, wherein the ultrafiltration membrane is CdS/g-C3N4PVDF ultrafiltration membrane modified by/rGO nano photocatalyst, wherein in the ultrafiltration membrane, PVDF is used as a matrix, and CdS/g-C3N4the/rGO nano photocatalyst is used as an active component, and the active component is uniformly distributed in the matrix; the ultrafiltration membrane is prepared from the following components in parts by weight: 17-19 parts of polyvinylidene fluoride, 2.5-3.5 parts of polyvinylpyrrolidone, 77-79 parts of N, N-dimethylacetamide and CdS/g-C3N40.3-1.3 parts of/rGO nano photocatalyst; the modified PVDF ultrafiltration membrane is applied to resisting organic membrane pollutants or bacteria. Compared with the prior art, the modified membrane provided by the invention has high hydrophilicity and good photocatalytic activity, can effectively reduce membrane pore blockage caused by organic pollutants under the irradiation of visible light, has good killing effect on gram-negative bacteria represented by escherichia coli and gram-positive bacteria represented by staphylococcus aureus, can obviously inhibit the formation of a biological membrane on the surface of the membrane, and has good synchronous anti-pollution and antibacterial effects.
Description
Technical Field
The invention belongs to the technical field of membrane separation in water treatment, and relates to CdS/g-C3N4A PVDF ultrafiltration membrane modified by/rGO visible light photocatalyst, a preparation method and application thereof.
Background
The membrane separation technology is one of the preferable technologies in the field of water pollution control engineering, and is widely applied to drinking water purification and sewage and wastewater treatment and reutilization due to low cost, good effluent quality, high intensification degree, simple equipment and convenient operation. However, membrane fouling, especially membrane bio-fouling, often causes membrane flux attenuation, increased operation cost and shortened membrane service life, and thus becomes a major obstacle for the wide application of membrane separation technology in drinking water, sewage and wastewater treatment.
Polyvinylidene fluoride (PVDF) is a vinylidene fluoride homopolymer or a copolymer of vinylidene fluoride and other small amount of fluorine-containing vinyl monomers, has the characteristics of good chemical corrosion resistance, high temperature resistance, radiation resistance, easy film formation and the like, and is widely applied to various water treatment fields such as domestic sewage treatment, industrial wastewater treatment and the like as a typical ultrafiltration membrane material. However, the surface energy of the PVDF membrane material is low, the affinity with water is poor, and hydrophobic organic pollutants such as proteins or oils are easily adsorbed to the surface of the membrane to cause membrane pollution, so that the economy and reliability of the membrane are affected, and the development, application and popularization of the PVDF membrane material are restricted. It is known that the pollution resistance of PVDF membranes can be improved by physical and chemical means, and the modification methods can be largely classified into membrane surface modification and membrane material modification. The modification of the membrane material can be divided into chemical modification and blending modification of the membrane material, and the latter is convenient for large-scale popularization due to simple operation and difficult falling of hydrophilic groups, and is a hotspot of research in recent years.
The photocatalysis technology is a emerging, high-efficiency and environment-friendly technical means in the field of water treatment in recent years, and the technology utilizes renewable light energy to generate active groups to realize the degradation of organic pollutants in water and the inactivation of bacteria. Therefore, the photocatalysis technology is combined with the membrane modification technology to form the composite photocatalysis separation modified membrane, and the pollution resistance, the antibacterial capacity, the hydrophilic performance and the interception characteristic of the membrane can be effectively improved. The technology of coupling photocatalysis and membrane separation is gradually applied to membrane separation research, and TiO has been reported2The PVDF cast membrane system is introduced through blending modification, and the photocatalytic efficiency of the membrane is improved under the irradiation of ultraviolet light. However, this TiO compound2The modified composite membrane has better pollution resistance only under the irradiation of ultraviolet light, and the ultraviolet light only accounts for 4 percent of the solar spectrum, so the high energy consumption and the high cost of the ultraviolet light photocatalyst become main problems in the blending modification application of the ultraviolet light photocatalyst in the membrane.
Disclosure of Invention
The invention aims to overcome the defects of the composite photocatalytic separation membrane in the prior art, and provides a visible-light-catalyst-modified PVDF ultrafiltration membrane, and a preparation method and application thereof. By adopting a novel visible light photocatalyst CdS/g-C3N4the/rGO replaces an ultraviolet photocatalyst to carry out blending modification on the PVDF membrane, so that the prepared modified PVDF membrane has good pollution resistance and antibacterial performance under the irradiation of visible light, and the biological pollution problem of the PVDF membrane in the water treatment process is solved in an energy-saving, environment-friendly and sustainable manner.
The purpose of the invention can be realized by the following technical scheme:
a visible light photocatalyst modified PVDF ultrafiltration membrane is a CdS/g-C ultrafiltration membrane3N4PVDF ultrafiltration membrane modified by rGO nano photocatalyst, wherein in the ultrafiltration membrane, PVDF is used as a matrix, and CdS/g-C3N4the/rGO nano photocatalyst is used as an active component which is uniformly distributed inIn the matrix.
Further, the CdS/g-C3N4CdS and g-C in/rGO nano photocatalyst3N4The mass ratio of the CdS to the rGO is (10-20):1, and the mass ratio of the CdS to the rGO is (20-30): 1.
Further, the CdS/g-C3N4In the/rGO nano photocatalyst, CdS is in a nano rod shape, rGO (reduced graphene oxide) is in a nano sheet shape, and g-C3N4Coating CdS nano-rods to form CdS/g-C with shell-core structure3N4Sleeving a tube, and uniformly dispersing the tube on the rGO nano-sheet.
Further, the CdS/g-C3N4The preparation method of the/rGO nano photocatalyst comprises the following steps:
1) g to C3N4Ultrasonically dispersing in organic solvent, adding CdS, mixing, removing residual methanol, and drying to obtain CdS/g-C3N4；
2) Dispersing GO in a mixed solvent by ultrasonic, and then adding CdS/g-C3N4Mixing uniformly, and then centrifuging to separate out precipitate;
3) dispersing the precipitate in water, adjusting the pH of the solution to alkalinity with ammonia water, adding hydrazine hydrate, carrying out hydrothermal reaction, cooling, washing and drying to obtain CdS/g-C3N4a/rGO nano photocatalyst.
Among them, the organic solvent is preferably methanol or ethanol. The mixed solvent is preferably a mixed solvent of ethanol and water in a volume ratio of 1: 3.
Further, in the hydrothermal reaction process in the step 3), the reaction temperature is 80-90 ℃ and the reaction time is 2-2.5 h.
