CN116392979A - Visible light driven separation membrane, preparation method and application thereof in organic wastewater - Google Patents
Visible light driven separation membrane, preparation method and application thereof in organic wastewater Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 125
- 238000000926 separation method Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002351 wastewater Substances 0.000 title claims abstract description 14
- 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 120
- 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 120
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- 229920002258 tannic acid Polymers 0.000 claims abstract description 120
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 118
- 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 118
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- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 15
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000012986 modification Methods 0.000 claims abstract description 11
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 11
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- 239000007788 liquid Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 description 103
- 239000000243 solution Substances 0.000 description 21
- 230000004907 flux Effects 0.000 description 20
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 15
- 229960000907 methylthioninium chloride Drugs 0.000 description 15
- 239000000975 dye Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 6
- 239000004098 Tetracycline Substances 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 229960002180 tetracycline Drugs 0.000 description 5
- 229930101283 tetracycline Natural products 0.000 description 5
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- 239000002033 PVDF binder Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 150000003522 tetracyclines Chemical class 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
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- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 1
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Images
Classifications
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- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of membrane materials, and discloses a visible light driven separation membrane, a preparation method and application thereof in organic wastewater, wherein the membrane material comprises a modification layer formed on the surface of a substrate membrane; the modification layer is obtained by depositing silver nanowires on the surface of the graphene oxide sheet layer, and the modification layer is loaded with ferric hydroxide. The invention successfully deposits tannic acid molecules and silver nanowires on the graphene oxide sheet layer, and prepares the separation membrane by taking the membrane as a substrate.
Description
Technical Field
The invention relates to the technical field of membrane materials, in particular to a visible light driven separation membrane, a preparation method and application thereof in organic wastewater.
Background
The membrane separation technology has the characteristics of low cost, simple operation and the like, is widely considered to have huge application prospect in the aspect of treating organic wastewater, and can realize sewage reclamation, reduce environmental problems and further relieve the current situation of water resource shortage.
However, when the nanofiltration membrane is used for treating organic wastewater, the problems of low flux and membrane pollution are generally existed, and in the process of treating the organic wastewater, the surface of the membrane material is extremely easy to be adsorbed by pollutants to cause serious membrane pollution, so that the membrane pores are blocked, the separation efficiency of the membrane is reduced, and the service life of the separation membrane is shortened. Therefore, the method improves the anti-pollution performance of the membrane material, improves the treatment flux of organic pollutants such as membrane material separation dye, is an important research direction for the development of nanofiltration membranes at present, and has great significance for the practical application of the membrane separation technology in the treatment of organic wastewater.
Disclosure of Invention
The invention solves the technical problems that:
the method is used for solving the problem that the service life of the membrane is reduced due to the fact that the membrane material is easy to be polluted in the prior art.
The invention adopts the technical scheme that:
aiming at the technical problems, the invention aims to provide a visible light driven separation membrane, a preparation method and application thereof in organic wastewater.
The specific contents are as follows:
first, the invention provides a visible light driven separation membrane, which comprises a modification layer formed on the surface of a substrate membrane; the modification layer is obtained by depositing silver nanowires on the surface of the graphene oxide sheet layer, and the modification layer is loaded with ferric hydroxide.
Second, the present invention provides a method for preparing the aforementioned visible light driven separation membrane, comprising the steps of:
dispersing tannic acid, GO and silver nanowires in water, and performing film drawing with a substrate film to obtain a film body;
configuration of FeCl 3 ·6H 2 And (3) filtering the O solution to the surface of the membrane body to obtain the separation membrane.
Thirdly, the present invention provides a method for preparing the aforementioned visible light driven separation membrane, comprising the following steps:
dispersing tannic acid, GO and silver nanowires in water, and performing film drawing with a substrate film to obtain a film body;
configuration of FeCl 3 ·6H 2 Filtering the O solution to the surface of the membrane body to obtain an intermediate membrane;
intermediate film impregnation into FeCl 3 ·6H 2 And (3) drying the O solution to obtain the separation membrane material.
Fourth, the present invention is directed to the use of a visible light driven separation membrane as described above in organic wastewater.
