CN109432825A - It is a kind of to pollute difunctional patterning porous nano-fibre material and its preparation method and application with water-oil separating and oil resistant - Google Patents

It is a kind of to pollute difunctional patterning porous nano-fibre material and its preparation method and application with water-oil separating and oil resistant Download PDF

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CN109432825A
CN109432825A CN201811239704.9A CN201811239704A CN109432825A CN 109432825 A CN109432825 A CN 109432825A CN 201811239704 A CN201811239704 A CN 201811239704A CN 109432825 A CN109432825 A CN 109432825A
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oil
water
pvb
pattern
pda
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徐合
柯勤飞
应婷
江依静
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Shanghai Normal University
University of Shanghai for Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • 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
    • B01D67/0002—Organic membrane manufacture
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
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    • 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
    • D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—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 nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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    • 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
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/39—Electrospinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
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    • 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
    • D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
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Abstract

The invention belongs to environmental material fields, and in particular to a kind of that difunctional patterning porous nano-fibre material and its preparation method and application is polluted with water-oil separating and oil resistant.Using the hydrophobicity spinning nanofiber being intertwined as skeleton, the micro/nano level pattern structure of ordered arrangement is formed；The pattern structure improves the porous structure of the open three-dimensional perforation of fibrous material, improves the water-oil separating flux of fibrous material；In conjunction with dopamine and photochemical catalyst, increase the oily waste water type of processing, and oil resistant pollutes during the separation process.The preparation method comprises the following steps: the material for forming spinning fibre is dissolved in organic solvent, after electrostatic spinning, immerses dopamine solution and be protected from light modification, then immerse photochemical catalyst aqueous suspension loaded optic catalyst.The material hydrophilic and lipophilicity are good, according to oil water mixture species selectivity oil excessively or cross water, and keep efficient separative efficiency and separation flux, and can photocatalytic degradation of organic matter, oil resistant pollution repeats and is recycled.

Description

It is a kind of to pollute difunctional patterning porous nano-fibre with water-oil separating and oil resistant Material and its preparation method and application
Technical field
The invention belongs to environmental material fields, and in particular to a kind of that difunctional pattern is polluted with water-oil separating and oil resistant Change porous nano-fibre material and its preparation method and application.
Background technique
With the fast development of offshore oil and petrochemical industry, oil spilling, oil leak and oily waste water discharge are increasing, Serious harm is caused to the mankind and natural environment.Investigation shows that the industries such as petroleum in global range, chemical industry and food processing are every Probably there is the oil of 3,200,000,000 cubic tons to enter water body in year and forms oily waste water, the type and Nature comparison of these oily waste waters are complicated, Deal with also extremely difficult, low efficiency and at high cost.
In general, oily waste water is mainly the waste water of some hydrocarbon-containifirsts or fat glycerides etc..According to phase oily in waste water Partial size and existence form, oily waste water can be divided into oil slick, dispersed oil, oil emulsion and four kinds of dissolved oil.Currently, main use suction The tradition oily water separation technique such as attached, air bearing, centrifugation or chemical coagulation handles oily pollution, but the generally existing disadvantage of these technologies, example Such as, low separation efficiency, complicated for operation or recycling rate of waterused are low etc..
Recently, membrane separation technique is since low energy consumption, single-stage separative efficiency is high, process flexible is simple, environmental pollution is low, general The advantages that property is strong, causes the concern of many environmentalists.Traditional membrane separation technique includes filtering, ultrafiltration and nanofiltration, but this A little technologies the disadvantages of there are hyposmosis flux and high driving pressures, resistance tocrocking of the separative efficiency of separation process by film, heat The limitation of the external factors such as the internal factors such as stability, chemical stability and membrane module form, operating condition.Therefore, film is improved Separative efficiency, the reuse ability of material are the hot spots of current research.
In membrane separation technique, super-hydrophobic-super oil-wet film can repel the water phase in oil water mixture and oily phase is allowed to permeate To reach high efficiency oil-water separation, therefore, constructing, there is the membrane material of super-hydrophobic-super oil-wetted surface performance to become current grind Study carefully hot spot.In one's early years, the nanoscale column that German botanist has found the micron order mastoid process structure of lotus leaf surface and is distributed in mastoid process Micro/nano level composite construction composed by shape structure is that lotus leaf has the main reason for super-hydrophobic and self-cleaning ability.It is opened by lotus leaf Hair, improves its super-hydrophobicity by constructing certain micro/nano level structure on membrane material surface, to improve its water-oil separating efficiency This strategy causes the concern of many researchers.
Electrostatic spinning is a kind of by applying the polymer that extra electric field preparation has micro-nano-scale to polymer solution The technology of fiber.By designing and changing the surface microscopic topographic for receiving template, surface, which is made, has controllable micro-nano meter level structure Nano fibrous membrane.Compared with traditional separation membrane, patterned fibrous film made from electrostatic spinning technique have porosity it is high, The features such as large specific surface area, high fiber fine degree, but also can be by designing material surface micronano structure to regulate and control material Expect surface hydrophilic and hydrophobic, these advantages to pattern electrostatic spinning fiber material as high permeating flux grease under low driving pressure Isolated ideal candidates material.
On the other hand, due to the potential lipophilicity of super-hydrophobic-super oleophylic membrane material, that is, the fabulous affinity with oil droplet makes It is stronger in the adhesion strength of mould surface to obtain oil droplet.Therefore, oil droplet and other impurities are easy to be adsorbed on mould by a large amount of, irreversible Inside surface or the duct of film, cause fouling membrane serious, flux decline is fast, and the emulsified oil droplet generated in cleaning process easily exists Film surface coalescence is sprawled, and causing film to repeat, the practicability is poor；But also because cleaning is more difficult, it is easy generation again and largely contains Oily waste water, leads to secondary pollution.Therefore, the organic contamination being detained from membrane material after practical application, removing water-oil separating Object, improve membrane material reusability and current research important task.
In numerous organic pollutant processing techniques, photocatalytic degradation is considered as a kind of environmental-friendly pollutant process Technology.And studies have shown that TiO under ultraviolet light (UV)2Photocatalysis be it is a kind of by Photoinduced Electron/hole to and high oxidation OH free radical decomposing organic pollutant effective ways.It is disadvantageous that TiO2Photocatalysis can only be played under ultraviolet light Effect, this greatly limits TiO2Use.It is a kind of to realize photocatalysis degradation organic contaminant under visible light based on this Visible light responsive photocatalyst is required.Bismuth-containing nanostructured materials catalyst, especially pucherite (BiVO4), it is unique by it Optics, photocatalytic activity excellent under electricity and visible light cause the concerns of many researchers.
To sum up, the application imagination do not influencing this body structure of nano fibrous membrane, do not damage membrane material water-oil separating efficiency with Separate flux under the premise of, by intermediate connecting layer by organic matter degradation catalyst (degradation catalyst especially under visible light, Such as BiVO4) load on the nano fibrous membrane with super-hydrophobic-super oleophylic, increase the reuse energy of nano fibrous membrane with this Power.
