CN112619622A - Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof - Google Patents
Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof Download PDFInfo
- Publication number
- CN112619622A CN112619622A CN202011537508.7A CN202011537508A CN112619622A CN 112619622 A CN112619622 A CN 112619622A CN 202011537508 A CN202011537508 A CN 202011537508A CN 112619622 A CN112619622 A CN 112619622A
- Authority
- CN
- China
- Prior art keywords
- membrane
- electrostatic spinning
- pan
- heavy metal
- fiber membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Abstract
The invention discloses a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water, and a preparation method and application thereof. The method comprises the following steps: (1) preparing a polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: the membrane preparation is divided into an electrostatic spinning part of PAN solution and an ethanol solution part of GO ultrasonic spraying, and is carried out on two sides of a receiving device; (2) polydopamine modification of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a dopamine aqueous solution, then immersing the polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane into the dopamine aqueous solution, stirring for reaction, washing the membrane with water, and freeze-drying to obtain the nano composite fiber membrane. The nano composite fiber membrane synthesized by the method has good filtering effect on ionic dye and heavy metal ions, has complete and stable structure and good mechanical property, and has good application prospect in industrial wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of ionic dye and heavy metal sewage treatment, and particularly relates to a nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and a preparation method and application thereof.
Background
With the rapid development of modern industry, environmental pollution is considered as one of the most serious crises in the world, in which water pollution caused by the discharge of sewage containing hazardous chemicals is endangering the health and ecological environment of people. These contaminating ionic dyes and heavy metal ions are the most harmful poisons in the industries of coatings, electroplating, textiles, cosmetics, metallurgy, etc., and due to their stable and non-degrading aromatic structures, these pollutants can cause damage to the human body, including hepatotoxicity, digestive system and central nervous system damage. In order to remove pollutants from industrial wastewater, researchers have studied chemical oxidation, photocatalytic degradation, ion exchange, flocculation, ultrafiltration, and other methods. Corresponding to these new processes, people have prepared a large amount of new materials with the goals of high removal efficiency, convenient operation, low cost, and reusability.
In order to purify water body pollution such as ionic dyes and even heavy metal ions, a large number of adsorbing materials are developed by many researchers, and most of the adsorbing materials need to be immersed in a liquid system to complete the adsorption process. Most of adsorbing materials used for the traditional ionic dye sewage treatment are in a powder shape, a sponge shape and a film shape, wherein the powder material is difficult to recover and activate; the sponge-like adsorbing material has high adsorption efficiency, but the activating treatment difficulty is high, so that the sponge-like adsorbing material is not beneficial to repeated utilization; most of membrane-shaped filtering and adsorbing materials need external pressure, so that sewage permeates membrane materials, the energy consumption is high, and the problems of incomplete activation and low repeated utilization rate also need to be solved. And the methods fully utilize the adsorption performance of the materials by enriching the pollutants in the materials, and the materials have defects in practical application because long-time stirring or shaking of the water body is not practical in practical situations. In addition, the recovery, activation and reutilization of the materials are limited to a certain extent, and the application prospect of the materials is limited to a certain extent.
The electrostatic spinning fiber is one of the safest nano materials, and has wide application prospects in the fields of high-flux filtration membrane separation of pollutants in water, environmental remediation and the like. The diameter of the nanofiber prepared by the electrospinning method is between dozens of nanometers and several micrometers, and the nanofiber can be accumulated in a non-woven fiber membrane with abundant mutual flow holes, so that the electrostatic spinning membrane arouses great interest of people and has good application prospect in the field of water treatment. Due to the high porosity and fully open pore structure of the electrospun membrane, the filtration flux in the field of liquid filtration is higher than that of conventional materials. However, due to the limitations of electrospinning, it seems very difficult to prepare nanofibers with diameters less than 100 nm, and further reduction of pore size is almost limited. Generally, the electrospun nonwoven fabric can effectively remove particles having a diameter of 300nm or more. Therefore, there are two methods to remove nanoparticles, water-soluble organic molecules and even heavy metal ions in aqueous systems, while taking advantage of the high porosity and open porous structure of electrospun nonwovens. One method is to carry out post-treatment on the electrostatic spinning fiber non-woven fabric to reduce the aperture of the electrostatic spinning fiber non-woven fabric, and the other method is to utilize the high specific surface area of the electrostatic spinning fiber non-woven fabric to realize the special adsorption performance of the electrostatic spinning fiber non-woven fabric.
Although the prior method carries out a great deal of research on liquid filtration of the electrostatic spinning fiber membrane, the further application of the electrostatic spinning fiber membrane in water treatment is restricted by the defects of incomplete pollutant removal, inconvenient operation, difficult separation, difficult recovery and the like. To solve these deficiencies, many new studies have been made on composite films based on electrospun fibers and composites thereof. In this problem, composite membranes composed of electrospun fibers and other functional materials are typically designed as a layered structure.