The invention has the beneficial effects that:
(1) Through contact angle tests, the results show that the prepared AgNWS/TA@GO and AgNWS/TA@FeOOH/GO-1, agNWS/TA@FeOOH/GO-2 and AgNWS/TA@FeOOH/GO-3 composite films have good super-hydrophilic performance. The pure water flux of the composite membrane is 1529.8L m respectively -2 ·h -1 ·bar -1 、898.3 L·m -2 ·h -1 ·bar -1 、696.2 L·m -2 ·h -1 ·bar -1 、246.3 L·m -2 ·h -1 ·bar -1 The prepared composite membrane has higher pure water flux.
(2) The composite membrane provided by the invention has good separation effect on various dye wastewater, and the result shows that the separation effect of the AgNWs/TA@FeOOH/GO-1 composite membrane on at least 20mL and 10ppm of Methylene Blue (MB), crystal Violet (CV) and Congo Red (CR) can reach more than 97.0%. Meanwhile, after iron oxyhydroxide is loaded, a multi-layer micro-nano rough structure is formed on the surface of the AgNWs/TA@FeOOH/GO composite film, so that the AgNWs/TA@FeOOH/GO composite film has excellent anti-pollution performance.
(3) The AgNWs/TA@FeOOH/GO composite film has good visible light catalytic degradation performance. The result shows that under the drive of visible light, the AgNWs/TA@FeOOH/GO-1 composite film can realize the complete degradation of Methylene Blue (MB) with the concentration of 10ppm within 60 min. The prepared composite film has excellent visible light driving self-cleaning capability.
Drawings
FIG. 1 is an XRD spectrum of AgNWS/TA@GO composite film and AgNWS/TA@FeOOH/GO composite film; (AgNWs/TA@GO on top and AgNWs/TA@FeOOH/GO on bottom);
FIG. 2 is an XPS spectrum of AgNWS/TA@GO composite film and AgNWS/TA@FeOOH/GO composite film; (AgNWs/TA@GO on top and AgNWs/TA@FeOOH/GO on bottom);
FIG. 3 is a graph of water contact angle in air of AgNWS/TA@GO composite membrane and AgNWS/TA@FeOOH/GO composite membrane as a function of wetting time;
fig. 4 a), b), c) are SEM images of AgNWs/ta@feooh/GO-1 composite films and d) physical images of AgNWs/ta@feooh/GO-1 composite films, respectively, at different magnifications;
FIG. 5 is the pure water flux of AgNWs/TA@GO composite membrane and AgNWs/TA@FeOOH/GO composite membrane;
FIG. 6 is a graph of the separation effect of AgNWs/TA@FeOOH/GO-1 composite membrane on dye (methylene blue, crystal violet, congo red); a) 20mL of 10ppm of the composite membrane is used as a separation effect graph; b) The separation effect diagram of the composite membrane within a certain time (5-20 min);
FIG. 7 is a) the UV-visible absorption peak of AgNWs/TA@FeOOH/GO-1 composite film for degradation of methylene blue under visible light, B) the UV-visible absorption peak of AgNWs/TA@FeOOH/GO-1 composite film for rhodamine B under visible light;
FIG. 8 is a graph of photodegradation performance of TA/FeOOH@GO and AgNWs/TA@FeOOH/GO-1 composite films for tetracycline;
FIG. 9 is the water flux and water contact angle in air of AgNWs/TA@FeOOH/GO-1 composite membrane after testing against four severe conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Technical proposal
The separation membrane material provided by the invention is a nanofiltration membrane formed by a nano structure constructed by silver nanowires and graphene oxide and a substrate membrane, and is used for treating organic wastewater.
The specific scheme is that the separation membrane material for treating the organic wastewater comprises the following steps:
(1) Preparation of AgNWs/TA@GO composite membrane
Dispersing 0.012 g Tannic Acid (TA) in 100mL deionized water for 2 hours by ultrasonic dispersion, and dispersing 5-20 mL TA (0.005-0.015 wt%), 2-10 mL GO (0.005-0.015 mg/mL) and 0.5-5 mL AgNWs (0.2-0.6 wt%) in 100mL deionized water. PVDF film is used as a substrate, and film drawing is carried out under 0.09 MPa. Preparation of FeCl 3 ·6H 2 O solution (0.02 g FeCl) 3 ·6H 2 O dissolved in 100mL deionized water) and then 5mL FeCl 3 ·6H 2 And (3) carrying out reduced pressure suction filtration on the O to the surface of the membrane, and obtaining the AgNWs/TA@GO composite membrane through reduced pressure suction filtration.