Dopamine occurs to polymerize anti-as a kind of green matter that can be coated with autohemagglutination under the aerobic water environment of alkalinity It answers, generates the poly-dopamine (PDA) with strongly adherent.On the one hand, the higher poly- DOPA of concentration is introduced on nano fibrous membrane Amine will improve the hydrophily of material.On the other hand, since poly-dopamine can be formed between metal or its oxide solid matrix Reversible coordination key makes poly-dopamine coat strongly adherent on the surface of the material.Therefore, based on the adhesion characteristics of poly-dopamine, if Want using poly-dopamine as intermediate connecting layer, by organic matter degradation catalyst (degradation catalyst especially under visible light, such as BiVO4) load on the nano fibrous membrane of super-hydrophobic-super oleophylic, improve the service performance of micro/nano fibrous membrane material.
The application by electrostatic spinning technique and the preparation of PDA surface modification technology there is water-oil separating and oil resistant to pollute double function The patterning porous nano-fibre material of energy, has many advantages, such as that simple process, condition are easily controllable.The material combine patterning with PDA is surface modified, realizes and selectively crosses water or excessively oily separation function to the oil water mixture of different conditions, and keeps high The water-oil separating efficiency of effect with separate flux；In conjunction with organic matter degradation catalyst (degradation catalyst especially under visible light, Such as BiVO4), avoid the delay of the organic matters such as oil from polluting, further increase water-oil separating efficiency with separate flux, and realize repetition Function is recycled.Therefore, the application preparation there is water-oil separating and oil resistant to pollute difunctional patterning porous nano fibre Tieing up material has very strong Practical significance.
Summary of the invention
Difunctional patterning porous nano fibre is polluted with water-oil separating and oil resistant the object of the present invention is to provide a kind of Material, material combination pattern structure processing and the surface modified technology of poly-dopamine are tieed up, its hydrophily is greatly improved With lipophilicity, amphiphilic material is formed, according to the oil excessively of oil water mixture state selectivity or crosses water, and during the separation process Keep efficient water-oil separating efficiency and water-oil separating flux, and can photocatalytic degradation of organic matter, oil resistant pollution realizes repeatable It is recycled.
Difunctional patterning porous nano-fibre material is polluted with water-oil separating and oil resistant the present invention also provides a kind of Preparation method, the preparation method combination electrostatic spinning technique and PDA (poly-dopamine) surface modified technology, easy easily behaviour Make, it is low in cost, it is suitable for industrialized production.
It is a kind of to pollute difunctional patterning porous nano-fibre material with water-oil separating and oil resistant, with interlaced row The hydrophobicity spinning nanofiber of column is skeleton, the pattern structure of ordered arrangement micro/nano level, and be distributed open three-dimensional and pass through Logical porous structure；Hydrophobicity spinning nanofiber surface coats poly-dopamine, poly-dopamine loaded optic catalyst.Nanofiber The pattern structure of material is uniformly integrally formed in the full mistake of electrostatic spinning that hydrophobicity spinning nanofiber is intertwined Journey, pattern structure by be spaced apart from each other be in laterally, longitudinally, laterally with longitudinally perpendicular or laterally and longitudinally multi-angle intersects row Column, multiple unit cell patterns of size adjustable composition, unit cell pattern include circle, ellipse, parallelogram, rectangle, diamond shape, Rectangular, trapezoidal or regular polygon (n≤5), unit cell pattern is preferably circular or oval, more preferably 30~500 μm of circles of radius Shape.
The density and thickness that unit cell pattern structure central part hydrophobicity spinning nanofiber is intertwined are respectively less than The density and thickness that unit cell pattern structural edge position hydrophobicity spinning nanofiber is intertwined, in unit cell pattern structure Entreat the three-dimensional perforation of opening of the interlaced formation aperture of position hydrophobicity spinning nanofiber between micron and nanometer Porous structure, it is preferred that unit cell pattern structure central part hydrophobicity spinning nanofiber is interlaced to form open three-dimensional The meso-hole structure of perforation.
Patterning method can regulate and control hydrophobicity spinning nanofiber in different zones and be intertwined density And thickness, adjustment pattern structure interior hydrophobicity spinning nanofiber are intertwined the pore size and Kong Daochang to be formed It is short, the resistance of hydrophobicity spinning nanofiber is minimized, while retaining retention functions, improves separation flux and separative efficiency； In conjunction with poly-dopamine, improvement fiber is amphipathic, makes its not only hydrophilic but also oleophylic, and pure water can pass through with pure oil, and mixed according to grease It closes the excessively oily trap water (Water-In-Oil) of object state selectivity or crosses water and retain oily (oil-in-water), and guarantee efficient separation flux With separative efficiency；Further combined with the photochemical catalyst loaded in poly-dopamine, the organic matters such as photocatalytic degradation oil, solving oil etc. has Machine object is detained in the attachment of hydrophobicity spinning nanofiber surface, and avoiding being detained leads to obstruction caused by the reduction of aperture, resists The pollution of the organic matters such as oil, further improve separation process separative efficiency with separate the organic pollutions such as flux, and oil resistant The repetitive cycling that function can also be achieved the porous nano-fibre material uses, and the knot of itself is still kept in repetitive cycling use process Structure and function.
Photochemical catalyst has the function of the catalytic degradation function under the organic matters such as photocatalytic degradation oil, especially visible light, Including TiO2Compound photochemical catalyst, zinc oxide composites photochemical catalyst or visible light responsive photocatalyst, TiO2Compound object light is urged Agent includes CdS-TiO2Laminated film, zinc oxide composites photochemical catalyst include nitrogenous MOx-ZnO compound (M=Fe, W) Or TiO2/ CdO-ZnO nanoporous infiltration laminated film, it is seen that photoresponse photochemical catalyst includes pucherite, bismuth tungstate or vanadic acid Silver.The preferred pucherite of photochemical catalyst, it is seen that good to the catalytic degradation function of the organic matters such as oil under light.Photochemical catalyst is micro-nano The photochemical catalyst of grade, preferably micron-sized photochemical catalyst, specially 10~98 μm, preferably 75 μm.
The material of hydrophobicity spinning nanofiber includes polyvinyl butyral (PVB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Kynoar (PVDF), carboxymethyl cellulose acetate butyrate (CMCAB), Polylactic acid (PLLA), polytetrafluoroethylene (PTFE) (PTFE), polyethylene (PE) or polyester, preferably polyvinyl butyral (PVB).It is hydrophobic Property spinning nanofiber diameter be 50~980nm, preferably 600~700nm.
The above-mentioned preparation method that difunctional patterning porous nano-fibre material is polluted with water-oil separating and oil resistant, step Suddenly include:
(1) material for forming hydrophobicity spinning nanofiber is dissolved in organic solvent, using patterned reception template, Electrostatic spinning is deposited on hydrophobicity spinning nanofiber with being intertwined to receive in template, prepare patterned porous receive Rice fibrous material；
(2) Tris-HCL buffer of the porous nano-fibre material immersion that will be patterned into dissolved with dopamine, avoid light place, Hydrophobicity spinning nanofiber surface coats poly-dopamine, the modified patterning porous nano-fibre material in preparation poly-dopamine surface Material；
(3) suspension for the modified patterning porous nano-fibre material in poly-dopamine surface being immersed photochemical catalyst is water-soluble There is water-oil separating and oil resistant to pollute difunctional patterning porous nano-fibre for liquid, poly-dopamine loaded optic catalyst, preparation Material.