CdS/g-C3N4The preparation method of the/rGO nano photocatalyst specifically comprises the following steps:
firstly, enough cadmium sulfide (CdS) and graphite phase carbon nitride (g-C) are prepared3N4) And Graphene Oxide (GO), weighing 100mg g-C3N4Dispersing in 30-50mL methanol with ultrasonic wave for 60-80min, adding 1-2g CdS, stirring and mixing for 20-30h, removing with rotary evaporatorResidual methanol, drying the product at 50-70 deg.C to obtain CdS/g-C3N4(ii) a 33.3-100mg of GO is weighed and dispersed in a mixed solution of 100-150mL of ethanol and water by ultrasonic treatment for 20-30min, and then the CdS/g-C is added3N4Performing ultrasonic treatment for 20-30min and stirring for 40-60min, and performing centrifugal separation at 7000-8000 rpm; re-dispersing the obtained precipitate in 80-100mL of deionized water, adjusting the pH of the solution to alkalinity (8.5-9.5) by using ammonia water, adding a small amount of hydrazine hydrate (the concentration is 30%, and the volume is 0.5-1mL), transferring the solution into a high-pressure reaction kettle for hydrothermal reaction, naturally cooling, washing the solution for 3 times by using the deionized water, and drying the product at the temperature of 50-70 ℃ in vacuum to obtain the yellow-green CdS/g-C3N4a/rGO nano photocatalyst.
Further, the ultrafiltration membrane is prepared from the following components in parts by weight: 17-19 parts of polyvinylidene fluoride, 2.5-3.5 parts of polyvinylpyrrolidone, 77-79 parts of N, N-dimethylacetamide and CdS/g-C3N40.3-1.3 parts of/rGO nano photocatalyst.
A preparation method of a PVDF ultrafiltration membrane modified by a visible light photocatalyst comprises the following steps:
1) CdS/g-C3N4Dispersing the/rGO nano photocatalyst in N, N-dimethylacetamide in an ultrasonic manner, then adding polyvinylidene fluoride and polyvinylpyrrolidone, and heating and stirring to form a uniform membrane casting solution;
2) vacuum defoaming the casting solution, and scraping to obtain a liquid film;
3) standing the scraped liquid film in air, putting the liquid film into a water coagulating bath, taking out the liquid film after the film falls off, immersing the liquid film into water for 16-30h, and drying to obtain CdS/g-C3N4A PVDF ultrafiltration membrane modified by rGO nano photocatalyst.
Further, in the heating and stirring process of the step 1), the heating temperature is 80-90 ℃, and the stirring time is 12-16 h.
Further, in the step 2), the scraping process is performed in a film scraper, and the specification of a film scraper in the film scraper is 300 μm.
The preparation method of the PVDF ultrafiltration membrane modified by the visible light photocatalyst comprises the following steps:
weighing proper amounts of polyvinylidene fluoride (PVDF), polyvinylpyrrolidone and CdS/g-C3N4Drying the/rGO photocatalyst at 60-80 ℃ for 20-30h to obtain CdS/g-C3N4dispersing/rGO powder in N, N-dimethylacetamide by ultrasonic wave for 10-20min, then adding the PVDF and polyvinylpyrrolidone powder, and heating and stirring to form a uniform membrane casting solution; defoaming the casting solution in a vacuum drying oven for 2-4h, and scraping the casting solution on a film scraper to form a film; standing the scraped liquid film in air for 20-40s, putting the liquid film into a coagulation bath of deionized water, taking out the liquid film after the film falls off, and immersing the liquid film into the deionized water for 24 h; drying in a drying oven at 30-50 ℃ to obtain CdS/g-C3N4PVDF ultrafiltration membrane modified by rGO photocatalyst.
An application of a PVDF ultrafiltration membrane modified by a visible light photocatalyst in resisting organic pollutants of the membrane or resisting bacteria.
CdS/g-C of the invention3N4the/rGO photocatalyst modified PVDF ultrafiltration membrane can be used for catalyzing a membrane reactor device, and can resist bacteria on the surface of the membrane and degrade organic pollutants on the surface of the membrane under the irradiation of a visible light lamp, so that the phenomenon of membrane pollution is inhibited. Using CdS/g-C of the present invention3N4The method for realizing pollution resistance and antibiosis of the PVDF ultrafiltration membrane modified by the rGO photocatalyst under the irradiation of visible light comprises the following steps:
constructing a catalytic membrane reactor device by reacting CdS/g-C3N4the/rGO photocatalyst modified PVDF ultrafiltration membrane is fixed on the membrane component and is arranged in the membrane bioreactor. Preparing organic pollutant solution in a reactor, fixing a waterproof LED visible light lamp on the surface of the film, and passing the solution through the CdS/g-C3N4After being filtered, the PVDF ultrafiltration membrane modified by the rGO photocatalyst flows out of a water outlet of the membrane component, and organic pollution resistance is realized under the irradiation and stirring of an LED visible light lamp; preparing bacterial suspension into a reactor, and inactivating bacteria on the surface of the membrane under the conditions of irradiation and stirring of an LED visible light lamp.
The organic pollutants comprise protein, humic acid and polysaccharide; the bacteria are gram-negative bacteria represented by escherichia coli and gram-positive bacteria represented by staphylococcus aureus.
CdS/g-C of the invention3N4PVDF ultrafiltration membrane modified by rGO photocatalyst can activate CdS/g-C on membrane surface under visible light irradiation3N4the/rGO photocatalyst generates active oxygen free radicals with oxidability, and the active oxygen free radicals can kill bacteria on the surface of the membrane and have degradation reaction with organic pollutants to mineralize the pollutants into CO2And H2O。
The invention provides CdS/g-C3N4The preparation method of the modified PVDF ultrafiltration membrane comprises the following steps: firstly, CdS and g-C are respectively synthesized3N4And GO nano-particles, then synthesizing CdS/g-C3N4a/rGO nanocomposite; CdS/g-C3N4Performing ultrasonic dispersion on/rGO nano particles in N, N-dimethylacetamide, sequentially adding polyvinylpyrrolidone and polyvinylidene fluoride, and preparing a uniformly dispersed casting solution at a high temperature; scraping the casting film liquid into a liquid film by using a film scraping machine after vacuum defoaming, standing in the air for 20-40s, then putting into a coagulation bath of deionized water, taking out after the film falls off, and soaking into the deionized water for 24 h; drying in a drying oven at 30-50 ℃ to obtain CdS/g-C3N4PVDF ultrafiltration membrane modified by rGO photocatalyst. The modified membrane provided by the invention has high hydrophilicity and good photocatalytic activity, can effectively reduce membrane pore blockage caused by organic pollutants under the irradiation of visible light, has good killing effect on gram-negative bacteria represented by escherichia coli and gram-positive bacteria represented by staphylococcus aureus, can obviously inhibit the formation of a biological membrane on the surface of the membrane, and has good synchronous anti-pollution and antibacterial effects.
