CN105951304A - ZIF-8/poly(vinyl alcohol) (PVA) composite nanofiber membrane as well as preparation method and application thereof - Google Patents

ZIF-8/poly(vinyl alcohol) (PVA) composite nanofiber membrane as well as preparation method and application thereof Download PDF

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Publication number
CN105951304A
CN105951304A CN201610485199.0A CN201610485199A CN105951304A CN 105951304 A CN105951304 A CN 105951304A CN 201610485199 A CN201610485199 A CN 201610485199A CN 105951304 A CN105951304 A CN 105951304A
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zif
preparation
polyvinyl alcohol
pva
fiber membrane
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Inventor
程建华
范笑笑
张鹏
陈杰峰
谢明容
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GUANGZHOU CHAOHUI CHEMICAL TECHNOLOGY Co Ltd
South China University of Technology SCUT
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GUANGZHOU CHAOHUI CHEMICAL TECHNOLOGY Co Ltd
South China University of Technology SCUT
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Priority to CN201610485199.0A priority Critical patent/CN105951304A/en
Publication of CN105951304A publication Critical patent/CN105951304A/en
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282Addition polymers
    • D04H1/4309Polyvinyl alcohol

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses a ZIF-8/poly(vinyl alcohol) (PVA) composite nanofiber membrane as well as a preparation method and application thereof, belonging to the technical field of preparation of functional nanofiber membranes. The method comprises the following steps of: (1) carrying out hybrid reaction on a methanol solution of soluble zinc salt and a methanol solution of 2-methylimidazole under room temperature and purifying an obtained reaction liquid after reaction ends, thus obtaining nano ZIF-8; (2) mixing obtained nano ZIF-8 with PVA, dissolving the mixture in deionized water, stirring the mixture to swell, then carrying out stirring heating reaction and cooling the reactant to the room temperature after reaction ends, thus obtaining an electrostatic spinning solution; and (3) putting the obtained electrostatic spinning solution in an injector to carry out electrostatic spinning, thus obtaining the ZIF-8/PVA composite nanofiber membrane. The method not only has the effect of overcoming the defect that the ZIF-8 material is difficult to recover and industrially apply in a water phase but also has better selective adsorption property and can be applied to sewage treatment.

Description

A kind of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane and its preparation method and application
Technical field
The invention belongs to the preparing technical field of functional nanofiber membrane, particularly to a kind of poly-second of ZIF-8/ Enol composite nano-fiber membrane and its preparation method and application.
Background technology
Along with the development of printing and dyeing industry, dyeing waste water become current topmost water body, cure of Soil pollution it One, it is one of industrial wastewater being most difficult to improvement at present.The waste water from dyestuff of high chroma has a strong impact on water quality, and meeting Organism is produced toxic action even " three cause " effect.Traditional waste water from dyestuff generally goes through physics, change Process process, but these technology generally to dyestuff remove have some defects, as cost height, secondary pollution, The most recyclable, waste water from dyestuff etc. can not be widely used in.Adsorption technology is because its feasibility is high and cost benefit is good Feature, is widely used in processing large-scale industrial wastewater.
In recent years, metal-organic framework compound (metal organic frameworks, MOFs) because of Its specific surface area is huge, physicochemical property is adjustable, easy functionalization and synthesis strategy variation etc. advantage absorption The fields such as separation show good potential application foreground.Wherein, ZIF-8 be a kind of good hydrothermal stability and There is the MOFs material of high-ratio surface.But simple ZIF-8 there is also some not directly as aqueous phase adsorbent Foot, as easily reunited, is not easily recycled after absorption, causes the waste of secondary pollution and resource, it is difficult to industrialization profit With.The most also there is no the technique for fixing of researcher research ZIF-8.
