CN115463564A - Modification method for in-situ growth of manganese dioxide on surface of ultrafiltration membrane based on metal polyphenol network - Google Patents
Modification method for in-situ growth of manganese dioxide on surface of ultrafiltration membrane based on metal polyphenol network Download PDFInfo
- Publication number
- CN115463564A CN115463564A CN202211097275.2A CN202211097275A CN115463564A CN 115463564 A CN115463564 A CN 115463564A CN 202211097275 A CN202211097275 A CN 202211097275A CN 115463564 A CN115463564 A CN 115463564A
- Authority
- CN
- China
- Prior art keywords
- solution
- manganese dioxide
- ultrafiltration membrane
- pes
- metal polyphenol
- 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000012528 membrane Substances 0.000 title claims abstract description 107
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims abstract description 56
- 235000013824 polyphenols Nutrition 0.000 title claims abstract description 56
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 52
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 27
- 238000002715 modification method Methods 0.000 title claims abstract description 19
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 123
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 123
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 27
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 27
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 18
- 229940033123 tannic acid Drugs 0.000 claims abstract description 18
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 18
- 229920002258 tannic acid Polymers 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 230000010355 oscillation Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 28
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 49
- 239000003921 oil Substances 0.000 description 40
- 235000019198 oils Nutrition 0.000 description 40
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 238000012876 topography Methods 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004045 soybean oil emulsion Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- 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
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a modification method for in-situ growth of manganese dioxide on the surface of an ultrafiltration membrane based on a metal polyphenol network, and belongs to the field of membrane material modification. The invention aims to solve the technical problems that the existing ultrafiltration membrane has low retention rate on emulsified oil and the surface of the membrane has small rejection effect on emulsified oil pollutants. The modification method comprises the following steps: 1. preparing a tannic acid solution and a manganese acetate solution, mixing to obtain a metal polyphenol network modified solution, and infiltrating a polyether sulfone ultrafiltration membrane; 2. preparing a manganese acetate growth solution, soaking, and then carrying out hydrothermal reaction; 3. soaking in potassium permanganate solution. The modified organic-inorganic composite membrane has obviously enhanced emulsified oil retention performance, pollution resistance and long-term operation stability, improves the treatment effect of the organic ultrafiltration membrane in the application of oily wastewater, and prolongs the service life of the organic-inorganic composite membrane. The ultrafiltration membrane prepared by the invention is applied to the field of oily wastewater treatment.
Description
Technical Field
The invention belongs to the field of membrane material modification, and particularly relates to a modification method for in-situ growth of manganese dioxide on the surface of an ultrafiltration membrane based on a metal polyphenol network.
Background
With the rapid development of industry, the demand of oil is more and more, a large amount of oily sewage is generated worldwide every year, but a large amount of oil enters a water body due to the reasons of imperfect treatment technology, insufficient management and the like, and great threat is caused to the environment and human health. Compared with the traditional technology for treating the oily wastewater, the ultrafiltration membrane treatment technology has the advantages of no need of adding other reagents, easy recovery or treatment of concentrated products, superior separation performance, low equipment cost and operation cost and the like, and has larger practical application prospect. However, the common organic ultrafiltration membrane material has the defects of low water flux and easy pollution, and the practical application of the ultrafiltration membrane in the oily wastewater treatment industry is limited by the difficult-to-avoid conditions.
Disclosure of Invention
The invention provides a modification method for in-situ growth of manganese dioxide on the surface of an ultrafiltration membrane based on a metal polyphenol network, aiming at solving the technical problems that the retention rate of the existing ultrafiltration membrane on emulsified oil is low and the rejection effect of the membrane surface on the emulsified oil pollutants is small.
A modification method for in-situ growth of manganese dioxide on the surface of an ultrafiltration membrane based on a metal polyphenol network comprises the following steps:
preparing a tannic acid solution and a manganese acetate solution, stirring and mixing uniformly, adding a sodium hydroxide solution to adjust the pH value to obtain a metal polyphenol network modified solution, infiltrating one side of an active layer of a polyether sulfone ultrafiltration membrane to be modified by using the metal polyphenol network modified solution, and oscillating during the infiltration process to obtain a metal polyphenol network modified membrane;
step two, preparing a manganese acetate growth solution, soaking the metal polyphenol network modified film obtained in the step one in the manganese acetate growth solution, and then carrying out hydrothermal reaction to obtain an amorphous manganese dioxide modified film growing on the surface;
and step three, preparing a potassium permanganate solution, soaking the amorphous manganese dioxide modified film growing on the surface obtained in the step two in the potassium permanganate solution, and performing oscillation contact reaction to obtain a delta-manganese dioxide modified film growing on the surface, thereby completing modification.