Compared with the prior art, the invention has the following characteristics:
1) the invention provides CdS/g-C3N4Compared with the traditional PVDF ultrafiltration membrane, the PVDF ultrafiltration membrane modified by the rGO photocatalyst has higher hydrophilicity and remarkable photocatalytic performance; in CdS/g-C3N4CdS and g-C in/rGO photocatalyst3N4Can form a heterojunction structure and improve the optical response performance of the twoMeanwhile, the photo-corrosion phenomenon of CdS is avoided, and the addition of rGO further improves the electron transmission rate of the CdS and effectively promotes the CdS/g-C3N4The rGO has good antibacterial and anti-pollution effects under the irradiation of visible light, and can effectively reduce the membrane pollution phenomenon and slow down the reduction rate of the membrane flux.
2) The invention provides CdS/g-C3N4PVDF ultrafiltration membrane modified by/rGO photocatalyst and ultraviolet photocatalyst (such as TiO)2) Compared with the modified PVDF membrane, the modified PVDF membrane has the advantages that the energy consumption and the cost are obviously reduced, and meanwhile, the adverse effects brought by the ultraviolet illumination process are avoided, such as the ultraviolet light can inactivate functional bacteria in the MBR.
3) The invention prepares CdS/g-C3N4The method for preparing the PVDF ultrafiltration membrane modified by the rGO photocatalyst is simple and easy to operate, the used equipment is conventional instruments in the field, the process period is short, the requirement on the process environment is low, the cost is low, and the method can be widely applied to preparation of the PVDF membrane modified by the photocatalyst.
4) The invention prepares CdS/g-C3N4The method for modifying PVDF ultrafiltration membrane by rGO photocatalyst is a blending modification method, wherein the photocatalyst CdS/g-C in the modified membrane3N4the/rGO is not easy to dissolve out along with water flow in the using process, thereby avoiding poisoning and potential secondary pollution to the water body and ensuring the durability and stability of the membrane structure.
Drawings
FIG. 1 is CdS/g-C prepared in example 13N4Transmission electron microscopy of/rGO photocatalyst.
FIG. 2 is CdS/g-C prepared in example 23N4the/rGO photocatalyst modified PVDF membrane M2 and PVDF protomembrane M0 filtered the water flux versus time curves of Bovine Serum Albumin (BSA) (fig. 2a), Humic Acid (HA) (fig. 2b) and Sodium Alginate (SA) (fig. 2c) solutions with and without visible light illumination.
FIG. 3 is CdS/g-C prepared in example 23N4the/rGO photocatalyst modified PVDF membrane M2 and PVDF original membrane M0 have the inactivation performance on Escherichia coli and staphylococcus aureus under the condition of visible light or no visible light.
FIG. 4 is CdS/g-C prepared in example 23N4Surface morphology of bacteria after inactivation of E.coli (FIGS. 4a and 4b) and S.aureus (FIGS. 4c and 4d) by the/rGO photocatalyst modified PVDF membrane M2 (FIGS. 4b and 4d) and the PVDF original membrane M0 (FIGS. 4a and 4c) under visible light.
FIG. 5 is CdS/g-C prepared in example 23N4the/rGO photocatalyst modified PVDF membrane M2 and PVDF native membrane M0 showed a band diagram of inhibition of bacterial diffusion after inactivation of escherichia coli (fig. 5a and 5b) and staphylococcus aureus (fig. 5c and 5d) with (fig. 5b and 5d) or without (fig. 5a and 5c) visible light illumination.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
(1)CdS/g-C3N4preparation of/rGO nano photocatalyst
Firstly, enough cadmium sulfide (CdS) and graphite phase carbon nitride (g-C) are prepared3N4) And Graphene Oxide (GO), weighing 100mg g-C3N4Dispersing in 30mL methanol with ultrasonic wave for 60min, adding 1g CdS, stirring and mixing for 20h, removing residual methanol with rotary evaporator, and drying at 50 deg.C to obtain CdS/g-C3N4(ii) a 50mg of GO is weighed and ultrasonically dispersed in 100mL of mixed solution of ethanol and water for 20min, wherein the volume ratio of the ethanol to the water is 1:3, and then the CdS/g-C is added3N4Performing ultrasonic treatment for 20min and stirring for 40min, and performing centrifugal separation at 7000 rpm; re-dispersing the obtained precipitate in 80mL of deionized water, adjusting the pH of the solution to 8.5 by using ammonia water, adding 0.5mL of hydrazine hydrate with the concentration of 30%, transferring the solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 80 ℃ for 2h, naturally cooling, washing with deionized water for 3 times, and drying the product at 50 ℃ in vacuum to obtain the yellow-green CdS/g-C3N4a/rGO nano photocatalyst.
(2)CdS/g-C3N4Preparation of/rGO modified PVDF ultrafiltration membrane
Weighing 17.5g polyvinylidene fluoride (PVDF), 3g polyvinylpyrrolidone and 0.5g CdS/g-C3N4Drying the/rGO photocatalyst at 60 ℃ for 20h to obtain CdS/g-C3N4dispersing/rGO powder in 79g N, N-dimethylacetamide by ultrasonic for 10min, then adding the PVDF and polyvinylpyrrolidone powder, and stirring at 80 ℃ for 12h to form uniform membrane casting solution; defoaming the casting solution in a vacuum drying oven for 2 hours, and scraping the casting solution on a film scraper with the specification of 300 mu m to form a film; standing the scraped liquid film in air for 20s, putting the liquid film into a coagulation bath of deionized water, taking out the liquid film after the film falls off, and immersing the liquid film into the deionized water for 24 h; drying in a drying oven at 30 ℃ to obtain CdS/g-C3N4PVDF ultrafiltration membrane modified by rGO photocatalyst.
FIG. 1 is CdS/g-C prepared in this example3N4Transmission electron microscopy of/rGO photocatalyst, CdS/g-C can be seen in FIG. 13N4The structure of the/rGO photocatalytic particle is as follows: CdS and rGO are respectively in nano-rod shape and nano-sheet shape, g-C3N4Coating CdS nano-rods to form CdS/g-C with shell-core structure3N4The sleeve is uniformly dispersed on the rGO nano-chip, and the CdS/g-C can be effectively improved by the structure3N4The visible light response capability of the/rGO photocatalyst, thereby ensuring CdS/g-C3N4The photocatalytic degradation effect of the PVDF membrane modified by the rGO photocatalyst.