Graphene Oxide (GO) is a graphene derivative containing a large number of oxygen-producing functional groups, and has a great deal of attention in application prospects in film science due to good dispersibility, chemical reactivity and film-forming properties in a solution. The membrane composed of graphene oxide layers has good mechanical properties, excellent hydrophilicity and easy derivatization, and thus, the graphene oxide membrane has unique advantages in nanoscale filtration and screening applications.
Disclosure of Invention
The invention aims to provide a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water. Aiming at the defects of the materials, the invention designs a mode of compounding the electrostatic spinning fibers and the two-dimensional nano materials, and prepares the composite fiber membrane stacked layer by layer. Because the surface of the membrane is modified by dopamine to form a polydopamine layer, the polydopamine layer has an adsorption effect on ionic dye molecules, when sewage passes through the membrane, the dye and heavy metal ions are removed, and finally, the water purification effect is achieved.
The invention also aims to provide a preparation method of the nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water. According to the invention, the nanofiber and the two-dimensional nanomaterial are combined to prepare the composite fiber membrane assembled layer by layer, and polydopamine is used for treatment, so that sewage can penetrate through the membrane under the driving of self gravity, dye molecules are adsorbed in the membrane, a good purification effect is achieved, and the membrane can be repeatedly used through cleaning and activation and has good integrity and mechanical properties.
The invention further aims to provide the application of the nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water comprises the following steps:
(1) preparation of polyacrylonitrile electrospun nanofiber and graphene oxide composite membranes (PAN/GO NFMs): the membrane preparation is divided into an electrostatic spinning part of PAN solution and an ethanol solution part of GO ultrasonic spraying, and is carried out on two sides of a receiving device; dissolving PAN (polyacrylonitrile) in a solvent to prepare a uniform PAN solution, and then preparing a fiber membrane in an electrostatic spinning mode; preparing an ethanol solution of GO, and spraying the ethanol solution onto a fiber membrane prepared by electrostatic spinning in an ultrasonic spraying manner; carrying out electrostatic spinning and ultrasonic spraying on two sides of the receiving device simultaneously to enable the GO sheet layer to be wrapped and clamped in a membrane structure in the fiber forming process, so as to prepare a polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane;
(2) polydopamine modification (PAN/GO/PDA NFMs) of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a dopamine aqueous solution, then immersing the polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane prepared in the step (1) into the dopamine aqueous solution, stirring and reacting, washing the membrane with water, and freeze-drying to obtain the nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water.
Further, the mass concentration of the PAN solution in the step (1) is 8-14%.
Further, the solvent in the step (1) is DMF.
Further, the electrostatic spinning in the step (1) is carried out under the conditions of room temperature and humidity of 45 +/-2%, the solution sampling speed is 0.5-1.2mL/h, the voltage is 12-18kV, the fiber receiving distance is 10-15cm, the receiving device is a metal roller, and the rotating speed is 150-350 r/min.
Further, the concentration of the ethanol solution of GO in the step (1) is 0.1-0.5 mg/mL.
Further, the ultrasonic spraying power in the step (1) is 20W, the distance from the roller is 10cm, the sample injection speed can be 0.25-2.0mL/min, the spraying width is 5-10cm, the airflow is nitrogen, and the flow rate is 5-15L/min. Under the above operations the GO sheet layer may be wrapped in the film structure during fiber formation.
Further, the concentration of the dopamine in the dopamine aqueous solution in the step (2) is 0.5-1.2g/L, and the concentration of tris is 1.2 g/L.
Further, the stirring reaction in the step (2) refers to stirring at room temperature for 3-8 h.
The nano composite fiber membrane can be used for adsorbing ionic dyes and heavy metal ions in water, and comprises azo dyes (such as chrome black T (EBT), ionic dyes (such as Methylene Blue (MB)), rhodamine B, gentian violet, cation yellow X-6G and heavy metal ions Cr6+、Cr3+、Cu2+、Hg2+And the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the nano composite fiber membrane prepared by the invention, the GO sheet layers are assembled layer by layer in the membrane, the filtered water solution can pass through the membrane in a natural filtering manner, and the tower plate type structure is helpful for improving the specific surface area of the membrane and the residence time of the liquid, improving the contact efficiency of the liquid and an adsorption interface and further improving the adsorption efficiency of the membrane. The film has good hydrophilicity and good water solution wettability. In addition, the membrane can be cleaned and activated by filtering an alkaline solution or an acidic solution, and the activation process is simple and efficient and is similar to a filtration and adsorption step.
The nano composite fiber membrane prepared by the invention can complete filtration and adsorption under the gravity of the solution, and an external pump is not needed for suction filtration, so that the energy is saved, and the use is convenient.