Step (1), using patterned reception template, so that pattern structure is uniformly integrally formed at hydrophobicity spinning The electrostatic spinning overall process that nanofiber is intertwined guarantees the uniformity and controllability of pattern structure inner tissue, from And regulate and control hydrophobicity spinning nanofiber and be intertwined density and thickness in different zones, it adjusts in pattern structure and dredges Aqueous spinning nanofiber is intertwined the pore size to be formed and duct length, minimizes hydrophobicity spinning nanofiber Resistance, while retaining retention functions.
Step (1), electrospinning parameters are as follows: room temperature, indoor humidity be 40%~60%, spinning voltage be 6.8kv~ 7.0kv, flow be 0.01~0.02mL/min, preferably 0.016mL/min, collect distance be 8~12cm, preferably 10cm, Time is 5~10min, preferably 5~8min, more preferably 5min.
Step (1), the material of hydrophobicity spinning nanofiber include polyvinyl butyral (PVB), poly terephthalic acid Second diester (PET), polybutylene terephthalate (PBT), Kynoar (PVDF), carboxymethyl cellulose acetate butyrate (CMCAB), polylactic acid (PLLA), polytetrafluoroethylene (PTFE) (PTFE), polyethylene (PE) or polyester, preferably polyvinyl butyral (PVB)；Organic solvent includes dehydrated alcohol, toluene, chloroform, n-butanol or methanol, preferably dehydrated alcohol；Hydrophobicity spinning is received The material of rice fiber and the amount ratio of organic solvent are 0.5~1g/mL, preferably 0.6~0.8g/mL.
Step (2), on the basis of patterned, in conjunction with the modification of hydrophobicity spinning nanofiber surface cladding poly-dopamine Modification improves the amphipathic of porous nano-fibre material, makes its not only hydrophilic but also oleophylic, pure water can pass through with pure oil；In conjunction with more The crown_interception of hole nano-fiber material porous structure, the crown_interception of porous structure, phase interaction especially in pattern structure With, it influences each other, the realization effect excessively oily or that cross water selective according to oil water mixture state.
Step (2), dissolved with the parameter of the Tris-HCL buffer of dopamine are as follows: PH=8.5, the concentration of dopamine are 1.5 ~3mg/mL, preferably 2mg/mL.The parameter of Tris-HCL buffer are as follows: the concentration of PH=8.5, Tris are 9.5~11mmol/ L, preferably 10mmol/L.
Step (2), patterned porous nano-fibre material immerse dissolved with the Tris-HCL buffer of dopamine before, Carry out Tris-HCL buffer immersion treatment.The parameter of Tris-HCL buffer are as follows: the concentration of PH=8.5, Tris be 9.5~ 11mmol/L, preferably 10mmol/L.The parameter of immersion treatment are as follows: room temperature, 2~8min of time, preferably 2min.It is preferred that ultrasound Immersion treatment.Room temperature is specially room temperature or 25 DEG C~28 DEG C.
Step (2), 2~10h of room temperature avoid light place.Room temperature is specially room temperature or 25 DEG C~28 DEG C, and standing time is preferably 4 ~8h.
Step (2) after avoid light place, cleans the modified patterning porous nano in poly-dopamine surface with deionized water Fibrous material, and air-dry.
Step (3), the concentration of photochemical catalyst is 0.5mg/mL~2mg/mL in the aqueous suspension of photochemical catalyst, preferably 1mg/mL.Photochemical catalyst includes TiO2Compound photochemical catalyst, zinc oxide composites photochemical catalyst or visible light responsible photocatalytic Agent, TiO2Compound photochemical catalyst includes CdS-TiO2Laminated film, zinc oxide composites photochemical catalyst include nitrogenous MOx- ZnO compound (M=Fe, W) or TiO2/ CdO-ZnO nanoporous infiltration laminated film, it is seen that photoresponse photochemical catalyst includes vanadium Sour bismuth, bismuth tungstate or silver vanadate.The preferred pucherite of photochemical catalyst, it is seen that good to the catalytic degradation function of the organic matters such as oil under light It is good.Photochemical catalyst of the photochemical catalyst for micro/nano level, preferably micron-sized photochemical catalyst, specially 10~98 μm, preferably 75μm。
Step (3), the modified patterning porous nano-fibre material in poly-dopamine surface immerse the water in suspension of photochemical catalyst Solution is placed 0.5~1.5 hour.Preferably, the modified patterning porous nano-fibre material in poly-dopamine surface immerses light and urges The oscillation treatment while aqueous suspension of agent is placed.
Step (3), after loaded optic catalyst, there is water-oil separating and oil resistant to pollute, and difunctional patterning is porous to be received Rice fibrous material is cleaned with deionized water, and natural air drying.
Step (3), pucherite the preparation method comprises the following steps: by dissolved with the aqueous solution of bismuth salt and PH=6~11 of ammonium metavanadate in 80 DEG C~95 DEG C heating reactions, prepare pucherite.Specifically, by the aqueous solution of nitric acid dissolved with bismuth salt and the nitric acid dissolved with ammonium vanadate After aqueous solution mixes, alkali metal hydroxide and/or strong base-weak acid salt is added to PH=6~11, is heated in 80 DEG C~95 DEG C anti- It answers, prepares pucherite.First bismuth salt is dissolved in concentrated nitric acid, is added water, the aqueous solution of nitric acid dissolved with bismuth salt is prepared.First by ammonium vanadate It is dissolved in concentrated nitric acid, is added water, the aqueous solution of nitric acid dissolved with ammonium vanadate is prepared.Stirring, the side of stirring are mixed while heating reaction Formula has mechanical stirring or sonic agitation.
It prepares in the heating reaction system of pucherite, the molar ratio of bismuth element and vanadic acid root is 1:1~3, preferably 1:1； The concentration of bismuth element is 0.045~0.055mol/L, preferably 0.05mol/L.
The alkali metal hydroxide includes sodium hydroxide and/or potassium hydroxide, and strong base-weak acid salt includes sodium carbonate, carbonic acid Any one in potassium, sodium bicarbonate or saleratus or combination.
As a preferred solution of the present invention, step includes:
(1) polyvinyl butyral (PVB) is dissolved in dehydrated alcohol, using patterned reception template, electrostatic spinning Patterned porous nano-fibre material is prepared, using the polyvinyl butyral spinning nanofiber being intertwined as bone Frame；
Electrospinning parameters are as follows: room temperature, indoor humidity are 40%~60%, and spinning voltage is 6.8kv~7.0kv, flow For 0.016mL/min, collecting distance is 10cm, and the time is 5~10min, preferably 5min；
(2) the porous nano-fibre material that will be patterned into immerses the Tris-HCL that PH=8.5, Tris concentration are 10mmol/L After buffer ultrasonic treatment, then immerse the Tris-HCL buffer dissolved with dopamine, room temperature avoid light place, polyvinyl butyral Spinning nanofiber surface coats poly-dopamine, the modified patterning porous nano-fibre material in preparation poly-dopamine surface；
Dissolved with the parameter of the Tris-HCL buffer of dopamine are as follows: PH=8.5, dopamine concentration 2mg/mL；Tris- The parameter of HCL buffer are as follows: PH=8.5, Tris concentration are 10mmol/L；
(3) the modified patterning porous nano-fibre material in poly-dopamine surface is immersed into the pucherite that concentration is 1mg/mL Aqueous suspension simultaneously vibrates, and poly-dopamine loads pucherite, and there is water-oil separating and oil resistant to pollute difunctional patterning for preparation Porous nano-fibre material.