CdS/g-C prepared by using the embodiment3N4The method for realizing pollution resistance and antibiosis of the PVDF ultrafiltration membrane modified by the rGO photocatalyst under the irradiation of visible light comprises the following steps:
constructing a catalytic membrane reactor device by reacting CdS/g-C3N4the/rGO photocatalyst modified PVDF ultrafiltration membrane is fixed on the membrane component and is arranged in the membrane bioreactor, and the waterproof LED visible light lamp is fixed on the surface of the membrane.
Preparing BSA, HA and SA solutions in a reactor, and passing the solutions through the CdS/g-C3N4Filtering with PVDF ultrafilter membrane modified by rGO photocatalyst and then passing through the water outlet of the membrane moduleThe mixture was stirred under visible light irradiation to examine its ability to resist organic contamination. The results show that the CdS/g-C prepared in the example is compared with the original PVDF film after 40min filtration under the irradiation of visible light3N4The water flux reduction rates of the/rGO photocatalyst modified PVDF membrane in filtering BSA, HA and SA solutions are respectively reduced by 19.6%, 40% and 17.6%, which shows that the modified membrane prepared in the embodiment HAs a good membrane pollution reduction effect under the irradiation of visible light.
And preparing a suspension of escherichia coli and staphylococcus aureus in a reactor, stirring under the irradiation of visible light, and inspecting the antibacterial capacity of the suspension. The results show that the CdS/g-C prepared in this example are compared to the original PVDF film under visible light irradiation3N4The inactivation rates of the PVDF membrane modified by the rGO photocatalyst to escherichia coli and staphylococcus aureus reach 90% and 88% respectively, which shows that the modified membrane prepared by the embodiment has good antibacterial effect under the irradiation of visible light.
Example 2:
(1)CdS/g-C3N4preparation of/rGO nano photocatalyst
Firstly, enough CdS and g-C are prepared3N4And GO, weighing 100mg g-C3N4Dispersing in 40mL methanol with ultrasonic wave for 70min, adding 1.5g CdS, stirring and mixing for 24h, removing residual methanol with rotary evaporator, and drying at 60 deg.C to obtain CdS/g-C3N4(ii) a Weighing 75mg of GO, and dispersing in a mixed solution of 120mL of ethanol and water by ultrasonic for 25min, wherein the volume ratio of the ethanol to the water is 1:3, then adding the CdS/g-C3N4Performing ultrasonic treatment for 25min, stirring for 50min, and centrifuging at 7500 rpm; re-dispersing the obtained precipitate in 90mL of deionized water, adjusting the pH of the solution to 9.0 by using ammonia water, adding 0.8mL of hydrazine hydrate with the concentration of 30%, transferring the solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at 85 ℃ for 2h, naturally cooling, washing with deionized water for 3 times, and drying the product at 60 ℃ in vacuum to obtain the yellow-green CdS/g-C3N4a/rGO nano photocatalyst.
(2)CdS/g-C3N4Preparation of/rGO modified PVDF ultrafiltration membrane
18g PVDF, 2.5g polyvinylpyrrolidone and 1g CdS/g-C were weighed3N4Drying the/rGO photocatalyst at 70 ℃ for 24h to obtain CdS/g-C3N4Dispersing the/rGO powder in 78.5g N, N-dimethylacetamide by ultrasonic for 15min, then adding the PVDF and polyvinylpyrrolidone powder, and stirring for 14h at 85 ℃ to form uniform membrane casting solution; defoaming the casting solution in a vacuum drying oven for 3 hours, and scraping the casting solution on a film scraper with the specification of 300 mu m to form a film; standing the scraped liquid film in air for 30s, putting the liquid film into a coagulation bath of deionized water, taking out the liquid film after the film falls off, and immersing the liquid film into the deionized water for 24 h; drying in a drying oven at 40 ℃ to obtain CdS/g-C3N4PVDF ultrafiltration membrane modified by rGO photocatalyst.
CdS/g-C prepared by using the embodiment3N4The method for realizing pollution resistance and antibiosis of the PVDF ultrafiltration membrane modified by the rGO photocatalyst under the irradiation of visible light comprises the following steps:
constructing a catalytic membrane reactor device by reacting CdS/g-C3N4the/rGO photocatalyst modified PVDF ultrafiltration membrane is fixed on the membrane component and is arranged in the membrane bioreactor, and the waterproof LED visible light lamp is fixed on the surface of the membrane.
Preparing BSA, HA and SA solutions in a reactor, passing the solutions through the CdS/g-C3N4The PVDF ultrafiltration membrane modified by the rGO photocatalyst flows out of a water outlet of the membrane component after being filtered, and is stirred under the irradiation of visible light, so that the organic pollution resistance of the PVDF ultrafiltration membrane is inspected. FIG. 2 shows CdS/g-C prepared in this example3N4Curves of water flux versus time for the/rGO photocatalyst modified PVDF membrane M2 filtered BSA (fig. 2a), HA (fig. 2b) and SA (fig. 2c) solutions. The results show that the water flux reduction rates of the modified membrane M2 in filtering BSA, HA and SA solutions were respectively reduced by 20.1%, 48% and 18.3% compared with the original PVDF membrane M0 after 40min of filtration under the irradiation of visible light, which indicates that the modified membrane prepared in this example HAs a good membrane pollution reducing effect under the irradiation of visible light.
And preparing a suspension of escherichia coli and staphylococcus aureus in a reactor, stirring under the irradiation of visible light, and inspecting the antibacterial capacity of the suspension. FIG. 3 is a drawing showingCdS/g-C prepared in this example3N4the/rGO photocatalyst modified PVDF membrane M2 has the inactivation performance on Escherichia coli and staphylococcus aureus. The results show that the CdS/g-C prepared in this example are compared to the original PVDF film under visible light irradiation3N4The inactivation rates of the PVDF membrane modified by the rGO photocatalyst to escherichia coli and staphylococcus aureus reach 92% and 95% respectively, which shows that the modified membrane prepared by the embodiment has good antibacterial effect under the irradiation of visible light.
Fig. 4 is a surface morphology diagram of the modified membrane M2 (fig. 4b and 4d) and the original membrane M0 (fig. 4a and 4c) prepared in this example after inactivation of escherichia coli (fig. 4a and 4b) and staphylococcus aureus (fig. 4c and 4d) under visible light, as shown in the figure, the cell integrity of the M2 surface bacteria is destroyed, and the cell contents flow out and cause cell death.