Electrostatic spinning technique is to produce high velocity jet based on high-pressure electrostatic conductor fluid after the match to prepare Nanowire The method of dimension, the advantage of its maximum is easy to operate, low cost, can be mass-produced and be easily recycled profit Paid close attention to widely by people by, it is simple to commercial application.Compared with common nanofiber, Static Spinning is fine Dimension has on high porosity, high-specific surface area, and fiber and also has nanoscale hole, therefore Static Spinning Nanowire Dimension demonstrates obvious application prospect in fields such as active substance loading, sensor, adsorbent and filtering materials. At present in the research of Static Spinning, utilize Electrospun nano-fibers film as the support of adsorbent and for contaminating The process of material waste water rarely has report.Number of polymers such as polystyrene (PST) Pluronic F-127 (PEO), Polyacrylonitrile (PAN), polylactic acid (PLA), polyvinyl alcohol (PVA) etc. are prepared as receiving by method of electrostatic spinning Rice fibrous membrane has been applied to the necks such as filtering material, bio-medical engineering material, medicament slow release, catalyst application Territory.But PST is polystyrene, PVP polyvinylpyrrolidone, these polymerization prices of PS polystyrene Lattice are relatively expensive, and solvent used is organic solvent, it is desirable to find a kind of polymer low price, molten Agent safety non-toxic.Research finds, polyvinyl alcohol (poly (vinyl alcohol), PVA) is a kind of hypocrystalline parent Waterborne polymeric, has the most chemically and thermally stability, has excellent physical and mechanical property and processability, The electrostatic spinning performance better than other polymer and low price, be dissolved only in water.The more important thing is PVA, with hydroxy functional group, can be combined with some molecules by hydrogen bond, overcome some molecules in aqueous phase Easily reuniting makes it preferably be dispersed on the linear chain of PVA, and PVA can promote as a kind of plasticiser Orientation improves spinnability.Therefore, it is contemplated that to can be using PVA as immobilized dose of ZIF-8, existing skill In art the most not using PVA as the report of immobilized dose of ZIF-8.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the primary and foremost purpose of the present invention is to provide one The electrostatic spinning preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane.
Another object of the present invention is the ZIF-8/ polyvinyl alcohol composite nano fiber providing said method to prepare Film.
Still a further object of the present invention is to provide above-mentioned ZIF-8/ polyvinyl alcohol composite nano-fiber membrane at sewage Application in terms of reason.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane, it comprises the following steps:
(1) preparation of nanometer ZIF-8: by methanol solution and the methanol of 2-methylimidazole of soluble zinc salt Solution at room temperature mixes and reacts, and gained reactant liquor is centrifuged after terminating by reaction, takes off a layer solid, Cleaning with methanol, the solid after then cleaning is drying to obtain nanometer ZIF-8;
(2) preparation of electrostatic spinning solution: nanometer ZIF-8 that step (1) is obtained and polyvinyl alcohol (PVA) Mixing and be dissolved in deionized water, stirring 20~40min makes it swelling, and heating is anti-the most under agitation Should, question response is cooled to room temperature and i.e. obtains finely dispersed electrostatic spinning solution after terminating;
(3) electrostatic spinning: be placed in 10mL syringe by the electrostatic spinning solution of step (2) gained Row electrostatic spinning, i.e. obtains ZIF-8/ polyvinyl alcohol composite nano-fiber membrane.
The methanol solution of the soluble zinc salt described in step (1) refers to add in the methanol of every 1mL The soluble zinc salt of (0.013~0.017) g;The methanol solution of described 2-methylimidazole refers to every 1mL Methanol in add (0.030~0.035) g 2-methylimidazole;The methanol of soluble zinc salt used is molten The volume ratio of the methanol solution of liquid and 2-methylimidazole is 1:1.
Soluble zinc salt described in step (1) is Zn (NO3)·6H2O。
Reaction described in step (1) refers to stirring reaction 20~24h under the speed of 350~400rpm.
Centrifugal speed described in step (1) is 5000~8000rpm, and centrifugation time is 10~20min.
Dry referring to described in step (1) is vacuum dried 12~24h at 40~60 DEG C.