It is prepared by the present invention that there is water-oil separating and oil resistant to pollute difunctional patterning porous nano-fibre material, it uses Patterning combine poly-dopamine it is surface modified, make porous nano-fibre material have hydrophily and it is lipophilic simultaneously, also With crossing water still excessively oily separation function according to oil water mixture state selectivity, and keep efficient separative efficiency with point From flux；In conjunction with the photochemical catalyst (especially pucherite) of poly-dopamine load, the organic matters such as catalytic degradation oil have material There is the ability of the organic pollutions such as oil resistant, avoids attached in hydrophobicity spinning nanofiber surface because of organic matters such as oil in separation process Retention effects separating effect, further improve separative efficiency with separate flux, and to the structure of the porous nano-fibre material With performance without influence；Based on photochemical catalyst to the degradation function of the organic matters such as oil, the repeatable circulation of the porous nano-fibre material Use, and keep in repetitive cycling use process efficient separative efficiency with separate flux.
Therefore the application preparation there is water-oil separating and oil resistant to pollute difunctional patterning porous nano-fibre material can It is used to prepare separation material, the oil mixing with water of oil-in-water Yu Water-In-Oil state is separated using selectivity oil excessively or by the way of crossing water Object, and recyclable reuse, and there is oil resistant pollution and/or photocatalytic Degradation.
The patterning porous nano-fibre material difunctional with water-oil separating and oil rub resistance of the application preparation also can be used In preparing photocatalytic degradation material, for the photocatalytic degradation under the photocatalytic degradation of pollutant, especially visible light, and have Separation and/or oil resistant contamination.
The application preparation there is water-oil separating and oil resistant to pollute difunctional patterning porous nano-fibre material may be used also Oil resistant contaminated materials are used to prepare, based on photochemical catalyst to the degradation function of the organic matters such as oil, resist the attachment of the organic matters such as oil Pollution, and there is separation and/or photocatalytic Degradation.
The present invention also provides a kind of separation materials, have water-oil separating and oil resistant pollution difunctional containing prepared by the present invention Patterning porous nano-fibre material.And have the function of oil resistant pollution and/or photocatalytic degradation.
The present invention also provides a kind of photocatalytic degradation materials, containing prepared by the present invention there is water-oil separating and oil resistant to pollute Difunctional patterning porous nano-fibre material.And there is separation and/or oil resistant anti-contamination function.
The present invention also provides a kind of oil resistant contaminated materials, have water-oil separating and oil resistant pollution double containing prepared by the present invention The patterning porous nano-fibre material of function.And have the function of separation and/or the organic oil contaminants of photocatalytic degradation.
The beneficial effects of the present invention are:
(1) it is prepared by the present invention there is water-oil separating and oil resistant to pollute difunctional patterning porous nano-fibre material can The oil water mixture of Water-In-Oil state and oil-in-water state is efficiently separated, and separates flux height, separative efficiency is excellent, can be used for making Standby separation material；When the porous nano-fibre material surface loaded optic catalyst of the hydrophilic and oleophilic with pattern structure, into One step improves the separation flux and separative efficiency of the oil water mixture for Water-In-Oil state and oil-in-water state, and the light loaded Catalyst can effective photocatalytic degradation of organic matter, can be used for preparing photocatalytic degradation material, realize oil rub resistance during the separation process Dye makes material is repeatable to be recycled.
(2) preparation method of the present invention, have many advantages, such as it is simple and easy to control, at low cost, be suitable for industrialized production.
Detailed description of the invention
Fig. 1 is pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa and BiVO prepared by embodiment 14/PDA@ The FTIR map (A) and pucherite (BiVO of pattern PVB tunica fibrosa4) XRD spectrum (B).
Fig. 2 be implement 1 preparation no pattern PVB tunica fibrosa (a1, b1, C1), pattern PVB tunica fibrosa (a2, B2, C2), PDA@pattern PVB tunica fibrosa (a3, b3, C3), BiVO4/ PDA@pattern PVB tunica fibrosa (a4, b4, C4) Scanning electron microscope (SEM) photograph, oily contact angle (O) and water contact angle (W) test chart.
Fig. 3 is pattern PVB tunica fibrosa (A1, A2, A3, A4, A5, D1), PDA@pattern prepared by embodiment 1 PVB tunica fibrosa (B1, B2, B3, B4, B5, D2), BiVO4/ PDA@pattern PVB tunica fibrosa (C1, C2, C3, C4, C5, D3) Element surface scan figure and energy spectrum diagram (EDS).
Fig. 4 is BiVO prepared by embodiment 14/ PDA@pattern PVB tunica fibrosa carries out the procedure chart of water-oil separating, a1 (before separation), a2 (before separation and after separation) and a3 (after separation) are the discrete state figure of the oil water mixture of oil-in-water state, B1 (before separation), b2 (before separation and after separation) and b3 (after separation) are the discrete state of the oil water mixture of Water-In-Oil state Figure.
Fig. 5 is no pattern PVB tunica fibrosa, pattern PVB tunica fibrosa, PDA@pattern prepared by embodiment 1 PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa is for oil-in-water (9:1, VWater/VOil) state and Water-In-Oil (100:1, VOil/VWater) state oil water mixture water-oil separating efficiency and water-oil separating flux result figure.
Fig. 6 is BiVO prepared by embodiment 14/ PDA@pattern PVB tunica fibrosa distinguish circular treatment oil-in-water state and The water-oil separating efficiency and water-oil separating flux result figure of the oil water mixture of Water-In-Oil state.
Fig. 7 is no pattern PVB tunica fibrosa, pattern PVB tunica fibrosa, PDA@pattern prepared by embodiment 1 PVB tunica fibrosa, BiVO4The efficiency chart of/PDA@pattern PVB tunica fibrosa visible light photocatalytic degradation of organic pollutants rhodamine B.
Specific embodiment
Further illustratively the present invention will be described in detail combined with specific embodiments below.It should be noted that for these The explanation of embodiment is used to help understand the present invention, but and does not constitute a limitation of the invention.
Embodiment 1
(1) electrostatic spinning prepares PVB (polyvinyl butyral) fiber
The amount ratio of PVB powder end and dehydrated alcohol is 0.5mg/mL, stirs to PVB be completely dissolved at room temperature, is obtained uniformly Stable electrostatic spinning liquid.
In room temperature, indoor humidity 40%, voltage 6.8Kv, flow 0.016mL/min, collecting distance is 10cm's Under the conditions of, carry out electrostatic spinning.