When the modified film M2 and the original film M0 prepared in the embodiment are subjected to diffusion inhibition zone tests on escherichia coli (shown in FIGS. 5a and 5b) and staphylococcus aureus (shown in FIGS. 5C and 5d) under the condition of visible light illumination (shown in FIGS. 5b and 5d) or no visible light illumination (shown in FIGS. 5a and 5C), it can be seen from the graphs that active oxygen radicals generated by the modified film M2 under the condition of visible light illumination can obviously inactivate escherichia coli and staphylococcus aureus around the film, and the CdS/g-C is proved again3N4The PVDF membrane modified by the rGO photocatalyst has good antibacterial ability.
Example 3:
(1)CdS/g-C3N4preparation of/rGO nano photocatalyst
Firstly, enough CdS and g-C are prepared3N4And GO, weighing 100mg g-C3N4Dispersing in 50mL methanol with ultrasound for 80min, adding 2g CdS, stirring and mixing for 30h, removing residual methanol with rotary evaporator, and drying at 70 deg.C to obtain CdS/g-C3N4(ii) a 100mg of GO is weighed and ultrasonically dispersed in a mixed solution of 150mL of ethanol and water for 30min, wherein the volume ratio of the ethanol to the water is 1:3, then adding the CdS/g-C3N4Performing ultrasonic treatment for 30min while stirring for 60min, and centrifuging at 8000 rpm; the resulting precipitate was redispersed in 100mL of deionized water and washed with ammoniaAdjusting the pH value of the solution to 9.5 with water, adding 1mL of hydrazine hydrate with the concentration of 30%, transferring the solution into a high-pressure reaction kettle, carrying out hydrothermal reaction for 2.5h at 90 ℃, naturally cooling, washing with deionized water for 3 times, and drying the product at 70 ℃ in vacuum to obtain the yellow-green CdS/g-C3N4a/rGO nano photocatalyst.
(2)CdS/g-C3N4Preparation of/rGO modified PVDF ultrafiltration membrane
17.7g PVDF, 3g polyvinylpyrrolidone and 1.3g CdS/g-C were weighed3N4Drying the/rGO photocatalyst at 80 ℃ for 30h to obtain CdS/g-C3N4Dispersing the/rGO powder in 78g N N-dimethylacetamide by ultrasonic for 20min, then adding the PVDF and polyvinylpyrrolidone powder, and stirring for 16h at 90 ℃ to form uniform membrane casting solution; defoaming the casting solution in a vacuum drying oven for 4 hours, and scraping the casting solution on a film scraper with the specification of 300 mu m to form a film; standing the scraped liquid film in air for 40s, putting the liquid film into a coagulation bath of deionized water, taking out the liquid film after the film falls off, and immersing the liquid film into the deionized water for 24 h; drying in a drying oven at 50 ℃ to obtain CdS/g-C3N4PVDF ultrafiltration membrane modified by rGO photocatalyst.
CdS/g-C prepared by using the embodiment3N4The method for realizing pollution resistance and antibiosis of the PVDF ultrafiltration membrane modified by the rGO photocatalyst under the irradiation of visible light comprises the following steps:
constructing a catalytic membrane reactor device by reacting CdS/g-C3N4the/rGO photocatalyst modified PVDF ultrafiltration membrane is fixed on the membrane component and is arranged in the membrane bioreactor, and the waterproof LED visible light lamp is fixed on the surface of the membrane.
Preparing BSA, HA and SA solutions in a reactor, passing the solutions through the CdS/g-C3N4The PVDF ultrafiltration membrane modified by the rGO photocatalyst flows out of a water outlet of the membrane component after being filtered, and is stirred under the irradiation of visible light, so that the organic pollution resistance of the PVDF ultrafiltration membrane is inspected. The results show that the CdS/g-C prepared in the example is compared with the original PVDF film after 40min filtration under the irradiation of visible light3N4The reduction rates of water flux when the PVDF membrane modified by the rGO photocatalyst is used for filtering BSA, HA and SA solutions are respectively reduced by 21.8 percent, 49.7 percent and19.5%, indicating that the modified film prepared in this example has a good film contamination reduction effect under visible light irradiation.
And preparing a suspension of escherichia coli and staphylococcus aureus in a reactor, stirring under the irradiation of visible light, and inspecting the antibacterial capacity of the suspension. The results show that the CdS/g-C prepared in this example are compared to the original PVDF film under visible light irradiation3N4The inactivation rates of the PVDF membrane modified by the rGO photocatalyst to escherichia coli and staphylococcus aureus reach 94% and 97% respectively, which shows that the modified membrane prepared by the embodiment has good antibacterial effect under the irradiation of visible light.
Example 4:
a visible light photocatalyst is CdS/g-C3N4rGO nano-photocatalyst, CdS/g-C3N4CdS and g-C in/rGO nano photocatalyst3N4The mass ratio of the CdS to the rGO is 10:1, and the mass ratio of the CdS to the rGO is 30: 1. CdS/g-C3N4In the/rGO nano photocatalyst, CdS is in a nano rod shape, rGO is in a nano sheet shape, and g-C3N4Coating CdS nano-rods to form CdS/g-C with shell-core structure3N4Sleeving a tube, and uniformly dispersing the tube on the rGO nano-sheet.
The preparation method of the visible light photocatalyst comprises the following steps:
1) g to C3N4Ultrasonically dispersing in organic solvent, adding CdS, mixing, removing residual methanol, and drying to obtain CdS/g-C3N4；
2) Dispersing GO in a mixed solvent by ultrasonic, and then adding CdS/g-C3N4Mixing uniformly, and then centrifuging to separate out precipitate;
3) dispersing the precipitate in water, adjusting the pH of the solution to alkalinity with ammonia water, adding hydrazine hydrate, carrying out hydrothermal reaction at 80 ℃ for 2.5h, cooling, washing and drying to obtain CdS/g-C3N4a/rGO nano photocatalyst.
A PVDF ultrafiltration membrane modified by a visible light photocatalyst, which is an ultrafiltration membraneCdS/g-C3N4PVDF ultrafiltration membrane modified by/rGO nano photocatalyst, wherein in the ultrafiltration membrane, PVDF is used as a matrix, and CdS/g-C3N4the/rGO nano photocatalyst is used as an active component, and the active component is uniformly distributed in the matrix. The ultrafiltration membrane is prepared from the following components in parts by weight: 17 parts of polyvinylidene fluoride, 3.5 parts of polyvinylpyrrolidone, 77 parts of N, N-dimethylacetamide and CdS/g-C3N41.3 parts of/rGO nano photocatalyst.