Nanometer ZIF-8 used in step (2) and mass ratio 0.01:1~0.03:1 of polyvinyl alcohol, used The mass ratio of polyvinyl alcohol and deionized water be 0.06:1~0.08:1.
Stirring described in step (2) refers both to be stirred with the speed of 350~400rpm.
Reacting by heating described in step (2) refers at 80 DEG C~90 DEG C stirring reaction 2h~3h.
The condition of the electrostatic spinning described in step (3) is temperature 30 DEG C, humidity 40%RH, advances speed Degree 0.1mL/h~0.3mL/h, voltage is 22kv~28kv, spinneret to receptor distance for 14cm~ 18cm。
A kind of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane prepared by said method, remains original The framing structure of ZIF-8.Meanwhile, overcoming the shortcoming that ZIF-8 material is easily reunited in aqueous phase, ratio is merely ZIF-8 is more easy to reclaim, and dispersion evenly, possesses more preferable adsorption selectivity compared to simple ZIF-8, Can well apply in terms of sewage disposal.
The present invention, relative to prior art, has such advantages as and beneficial effect:
(1) present invention is prepared for ZIF-8/PVA porous nanofiber membrane at normal temperatures by electrical spinning method, system Preparation Method is easy, and reaction condition is easily achieved and controls, and cost of material is the lowest.
(2) arbitrarily can be controlled in nano fibrous membrane by regulation nanometer ZIF-8 and the ratio of polyvinyl alcohol The content of nanometer ZIF-8.
(3) the ZIF-8/PVA porous nanofiber membrane that the present invention obtains remains the skeleton of original ZIF-8 Structure, makes ZIF-8 be evenly distributed on nano fibrous membrane by hydrogen bond, overcomes ZIF-8 material at aqueous phase In the shortcoming easily reunited, and film in removal process can directly by tweezers gripping without centrifugation, reduce The loss of ZIF-8, is more easy to reclaim than simple ZIF-8.And ZIF-8/PVA porous nanofiber membrane phase Ratio possesses more preferable adsorption selectivity in simple ZIF-8.
Accompanying drawing explanation
Fig. 1 is that the PVA porous nanofiber membrane of comparative example 1 preparation is prepared with embodiment 1,2,3 The powder X-ray RD spectrogram comparison diagram of ZIF-8/PVA porous nanofiber membrane.
Fig. 2 is PVA porous nanofiber membrane (a) and embodiment 3 preparation of comparative example 1 preparation The FTIR comparison diagram of ZIF-8/PVA porous nanofiber membrane (c) and ZIF-8 (b).
Fig. 3 is PVA porous nanofiber membrane (a) and embodiment 3 preparation of comparative example 1 preparation The SEM comparison diagram of ZIF-8/PVA porous nanofiber membrane (b).
Fig. 4 is ZIF-8/PVA porous nanofiber membrane and ZIF-8, the comparative example of embodiment 3 preparation The PVA nano fibrous membrane of the preparation adsorption effect comparison diagram to low concentration Congo red in 1.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but the embodiment party of the present invention Formula is not limited to this.
XRD phenetic analysis: use the Empyrean sharp shadow X-ray diffraction that PANalytical company of Holland produces The crystal structure of the porous material that the present invention is prepared by instrument characterizes, and wherein operating condition is: copper target, 40KV, 40mA, step-length 0.0131 degree, 9.664 seconds/step of scanning speed.
SEM phenetic analysis: use MERLIN field emission scanning electron microscope (Carl Zeiss company, Germany) surface topography of porous material for preparing of the present invention characterizes.
The preparation of comparative example's 1:PVA porous nanofiber membrane
1.6g polyvinyl alcohol (PVA) is dissolved in 18.4g deionized water and obtains 8wt%PVA spinning liquid, Magnetic stirring apparatus stirs 30min the most swelling, then 90 DEG C of heating in water bath stirring 3h, mixing speed For 400rpm.It is cooled to room temperature and obtains finely dispersed electrostatic spinning liquid.