(2) Preparation of AgNWs/TA@FeOOH/GO composite membrane
Immersing the AgNWs/TA@GO film into FeCl with concentration of 0.2 wt%, 0.4 wt% and 0.6wt%, respectively 3 ·6H 2 In O aqueous solution, the solution was placed in an oven at 60℃for 6 hours. After the reaction, taking out the composite film loaded with the ferric hydroxide (FeOOH), putting the composite film into a vacuum oven, and drying (40 ℃) the composite film at 24 h to obtain three composite films of AgNWS/TA@FeOOH/GO-1, agNWS/TA@FeOOH/GO-2 and AgNWS/TA@FeOOH/GO-3 respectively.
Specifically, by utilizing the complexation of ferric ions and Tannic Acid (TA), tannic acid molecules and silver nanowires (AgNWs) are successfully deposited on Graphene Oxide (GO) sheets, and a polyvinylidene fluoride (PVDF) film is used as a substrate, so that the AgNWs/TA@GO composite film is prepared. And ferric ions are mineralized in ferric trichloride solution to successfully load ferric hydroxide (FeOOH) on the surface of the AgNWs/TA@GO composite membrane in situ, and a micro-nano coarse structure is constructed, so that the AgNWs/TA@FeOOH/GO composite membrane is prepared. The photoFenton catalytic reaction of the ferric hydroxide is utilized to obtain the multifunctional composite membrane with high-efficiency dye separation performance and visible light driving self-cleaning capability.
Example 1
A preparation method of a separation membrane material comprises the following steps:
(1) Preparation of AgNWs/TA@GO composite membrane
0.012 g Tannic Acid (TA) was dispersed in 100mL deionized water, sonicated for 2 hours, and 10mL TA (0.012 wt%), 5mL GO (0.01 mg/mL), and 2mL AgNWs (0.3 wt%) were dispersed in 100mL deionized water. PVDF film is used as a substrate, and film drawing is carried out under 0.09 MPa. Preparation of FeCl 3 ·6H 2 O solution (0.02 g FeCl) 3 ·6H 2 O dissolved in 100mL deionized water) and then 5mL FeCl 3 ·6H 2 And (3) carrying out reduced pressure suction filtration on the O to the surface of the membrane, and obtaining the AgNWs/TA@GO composite membrane through reduced pressure suction filtration.
(2) Preparation of AgNWs/TA@FeOOH/GO-1 composite membrane
Immersing the AgNWs/TA@GO film into FeCl with concentration of 0.2 wt% 3 ·6H 2 In O aqueous solution, the solution was placed in an oven at 60℃for 6 hours. And taking out the composite film loaded with the iron oxyhydroxide (FeOOH) after the reaction, and putting the composite film into a vacuum oven for drying (40 ℃) 24 h to obtain the AgNWS/TA@FeOOH/GO-1 composite film respectively.
Example 2
A preparation method of a separation membrane material comprises the following steps:
(1) Preparation of AgNWs/TA@GO composite membrane
0.012 g Tannic Acid (TA) was dispersed in 100mL deionized water, sonicated for 2 hours, and 10mL TA (0.012 wt%), 5mL GO (0.01 mg/mL), and 2mL AgNWs (0.3 wt%) were dispersed in 100mL deionized water. PVDF film is used as a substrate, and film drawing is carried out under 0.09 MPa. Preparation of FeCl 3 ·6H 2 O solution (0.02 g FeCl) 3 ·6H 2 O dissolved in 100mL deionized water) and then 5mL FeCl 3 ·6H 2 And (3) carrying out reduced pressure suction filtration on the O to the surface of the membrane, and obtaining the AgNWs/TA@GO composite membrane through reduced pressure suction filtration.
(2) Preparation of AgNWs/TA@FeOOH/GO-2 composite membrane
Immersing the AgNWs/TA@GO film into FeCl with concentration of 0.4-wt% 3 ·6H 2 In O aqueous solution, the solution was placed in an oven at 60℃for 6 hours. And taking out the composite film loaded with the iron oxyhydroxide (FeOOH) after the reaction, and putting the composite film into a vacuum oven for drying (40 ℃) 24 h to obtain the AgNWS/TA@FeOOH/GO-2 composite film respectively.
Example 3
A preparation method of a separation membrane material comprises the following steps:
(1) Preparation of AgNWs/TA@GO composite membrane
0.012 g Tannic Acid (TA) was dispersed in 100mL deionized water, sonicated for 2 hours, and 10mL TA (0.012 wt%), 5mL GO (0.01 mg/mL), and 2mL AgNWs (0.3 wt%) were dispersed in 100mL deionized water. PVDF film is used as a substrate, and film drawing is carried out under 0.09 MPa. Preparation of FeCl 3 ·6H 2 O solution (0.02 g FeCl) 3 ·6H 2 O dissolved in 100mL deionized water) and then 5mL FeCl 3 ·6H 2 And (3) carrying out reduced pressure suction filtration on the O to the surface of the membrane, and obtaining the AgNWs/TA@GO composite membrane through reduced pressure suction filtration.
(2) Preparation of AgNWs/TA@FeOOH/GO-3 composite membrane
Immersing the AgNWs/TA@GO film into FeCl with concentration of 0.6-wt% 3 ·6H 2 In O aqueous solution, the solution was placed in an oven at 60℃for 6 hours. And taking out the composite film loaded with the iron oxyhydroxide (FeOOH) after the reaction, and putting the composite film into a vacuum oven for drying (40 ℃) 24 h to obtain the AgNWS/TA@FeOOH/GO-3 composite film respectively.
Test examples
Each composite film prepared in the previous examples was characterized in terms of chemical composition, microstructure and structure by using XRD, XPS, SEM and other instruments. The wettability, water flux, separation efficiency of organic dye and photocatalytic degradation performance of the surface of the composite membrane are evaluated.
(1) FIG. 1 is an XRD spectrum of AgNWS/TA@GO and AgNWS/TA@FeOOH/GO composite films. Comparing the XRD patterns of the AgNWS/TA@GO film, the original several strong characteristic diffraction peaks are covered in the XRD patterns of the AgNWS/TA@FeOOH/GO composite film loaded with the ferric hydroxide. And characteristic diffraction peaks of 28.3 degrees (486), 32.7 degrees (358) and 46.7 degrees (229) appear, which indicate the existence of the ferric hydroxide, and indicate that the ferric hydroxide is successfully loaded on the surface of the AgNWs/TA@FeOOH/GO composite film through mineralization.
(2) FIG. 2 is an XPS spectrum of AgNWS/TA@GO and AgNWS/TA@FeOOH/GO composite films. Signals of C1 s, O1 s, fe 2p and Ag 3d appear in the scanning spectrum of the AgNWS/TA@GO and AgNWS/TA@FeOOH/GO composite film. The Ag 3d signal of the AgNWS/TA@FeOOH/GO composite film is weak, which is related to the loading of the ferric hydroxide. The spectrogram shows the successful preparation of AgNWS/TA@GO and AgNWS/TA@FeOOH/GO composite films.
(3) The surface wettability of the film is an important index of the hydrophilic performance of the composite film, the wettability of AgNWS/TA@GO and AgNWS/TA@FeOOH/GO composite film is characterized by adopting a contact angle test, and the result of wetting the surface of the composite film by water in air is shown in figure 3. From fig. 3, it can be seen that the Water Contact Angles (WCA) when the water drops start to contact the surface of AgNWs/ta@go and AgNWs/ta@feooh/GO composite films were 34.2 ° and 8.7 °, respectively. The AgNWs/TA@GO and AgNWs/TA@FeOOH/GO composite films have good hydrophilic performance in air. According to the change of the contact angle with time, the Water Contact Angle (WCA) of the composite film can be rapidly reduced to 0 degree in a short time. Particularly, after loading the ferric hydroxide, the hydrophilicity of the composite membrane is obviously improved, because the ferric hydroxide loaded on the surface has strong hydrophilic performance, and meanwhile, the ferric hydroxide generated by in-situ mineralization on the surface of the membrane has a micro-nano coarse structure, which is favorable for the adsorption of the ferric hydroxide with high surface performance on water molecules, thus the composite membrane has strong hydrophilic capability.
(4) The pore structure of the membrane surface determines the selectivity and permeability of the membrane, and the separation performance of the membrane can be further analyzed intuitively from the microstructure of the surface and the section of the composite membrane by adopting a Scanning Electron Microscope (SEM). FIG. 4 is an SEM image of AgNWs/TA@FeOOH/GO-1 composite film. Wherein, the graphs in FIG. 4 a) -c) are microscopic morphology graphs of AgNWs/TA@FeOOH/GO-1 composite films, and the existence of one-dimensional AgNWs and GO sheets can be found under a large multiple. However, the microscopic morphology of the film surface mainly shows a layer of uniformly distributed iron oxyhydroxide, which is consistent with the appearance of a physical diagram (figure 4 d)) of the AgNWs/TA@FeOOH/GO-1 composite film, and the successful loading of the iron oxyhydroxide on the composite film is confirmed.
(5) The magnitude of the membrane flux has a close relationship with the membrane structure and the hydrophilicity of the membrane. The microporous membrane with high average pore diameter, high porosity and loose membrane structure has lower membrane passing resistance to water, thus having higher pure water flux. The membrane with higher hydrophilicity can have better affinity with water, and is beneficial to water molecules to pass through, so the membrane with higher hydrophilicity also has higher water flux. The pure water flux of the prepared AgNWs/TA@GO composite membrane and a series of AgNWs/TA@FeOOH/GO-x composite membranes is measured, and the result is shown in FIG. 5. The results show that the pure water flux of AgNWS/TA@GO, agNWS/TA@FeOOH/GO-1, agNWS/TA@FeOOH/GO-2 and AgNWS/TA@FeOOH/GO-3 is 1529.8L.m respectively -2 ·h -1 ·bar -1 、898.3 L·m -2 ·h -1 ·bar -1 、696.2 L·m -2 ·h -1 ·bar -1 、246.3 L·m -2 ·h -1 ·bar -1 . The three composite membranes are high in pure water flux, and the water flux of the composite membranes is slightly reduced after the iron oxyhydroxide is loaded, because the pore diameter of the composite membranes is reduced due to the loading of the compact iron oxyhydroxide on AgNWs/TA@ GO, the membrane passing resistance of water molecules is increased, and the water flux of the membranes is reduced. And as the concentration of the ferric trichloride solution increases, the water flux decrease degree increases, which indicates that the AgNWs/TA@ GO composite membrane forms larger ferric hydroxide in the high-concentration ferric trichloride solution, so that the surface pores of the membrane are more compact, and the water flux decrease degree increases.
(6) FIG. 6 is a graph of separation performance of AgNWs/TA@FeOOH/GO-1 composite membrane against dye. FIG. 6 a) shows the separation effect of 20mL of 10ppm of Methylene Blue (MB), crystal Violet (CV) and Congo Red (CR) on the composite film. The results indicate AgNWsThe composite membrane of the/TA@FeOOH/GO-1 has good separation effect on a plurality of dyes, the separation efficiency is respectively more than 98.7%, 97.7% and 99.3%, and the separation flux of the dyes is 325.7L.m -2 ·h -1 ·bar -1 、298.6 L·m -2 ·h -1 ·bar -1 、368.1 L·m -2 ·h -1 ·bar -1 . The AgNWs/TA@FeOOH/GO-1 composite membrane can be used for rapidly and effectively separating organic dye.
FIG. 6 b) shows separation performance of AgNWS/TA@FeOOH/GO-1 composite membrane against 10ppm MB, 10ppm CV and 20ppm CR in a predetermined period of time. The result shows that the AgNWs/TA@FeOOH/GO-1 composite film has higher separation performance on the dyes. The separation efficiency of the three dyes under continuous separation within 20min is still above 92.9%.
(7) FIG. 7 shows the results of degradation experiments of AgNWs/TA@FeOOH/GO-1 composite film on film surface pollutants under visible light. When testing the photo-Fenton catalytic reaction activity of the AgNWs/TA@FeOOH/GO-1 composite film, adopting Methylene Blue (MB) and rhodamine B (Rd B) as pollutants, respectively preparing 10ppm of methylene blue and rhodamine B solution, and inspecting the degradation performance of the composite film on organic pollutants under visible light. The results are shown in FIG. 7, and the AgNWs/TA@FeOOH/GO-1 composite film can realize complete degradation of the two dyes only in 60 min. The dye concentration in the solution was characterized by the uv-visible absorption peaks of the solution (see fig. 7 a) -B)), with stronger absorption peaks for MB and Rd B being observed at 664 nm and 570nm prior to treatment, with progressively smaller absorption peaks as the light irradiation time increases, indicating progressively smaller concentrations of MB and Rd B in the solution, and complete degradation of MB and Rd B achieved after 60min of treatment. Experimental results show that the AgNWS/TA@FeOOH/GO-1 composite membrane has excellent visible light Fenton catalytic activity, and can effectively degrade membrane organic pollutants in a short time, so that the AgNWS/TA@FeOOH/GO-1 composite membrane has good visible light driving self-cleaning capability.
(8) FIG. 8 is a graph of the photocatalytic degradation performance of the TA/FeOOH@GO and AgNWs/TA@FeOOH/GO-1 composite films on tetracycline, further explores the effect of the addition of AgNWs on the photocatalytic degradation performance of the composite films, and selects Tetracycline (TC) which is more difficult to degrade as a treatment object. As shown in FIG. 8, the degradation efficiencies of the TA/FeOOH@GO and AgNWs/TA@FeOOH/GO-1 composite films were 88.7% and 99.7% respectively after 30 min for 10ppm TC. The addition of AgNWs effectively improves the photocatalytic performance of the composite film.
(9) FIG. 9 shows the results of stability test experiments on AgNWs/TA@FeOOH/GO-1 composite films. As shown in the figure, after AgNWs/TA@FeOOH/GO-1 composite membranes are respectively soaked in extreme environments such as pH 4, pH 10, 3.5wt% NaCl solution and high temperature (90 ℃) for 7 days, the water flux and the water contact angle in air of the membranes are tested, and the results show that the water flux is not changed too much, and the water contact angle can be completely spread in a very fast time. The AgNWs/TA@FeOOH/GO-1 composite film has excellent stability. This provides a guarantee for the practical application at a later time.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A visible light driven separation membrane, characterized in that the separation membrane comprises a modification layer formed on the surface of a base membrane; the modification layer is obtained by depositing silver nanowires on the surface of the graphene oxide sheet layer, and the modification layer is loaded with ferric hydroxide.
2. The method for preparing a visible light driven separation membrane according to claim 1, comprising the steps of:
dispersing tannic acid, GO and silver nanowires in water, and performing film drawing with a substrate film to obtain a film body;
configuration of FeCl 3 ·6H 2 And (3) filtering the O solution to the surface of the membrane body to obtain the separation membrane.
3. The method of preparing a visible light driven separation membrane according to claim 2, wherein the pre-dispersion treatment is performed before the tannic acid, GO, silver nanowires are dispersed.
4. The method for producing a visible light driven separation membrane according to claim 3, wherein the concentration of tannic acid is 0.005 to 0.015wt%.
5. The method for preparing a visible light driven separation membrane according to claim 3, wherein the GO concentration is 0.005-0.015 mg/mL.
6. The method for preparing a visible light driven separation membrane according to claim 3, wherein the concentration of silver nanowires is 0.2-0.6wt%.
7. The method for preparing a visible light driven separation membrane according to any one of claims 3 to 6, wherein the volume ratio of the tannic acid pre-dispersion, the GO pre-dispersion and the silver nanowire pre-dispersion is 5-20:2-10:0.5-5.
8. The method for producing a visible light-driven separation membrane according to any one of claims 3 to 6, wherein feci 3 ·6H 2 The volume ratio of the O solution to the tannic acid pre-dispersion liquid is 2-10:5-20.
9. The method for preparing a visible light driven separation membrane according to claim 1, comprising the steps of:
dispersing tannic acid, GO and silver nanowires in water, and performing film drawing with a substrate film to obtain a film body;
configuration of FeCl 3 ·6H 2 Filtering the O solution to the surface of the membrane body to obtain an intermediate membrane;
intermediate film impregnation into FeCl 3 ·6H 2 And (3) drying the O solution to obtain the separation membrane material.
10. Use of a visible light driven separation membrane according to claim 1, or a visible light driven separation membrane obtained according to the preparation method of any one of claims 2 to 8, or a visible light driven separation membrane obtained according to the preparation method of claim 9, in organic wastewater.
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