The preparation method of the visible light photocatalyst modified PVDF ultrafiltration membrane comprises the following steps:
1) CdS/g-C3N4Dispersing the/rGO nano photocatalyst in N, N-dimethylacetamide in an ultrasonic manner, then adding polyvinylidene fluoride and polyvinylpyrrolidone, heating and stirring at the temperature of 80 ℃ for 16 hours to form a uniform casting solution;
2) after the casting film liquid is defoamed in vacuum, scraping the casting film liquid into a liquid film, wherein the scraping process is carried out in a film scraping machine, and the specification of a film scraper in the film scraping machine is 300 mu m;
3) standing the scraped liquid film in air, putting the liquid film into a water coagulating bath, taking out the liquid film after the film falls off, immersing the liquid film into water for 16 hours, and drying to obtain CdS/g-C3N4A PVDF ultrafiltration membrane modified by rGO nano photocatalyst.
The PVDF ultrafiltration membrane modified by the visible light photocatalyst is applied to resisting organic pollutants or bacteria.
Example 5:
a visible light photocatalyst is CdS/g-C3N4rGO nano-photocatalyst, CdS/g-C3N4CdS and g-C in/rGO nano photocatalyst3N4The mass ratio of the CdS to the rGO is 20:1, and the mass ratio of the CdS to the rGO is 20: 1. CdS/g-C3N4In the/rGO nano photocatalyst, CdS is in a nano rod shape, rGO is in a nano sheet shape, and g-C3N4Coating CdS nano-rods to form CdS/g-C with shell-core structure3N4Sleeving a tube, and uniformly dispersing the tube on the rGO nano-sheet.
The preparation method of the visible light photocatalyst comprises the following steps:
1) g to C3N4Ultrasonically dispersing in organic solvent, adding CdS, mixing, removing residual methanol, and drying to obtain CdS/g-C3N4；
2) Dispersing GO in a mixed solvent by ultrasonic, and then adding CdS/g-C3N4Mixing uniformly, and then centrifuging to separate out precipitate;
3) dispersing the precipitate in water, adjusting the pH of the solution to alkalinity with ammonia water, adding hydrazine hydrate, carrying out hydrothermal reaction at 90 ℃ for 2h, cooling, washing and drying to obtain CdS/g-C3N4a/rGO nano photocatalyst.
A visible light photocatalyst modified PVDF ultrafiltration membrane is a CdS/g-C ultrafiltration membrane3N4PVDF ultrafiltration membrane modified by/rGO nano photocatalyst, wherein in the ultrafiltration membrane, PVDF is used as a matrix, and CdS/g-C3N4the/rGO nano photocatalyst is used as an active component, and the active component is uniformly distributed in the matrix. The ultrafiltration membrane is prepared from the following components in parts by weight: 19 parts of polyvinylidene fluoride, 2.5 parts of polyvinylpyrrolidone, 79 parts of N, N-dimethylacetamide and CdS/g-C3N40.3 part of/rGO nano photocatalyst.
The preparation method of the visible light photocatalyst modified PVDF ultrafiltration membrane comprises the following steps:
1) CdS/g-C3N4Dispersing the/rGO nano photocatalyst in N, N-dimethylacetamide in an ultrasonic manner, then adding polyvinylidene fluoride and polyvinylpyrrolidone, heating and stirring at 90 ℃ for 12 hours to form a uniform casting solution;
2) after the casting film liquid is defoamed in vacuum, scraping the casting film liquid into a liquid film, wherein the scraping process is carried out in a film scraping machine, and the specification of a film scraper in the film scraping machine is 300 mu m;
3) standing the scraped liquid film in air, putting the liquid film into a water coagulating bath, taking out the liquid film after the film falls off, immersing the liquid film into water for 30 hours, and drying to obtain CdS/g-C3N4A PVDF ultrafiltration membrane modified by rGO nano photocatalyst.
The PVDF ultrafiltration membrane modified by the visible light photocatalyst is applied to resisting organic pollutants or bacteria.
Example 6:
a visible light photocatalyst is CdS/g-C3N4rGO nano-photocatalyst, CdS/g-C3N4CdS and g-C in/rGO nano photocatalyst3N4The mass ratio of the CdS to the rGO is 15:1, and the mass ratio of the CdS to the rGO is 25: 1. CdS/g-C3N4In the/rGO nano photocatalyst, CdS is in a nano rod shape, rGO is in a nano sheet shape, and g-C3N4Coating CdS nano-rods to form CdS/g-C with shell-core structure3N4Sleeving a tube, and uniformly dispersing the tube on the rGO nano-sheet.
The preparation method of the visible light photocatalyst comprises the following steps:
1) g to C3N4Ultrasonically dispersing in organic solvent, adding CdS, mixing, removing residual methanol, and drying to obtain CdS/g-C3N4；
2) Dispersing GO in a mixed solvent by ultrasonic, and then adding CdS/g-C3N4Mixing uniformly, and then centrifuging to separate out precipitate;
3) dispersing the precipitate in water, adjusting the pH of the solution to alkalinity with ammonia water, adding hydrazine hydrate, carrying out hydrothermal reaction at 85 ℃ for 2.2h, cooling, washing and drying to obtain CdS/g-C3N4a/rGO nano photocatalyst.
A visible light photocatalyst modified PVDF ultrafiltration membrane is a CdS/g-C ultrafiltration membrane3N4PVDF ultrafiltration membrane modified by/rGO nano photocatalyst, wherein in the ultrafiltration membrane, PVDF is used as a matrix, and CdS/g-C3N4the/rGO nano photocatalyst is used as an active component, and the active component is uniformly distributed in the matrix. The ultrafiltration membrane is prepared from the following components in parts by weight: 18 parts of polyvinylidene fluoride, 3 parts of polyvinylpyrrolidone, 78 parts of N, N-dimethylacetamide and CdS/g-C3N41 part of/rGO nano photocatalyst.
The preparation method of the visible light photocatalyst modified PVDF ultrafiltration membrane comprises the following steps:
1) CdS/g-C3N4Dispersing the/rGO nano photocatalyst in N, N-dimethylacetamide in an ultrasonic manner, then adding polyvinylidene fluoride and polyvinylpyrrolidone, heating and stirring at 85 ℃ for 14 hours to form a uniform casting solution;
2) after the casting film liquid is defoamed in vacuum, scraping the casting film liquid into a liquid film, wherein the scraping process is carried out in a film scraping machine, and the specification of a film scraper in the film scraping machine is 300 mu m;
3) standing the scraped liquid film in air, putting the liquid film into a water coagulating bath, taking out the liquid film after the film falls off, immersing the liquid film into water for 24 hours, and drying to obtain CdS/g-C3N4A PVDF ultrafiltration membrane modified by rGO nano photocatalyst.