The electrostatic spinning solution of gained is placed in 10mL syringe and carries out electrostatic spinning, spinning temperature is set 30 DEG C, humidity 40%RH, fltting speed 0.1mL/h, voltage is 22kv, and spinneret is to receptor distance For 14cm, obtain ZIF-8/ polyvinyl alcohol composite nano-fiber membrane.
The preparation of embodiment 1:3wt%ZIF-8/PVA porous nanofiber membrane
By the methanol solution of the 200mL containing 2.6g zinc nitrate hexahydrate with containing 6.0g2-Methylimidazole. Magnetic agitation mixing 20h under 200mL methanol solution room temperature, mixing speed is 1000rpm, prepares ZIF-8 Nano-particle, 5000rpm centrifugation 20min also washes with methanol, and the nanocrystal obtained is true at 40 DEG C Empty dry 24h, obtains ZIF-8 nano-particle.
The ZIF-8 nano-particle obtained is taken 0.036g with 1.2g polyvinyl alcohol (PVA) and mixes the most molten In 18.764g deionized water, magnetic stirring apparatus stirs 20min the most swelling, then 80 DEG C of water-baths Heated and stirred 2h, mixing speed is 350rpm.It is cooled to room temperature and obtains finely dispersed spinning liquid.
The electrostatic spinning solution of gained is placed in 10mL syringe and carries out electrostatic spinning, spinning temperature is set 30 DEG C, humidity 40%RH, fltting speed 0.1mL/h, voltage is 28kv, and spinneret is to receptor distance For 18cm, obtain ZIF-8/ polyvinyl alcohol composite nano-fiber membrane.
The preparation of embodiment 2:1wt%ZIF-8/PVA porous nanofiber membrane
By the methanol solution of the 200mL containing 2.933g zinc nitrate hexahydrate with containing 6.489g2-methyl miaow Magnetic agitation mixing 22h under the 200mL methanol solution room temperature of azoles, mixing speed is 1100rpm, prepares ZIF-8 nano-particle, 7000rpm centrifugation 15min also washes with methanol, and the nanocrystal obtained is at 50 DEG C Vacuum 20h is dried, and obtains ZIF-8 nano-particle.
The ZIF-8 nano-particle obtained is taken 0.014g with 1.4g polyvinyl alcohol (PVA) and mixes the most molten In 18.596g deionized water, magnetic stirring apparatus stirs 30min the most swelling, then 85 DEG C of water-baths Heated and stirred 2.5h, mixing speed is 370rpm.It is cooled to room temperature and obtains finely dispersed spinning liquid.
The electrostatic spinning solution of gained is placed in 10mL syringe and carries out electrostatic spinning, spinning temperature is set 30 DEG C, humidity 40%RH, fltting speed 0.2mL/h, voltage is 25kv, and spinneret is to receptor distance For 18cm, obtain ZIF-8/ polyvinyl alcohol composite nano-fiber membrane.
The preparation of embodiment 3:2wt%ZIF-8/PVA porous nanofiber membrane
By the methanol solution of the 200mL containing 3.4g zinc nitrate hexahydrate with containing 7.0g2-Methylimidazole. Magnetic agitation mixing 24h under 200mL methanol solution room temperature, mixing speed is 1200rpm, prepares ZIF-8 Nano-particle 8000rpm centrifugation 10min also washes with methanol, and the nanocrystal obtained is in 60 DEG C of vacuum It is dried 12h, obtains ZIF-8 nano-particle.
The ZIF-8 nano-particle obtained is taken 0.032g with 1.6g polyvinyl alcohol (PVA) and mixes the most molten In 18.368g deionized water, magnetic stirring apparatus stirs 40min the most swelling, then 90 DEG C of water-baths Heated and stirred 3h, mixing speed is 400rpm.It is cooled to room temperature and obtains finely dispersed spinning liquid.
The electrostatic spinning solution of gained is placed in 10mL syringe and carries out electrostatic spinning, spinning temperature is set 30 DEG C, humidity 40%RH, fltting speed 0.3mL/h, voltage is 22kv, and spinneret is to receptor distance For 16cm, obtain ZIF-8/ polyvinyl alcohol composite nano-fiber membrane.
The adsorption test of embodiment 4:ZIF-8/ polyvinyl alcohol composite nano-fiber membrane
The Congo red solution of preparation 7mg/L, ZIF-8 0.02g embodiment 3 prepared respectively, contrast are in fact Execute 1gPVA nano fibrous membrane and the ZIF-8/PVA nanofiber of 1.02g embodiment 3 preparation of example 1 preparation Film joins in 100mL above-mentioned Congo red solution, is 308K in temperature, and rotating speed is 150r min-1Bar Constant temperature oscillation under part.In 5,10,20,30,40,60,90,120,180,240,300,360, Duration of oscillation samplings different for 600min, need to use 0.45 μm with 0.02g ZIF-8 again when processing by sample Filtering with microporous membrane after, measure its absorbance in 497nm;During nano fibrous membrane absorption research sampling not Need to use micro-pore-film filtration, other steps are carried out by above step.
Fig. 4 is under 298K, prepared by the PVA nano fibrous membrane of comparative example 1 preparation, embodiment 3 The ZIF-8/PVA composite nano-fiber membrane adsorption of Low Concentration Congo red solution of ZIF-8 and embodiment 3 preparation Absorption property curve chart, is dried 12h by sample ambient temperature in vacuum in vacuum drying oven before test, goes membrane removal On the moisture that volatilizees the most completely.
Crystal by the porous material prepared in the comparative example 1 in the present invention and embodiment 1~3 Structure carries out XRD sign and contrasts with the XRD figure of ZIF-8, and result is as it is shown in figure 1, can from Fig. 1 To find out, in embodiment 1~3, the ZIF-8/PVA porous nanofiber membrane of preparation remains comparative example 1 The characteristic peak of the PVA porous nanofiber membrane of preparation, and add the peak of ZIF-8, peak is strong and sharp-pointed, Show that it has good crystal structure, illustrate to be successfully prepared ZIF-8/ polyvinyl alcohol composite nano fiber Film.
The porous material prepared in the comparative example 1 of the present invention and embodiment 3 is carried out FTIR Characterizing, compared with the infrared spectrum of ZIF-8, result is as in figure 2 it is shown, embodiment as can be seen from Figure 2 The nano fibrous membrane of 3 preparations had both remained the functional group (2932cm of PVA-1And 1090cm-1) include again Characteristic group (the 1450cm of ZIF-8-1、690cm-1And 421cm-1), illustrate that ZIF-8 is successfully supported on On PVA.ZIF-8/PVA nano fibrous membrane is at 3350cm simultaneously-1Near hydroxyl vibration peak compared to ZIF-8 broadens, and illustrates have hydrogen bond to be formed between ZIF-8 and PVA.
Surface topography to the porous material prepared in the comparative example 1 of the present invention and embodiment 3 Carrying out SEM sign, result is as it is shown on figure 3, the ZIF-8/PVA nanometer as can be seen from Figure 3 prepared Fiber continuous uniform is evenly distributed in the fibre without beading, ZIF-8, solves ZIF-8 and is dispersed directly into water The shortcoming easily reunited in mutually, makes ZIF-8 will expose more avtive spot, sufficiently contacts with pollutant.
Fig. 4 be ZIF-8/PVA nano fibrous membrane and embodiment 3 preparation of embodiment 3 preparation ZIF-8 and The PVA nano fibrous membrane of the comparative example 1 preparation adsorption effect comparison diagram to low concentration Congo red.From Figure can be seen that PVA film to Congo red almost without adsorption effect.The suction of ZIF-8/PVA nano fibrous membrane The attached amount summation higher than the ZIF-8 under equal experiment condition with the single adsorbance of PVA film, illustrates receiving In rice fibrous membrane, ZIF-8 has more avtive spot to contact with pollutant, and ZIF-8 disperses more equal in film Even, ZIF-8/PVA porous nanofiber membrane possesses more preferable adsorption selectivity compared to simple ZIF-8, And be more easy to reclaim.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality Execute the restriction of example, the change made under other any spirit without departing from the present invention and principle, modification, Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (10)

1. the preparation method of a ZIF-8/ polyvinyl alcohol composite nano-fiber membrane, it is characterised in that include with Lower step:
(1) preparation of nanometer ZIF-8: by methanol solution and the methanol of 2-methylimidazole of soluble zinc salt Solution at room temperature mixes and reacts, and gained reactant liquor is centrifuged after terminating by reaction, takes off a layer solid, Cleaning with methanol, the solid after then cleaning is drying to obtain nanometer ZIF-8;
(2) preparation of electrostatic spinning solution: nanometer ZIF-8 step (1) obtained is with PVA mixed Merging and be dissolved in deionized water, stirring 20~40min makes it swelling, reacting by heating the most under agitation, Question response is cooled to room temperature and i.e. obtains finely dispersed electrostatic spinning solution after terminating;
(3) electrostatic spinning: be placed in 10mL syringe by the electrostatic spinning solution of step (2) gained Row electrostatic spinning, i.e. obtains ZIF-8/ polyvinyl alcohol composite nano-fiber membrane.
The preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 1, It is characterized in that:
The methanol solution of the soluble zinc salt described in step (1) refers to add in the methanol of every 1mL The soluble zinc salt of (0.013~0.017) g;The methanol solution of described 2-methylimidazole refers to every 1mL Methanol in add (0.030~0.035) g 2-methylimidazole;The methanol of soluble zinc salt used is molten The volume ratio of the methanol solution of liquid and 2-methylimidazole is 1:1.
The preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 1, It is characterized in that:
Soluble zinc salt described in step (1) is Zn (NO3)·6H2O。
The preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 1, It is characterized in that:
Reaction described in step (1) refers to stirring reaction 20~24h under the speed of 350~400rpm.
The preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 1, It is characterized in that:
Centrifugal described in step (1) refers to that centrifugal speed is 5000~8000rpm, and centrifugation time is 10~20min;
Dry referring to described in step (1) is vacuum dried 12~24h at 40~60 DEG C.
The preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 1, It is characterized in that:
Nanometer ZIF-8 used in step (2) and mass ratio 0.01:1~0.03:1 of polyvinyl alcohol, used The mass ratio of polyvinyl alcohol and deionized water be 0.06:1~0.08:1.
The preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 1, It is characterized in that:
Stirring described in step (2) refers both to be stirred with the speed of 350~400rpm.
The preparation method of ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 1, It is characterized in that:
The condition of the electrostatic spinning described in step (3) is temperature 30 DEG C, humidity 40%RH, advances speed Degree 0.1mL/h~0.3mL/h, voltage is 22kv~28kv, spinneret to receptor distance for 14cm~ 18cm。
9. the ZIF-8/ polyvinyl alcohol prepared according to the method described in any one of claim 1~8 is combined Nano fibrous membrane.
ZIF-8/ polyvinyl alcohol composite nano-fiber membrane the most according to claim 9 is in sewage disposal side The application in face.
CN201610485199.0A 2016-06-24 2016-06-24 ZIF-8/poly(vinyl alcohol) (PVA) composite nanofiber membrane as well as preparation method and application thereof Pending CN105951304A (en)

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CN106948087A (en) * 2017-02-28 2017-07-14 青岛大学 A kind of zeolite imidazole ester framework Nanocomposites tunica fibrosa and preparation method thereof
CN106988017A (en) * 2017-03-20 2017-07-28 南京理工大学 A kind of high adsorption porous compound film for being used to adsorb PM2.5
CN107142556A (en) * 2017-06-01 2017-09-08 济南大学 A kind of SnO2Preparation method of/ZnO composite micro-nanos rice fiber and products thereof
CN107503044A (en) * 2017-09-15 2017-12-22 南京工业大学 ZIF-8-loaded silica nanofiber membrane for air purification
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