During electrostatic spinning, using the aluminium foil of pattern-free structure as Static Spinning receiver board, carry out 5min's on it Electrostatic fibre film deposition, prepares the PVB tunica fibrosa (no pattern PVB) of disordered structure, for use.
To there is the metal mesh of patterning (pattern, circular hole) as Static Spinning receiver board, the quiet of 5min is carried out on it Electric tunica fibrosa deposition, prepares the PVB tunica fibrosa (pattern PVB) with pattern structure, for use, pattern PVB fiber Film is using PVB electrospun fibers as skeleton, and about 50~100 μm of the diameter of circular pattern.The FTIR of pattern PVB tunica fibrosa schemes Spectrum is as shown in Figure 1.
(2) photochemical catalyst pucherite (BiVO is prepared4)
By five water bismuth nitrate (Bi (NO of 0.97g3)3*5H2) and 0.234g ammonium metavanadate (NH O4VO3) 5mL concentrated nitric acid is used respectively Dissolution, is respectively designated as solution A and solution B；30mL deionized water is separately added into solution A and solution B again, later by solution A is uniformly mixed with solution B；15g NaHCO is slowly added into uniformly mixed solution A and B3, PH ≈ 6~11, later, by it Mixed liquor heats and stirs 15h in 90 DEG C, and the molar ratio of bismuth element and vanadic acid root is about 1:1 in mixed liquor；Centrifugation (uses deionization Water and ethyl alcohol are cleaned) for several times；At 60 DEG C, vacuum drying is for 24 hours；Grinding packs spare, pucherite (BiVO4) XRD diagram Spectrum is as shown in Fig. 1 (B).
(3) BiVO4/PDA@pattern PVB dual-functional nanometer tunica fibrosa is prepared
By the Tris-HCL buffer of pattern PVB tunica fibrosa immersion PH=8.5, (Tris concentration is 10mmol/ first L) it is ultrasonically treated 2min；Tris-HCL buffer (PH=8.5, dopamine concentration 1.5mg/mL dissolved with dopamine are immersed again； Tris-HCL buffer: PH=8.5, Tris concentration are 10mmol/L), 25 DEG C are protected from light 2h；It is finally washed with deionized, wind Dry, PDA@pattern PVB tunica fibrosa, FTIR map is made in PVB electrospun fibers surface modification poly-dopamine (PDA) As shown in Figure 1.
PDA@pattern PVB tunica fibrosa is immersed into BiVO4Aqueous suspension (BiVO4Concentration be 1mg/mL) in, shaking table Under the conditions of handle 0.5h, be washed with deionized water, natural air drying, poly-dopamine of the PVB electrospun fibers based on surface modification (PDA) BiVO is loaded4, BiVO is made4/ PDA@pattern PVB tunica fibrosa, FTIR map are as shown in Figure 1.
By Fig. 1 (A) pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa and BiVO4/PDA@pattern The FTIR map of PVB tunica fibrosa is it is found that PDA@pattern PVB and BiVO4/ PDA@pattern two groups of materials of PVB occur Apparent PDA characteristic peak, BiVO4/ PDA@pattern PVB tunica fibrosa is in 748cm-1There is the characteristic absorption of vanadic acid radical ion in place Peak.
By Fig. 1 (B) pucherite (BiVO4) XRD spectrum it is found that standard card No.14-688, the BiVO of monocline type4In 2 θ 18.7 °, 19.0 °, 28.6 °, 28.8 °, 28.9 ° and 30.5 ° of diffraction maximum be respectively belong to (110), (011), (- 130), (- 121), (121) and (040) face；Standard card No.41-575, the BiVO of orthogonal type431.9 °, 32.4 ° of diffraction maximum in 2 θ and 32.9 ° are belonging respectively to (020), (200) and (022) face, the BiVO of the application preparation4XRD diagram spectral peak it is corresponding with standard card, Confirm that the preparation of this implementation success has the pucherite (BiVO of photocatalysis performance4)。
As shown in Figure 1, the present invention has prepared the BiVO that area load has photochemical catalyst pucherite4/PDA@pattern PVB electrospinning fibre membrane material.
No pattern PVB tunica fibrosa manufactured in the present embodiment, pattern PVB tunica fibrosa, PDA@pattern PVB Tunica fibrosa, BiVO4The scanning electron microscope (SEM) photograph of/PDA@pattern PVB tunica fibrosa, oily contact angle (O) and water contact angle (W) such as Fig. 2 It is shown.
By no pattern PVB tunica fibrosa (a1, b1), pattern PVB tunica fibrosa (a2, b2), PDA@pattern PVB tunica fibrosa (a3, b3), BiVO4The scanning electron microscope (SEM) photograph of/PDA@pattern PVB tunica fibrosa (a4, b4) is it is found that each Static Spinning Cortina material using PVB electrospun fibers (diameter is about 600~700nm) as the skeleton of entire water-oil separating material, The porous fiber film of the interlaced three-dimensional perforation for forming the opening that aperture is small, porosity is high, hole connectivity is good and surface density is small Poly-dopamine, poly-dopamine are uniformly modified in structure, the PVB electrospun fibers surface for constituting PDA@pattern PVB tunica fibrosa Into inside tunica fibrosa, modify in PVB electrospun fibers surface；Constitute BiVO4The PVB of/PDA@pattern PVB tunica fibrosa Electrospun fibers have pucherite (BiVO based on the poly-dopamine uniform load of surface modification4) (diameter is about 75 μ to particle M), pucherite particle is carried on PVB electrospun fibers surface by the adhesive attraction of intermediate connecting layer poly-dopamine.
By no pattern PVB tunica fibrosa (C1), pattern PVB tunica fibrosa (C2), PDA@pattern PVB fiber Film (C3), BiVO4The oily contact angle (O) and water contact angle (W) of/PDA@pattern PVB tunica fibrosa (C4) are it is found that no Pattern PVB tunica fibrosa and pattern PVB tunica fibrosa are lipophilic-hydrophobic property, and the two can only be used to processing Water-In-Oil state Oil water mixture；PDA@pattern PVB tunica fibrosa and BiVO4/PDA@pattern PVB tunica fibrosa, because being modified with PDA, It is transformed by original lipophilic-hydrophobic property amphiphilic, that is, hydrophilic and oleophylic, fiber film material at this time are then according to need to handle oil The oil excessively of state (the Water-In-Oil or oil-in-water) selectivity of aqueous mixtures still crosses water, to reach water-oil separating.
Pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa Element surface scan figure and energy spectrum diagram (EDS) are as shown in Figure 3.
Pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa For C element Surface scan figure successively as shown in A1, B1, C1 in Fig. 3, three kinds of tunica fibrosas contain carbon.
Pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa N element Surface scan figure is successively as shown in A2, B2, C2 in Fig. 3, pattern PVB tunica fibrosa and PDA@pattern PVB tunica fibrosa Display nitrogen, and BiVO4/ PDA@pattern PVB tunica fibrosa does not show nitrogen, derived from composition BiVO4/PDA@pattern The BiVO of the PVB electrospun fibrous surface load of PVB tunica fibrosa4Particle when carrying out Surface scan, cover by the signal of two kinds of elements of Bi and V The N element signal that the PDA of PVB electrospun fibrous surface modification is issued is covered, PDA is as intermediate connecting layer, by BiVO4It loads to On electrospinning fibre.
Pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa For O element surface scan figure successively as shown in A3, B3, C3 in Fig. 3, three kinds of tunica fibrosas contain oxygen element.
Pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa Bi element surface scan figure is successively as shown in A4, B4, C4 in Fig. 3, only BiVO4/ PDA@pattern PVB tunica fibrosa contains bismuth member Element.
Pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa V element Surface scan figure is successively as shown in A5, B5, C5 in Fig. 3, only BiVO4/ PDA@pattern PVB tunica fibrosa contains vanadium.
Pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa Element surface scan figure forms PDA@pattern PVB tunica fibrosa, PDA@it is found that pattern PVB tunica fibrosa successfully modifies PDA Pattern PVB tunica fibrosa successfully loads BiVO4Form BiVO4/ PDA@pattern PVB tunica fibrosa.
The energy spectrum diagram (EDS) of pattern PVB tunica fibrosa is as shown in D1 in Fig. 3, the energy of PDA@pattern PVB tunica fibrosa Spectrogram (EDS) is as shown in D2 in Fig. 3, BiVO4The energy spectrum diagram (EDS) of/PDA@pattern PVB tunica fibrosa is as shown in D3 in Fig. 3. Energy spectrum diagram is reconfirmed in Fig. 3, and pattern PVB tunica fibrosa successfully modifies PDA and forms PDA@pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa successfully loads BiVO4Form BiVO4/ PDA@pattern PVB tunica fibrosa.
Use BiVO manufactured in the present embodiment4/ PDA@pattern PVB tunica fibrosa carries out the procedure chart of water-oil separating as schemed Shown in 4.In Fig. 4, a1 is effect picture before the separation of the oil water mixture of oil-in-water state, and a2 is the oil mixing with water of oil-in-water state Object distinguishes the state diagram of (B) after (A) before separation and separation, and a3 is effect after the separation of the oil water mixture of oil-in-water state Figure, by BiVO4After/PDA pattern PVB tunica fibrosa selectively crosses water retention oil separation, there is no apparent oil in water Drop.In Fig. 4, b1 is effect picture before the separation of the oil water mixture of Water-In-Oil state, the oil water mixture point of b2 Water-In-Oil state Not before separation (A) and separation after (B) state diagram, b3 be Water-In-Oil state oil water mixture separation after effect picture, warp Cross BiVO4The excessively oily traps moisture of/PDA@pattern PVB tunica fibrosa selectivity is from rear, without apparent water droplet in oil.It is comprehensive On, BiVO manufactured in the present embodiment4/ PDA@pattern PVB micro/nano fibrous membrane material can be used for oil-in-water and two kinds of Water-In-Oil Different conditions oil water mixture selectively crosses water or excessively oily water-oil separating.
No pattern PVB tunica fibrosa, pattern PVB tunica fibrosa, PDA@pattern PVB tunica fibrosa, BiVO4/ PDA@pattern PVB tunica fibrosa is for oil-in-water (9:1, VWater/VOil) state and Water-In-Oil (100:1, VOil/VWater) state grease The water-oil separating efficiency and water-oil separating flux result of mixture are as shown in Figure 5.Under Water-In-Oil state, four groups of fiber film materials are equal With oil and water separation capability, with the gradually modification to fiber film material, four groups of fiber film materials do not have in water-oil separating efficiency Have and show apparent variation, but on separation flux, successively shows as no pattern PVB < pattern PVB < PDA@ pattern PVB<BiVO4/PDA@pattern PVB.Under oil-in-water state, no pattern PVB and pattern PVB two Group fiber film material does not have an oil and water separation capability, and PDA@pattern PVB and BiVO4Two groups of/PDA@pattern PVB fine Membrane material is tieed up because of the effect of PDA, has oil and water separation capability, and do not have notable difference in separative efficiency；It is logical with regard to separating For amount, PDA@pattern PVB < BiVO4/PDA@pattern PVB.To sum up, illustrate BiVO4/ PDA@pattern PVB electricity Spinning fibrous material, which has, all has efficient oil and water separation capability under oil-in-water and the two different states of Water-In-Oil.
Use BiVO manufactured in the present embodiment4/ PDA@pattern PVB tunica fibrosa distinguish circular treatment oil-in-water state and The result of the oil water mixture of Water-In-Oil state is as shown in Figure 6.Use BiVO4/ PDA@pattern PVB tunica fibrosa recycles respectively The oil water mixture for handling oil-in-water state and Water-In-Oil state, during carrying out 15 multi-cycle separations, BiVO4/PDA@ The separation flux of pattern PVB fiber film material is held essentially constant, and separative efficiency also remains at 95% or more, can Keep high separating efficiency.BiVO manufactured in the present embodiment4There is/PDA@pattern PVB fiber film material preferable circulation to make With ability, to be recycled nonexpondable high efficiency oil-water separation material.
It tests whether fiber film material has the function of photocatalysis degradation organic contaminant rhodamine B under dynamic condition, puts down Row prepares 4 groups of quantitative rhodamine B solutions, by no pattern PVB tunica fibrosa, pattern PVB tunica fibrosa, PDA@ Pattern PVB tunica fibrosa and BiVO4/ PDA@pattern PVB tunica fibrosa is separately immersed in quantitative rhodamine B solution, It is first protected from light 1.5h, fiber film material is made to reach absorption-desorption balance to rhodamine B；Xenon lamp simulated solar irradiation is recycled, each group is fine It ties up membrane material and degradation treatment is carried out to rhodamine B under illumination condition.Rhodamine B is measured by ultraviolet-visible spectrophotometer The concentration of solution, with T-C/C0Light degradation ability is characterized, wherein T is the time of photocatalytic degradation, C and C0It is processing solution respectively With the concentration of original solution.No pattern PVB tunica fibrosa, pattern PVB tunica fibrosa, PDA@pattern PVB fiber Film, BiVO4The efficiency chart of/PDA@pattern PVB tunica fibrosa photocatalysis degradation organic contaminant rhodamine B is as shown in Figure 7.
As shown in Figure 7, before giving illumination, PDA@pattern PVB tunica fibrosa and BiVO4/ PDA@pattern PVB is fine Tie up rhodamine B in membrane material group concentration reduce it is very fast, mainly because containing PDA in two groups of materials, absorbed portion rhodamine B, It is reduced so as to cause the concentration of rhodamine B in solution.After giving illumination, BiVO4/ PDA@pattern PVB fiber film material The rhodamine B concentration of group is maximum compared to the degree of other three groups of reductions, mainly because turning on light after, be supported on PVB nanofiber Photochemical catalyst BiVO on film4The ability of its photocatalysis contaminant degradation is played, so that the rhodamine B concentration in solution reduces. Therefore, the BiVO prepared by the present invention4/ PDA pattern PVB electrospinning fibre membrane material is with excellent photocatalytic degradation The water-oil separationg film of pollutant.
Embodiment 2
(1) electrostatic spinning prepares PVB fiber
The amount ratio of PVB powder end and dehydrated alcohol is 0.6mg/mL, stirs to PVB be completely dissolved at room temperature, is obtained uniformly Stable electrostatic spinning liquid.
In room temperature, indoor humidity 50%, voltage 6.8Kv, flow 0.016mL/min, collecting distance is 10cm's Under the conditions of, carry out electrostatic spinning.
Using the metal mesh of pattern structure (pattern) as Static Spinning receiver board, the electrostatic for carrying out 5min on it is fine Tie up film deposition, prepare have pattern structure PVB tunica fibrosa (pattern PVB), for use, pattern PVB tunica fibrosa with PVB electrospun fibers are skeleton.
(2) photochemical catalyst pucherite (BiVO is prepared4)
The preparation method is the same as that of Example 1, prepares pucherite (BiVO4)。
(3) BiVO is prepared4/ PDA@pattern PVB dual-functional nanometer tunica fibrosa
By the Tris-HCL buffer of pattern PVB tunica fibrosa immersion PH=8.5, (Tris concentration is 10mmol/ first L) it is ultrasonically treated 4min；Tris-HCL buffer (PH=8.5, dopamine concentration 2mg/mL dissolved with dopamine are immersed again； Tris-HCL buffer: PH=8.5, Tris concentration are 10mmol/L), 25 DEG C are protected from light 4h；It is finally washed with deionized, wind Dry, PDA@pattern PVB tunica fibrosa is made in PVB electrospun fibers surface modification poly-dopamine (PDA).
PDA@pattern PVB tunica fibrosa is immersed into BiVO4Aqueous suspension (BiVO4Concentration be 1.5mg/mL) in, shake 0.5h is handled under the conditions of bed, is washed with deionized water, natural air drying, poly- DOPA of the PVB electrospun fibers based on surface modification Amine (PDA) loads BiVO4, BiVO is made4/ PDA@pattern PVB tunica fibrosa.
Embodiment 3
(1) electrostatic spinning prepares PVB fiber
The amount ratio of PVB powder end and dehydrated alcohol is 1mg/mL, stirs to PVB be completely dissolved at room temperature, is obtained uniformly steady Fixed electrostatic spinning liquid.
In room temperature, indoor humidity 60%, voltage 6.9Kv, flow 0.016mL/min, collecting distance is 10cm's Under the conditions of, carry out electrostatic spinning.
Using the metal mesh of pattern structure (pattern) as Static Spinning receiver board, the electrostatic for carrying out 5min on it is fine Tie up film deposition, prepare have pattern structure PVB tunica fibrosa (pattern PVB), for use, pattern PVB tunica fibrosa with PVB electrospun fibers are skeleton.
(2) photochemical catalyst pucherite (BiVO is prepared4)
The preparation method is the same as that of Example 1, prepares pucherite (BiVO4)。
(3) BiVO4/PDA@pattern PVB dual-functional nanometer tunica fibrosa is prepared
By the Tris-HCL buffer of pattern PVB tunica fibrosa immersion PH=8.5, (Tris concentration is 10mmol/ first L) it is ultrasonically treated 2min；Tris-HCL buffer (PH=8.5, dopamine concentration 2.5mg/mL dissolved with dopamine are immersed again； Tris-HCL buffer: PH=8.5, Tris concentration are 10mmol/L), 25 DEG C are protected from light 6h；It is finally washed with deionized, wind Dry, poly-dopamine (PDA) of the PVB electrospun fibers based on surface modification loads BiVO4, it is fine that PDA@pattern PVB is made Tie up film.
PDA@pattern PVB tunica fibrosa is immersed into BiVO4Aqueous suspension (BiVO4Concentration be 0.5mg/mL) in, shake 0.5h is handled under the conditions of bed, is washed with deionized water, natural air drying, loads BiVO on PDA pattern PVB tunica fibrosa4, system Obtain BiVO4/ PDA@pattern PVB tunica fibrosa.
Embodiment 4
(1) electrostatic spinning prepares PVB fiber
The amount ratio of PVB powder end and dehydrated alcohol is 0.8mg/mL, stirs to PVB be completely dissolved at room temperature, is obtained uniformly Stable electrostatic spinning liquid.
In room temperature, indoor humidity 60%, voltage 7Kv, flow 0.016mL/min collect the item that distance is 10cm Under part, electrostatic spinning is carried out.
Using the metal mesh of pattern structure (pattern) as Static Spinning receiver board, the electrostatic for carrying out 5min on it is fine Tie up film deposition, prepare have pattern structure PVB tunica fibrosa (pattern PVB), for use, pattern PVB tunica fibrosa with PVB electrospun fibers are skeleton.
(2) photochemical catalyst pucherite (BiVO is prepared4)
The preparation method is the same as that of Example 1, prepares pucherite (BiVO4)。
(3) BiVO4/PDA@pattern PVB dual-functional nanometer tunica fibrosa is prepared
By the Tris-HCL buffer of pattern PVB tunica fibrosa immersion PH=8.5, (Tris concentration is 10mmol/ first L) it is ultrasonically treated 2min；Tris-HCL buffer (PH=8.5, dopamine concentration 3mg/mL dissolved with dopamine are immersed again； Tris-HCL buffer: PH=8.5, Tris concentration are 10mmol/L), 25 DEG C are protected from light 8h；It is finally washed with deionized, wind Dry, PDA@pattern PVB tunica fibrosa is made in PVB electrospun fibers surface modification poly-dopamine (PDA).
PDA@pattern PVB tunica fibrosa is immersed into BiVO4Aqueous suspension (BiVO4Concentration be 2mg/mL) in, shaking table Under the conditions of handle 0.5h, be washed with deionized water, natural air drying, poly-dopamine of the PVB electrospun fibers based on surface modification (PDA) BiVO is loaded4, BiVO is made4/ PDA@pattern PVB tunica fibrosa.
BiVO prepared by embodiment 2 to 44The FTIR profiling results of/PDA@pattern PVB tunica fibrosa are the same as embodiment 1 Fig. 1 (A), BiVO4There is PDA characteristic peak and 748cm in the FTIR map of/PDA@pattern PVB tunica fibrosa-1Locate vanadic acid root from Subcharacter peak, BiVO4The successful negative photocatalyst-bearing pucherite of/PDA pattern PVB fiber film surface.
BiVO prepared by embodiment 2 to 44The scanning electron microscope (SEM) photograph of/PDA@pattern PVB tunica fibrosa, oily contact angle (O) and The Fig. 2, BiVO of water contact angle (W) test result with embodiment 14/ PDA@pattern PVB tunica fibrosa is with PVB electrostatic spinning Skeleton of the fiber as entire water-oil separating material, interlaced formation aperture is small, porosity is high, hole connectivity is good and surface density The porous fibre membrane structure of the three-dimensional perforation of small opening, constitutes BiVO4The PVB Static Spinning of/PDA@pattern PVB tunica fibrosa Silk fiber has pucherite (BiVO based on the poly-dopamine uniform load of surface modification4) particle.
BiVO4/PDA pattern PVB tunica fibrosa is hydrophilic and oleophylic, and parents are functional, can be mixed according to that need to handle grease It closes the oil excessively of state (the Water-In-Oil or oil-in-water) selectivity of object or crosses water, to reach water-oil separating.
BiVO prepared by embodiment 2 to 44The element surface scan figure and energy spectrum diagram of/PDA@pattern PVB tunica fibrosa (EDS) Fig. 3 of result with embodiment 1, it was demonstrated that BiVO4/ PDA@pattern PVB tunica fibrosa is based on PVB electrospinning fibre fiber table The PDA of face modification successfully loads BiVO4。
BiVO prepared by embodiment 2 to 44The same embodiment of result of/PDA@pattern PVB tunica fibrosa progress water-oil separating 1 Fig. 4, it was demonstrated that the BiVO of each embodiment preparation4/ PDA@pattern PVB tunica fibrosa is to oil-in-water state (crossing water retention oil) Good separating effect is all had with the oil water mixture of Water-In-Oil state (excessively oily trap water).
BiVO prepared by embodiment 2 to 44/ PDA@pattern PVB tunica fibrosa is for oil-in-water state and Water-In-Oil state Oil water mixture water-oil separating efficiency and water-oil separating flux result it is close with Fig. 5 of embodiment 1, in oil-in-water and You Bao Under water two states, the BiVO of each embodiment preparation4/ PDA@pattern PVB tunica fibrosa shows efficient water-oil separating Efficiency and water-oil separating flux.
BiVO prepared by embodiment 2 to 44/ PDA@pattern PVB distinguishes circular treatment oil-in-water state and Water-In-Oil shape The result of the oil water mixture of state is close with Fig. 6 of embodiment 1, uses BiVO4/ PDA@pattern PVB tunica fibrosa follows respectively Ring handles the oil water mixture of oil-in-water state and Water-In-Oil state, during carrying out 15 multi-cycle separations, BiVO4/PDA@ The separation flux of pattern PVB fiber film material is held essentially constant, and separative efficiency also remains at 95% or more, can Keep high separating efficiency.BiVO4/ PDA@pattern PVB fiber film material has preferable recycling ability, is recyclable Nonexpondable high efficiency oil-water separation material.
BiVO prepared by embodiment 2 to 44/ PDA@pattern PVB tunica fibrosa photocatalysis degradation organic contaminant rhodamine The efficiencies of B are close with Fig. 7 of embodiment 1, before giving visible light illumination, BiVO4/ PDA@pattern PVB tunica fibrosa The concentration of rhodamine B reduces very fast in material group, mainly because containing PDA in the material, absorbed portion rhodamine B, so as to cause The concentration of rhodamine B reduces in solution.After giving visible light illumination, the BiVO of each embodiment4/ PDA@pattern PVB is fine The rhodamine B concentration for tieing up membrane material group occurs and embodiment 1BiVO4/ PDA@pattern PVB tunica fibrosa is similar largely Reduction, mainly because of photochemical catalyst BiVO4The ability of its photocatalysis contaminant degradation is played, so that the rhodamine B in solution is dense Degree reduces.BiVO4/ PDA pattern PVB electrospinning fibre membrane material is the grease with excellent photocatalytic pollutant degradation Seperation film.
The above-mentioned description to embodiment is for ease of ordinary skill in the art to understand and use the invention.It is ripe The personnel for knowing art technology obviously easily can make various modifications to these embodiments, and general original described herein It ought to use in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, this field Technical staff's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in guarantors of the invention Within the scope of shield.

Claims (10)

1. a kind of pollute difunctional patterning porous nano-fibre material with water-oil separating and oil resistant, which is characterized in that with The hydrophobicity spinning nanofiber being intertwined is skeleton, the pattern structure of ordered arrangement micro/nano level, and being distributed The porous structure for the three-dimensional perforation put；Hydrophobicity spinning nanofiber surface coats poly-dopamine, and poly-dopamine loads photocatalysis Agent.
2. patterning the preparation method of porous nano-fibre material described in claim 1, which is characterized in that step includes:
(1) material for forming hydrophobicity spinning nanofiber is dissolved in organic solvent, using patterned reception template, electrostatic Spinning is simultaneously deposited on hydrophobicity spinning nanofiber with being intertwined in reception template, prepares patterned porous nano Fibrous material；
(2) the porous nano-fibre material that will be patterned into immerses the Tris-HCL buffer dissolved with dopamine, and avoid light place is hydrophobic Property spinning nanofiber surface coat poly-dopamine, the modified patterning porous nano-fibre material in preparation poly-dopamine surface；
(3) aqueous suspension that the modified patterning porous nano-fibre material in poly-dopamine surface is immersed to photochemical catalyst, gathers There is water-oil separating and oil resistant to pollute difunctional patterning porous nano-fibre material for dopamine loaded optic catalyst, preparation.
3. preparation method according to claim 2, which is characterized in that step (1), electrospinning parameters are as follows: room temperature, it is indoor Humidity is 40%~60%, and spinning voltage is 6.8kv~7.0kv, and flow is 0.01~0.02mL/min, collect distance for 8~ 12cm, time are 5~10min.
4. preparation method according to claim 2, which is characterized in that step (1), the material of hydrophobicity spinning nanofiber It is fine including polyvinyl butyral, polyethylene terephthalate, polybutylene terephthalate, Kynoar, carboxymethyl Tie up plain acetate butyrate, polylactic acid, polytetrafluoroethylene (PTFE), polyethylene or polyester, organic solvent include dehydrated alcohol, toluene, chloroform, N-butanol or methanol, the material of hydrophobicity spinning nanofiber and the amount ratio of organic solvent are 0.5~1g/mL.
5. preparation method according to claim 2, which is characterized in that step (2) is buffered dissolved with the Tris-HCL of dopamine The parameter of liquid are as follows: PH=8.5, the concentration of dopamine are 1.5~3mg/mL；The parameter of Tris-HCL buffer are as follows: PH=8.5, The concentration of Tris is 9.5~11mmol/L.
6. preparation method according to claim 2, which is characterized in that step (3), light in the aqueous suspension of photochemical catalyst The concentration of catalyst is 0.5mg/mL~2mg/mL, and photochemical catalyst includes TiO2Compound photochemical catalyst, zinc oxide composites light Catalyst or visible light responsive photocatalyst.
7. described in claim 1 there is water-oil separating and oil resistant to pollute difunctional patterning porous nano-fibre material and prepare Application in terms of separation material, and/or photocatalytic degradation material, and/or oil resistant contaminated materials.
8. a kind of separation material, which is characterized in that difunctional containing having water-oil separating and oil resistant to pollute described in claim 1 Pattern porous nano-fibre material.
9. a kind of photocatalytic degradation material, which is characterized in that double containing having water-oil separating and oil resistant to pollute described in claim 1 The patterning porous nano-fibre material of function.
10. a kind of oil resistant contaminated materials, which is characterized in that double containing having water-oil separating and oil resistant to pollute described in claim 1 The patterning porous nano-fibre material of function.
CN201811239704.9A 2018-10-23 2018-10-23 It is a kind of to pollute difunctional patterning porous nano-fibre material and its preparation method and application with water-oil separating and oil resistant Pending CN109432825A (en)

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CN111926570A (en) * 2020-06-18 2020-11-13 北京服装学院 Janus fabric film based on polylactic acid and preparation method and application thereof
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Application publication date: 20190308