The PVDF ultrafiltration membrane modified by the visible light photocatalyst is applied to resisting organic pollutants or bacteria.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The visible light photocatalyst modified PVDF ultrafiltration membrane is characterized in that the ultrafiltration membrane is CdS/g-C3N4PVDF ultrafiltration membrane modified by rGO nano photocatalyst, wherein in the ultrafiltration membrane, PVDF is used as a matrix, and CdS/g-C3N4the/rGO nano photocatalyst is used as an active component, and the active component is uniformly distributed in the matrix.
2. The visible-light-photocatalyst-modified PVDF ultrafiltration membrane as claimed in claim 1, wherein the visible-light-photocatalyst-modified PVDF ultrafiltration membrane is characterized in thatCdS/g-C of3N4CdS and g-C in/rGO nano photocatalyst3N4The mass ratio of the CdS to the rGO is (10-20):1, and the mass ratio of the CdS to the rGO is (20-30): 1.
3. The visible-light-catalyst-modified PVDF ultrafiltration membrane as claimed in claim 2, wherein CdS/g-C3N4In the/rGO nano photocatalyst, CdS is in a nano rod shape, rGO is in a nano sheet shape, and g-C3N4Coating CdS nano-rods to form CdS/g-C with shell-core structure3N4Sleeving a tube, and uniformly dispersing the tube on the rGO nano-sheet.
4. The visible-light-catalyst-modified PVDF ultrafiltration membrane as claimed in claim 1, wherein CdS/g-C3N4The preparation method of the/rGO nano photocatalyst comprises the following steps:
1) g to C3N4Ultrasonically dispersing in organic solvent, adding CdS, mixing, removing residual methanol, and drying to obtain CdS/g-C3N4；
2) Dispersing GO in a mixed solvent by ultrasonic, and then adding CdS/g-C3N4Mixing uniformly, and then centrifuging to separate out precipitate;
3) dispersing the precipitate in water, adjusting the pH of the solution to alkalinity with ammonia water, adding hydrazine hydrate, carrying out hydrothermal reaction, cooling, washing and drying to obtain CdS/g-C3N4a/rGO nano photocatalyst.
5. The visible-light-photocatalyst-modified PVDF ultrafiltration membrane as claimed in claim 4, wherein in the hydrothermal reaction process in step 3), the reaction temperature is 80-90 ℃ and the reaction time is 2-2.5 h.
6. The visible light photocatalyst modified PVDF ultrafiltration membrane as claimed in claim 1, wherein the ultrafiltration membrane is prepared from the following components by weightThe components with the parts by weight are prepared as follows: 17-19 parts of polyvinylidene fluoride, 2.5-3.5 parts of polyvinylpyrrolidone, 77-79 parts of N, N-dimethylacetamide and CdS/g-C3N40.3-1.3 parts of/rGO nano photocatalyst.
7. The preparation method of the visible light photocatalyst modified PVDF ultrafiltration membrane as claimed in claim 1, which comprises the following steps:
1) CdS/g-C3N4Dispersing the/rGO nano photocatalyst in N, N-dimethylacetamide in an ultrasonic manner, then adding polyvinylidene fluoride and polyvinylpyrrolidone, and heating and stirring to form a uniform membrane casting solution;
2) vacuum defoaming the casting solution, and scraping to obtain a liquid film;
3) standing the scraped liquid film in air, putting the liquid film into a water coagulating bath, taking out the liquid film after the film falls off, immersing the liquid film into water for 16-30h, and drying to obtain CdS/g-C3N4A PVDF ultrafiltration membrane modified by rGO nano photocatalyst.
8. The method for preparing the visible light photocatalyst modified PVDF ultrafiltration membrane according to claim 7, wherein in the heating and stirring process of step 1), the heating temperature is 80-90 ℃ and the stirring time is 12-16 h.
9. The method for preparing the visible light photocatalyst modified PVDF ultrafiltration membrane according to claim 7, wherein in step 2), the scraping process is performed in a membrane scraper, and the size of a scraper in the membrane scraper is 300 μm.
10. Use of the visible light photocatalyst modified PVDF ultrafiltration membrane of any one of claims 1 to 6 for membrane organic contaminant resistance or antimicrobial.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910978918.6A CN110787645B (en) | 2019-10-15 | 2019-10-15 | Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910978918.6A CN110787645B (en) | 2019-10-15 | 2019-10-15 | Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110787645A true CN110787645A (en) | 2020-02-14 |
| CN110787645B CN110787645B (en) | 2021-05-11 |
Family
ID=69439185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910978918.6A Active CN110787645B (en) | 2019-10-15 | 2019-10-15 | Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110787645B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346650A (en) * | 2020-03-04 | 2020-06-30 | 同济大学 | Visible light photocatalyst, modified PVDF ultrafiltration membrane, and preparation method and application thereof |
| CN111871236A (en) * | 2020-07-27 | 2020-11-03 | 四川春语环保科技有限公司 | Double-membrane combined membrane separation and biological activity method wastewater treatment system |
| CN112174263A (en) * | 2020-11-10 | 2021-01-05 | 福州城建设计研究院有限公司 | Photocatalysis ultrafiltration purifier |
| CN113769787A (en) * | 2021-08-24 | 2021-12-10 | 同济大学 | Photocatalytic material based on plastic optical fiber and preparation method and application thereof |
| CN113877440A (en) * | 2021-09-28 | 2022-01-04 | 波塞冬(江苏)新材料科技有限公司 | Super nanofiltration membrane for recycling organic matters and preparation method thereof |
| CN114452818A (en) * | 2020-11-10 | 2022-05-10 | 南京理工大学 | Ultrafiltration membrane based on separation-catalysis structure and preparation method thereof |
| CN115041028A (en) * | 2022-06-08 | 2022-09-13 | 西安理工大学 | Composite membrane with photocatalytic performance and preparation method thereof |
| CN115364898A (en) * | 2022-08-31 | 2022-11-22 | 浙江大学 | Preparation method of fulvic acid film catalyst and application of fulvic acid film catalyst in piezoelectric catalytic pollutant removal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383820A (en) * | 2014-11-10 | 2015-03-04 | 华南师范大学 | Visible-light-response antibacterial and antifouling polyvinylidene fluoride film and preparation method thereof |
| CN110075898A (en) * | 2019-04-22 | 2019-08-02 | 浙江大学 | A kind of Photodeposition preparation g-C3N4The method of/CdS composite catalyst |
-
2019