The nano composite fiber membrane with the cross stacking structure of the polyacrylonitrile nanofiber, the oxidized graphene nanosheet layer and the polydopamine has a good filtering effect on ionic dyes and heavy metal ions, is complete and stable in structure and good in mechanical property, and has a good application prospect in industrial wastewater treatment.
The nano composite fiber membrane prepared by the invention also has good mechanical property and cyclic regeneration capability.
Drawings
FIG. 1 is a schematic diagram of the PAN/GO/PDA NFMs of the present invention.
FIG. 2 is a schematic diagram of the PAN/GO NFMs preparation process of the present invention.
Fig. 3 is a topographical map of PAN/GO NFMs and PAN/GO/PDA NFMs produced in examples 1-4, a, b, c, d correspond to the different ratios of GO containing films produced in examples 1-4, respectively, with-1 being PAN/GO NFMs, with-2 being PAN/GO/PDA NFMs, and with-3 being a high magnification picture of PAN/GO/PDA NFMs, with a, b, c, or d.
FIG. 4 is a graph of the adsorption capacity of PAN/GO/PDA NFMs prepared in example 4 for EBT and MB at different pH conditions.
FIG. 5 is a cycle performance test of PAN/GO/PDA NFMs prepared in example 4.
Fig. 6 is a graph of the PAN/GO/PDA NFMs and PAN NFMs prepared in example 4 after 10 reuses, the left graph is the PAN NFMs, and the right graph is the PAN/GO/PDA NFMs.
FIG. 7 is a comparison of pure water flux (10 cm height of filtrate without applied pressure) for PAN/GO/PDA NFMs obtained in examples 1-4.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.
The invention constructs a nano-fiber composite membrane taking electrostatic spinning fiber and graphene oxide as construction elements, and the nano-fiber composite membrane is modified by dopamine to ensure that the nano-fiber composite membrane isBecomes counter-ion type dye (such as methylene blue, chrome black T) and heavy metal ion (such as Cu)2+) A material having an adsorption function. The preparation method of the nanofiber composite membrane comprises the following steps:
(1) preparation of polyacrylonitrile electrospun nanofiber and graphene oxide composite membranes (PAN/GO NFMs): the membrane preparation is divided into an electrostatic spinning part and an ultrasonic spraying part, and is carried out on two sides of a receiving device at the same time; dissolving PAN (polyacrylonitrile) in a solvent to prepare a uniform PAN solution, and then preparing a fiber membrane in an electrostatic spinning mode; preparing an ethanol solution of GO, and spraying the ethanol solution onto a fiber membrane prepared by electrostatic spinning in an ultrasonic spraying manner; carrying out electrostatic spinning and ultrasonic spraying on two sides of the receiving device simultaneously to enable the GO sheet layer to be wrapped and clamped in a membrane structure in the fiber forming process, so as to prepare a polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane;
the membrane is composed of electrostatic spinning nano fibers and graphene oxide sheet layers, and the electrostatic spinning nano fibers and the graphene oxide sheet layers are combined in a layer-by-layer assembly mode, as shown in figure 1, the structure can fully utilize the structure and high porosity of the nano fibers, and the membrane can be endowed with high filtering efficiency and high flux; in order to utilize the stacking structure, the composite membrane is subjected to dopamine polymerization treatment, so that the surfaces of the fibers and the graphene oxide are modified with a layer of poly-dopamine (PDA);
(3) polydopamine modification (PAN/GO/PDA NFMs) of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a dopamine aqueous solution, then immersing the polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane prepared in the step (1) into the dopamine aqueous solution, stirring and reacting, washing the membrane with water, and freeze-drying to obtain the nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water. In the membrane, the poly-dopamine-modified graphene oxide nanosheets and the polyacrylonitrile nanofiber layer are stacked layer by layer to serve as a constituent unit of the composite membrane, so that the hydrophilicity can be enhanced, and the adsorption efficiency of ionic dyes and heavy metal ions can be improved. Moreover, the nano composite fiber membrane also has good mechanical property and cyclic regeneration capacity. Therefore, after repeated use, the membrane still maintains better adsorption performance, the integrity of the membrane is better, compared with the common electrostatic spinning membrane, the membrane still maintains better appearance after being rapidly stirred in an aqueous solution, and the common PAN membrane is completely loose, as shown in figure 6.
In one preferred embodiment, the nanofiber composite membrane is prepared by the following steps:
(1) preparation of polyacrylonitrile electrospun nanofiber and graphene oxide composite membranes (PAN/GO NFMs): dissolving PAN in DMF to prepare a uniform PAN solution with the concentration of 8-14% and preparing an ethanol solution of GO with the concentration of 0.1-0.5 mg/mL; then, simultaneously performing electrostatic spinning and ultrasonic spraying on two sides of the receiving device, so that the GO sheet layer is wrapped and clamped in a membrane structure in the fiber forming process, and preparing a polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane;
electrostatic spinning parameters: under the conditions of room temperature and humidity of 45 +/-2%, the sample injection speed of the PAN solution is 0.5-1.2mL/h, the voltage is 12-18kV, the fiber receiving distance is 10-15cm, the receiving device is a metal roller, and the rotating speed is 150 plus or minus 350 r/min;
ultrasonic spraying parameters: the ultrasonic spraying power is 20W, the distance from the roller is 10cm, the sample injection speed can be 0.25-2.0mL/min, the spraying width is 5-10cm, the airflow is nitrogen, and the flow rate is 5-15L/min.
(2) Polydopamine modification (PAN/GO/PDA NFMs) of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a dopamine aqueous solution (0.5-1.2 g/L of DA, 1.2g/L of tris), then immersing the polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane prepared in the step (1) into the dopamine aqueous solution, stirring for 3-8 hours at room temperature, washing the membrane with water after the reaction is finished, and freeze-drying to obtain the nanocomposite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water.
Examples of the invention
1. The preparation apparatus used: high voltage power supply (0-50kV), microsyringe, fiber receiving roller, and ultrasonic spraying instrument
2. The materials used were: polyacrylonitrile (PAN), Graphene Oxide (GO), dopamine hydrochloride, N-Dimethylformamide (DMF), buffer solution (DMF) (PAN)Tris), hydrochloric acid (HCl), sodium hydroxide (NaOH), copper sulfate (CuSO)4) Methylene Blue (MB), chrome Black T (EBT), deionized water
3. Characterization of the instrument: infrared spectrometer (FTIR, TENSOR II + Hyperion 2000), X-ray spectrometer (XPS, Escalab 250xi), atomic force microscope (AFM, Agilent 5500AFM), electron transmission microscope (FE-SEM, XL30ESEM-FEG), contact angle tester (ZHIIA ZJ-6900)
4. Testing of PAN/GO/PDA NFMs for ionic dye adsorption capacity: candidate ionic dyes were dissolved in deionized water at a concentration of 50mg/L, respectively, to evaluate the adsorption capacity of each membrane. The permeation flux of the NFMs prepared was characterized by an end-flow filtration experimental set-up connected to a sand-core funnel (sand-core piece diameter 43 mm). Before testing, the prepared film was spread on a sand core and the appropriate dye solution was poured into the reservoir until the level reached 10 cm. Thus, the membrane is soaked and the filtrate is dropped. At the same time, the dye solution was injected into the reservoir using a peristaltic pump to maintain the liquid level. The liquid flux of the membrane is calculated by the formula J ═ V/At
Wherein J is the membrane flux (mL cm)-2h-1) V, A, t is the volume of osmotic solution (mL) and the effective area of the membrane (cm), respectively2) And penetration time (h). We selected Methylene Blue (MB) and chrome black t (ebt) as candidate dyes, representing cationic and anionic dyes, respectively, to evaluate the adsorption capacity of the complex NFMs. The concentration of the filtrate was determined by UV absorption spectroscopy.
5. The reusability of PAN/GO/PDA NFMs was studied in a similar manner using MB and EBT solutions at a concentration of 50 mg/L. The dye solution was filtered through 20 micron thick composite NFMs and treated under the same conditions as above. The dye solution was adsorbed by PAN/GO/PDA NFMs filtration, while the filtrate was concentrated by uv spectroscopy. Until the filtrate concentration is the same as the crude dye solution, calculating the saturated adsorption capacity by the formula:
Ca＝(cd-cp)V M/m
cd、cpv, M, M is dye solution concentration, filtrate concentration, solution volume, dye molecular weightAnd the film quality. To elute the adsorbed EBT, the NFMs were first rinsed with an appropriate amount of NaOH solution (pH 10.2) until the leachate turned colorless. Then, the NFMs are rinsed with an amount of ethanol instead of NFMs. After repeating the above step 2 times, most of the EBT adsorbed in the NFMs is removed. The adsorption capacity of the recycled composite NFMs to EBT was tested more in a similar operation as above. Elution of MB in NFMs is similar to EBT. The membrane was first rinsed with dilute hydrochloric acid (pH ═ 1) until the percolate turned colorless. Thereafter, the NFMs were rinsed with the appropriate amount of ethanol. After repeating the above operation twice, most of the dye was removed. Also, the adsorption capacity of the cycling composite NFMs for MB was tested with the same EBT method.
6. Heavy metal ion Cu2+Adsorption capacity test of (2): NFMs vs Cu2+The adsorption capacity of (a) was also evaluated by a similar ionic dye adsorption method, and the filtrate concentration after adsorption was measured using an inductively coupled plasma emission spectrometer (ICP-OES).
7. Testing of mechanical properties of NFMs: tensile strength and Young's modulus were measured at room temperature using an electronic universal tester model UTM2203 with an aluminum sample holder at a constant crosshead speed of 5 mm/min.
Example 1
(1) Preparation of polyacrylonitrile electrospun nanofiber membranes (PAN NFMs): dissolving PAN in DMF, stirring uniformly to prepare a uniform solution (with the concentration of 9 wt.%), and carrying out electrostatic spinning at room temperature and humidity of 45 +/-2% to prepare PAN NFMs, wherein the PAN solution has the sample injection speed of 0.5mL/h, the voltage of 14kV, the fiber receiving distance of 12cm, the receiving device is a metal roller and the rotating speed of 200 r/min.
(2) Preparation of polyacrylonitrile electrospun nanofiber and graphene oxide composite membranes (PAN/GO NFMs): the film preparation was divided into an electrospinning part and an ultrasonic spraying part, and was performed simultaneously on both sides of a receiving roll, as shown in fig. 2. The technical parameters of the electrostatic spinning part are the same as those of the step (1), the ultrasonic spraying power of an ethanol solution (0.25mg/mL) of GO serving as a spraying solution is 18W, the distance from a roller is 10cm, the sampling speed can be selected to be 0.25mL/min, the spraying width is 8cm, the airflow is nitrogen, and the flow rate is 8L/min; under the above operations, the GO plies can be sandwiched in the film structure during fiber formation, making PAN/GO NFMs.
(3) Polydopamine modification (PAN/GO/PDA NFMs) of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a Dopamine (DA) aqueous solution (DA 0.8g/L, tris 1.2g/L), immersing the PAN/GO NFMs obtained in the step (2) into the solution, stirring for 5 hours at room temperature, washing for 3 times by deionized water after the reaction is finished, and then freeze-drying the membrane to obtain the PAN/GO/PDA NFMs.
Example 2
(1) Preparation of polyacrylonitrile electrospun nanofiber membranes (PAN NFMs): dissolving PAN in DMF, stirring uniformly to prepare a uniform solution (with the concentration of 10 wt.%), and carrying out electrostatic spinning at room temperature and the humidity of 45 +/-2% to prepare PAN NFMs, wherein the PAN solution has the sample injection speed of 0.8mL/h, the voltage of 16kV, the fiber receiving distance of 16cm, the receiving device is a metal roller and the rotating speed of 200 r/min.
(2) Preparation of polyacrylonitrile electrospun nanofiber and graphene oxide composite membranes (PAN/GO NFMs): the film preparation was divided into an electrospinning part and an ultrasonic spraying part, and was performed simultaneously on both sides of a receiving roll, as shown in fig. 2. The technical parameters of the electrostatic spinning part are the same as those of the step (1), the ultrasonic spraying power of an ethanol solution (0.3mg/mL) of GO serving as a spraying solution is 18W, the distance from a roller is 12cm, the sampling speed can be selected to be 0.5mL/min, the spraying width is 8cm, the airflow is nitrogen, and the flow rate is 9L/min; under the above operations, the GO plies can be sandwiched in the film structure during fiber formation, making PAN/GO NFMs.
(3) Polydopamine modification (PAN/GO/PDA NFMs) of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a Dopamine (DA) aqueous solution (0.75 g/L, 1.2g/L of tris), immersing the PAN/GO NFMs obtained in the step (2) into the solution, stirring for 6 hours at room temperature, washing for 3 times by deionized water after the reaction is finished, and freeze-drying the membrane to obtain the PAN/GO/PDA NFMs.
Example 3
(1) Preparation of polyacrylonitrile electrospun nanofiber membranes (PAN NFMs): dissolving PAN in DMF, stirring uniformly to prepare a uniform solution (with the concentration of 10 wt.%), and carrying out electrostatic spinning at room temperature and the humidity of 45 +/-2% to prepare PAN NFMs, wherein the PAN solution has the sample injection speed of 1.0mL/h, the voltage of 18kV, the fiber receiving distance of 16cm, the receiving device is a metal roller and the rotating speed of 250 r/min.
(2) Preparation of polyacrylonitrile electrospun nanofiber and graphene oxide composite membranes (PAN/GO NFMs): the film preparation was divided into an electrospinning part and an ultrasonic spraying part, and was performed simultaneously on both sides of a receiving roll, as shown in fig. 2. The technical parameters of the electrostatic spinning part are the same as those of the step (1), the ultrasonic spraying power of an ethanol solution (0.3mg/mL) of GO serving as a spraying solution is 16W, the distance from a roller is 12cm, the sampling speed can be selected to be 1.0mL/min, the spraying width is 10cm, the airflow is nitrogen, and the flow rate is 10L/min; under the above operations, the GO plies can be sandwiched in the film structure during fiber formation, making PAN/GO NFMs.
(3) Polydopamine modification (PAN/GO/PDA NFMs) of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a Dopamine (DA) aqueous solution (0.75 g/L, 1.2g/L of tris), immersing the PAN/GO NFMs obtained in the step (2) into the solution, stirring for 6 hours at room temperature, washing for 3 times by deionized water after the reaction is finished, and freeze-drying the membrane to obtain the PAN/GO/PDA NFMs.
Example 4
(1) Preparation of polyacrylonitrile electrospun nanofiber membranes (PAN NFMs): dissolving PAN in DMF, stirring uniformly to prepare a uniform solution (with the concentration of 12 wt.%), and carrying out electrostatic spinning at room temperature and the humidity of 45 +/-2% to prepare PAN NFMs, wherein the PAN solution has the sample injection speed of 0.9mL/h, the voltage of 18kV, the fiber receiving distance of 16cm, the receiving device is a metal roller and the rotating speed of 300 r/min.
(2) Preparation of polyacrylonitrile electrospun nanofiber and graphene oxide composite membranes (PAN/GO NFMs): the film preparation was divided into an electrospinning part and an ultrasonic spraying part, and was performed simultaneously on both sides of a receiving roll, as shown in fig. 2. The technical parameters of the electrostatic spinning part are the same as those of the step (1), the ultrasonic spraying power of an ethanol solution (0.3mg/mL) of GO serving as a spraying solution is 16W, the distance from a roller is 13cm, the sampling speed can be selected to be 2.0mL/min, the spraying width is 8cm, the airflow is nitrogen, and the flow rate is 9L/min; under the above operations, the GO plies can be sandwiched in the film structure during fiber formation, making PAN/GO NFMs.
(3) Polydopamine modification (PAN/GO/PDA NFMs) of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a Dopamine (DA) aqueous solution (0.75 g/L, 1.2g/L of tris), immersing the PAN/GO NFMs obtained in the step (2) into the solution, stirring for 6 hours at room temperature, washing for 3 times by deionized water after the reaction is finished, and freeze-drying the membrane to obtain the PAN/GO/PDA NFMs.
The morphologies of the PAN/GO NFMs and PAN/GO/PDA NFMs produced in examples 1-4 are shown in fig. 3, a, b, c, d correspond to the different ratios of GO containing films produced in examples 1-4, respectively, with-1 being the PAN/GO NFMs, 2 being the PAN/GO/PDA NFMs, and-3 being the high magnification pictures of the PAN/GO/PDA NFMs, with the fibers and GO interlamellar layers in each sample being superimposed.
FIG. 4 is a graph of the adsorption capacity of PAN/GO/PDA NFMs prepared in example 4 for EBT and MB at different pH conditions. Influence of the pH on the adsorption capacity of the NFMs ionic dyes: the adsorption capacity of PAN/GO/PDA NFMs to EBT and MB respectively show decrease and increase with increasing pH.
FIG. 5 is a cycle performance test of PAN/GO/PDA NFMs prepared in example 4. The cycle performance of PAN/GO/PDA NFMs, as shown in FIG. 5, can maintain 73.4% and 53.4% adsorption performance on MB and EBT after 10 cycles.
PAN/GO/PDA NFMs vs Cu2+The adsorption performance of (2): test PAN/GO/PDA NFMs prepared in example 4 for Cu2+The adsorption capacity of 62.9mg/g can be achieved.
Mechanical properties of PAN/GO/PDA NFMs: the PAN/GO/PDA NFMs prepared in example 4 were tested for tensile strength of 16.8MPa and tensile modulus of 232.1 MPa.
Fig. 6 is a graph of the PAN/GO/PDA NFMs and PAN NFMs prepared in example 4 after 10 reuses, the left graph is the PAN NFMs, and the right graph is the PAN/GO/PDA NFMs.
FIG. 7 is a comparison of pure water flux (10 cm height of filtrate without applied pressure) for PAN/GO/PDA NFMs obtained in examples 1-4.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water is characterized by comprising the following steps:
(1) preparing a polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: the membrane preparation is divided into an electrostatic spinning part of PAN solution and an ethanol solution part of GO ultrasonic spraying, and is carried out on two sides of a receiving device; dissolving PAN in a solvent to prepare a uniform PAN solution, and then preparing a fibrous membrane in an electrostatic spinning mode; preparing an ethanol solution of GO, and spraying the ethanol solution onto a fiber membrane prepared by electrostatic spinning in an ultrasonic spraying manner; carrying out electrostatic spinning and ultrasonic spraying on two sides of the receiving device simultaneously to enable the GO sheet layer to be wrapped and clamped in a membrane structure in the fiber forming process, so as to prepare a polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane;
(2) polydopamine modification of polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane: preparing a dopamine aqueous solution, then immersing the polyacrylonitrile electrostatic spinning nanofiber and graphene oxide composite membrane prepared in the step (1) into the dopamine aqueous solution, stirring and reacting, washing the membrane with water, and freeze-drying to obtain the nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water.
2. The method for preparing a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water according to claim 1, wherein the mass concentration of the PAN solution in the step (1) is 8-14%.
3. The method for preparing a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water according to claim 1, wherein the solvent in the step (1) is DMF.
4. The method as claimed in claim 1, wherein the electrospinning in step (1) is performed at room temperature and humidity of 45 ± 2%, the solution injection speed is 0.5-1.2mL/h, the voltage is 12-18kV, the fiber receiving distance is 10-15cm, the receiving device is a metal roller, and the rotation speed is 150-.
5. The preparation method of the nanocomposite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water according to claim 1, wherein the concentration of the ethanol solution of GO in the step (1) is 0.1-0.5 mg/mL.
6. The method for preparing a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water according to claim 1, wherein the ultrasonic spraying power in the step (1) is 20W, the distance from a roller is 10cm, the sample injection speed is 0.25-2.0mL/min, the spraying width is 5-10cm, the gas flow is nitrogen, and the flow rate is 5-15L/min.
7. The method for preparing a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water according to claim 1, wherein the concentration of dopamine in the dopamine aqueous solution in the step (2) is 0.5-1.2g/L, and the concentration of tris is 1.2 g/L.
8. The method for preparing a nano composite fiber membrane capable of efficiently removing ionic dyes and heavy metal ions in water according to claim 1, wherein the stirring reaction in the step (2) is stirring at room temperature for 3-8 h.
9. A nanocomposite fiber membrane produced by the method of any one of claims 1 to 8.
10. Use of the nanocomposite fiber membrane of claim 9 for adsorbing ionic dyes and heavy metal ions in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011537508.7A CN112619622A (en) | 2020-12-23 | 2020-12-23 | Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011537508.7A CN112619622A (en) | 2020-12-23 | 2020-12-23 | Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112619622A true CN112619622A (en) | 2021-04-09 |
Family
ID=75321840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011537508.7A Pending CN112619622A (en) | 2020-12-23 | 2020-12-23 | Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112619622A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113897787A (en) * | 2021-09-29 | 2022-01-07 | 浙江德普斯医疗科技股份有限公司 | Spring-like protein fiber and application thereof |
| CN114471483A (en) * | 2022-01-20 | 2022-05-13 | 南通大学 | Three-dimensional composite non-woven material for wastewater treatment and preparation method thereof |
| CN114990884A (en) * | 2022-04-15 | 2022-09-02 | 山东大学 | Composite nanofiber membrane for degrading antibiotic pollutants through photo-thermal enhancement and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409940A (en) * | 2013-07-11 | 2013-11-27 | 东华大学 | Preparation method of dopamine composite nano-fiber affinity membrane for adsorbing La3+ |
| CN105483939A (en) * | 2016-01-12 | 2016-04-13 | 山东佳星环保科技有限公司 | Preparation method of porous graphene nanofiber membrane |
| CN106245232A (en) * | 2016-07-27 | 2016-12-21 | 山东大学 | Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application |
| CN106835304A (en) * | 2017-03-06 | 2017-06-13 | 嘉兴学院 | A kind of electrostatic spinning electrical painting device and its application |
| CN109157928A (en) * | 2018-08-29 | 2019-01-08 | 清华大学 | A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof |
| CN109577005A (en) * | 2018-11-28 | 2019-04-05 | 吉林大学 | A kind of preparation method and applications of the ZIF-8 functionalized nano-fiber film of poly-dopamine modification |
| CN110508253A (en) * | 2019-06-27 | 2019-11-29 | 福建工程学院 | A kind of preparation method of nanofiber adsorbed film |
-
2020
- 2020-12-23 CN CN202011537508.7A patent/CN112619622A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409940A (en) * | 2013-07-11 | 2013-11-27 | 东华大学 | Preparation method of dopamine composite nano-fiber affinity membrane for adsorbing La3+ |
| CN105483939A (en) * | 2016-01-12 | 2016-04-13 | 山东佳星环保科技有限公司 | Preparation method of porous graphene nanofiber membrane |
| CN106245232A (en) * | 2016-07-27 | 2016-12-21 | 山东大学 | Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application |
| CN106835304A (en) * | 2017-03-06 | 2017-06-13 | 嘉兴学院 | A kind of electrostatic spinning electrical painting device and its application |
| CN109157928A (en) * | 2018-08-29 | 2019-01-08 | 清华大学 | A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof |
| CN109577005A (en) * | 2018-11-28 | 2019-04-05 | 吉林大学 | A kind of preparation method and applications of the ZIF-8 functionalized nano-fiber film of poly-dopamine modification |
| CN110508253A (en) * | 2019-06-27 | 2019-11-29 | 福建工程学院 | A kind of preparation method of nanofiber adsorbed film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113897787A (en) * | 2021-09-29 | 2022-01-07 | 浙江德普斯医疗科技股份有限公司 | Spring-like protein fiber and application thereof |
| CN113897787B (en) * | 2021-09-29 | 2024-01-30 | 浙江德普斯医疗科技股份有限公司 | Spring-like protein fiber and application thereof |
| CN114471483A (en) * | 2022-01-20 | 2022-05-13 | 南通大学 | Three-dimensional composite non-woven material for wastewater treatment and preparation method thereof |
| CN114990884A (en) * | 2022-04-15 | 2022-09-02 | 山东大学 | Composite nanofiber membrane for degrading antibiotic pollutants through photo-thermal enhancement and preparation method and application thereof |
| CN114990884B (en) * | 2022-04-15 | 2023-11-07 | 山东大学 | Composite nanofiber membrane for photo-thermal enhanced degradation of antibiotic pollutants and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cui et al. | Electrospun nanofiber membranes for wastewater treatment applications | |
| Zhang et al. | Structural design and environmental applications of electrospun nanofibers | |
| Cao et al. | Multifunctional nanofibrous membranes with sunlight-driven self-cleaning performance for complex oily wastewater remediation | |
| Du et al. | One-step electrospinning PVDF/PVP-TiO2 hydrophilic nanofiber membrane with strong oil-water separation and anti-fouling property | |
| Yu et al. | One-dimensional nanomaterial-assembled macroscopic membranes for water treatment | |
| CN112619622A (en) | Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof | |
| Zhao et al. | Diethylenetriamine-assisted synthesis of amino-rich hydrothermal carbon-coated electrospun polyacrylonitrile fiber adsorbents for the removal of Cr (VI) and 2, 4-dichlorophenoxyacetic acid | |
| Xu et al. | High flux and rejection of hierarchical composite membranes based on carbon nanotube network and ultrathin electrospun nanofibrous layer for dye removal | |
| Zheng et al. | Ionic liquid grafted polyethersulfone nanofibrous membrane as recyclable adsorbent with simultaneous dye, heavy metal removal and antibacterial property | |
| Zhang et al. | Porous nanofibrous superhydrophobic membrane with embedded Au nanoparticles for the integration of oil/water separation and catalytic degradation | |
| Sun et al. | Bioinspired design of underwater superoleophobic Poly (N-isopropylacrylamide)/polyacrylonitrile/TiO2 nanofibrous membranes for highly efficient oil/water separation and photocatalysis | |
| CN105032202B (en) | A kind of multi-layer composite ultrafiltration membrane and preparation method thereof | |
| Xue et al. | Multifunctional porphyrinic Zr-MOF composite membrane for high-performance oil-in-water separation and organic dye adsorption/photocatalysis | |
| Ni et al. | Synergistic effect on TiO2 doped poly (vinyl alcohol-co-ethylene) nanofibrous film for filtration and photocatalytic degradation of methylene blue | |
| Wu et al. | Chitosan-based hollow nanofiber membranes with polyvinylpyrrolidone and polyvinyl alcohol for efficient removal and filtration of organic dyes and heavy metals | |
| Wu et al. | Chitosan/polyvinylpyrrolidone/polyvinyl alcohol/carbon nanotubes dual layers nanofibrous membrane constructed by electrospinning-electrospray for water purification | |
| Bagbi et al. | Electrospun nanofibrous filtration membranes for heavy metals and dye removal | |
| Lee et al. | Electrospun nanofibrous rhodanine/polymethylmethacrylate membranes for the removal of heavy metal ions | |
| Ma et al. | Multifunctional nanofibrous membrane fabrication by a sacrifice template strategy for efficient emulsion oily wastewater separation and water purification | |
| CN110665377A (en) | High-flux anti-pollution reverse osmosis membrane and preparation method thereof | |
| Li et al. | Highly efficient sunlight-driven self-cleaning electrospun nanofiber membrane NM88B@ HPAN for water treatment | |
| Bai et al. | Efficient and recyclable ultra-thin diameter polyacrylonitrile nanofiber membrane: Selective adsorption of cationic dyes | |
| Lolla et al. | Functionalized polyvinylidene fluoride electrospun nanofibers and applications | |
| Chen et al. | One-step electrospinning of negatively-charged polyethersulfone nanofibrous membranes for selective removal of cationic dyes | |
| Wang et al. | Preparation of superhydrophilic/underwater superoleophobic membranes for separating oil-in-water emulsion: mechanism, progress, and perspective |
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 |