The polyethersulfone ultrafiltration membrane to be modified has asymmetric structures on two sides, the front surface of the membrane is a compact structure from the view of the cross section of the membrane, the bottom of the membrane is a loose finger-shaped pore structure, and one side of the active layer refers to a compact structure part which mainly plays a role in interception. During the filtration process, the front face of the membrane is in contact with pollutants, and the accumulation of the pollutants on the front face of the membrane causes membrane pollution. The purpose of membrane modification is to generate a hydrophilic modification layer on the front surface of the membrane, so that membrane pollution is effectively slowed down.
Further limiting, the metal polyphenol network modified film in the step one, the amorphous manganese dioxide modified film grown on the surface in the step two and the delta-manganese dioxide modified film grown on the surface in the step three are stored in pure water for later use at the temperature of 4 ℃.
The beneficial effects of the invention are:
1) The method uses a biomineralization thought for reference, and utilizes the metal polyphenol network modified layer to realize in-situ growth of metal oxide on the surface of the membrane, wherein the tannic acid-manganese ion metal polyphenol network modified layer is tightly combined with the surface of the membrane by means of the self-adhesion of tannic acid on one hand, and realizes in-situ deposition of metal ions on the surface of the membrane by means of the complexing capacity of tannic acid and metal ions on the other hand, so that stable growth sites are provided for the subsequent growth of the metal oxide, and the long-term operation stability of the modified membrane is greatly improved.
2) The delta-manganese dioxide realizes in-situ growth on the surface of the membrane, has a typical two-dimensional layered structure, can generate a micro structure of three-dimensional nanoflowers through regulation and control, has the potential of reducing the water passing resistance and improving the surface roughness of the membrane, has certain ozone catalytic oxidation capacity, and can greatly improve the hydrophilicity of the ultrafiltration membrane by using the delta-manganese dioxide as a surface modification substance of the ultrafiltration membrane.
3) The method provided by the invention maintains higher level permeability, improves interception performance to a certain extent, greatly improves the oil pollution resistance of the ultrafiltration membrane, slows down the pollution degree of the membrane in the operation process, reduces cleaning frequency, reduces energy consumption, and prolongs service life.
4) The method realizes the in-situ growth of the delta-manganese dioxide on the surface of the film, has mild reaction conditions, more controllable growth degree of the manganese dioxide, is easy to operate, and shows excellent large-scale production application prospect.
5) According to the invention, the metal polyphenol network modified layer is innovatively utilized, manganese dioxide grows in situ, the surface micro-morphology of the ultrafiltration membrane is optimized, the pore size of membrane pores is reduced, the hydrophilicity is improved, and the interception performance and the anti-pollution performance of the ultrafiltration membrane are improved simultaneously.
6) The method can obviously improve the removal rate of the ultrafiltration membrane on different emulsified oils, and has wide application prospect in the field of oily wastewater treatment.
The method is applied to the field of oily wastewater treatment.
Drawings
FIG. 1 shows PES, TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 Scanning electron micrographs and atomic force microscope micrographs of @ TA-PES;
FIG. 2 shows the surface of a delta-manganese dioxide modified film delta-MnO grown in example one 2 The X-ray diffraction pattern of @ TA-PES;
FIG. 3 shows PES ultrafiltration membranes of comparative experiment and TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 The pure water contact angle of @ TA-PES;
FIG. 4 shows delta-MnO with delta-manganese dioxide modified film grown on the surface of the manganese dioxide modified film prepared in the first example 2 @ TA-PES underwater oil drop contact angles of different oils;
FIG. 5 shows the PES ultrafiltration membrane of comparative experiment and the TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 @ TA-PES pore size distribution plot;
FIG. 6 shows PES ultrafiltration membranes of comparative experiment and TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 The pure water flux histogram of @ TA-PES;
FIG. 7 shows PES ultrafiltration membranes of comparative experiment and TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 The ott TA-PES is a bar graph of the retention rates of petroleum ether, n-hexadecane, cyclohexane, soybean oil, 1,2-dichloroethane and n-hexane emulsified oil solutions respectively;
FIG. 8 shows a PES ultrafiltration membrane obtained by a comparative experiment and a delta-MnO modified membrane grown on the surface of delta-manganese dioxide obtained in example I 2 The three-cycle contamination curve of @ TA-PES.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a modification method for in-situ growth of manganese dioxide on the surface of an ultrafiltration membrane based on a metal polyphenol network, which is characterized by comprising the following steps:
preparing a tannic acid solution and a manganese acetate solution, stirring and mixing uniformly, adding a sodium hydroxide solution to adjust the pH value to obtain a metal polyphenol network modified solution, infiltrating one side of an active layer of a polyether sulfone ultrafiltration membrane to be modified by using the metal polyphenol network modified solution, and oscillating during the infiltration process to obtain a metal polyphenol network modified membrane;
step two, preparing a manganese acetate growth solution, soaking the metal polyphenol network modified membrane obtained in the step one in the manganese acetate growth solution, and then carrying out hydrothermal reaction to obtain an amorphous manganese dioxide modified membrane growing on the surface;
and step three, preparing a potassium permanganate solution, soaking the amorphous manganese dioxide modified film growing on the surface obtained in the step two in the potassium permanganate solution, and performing oscillation contact reaction to obtain a delta-manganese dioxide modified film growing on the surface, thereby completing modification.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the metal polyphenol network modified solution of the first step is finished according to the following steps:
and 2, mixing the tannic acid solution obtained in the step 1 with a manganese acetate solution, then adjusting the pH value by using a sodium hydroxide solution, controlling the rotating speed to be 200-300 r/min, and uniformly mixing to obtain the metal polyphenol network modified solution. The rest is the same as the first embodiment.
The third concrete implementation mode: the first or second difference between the present embodiment and the specific embodiment is: and mixing the solution of the tannic acid and the solution of the manganese acetate according to the volume ratio of 1:1 in the step one. The other embodiments are the same as the first embodiment or the second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the first step, the concentration of the sodium hydroxide solution is 0.01 mol/L-0.05 mol/L. The others are the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: regulating the pH value to 5.5-6.5. The others are the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the first step, the oscillation speed is controlled to be 40-80 rmp/min, and the oscillation time is controlled to be 2-6 h. The others are the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the concentration of the manganese acetate growth solution prepared in the second step is 0.1-0.3 wt%, and the solvent is pure water. The others are the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: and step two, performing hydrothermal reaction, wherein the reaction temperature is controlled to be 50-70 ℃, and the reaction time is 1-3 h. The others are the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the concentration of the potassium permanganate solution prepared in the third step is 0.005wt% -0.01 wt%, and the solvent is pure water. The others are the same as the embodiments in one to eight.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and the vibration speed is controlled to be 40 r/min-80 r/min, and the vibration time is controlled to be 2 min-180 min. The others are the same as one of the first to ninth embodiments.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The first embodiment is as follows:
the embodiment of the invention relates to a modification method for in-situ growth of manganese dioxide on the surface of an ultrafiltration membrane based on a metal polyphenol network, which specifically comprises the following steps:
step one, preparing a tannic acid solution with the concentration of 2g/L and a manganese acetate solution with the concentration of 2g/L, stirring and mixing uniformly, adding a sodium hydroxide solution with the concentration of 0.025mol/L to adjust the pH to 5.8 to obtain a metal polyphenol network modified solution, fixing a polyether sulfone ultrafiltration membrane (PES) to be modified on a reactor, infiltrating one side of an active layer of the polyether sulfone ultrafiltration membrane to be modified with the metal polyphenol network modified solution, accompanying with vibration in the infiltration process, controlling the vibration speed to be 60rmp/min and the vibration time to be 4h to obtain a metal polyphenol network modified membrane (TA/Mn-PES);
step two, preparing a manganese acetate growth solution with the concentration of 0.2wt%, soaking the metal polyphenol network modified film obtained in the step one in the manganese acetate growth solution, and then carrying out hydrothermal reaction, wherein the reaction temperature is controlled to be 60 ℃, and the reaction time is 2 hours, so that an amorphous manganese dioxide modified film with the surface growing is obtained;
step three, preparing a potassium permanganate solution with the concentration of 0.005wt%, soaking the amorphous manganese dioxide modified film with the surface growth obtained in the step two in the potassium permanganate solution, oscillating for contact reaction, controlling the oscillation speed to be 60r/min and the oscillation time to be 20min, and obtaining a delta-manganese dioxide modified film (delta-MnO) with the surface growth 2 @ TA-PES), modification is completed.
The metal polyphenol network modification solution in the first step is completed according to the following steps:
and 2, mixing the tannic acid solution obtained in the step 1 with a manganese acetate solution, then adjusting the pH to 5.8 by adopting a sodium hydroxide solution with the concentration of 0.025mol/L, and uniformly mixing at the rotation speed of 250r/min to obtain the metal polyphenol network modified solution.
Comparative experiment: the comparative experiment differs from example one in that: the PES does not undergo surface modification and in-situ mineralization of a metal polyphenol network, is soaked in isopropanol to remove a protective agent, and is then soaked in pure water to obtain the PES ultrafiltration membrane.
Detection test
FIG. 1 shows PES, TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 Scanning electron micrographs and atomic force microscope micrographs of @ TA-PES; wherein the figure a 1 Is the surface topography of PES under 2 ten thousand times magnification, a graph 2 Is the surface topography of PES under 10 ten thousand times magnification, a graph 3 Is an atomic force microscope picture of PES, panel b 1 Is the surface topography of TA/Mn-PES under 2 ten thousand times magnification, and a graph b 2 Is the surface topography of TA/Mn-PES under 10 ten thousand times magnification, and a graph b 3 Is TA/Mn-Atomic force microscopy of PES, panel c 1 The surface topography of MnO @ TA-PES under 2 ten thousand times of magnification, graph c 2 The surface topography of MnO @ TA-PES under 10 ten thousand times of magnification, graph c 3 Atomic force micrograph of MnO @ TA-PES, panel d 1 Is delta-MnO 2 Surface topography of @ TA-PES under 2 ten thousand times magnification, graph d 2 Is delta-MnO 2 Surface topography of @ TA-PES under 10 ten thousand times magnification, graph d 3 Is delta-MnO 2 Atomic force microscopy of @ TA-PES.
(II) FIG. 2 shows a delta-MnO surface-grown delta-manganese dioxide modified film obtained in example one 2 X-ray diffraction pattern of @ TA-PES, as seen in FIG. 2, delta-MnO 2 The @ TA diffraction peaks at 13.0 °, 24.2 °, 36.7 ° and 65.9 °, with δ -MnO 2 The appearance positions of the characteristic peaks are very close, and the in-situ growth of delta-MnO on the surface of the film is proved 2 The feasibility of the method that the metal oxide can be grown on the surface of the film in situ by utilizing the metal polyphenol network is verified.
FIG. 3 shows PES ultrafiltration membranes of comparative experiment and TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 The pure water contact angle of @ TA-PES is 70.7% for the control film PES, 22.3% for the metal polyphenol network modified film TA/Mn-PES, 11.5% for the amorphous manganese dioxide modified film MnO @ TA-PES grown on the surface, and delta-manganese dioxide modified film delta-MnO grown on the surface, as can be seen from FIG. 3 2 The pure water contact angle of @ TA-PES was close to 0 deg., comparable to that of the control film, delta-MnO 2 The pure water contact angle of the @ TA-PES membrane is obviously reduced, and the hydrophilicity is obviously improved.
(IV) FIG. 4 shows the surface of the delta-manganese dioxide modified film delta-MnO prepared in example one 2 The underwater oil drop contact angles of different oils of @ TA-PES can be seen from figure 4, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The contact angle of the @ TA-PES with petroleum ether is 165.6 degrees, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The contact angle of n-hexadecane of @ TA-PES is 168.6 degrees, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The cyclohexane contact angle of @ TA-PES is 165.2 degrees, and a delta-manganese dioxide modified film is grown on the surfaceMnO 2 The contact angle of the soybean oil of @ TA-PES is 166.7 degrees, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The contact angle of 1,2-dichloroethane of @ TA-PES is 150.1 degrees, and delta-manganese dioxide modified film delta-MnO grows on the surface 2 The n-hexane contact angle of @ TA-PES is 163.9 DEG, delta-MnO 2 The underwater oil drop contact angles of the @ TA-PES films are all larger than 150 degrees, and excellent repulsion on oil drops is shown.
FIG. 5 shows PES ultrafiltration membranes and TA/Mn-PES, mnO @ TA-PES and delta-MnO in example I 2 The pore size distribution diagram of @ TA-PES, where graph a is PES, graph b is TA/Mn-PES, graph c is MnO @ TA-PES, and graph d is delta-MnO 2 @ TA-PES; from fig. 5, it can be seen that the metal polyphenol network modified solution is deposited on the surface of the ultrafiltration membrane but does not cause the reduction of the membrane pores, after manganese dioxide is grown in situ on the surface of the subsequent membrane, the manganese dioxide nanosheet partially covers the membrane pores, so that the size of the membrane pore diameter is slightly reduced, the size of the membrane pore diameter is further regulated and controlled along with the increase of the crystallinity of the manganese dioxide, and the membrane pore diameter is reduced and more uniform.
FIG. 6 shows PES ultrafiltration membranes of comparative experiment and TA/Mn-PES, mnO @ TA-PES and delta-MnO in example one 2 The pure water flux histogram of @ TA-PES, as seen from FIG. 6, was 293.9 L.m for PES as a control membrane -2 ·h -1 The pure water flux of the metal polyphenol network modified membrane TA/Mn-PES is 601.9 L.m -2 ·h -1 The pure water flux of the amorphous manganese dioxide modified film MnO @ TA-PES grown on the surface is 523.8 L.m -2 ·h -1 delta-MnO with delta-manganese dioxide modified film growing on the surface 2 The pure water flux of @ TA-PES is 389.4 L.m -2 ·h -1 Compared with the control membrane, the ultrafiltration membrane after modification has the advantages that although the membrane pore size is reduced and the water passing resistance is increased, the permeability is maintained at a higher level due to the obvious improvement of hydrophilicity.
FIG. 7 shows PES ultrafiltration membranes and TA/Mn-PES, mnO @ TA-PES and delta-MnO in example I 2 The ott TA-PES is a bar graph of the retention rates of petroleum ether, n-hexadecane, cyclohexane, soybean oil, 1,2-dichloroethane and n-hexane emulsified oil solutions (the concentration is 10g/L, and the concentration of surfactant SDS is 1 g/L) respectively;wherein 1 represents PES,2 represents TA/Mn-PES,3 represents MnO @ TA-PES,4 represents delta-MnO 2 @ TA-PES. As can be seen from fig. 7, the petroleum ether emulsified oil retention rate of the control membrane PES is 98.3%, the n-hexadecane emulsified oil retention rate of the control membrane PES is 99.7%, the cyclohexane emulsified oil retention rate of the control membrane PES is 88.1%, the soybean oil emulsified oil retention rate of the control membrane PES is 98.4%, the 1,2-dichloroethane emulsified oil retention rate of the control membrane PES is 95.6%, and the n-hexane emulsified oil retention rate of the control membrane PES is 92.0%; the petroleum ether emulsified oil retention rate of the metal polyphenol network modified membrane TA/Mn-PES is 98.7%, the n-hexadecane emulsified oil retention rate of the metal polyphenol network modified membrane TA/Mn-PES is 99.7%, the cyclohexane emulsified oil retention rate of the metal polyphenol network modified membrane TA/Mn-PES is 92.9%, the soybean emulsified oil retention rate of the metal polyphenol network modified membrane TA/Mn-PES is 98.4%, the 1,2-dichloroethane emulsified oil retention rate of the metal polyphenol network modified membrane TA/Mn-PES is 98.3%, and the n-hexane emulsified oil retention rate of the metal polyphenol network modified membrane TA/Mn-PES is 94.4%; the retention rate of petroleum ether emulsified oil with the amorphous manganese dioxide modified film MnO @ TA-PES growing on the surface is 98.7%, the retention rate of n-hexadecane emulsified oil with the amorphous manganese dioxide modified film MnO @ TA-PES growing on the surface is 99.8%, the retention rate of cyclohexane emulsified oil with the amorphous manganese dioxide modified film MnO @ TA-PES growing on the surface is 94.2%, the retention rate of soybean emulsified oil with the amorphous manganese dioxide modified film MnO @ TA-PES growing on the surface is 99.2%, the retention rate of 1,2-dichloroethane emulsified oil with the amorphous manganese dioxide modified film MnO @ TA-PES growing on the surface is 96.2%, and the retention rate of n-hexane emulsified oil with the amorphous manganese dioxide modified film MnO @ TA-PES growing on the surface is 94.8%; delta-MnO with delta-manganese dioxide modified film grown on surface 2 The petroleum ether emulsified oil retention rate of @ TA-PES is 99.0%, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The rejection rate of hexadecane emulsified oil of @ TA-PES is 99.7%, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The retention rate of cyclohexane emulsified oil of @ TA-PES is 98.6%, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The soybean oil emulsion oil retention rate of @ TA-PES is 99.3%, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 @ TA-PES 1,2-dichloroethyleneThe retention rate of the alkyl emulsified oil is 98.4 percent, and a delta-manganese dioxide modified film delta-MnO grows on the surface 2 The cut-off rate of the n-hexane emulsified oil of @ TA-PES is 98.2%. Compared with a control membrane, the retention performance of the ultrafiltration membrane after modification is improved to a certain degree.
(eighth) FIG. 8 is a view showing a PES ultrafiltration membrane of a comparative experiment and a delta-MnO modified membrane grown on the surface of delta-manganese dioxide obtained in example one 2 The three-cycle pollution curve of @ TA-PES (n-hexadecane emulsified oil, n-hexadecane concentration of 10g/L, surfactant SDS concentration of 1 g/L), in which ■ represents PES, ● represents delta-MnO 2 @ TA-PES. From FIG. 8, it can be found that delta-MnO of delta-manganese dioxide modified film is grown on the surface as compared with the control film 2 The pollution degree of the @ TA-PES is obviously reduced, and the oil pollution resistance is obviously improved.
Claims (10)
1. A modification method for in-situ growth of manganese dioxide on the surface of an ultrafiltration membrane based on a metal polyphenol network is characterized by comprising the following steps:
preparing a tannic acid solution and a manganese acetate solution, stirring and mixing uniformly, adding a sodium hydroxide solution to adjust the pH value to obtain a metal polyphenol network modified solution, infiltrating one side of an active layer of a polyether sulfone ultrafiltration membrane to be modified with the metal polyphenol network modified solution, and oscillating during infiltration to obtain a metal polyphenol network modified membrane;
step two, preparing a manganese acetate growth solution, soaking the metal polyphenol network modified film obtained in the step one in the manganese acetate growth solution, and then carrying out hydrothermal reaction to obtain an amorphous manganese dioxide modified film growing on the surface;
and step three, preparing a potassium permanganate solution, soaking the amorphous manganese dioxide modified film growing on the surface obtained in the step two in the potassium permanganate solution, and performing oscillation contact reaction to obtain a delta-manganese dioxide modified film growing on the surface, thereby completing modification.
2. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network as claimed in claim 1, wherein the metal polyphenol network modification solution in the first step is prepared by the following steps:
step 1, dissolving 0.06-0.18 g of tannic acid in 30-90 mL of pure water, dissolving 0.06-0.18 g of manganese acetate in 30-90 mL of pure water, and ultrasonically dissolving in an air environment to obtain a tannic acid solution and a manganese acetate solution;
and 2, mixing the tannic acid solution obtained in the step 1 with a manganese acetate solution, then adjusting the pH value by using a sodium hydroxide solution, controlling the rotating speed to be 200-300 r/min, and uniformly mixing to obtain the metal polyphenol network modified solution.
3. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network as claimed in claim 1, wherein the ratio of the volume of the solution of the tannic acid to the volume of the solution of the manganese acetate in the step one is 1:1.
4. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network as claimed in claim 1, wherein the concentration of the sodium hydroxide solution in the first step is 0.01 mol/L-0.05 mol/L.
5. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network as claimed in claim 1, characterized in that the pH value is adjusted to 5.5-6.5 in the first step.
6. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network as claimed in claim 1, characterized in that in the first step, the oscillation speed is controlled to be 40-80 rmp/min, and the oscillation time is controlled to be 2-6 h.
7. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network according to claim 1, characterized in that the concentration of the manganese acetate growth solution prepared in the second step is 0.1-0.3 wt%, and the solvent is pure water.
8. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network according to claim 1, characterized in that in the second hydrothermal reaction step, the reaction temperature is controlled to be 50-70 ℃, and the reaction time is 1-3 h.
9. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network according to claim 1, characterized in that the concentration of the potassium permanganate solution prepared in the step three is 0.005wt% -0.01 wt%, and the solvent is pure water.
10. The modification method for in-situ growth of manganese dioxide on the surface of the ultrafiltration membrane based on the metal polyphenol network according to claim 1, characterized in that in the step three control oscillation speeds are 40r/min to 80r/min, and oscillation time is 2min to 180min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211097275.2A CN115463564B (en) | 2022-09-08 | 2022-09-08 | Modification method for in-situ growth of manganese dioxide on ultrafiltration membrane surface based on metal polyphenol network |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211097275.2A CN115463564B (en) | 2022-09-08 | 2022-09-08 | Modification method for in-situ growth of manganese dioxide on ultrafiltration membrane surface based on metal polyphenol network |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115463564A true CN115463564A (en) | 2022-12-13 |
| CN115463564B CN115463564B (en) | 2023-08-15 |
Family
ID=84370661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211097275.2A Active CN115463564B (en) | 2022-09-08 | 2022-09-08 | Modification method for in-situ growth of manganese dioxide on ultrafiltration membrane surface based on metal polyphenol network |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115463564B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE877806A (en) * | 1978-07-20 | 1979-11-16 | Nippon Steel Corp | MANGANESE COATING DEPOSITED ON STEEL MATERIALS |
| JPS5518513A (en) * | 1978-07-20 | 1980-02-08 | Nippon Steel Corp | Electroplating apparatus with manganese |
| JP2011038173A (en) * | 2009-08-17 | 2011-02-24 | Nippon Parkerizing Co Ltd | Post-treatment liquid for self-deposition coating film on metal surface, and method for producing metal material having post-treated self-deposition coating film formed thereon |
| US20110142899A1 (en) * | 2008-06-25 | 2011-06-16 | Nanobiomatters, S.L. | Active nanocomposite materials and production method thereof |
| CN107266039A (en) * | 2017-06-06 | 2017-10-20 | 苏州轩朗塑料制品有限公司 | A kind of preparation method and applications of medical environment-friendly composite material |
| CN110280227A (en) * | 2019-07-04 | 2019-09-27 | 青岛科技大学 | MnO2The preparation and its application of the difunctional composite material of/PEI/TA |
| CN112717706A (en) * | 2020-11-03 | 2021-04-30 | 浙江师范大学 | Metal organic framework ZIF-8 film, preparation method and application thereof |
| CN113690429A (en) * | 2021-08-23 | 2021-11-23 | 武汉立承科技有限公司 | Carbon-coated graphene/metal oxide composite material and preparation method thereof |
| CN114084907A (en) * | 2021-10-26 | 2022-02-25 | 西安交通大学 | Mesoporous manganese dioxide synthesized by redox method, metal-doped mesoporous manganese dioxide and method |
| TW202211530A (en) * | 2020-05-07 | 2022-03-16 | 美商福恩能源公司 | Rechargeable battery using iron negative electrode and manganese oxide positive electrode |
-
2022
- 2022-09-08 CN CN202211097275.2A patent/CN115463564B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE877806A (en) * | 1978-07-20 | 1979-11-16 | Nippon Steel Corp | MANGANESE COATING DEPOSITED ON STEEL MATERIALS |
| JPS5518513A (en) * | 1978-07-20 | 1980-02-08 | Nippon Steel Corp | Electroplating apparatus with manganese |
| US20110142899A1 (en) * | 2008-06-25 | 2011-06-16 | Nanobiomatters, S.L. | Active nanocomposite materials and production method thereof |
| JP2011038173A (en) * | 2009-08-17 | 2011-02-24 | Nippon Parkerizing Co Ltd | Post-treatment liquid for self-deposition coating film on metal surface, and method for producing metal material having post-treated self-deposition coating film formed thereon |
| CN107266039A (en) * | 2017-06-06 | 2017-10-20 | 苏州轩朗塑料制品有限公司 | A kind of preparation method and applications of medical environment-friendly composite material |
| CN110280227A (en) * | 2019-07-04 | 2019-09-27 | 青岛科技大学 | MnO2The preparation and its application of the difunctional composite material of/PEI/TA |
| TW202211530A (en) * | 2020-05-07 | 2022-03-16 | 美商福恩能源公司 | Rechargeable battery using iron negative electrode and manganese oxide positive electrode |
| CN112717706A (en) * | 2020-11-03 | 2021-04-30 | 浙江师范大学 | Metal organic framework ZIF-8 film, preparation method and application thereof |
| CN113690429A (en) * | 2021-08-23 | 2021-11-23 | 武汉立承科技有限公司 | Carbon-coated graphene/metal oxide composite material and preparation method thereof |
| CN114084907A (en) * | 2021-10-26 | 2022-02-25 | 西安交通大学 | Mesoporous manganese dioxide synthesized by redox method, metal-doped mesoporous manganese dioxide and method |
Non-Patent Citations (3)
| Title |
|---|
| GANJALI, FATEMEH等: "Biocompatibility and Antimicrobial Investigation of Agar-Tannic Acid Hydrogel Reinforced with Silk Fibroin and Zinc Manganese Oxide Magnetic Microparticles", JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS * |
| HEIDARI, ALI AKBAR等: "TFC organic solvent nanofiltration membrane fabricated by a novel HDPE membrane support covered by manganese dioxide/tannic acid-Fe3+ layers", JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS * |
| 闫佳莹: "多酚-金属络合物改性膜的制备及除锰性能研究", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115463564B (en) | 2023-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ayyaru et al. | Enhanced antifouling performance of PVDF ultrafiltration membrane by blending zinc oxide with support of graphene oxide nanoparticle | |
| CN108421422B (en) | Nanofiltration composite membrane for selective ion separation and preparation method thereof | |
| CN109433023B (en) | Graphene oxide nanofiltration membrane with graphite-like carbon nitride intercalation, and preparation method and application thereof | |
| JP2017500195A (en) | Ultra-thin graphene-based films for water treatment and their formation and use | |
| CN107096393A (en) | A kind of thermally-stabilised, super-hydrophobic ceramic carbon nano-tube compound film and its membrane distillation water treatment applications | |
| CN114272766B (en) | Two-dimensional MXene-based oil-water separation membrane and preparation method thereof | |
| CN113648850B (en) | Preparation method of MXene/reduced porous graphene oxide (r-HGO) composite membrane with high flux and high removal rate | |
| Wang et al. | Enhanced high-salinity brines treatment using polyamide nanofiltration membrane with tunable interlayered MXene channel | |
| Jang et al. | Ti3C2TX-Ethylenediamine nanofiltration membrane for high rejection of heavy metals | |
| CN112023721B (en) | Visible light driven self-cleaning carbon nitride multifunctional composite film and preparation method and application thereof | |
| Gui et al. | g-C3N4 nanofibers network reinforced polyamide nanofiltration membrane for fast desalination | |
| CN111036082B (en) | Graphene oxide/TiO2Method for preparing composite membrane | |
| Ding et al. | 2D nanosheets optimized electrospray-assisted interfacial polymerization polyamide membrane with excellent separation performance | |
| Zhou et al. | Anti-fouling PVDF membranes incorporating photocatalytic biochar-TiO2 composite for lignin recycle | |
| Otitoju et al. | Efficient removal of chemical oxygen demand from lye wastewater by APTES-TIO2/GO mixed matrix membrane: Optimization using Box-Behnken Design | |
| CN115463564A (en) | Modification method for in-situ growth of manganese dioxide on surface of ultrafiltration membrane based on metal polyphenol network | |
| CN109173731B (en) | Method for preparing metal organic framework @ graphene oxide hybrid membrane by freeze drying technology | |
| Chen et al. | Hydrophilic-hydrophobic bilayer interlayer for high performance thin-film composite reverse osmosis membranes | |
| CN114130197A (en) | Graphene oxide titanium dioxide-dopamine PEI nanofiltration membrane and preparation method thereof | |
| CN115445451B (en) | Preparation method of amine molecule intercalation double-reduction graphene oxide composite membrane | |
| CN113069936A (en) | Preparation method of large-flux graphene oxide filter membrane and application of large-flux graphene oxide filter membrane in ion screening | |
| CN109173730B (en) | Method for in-situ preparation of MOFs @ f-GO hybrid membrane by freeze drying technology | |
| Feng et al. | Recent advances in covalent organic framework-Based membranes for water purification: Insights into separation mechanisms and applications | |
| CN114768555A (en) | Modified polyamide separation membrane and preparation method thereof | |
| CN114247305A (en) | Two-dimensional nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane and preparation method thereof |
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 |