- 2019-10-15 CN CN201910978918.6A patent/CN110787645B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383820A (en) * | 2014-11-10 | 2015-03-04 | 华南师范大学 | Visible-light-response antibacterial and antifouling polyvinylidene fluoride film and preparation method thereof |
| CN110075898A (en) * | 2019-04-22 | 2019-08-02 | 浙江大学 | A kind of Photodeposition preparation g-C3N4The method of/CdS composite catalyst |
Non-Patent Citations (5)
| Title |
|---|
| LI LIU，ETAL: "《Increased photocatalytic hydrogen evolution and stability over nano-sheet g-C3N4 hybridized CdS core@shell structure》", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| SURENDER TONDA ETAL: "《g-C3N4 (2D)_CdS (1D)_rGO (2D) dual-interface nano-composite for excellent and stable visible light photocatalytic hydrogen generation》", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY 》 * |
| WAN-KUEN JO，ET AL: "《Z-scheme CdS/g-C3N4 composites with RGO as an electron mediator for efficient photocatalytic H2 production and pollutant degradation》", 《CHEMICAL ENGINEERING JOURNAL》 * |
| YONGXU ，ETAL: "《Visible-light driven oxidative coupling of amines to imines with high selectivity in air over core-shell structured CdS@C3N4》", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| YUANGANG LI,ETAL: "《Fabrication of inorganic–organic core–shell heterostructure: novel CdS@g-C3N4 nanorod arrays for photoelectrochemical hydrogen evolution》", 《RSC ADVANCES》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346650A (en) * | 2020-03-04 | 2020-06-30 | 同济大学 | Visible light photocatalyst, modified PVDF ultrafiltration membrane, and preparation method and application thereof |
| CN111871236A (en) * | 2020-07-27 | 2020-11-03 | 四川春语环保科技有限公司 | Double-membrane combined membrane separation and biological activity method wastewater treatment system |
| CN112174263A (en) * | 2020-11-10 | 2021-01-05 | 福州城建设计研究院有限公司 | Photocatalysis ultrafiltration purifier |
| CN114452818A (en) * | 2020-11-10 | 2022-05-10 | 南京理工大学 | Ultrafiltration membrane based on separation-catalysis structure and preparation method thereof |
| CN114452818B (en) * | 2020-11-10 | 2024-03-19 | 南京理工大学 | Ultrafiltration membrane based on separation-catalysis sequence and preparation method thereof |
| CN112174263B (en) * | 2020-11-10 | 2024-04-09 | 福州城建设计研究院有限公司 | Photocatalysis ultrafiltration water purification device |
| CN113769787A (en) * | 2021-08-24 | 2021-12-10 | 同济大学 | Photocatalytic material based on plastic optical fiber and preparation method and application thereof |
| CN113769787B (en) * | 2021-08-24 | 2024-03-05 | 同济大学 | Photocatalytic material based on plastic optical fiber and preparation method and application thereof |
| CN113877440A (en) * | 2021-09-28 | 2022-01-04 | 波塞冬(江苏)新材料科技有限公司 | Super nanofiltration membrane for recycling organic matters and preparation method thereof |
| CN115041028A (en) * | 2022-06-08 | 2022-09-13 | 西安理工大学 | Composite membrane with photocatalytic performance and preparation method thereof |
| CN115364898A (en) * | 2022-08-31 | 2022-11-22 | 浙江大学 | Preparation method of fulvic acid film catalyst and application of fulvic acid film catalyst in piezoelectric catalytic pollutant removal |
| CN115364898B (en) * | 2022-08-31 | 2024-03-15 | 浙江大学 | Preparation method of Huang Wusuan membrane catalyst and application of Huang Wusuan membrane catalyst in piezocatalysis pollutant removal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110787645B (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110787645B (en) | Visible light photocatalyst modified PVDF ultrafiltration membrane as well as preparation method and application thereof | |
| CN111186881B (en) | Chitosan modified nano TiO2Preparation method of photocatalytic ultrafiltration membrane | |
| CN110170309B (en) | Two-dimensional metal organic framework composite membrane material, preparation method and application | |
| CN112156662B (en) | Self-cleaning electrostatic spinning nanofiber filter membrane, preparation method and application | |
| CN110485157A (en) | Chitosan graft mesoporous silicon dioxide nano tunica fibrosa preparation method and applications | |
| CN111760462B (en) | Preparation method, device and use method of photo-Fenton ceramic membrane for water treatment | |
| WO2021093832A1 (en) | C3n4 modified organic film preparation method and application | |
| CN111606464A (en) | High COD phenol-containing sewage treatment method | |
| CN108176383A (en) | A kind of preparation method of antibacterial absorption sponge material | |
| CN110813099B (en) | PVDF ultrafiltration membrane modified by CdS/MIL-101(Cr) photocatalyst and preparation method and application thereof | |
| CN108854595A (en) | Modified PVDF plate membrane of a kind of nano biological charcoal and the preparation method and application thereof | |
| CN111346650A (en) | Visible light photocatalyst, modified PVDF ultrafiltration membrane, and preparation method and application thereof | |
| CN111186880B (en) | Chitosan modified nano TiO2Application of photocatalytic ultrafiltration membrane in organic wastewater treatment | |
| CN101961605B (en) | Preparation process for diethylene triaminepentaacetic acid dianhydride modified polyvinylidene fluoride separation membrane and resin | |
| CN109019761A (en) | A kind of optical electro-chemistry filter for installation and its application | |
| CN112090296A (en) | Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof | |
| CN110563134B (en) | Anaerobic membrane bioreactor and application thereof in sewage treatment | |
| CN100430117C (en) | Process for preparing polyacrylic acid-Kynoar polyblend separation film and polyblend resin | |
| CN112121648A (en) | Polyvinylidene fluoride mixed matrix membrane with photocatalytic self-cleaning performance and preparation method and application thereof | |
| CN110813100A (en) | Composite separation membrane and preparation method thereof | |
| CN112320894A (en) | Bismuth sulfide modified iron-carbon filler, preparation method thereof and application thereof in sewage treatment | |
| CN113247990B (en) | Ship ballast water treatment system based on electrocatalysis membrane distillation integrated device | |
| CN113769787B (en) | Photocatalytic material based on plastic optical fiber and preparation method and application thereof | |
| CN101961606B (en) | Process for preparing ethylenediaminetetraacetic dianhydride modified polyvinylidene fluoride separation membrane and resin | |
| CN109382078A (en) | A kind of poly m-phenylene diamine/polyvinyl alcohol film and its preparation method and application |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |