CN103638827A - Iron-heavy metal nano particle/PVDF (polyvinylidene fluoride) hybrid membrane and preparation method thereof - Google Patents
Iron-heavy metal nano particle/PVDF (polyvinylidene fluoride) hybrid membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an iron-heavy metal nano particle/PVDF hybrid membrane and a preparation method thereof, which belongs to the field of polymer science and technology. The method comprises the steps of dispersing the PVDF powder and polyacrylic acid (PAA) microgel into N,N- dimethylformamide (DMF), and preparing a PVDF flat base membrane by adopting a phase inversion method; soaking the PVDF base membrane in an aqueous solution containing FeCl2 to react for a given time, then soaking the PVDF base membrane in an aqueous solution containing sodium borohydride to prepare a hybrid membrane containing FeO nano particles, and then soaking the hybrid membrane in an absolute ethyl alcohol aqueous solution containing heavy metal salt to prepare a hybrid membrane containing heavy metal-iron nano particles. The hybrid membrane can be used for degrading chlorinated organic compounds such as monochloroacetic acid, chlorophenesic acid, trichloro ethylene, tetrachlormethane and polychlorinated biphenyl and has high catalytic reaction activity. The preparation method is simple and easy to control, the cost is low, and the method is applicable to the mass production.
Description
Technical field
The present invention relates to a kind of polymeric hybrid membrane that contains iron-noble metal nano particles and microgel and preparation method thereof, belong to polymer science and technical field.This hybridized film can be used for the catalytic degradation of organic chloride in environment water, and it demonstrates high activity, good stability and excellent reusability in multiple catalyzed chemical reaction.
Background technology
During water pollutes, common are machine thing has 25 kinds, and wherein organochlorine has 10 kinds for thing (as trichloro-ethylene etc.).This class material toxicity is large, difficult degradation, once entered environment will cause long-term threat to the mankind and ecological environment thereof.In recent years, organochlorine has caused the very big attention of scientists on the impact of water quality for thing, and its degradation technique has also obtained broad research both domestic and external.The more processing method of research is to utilize nano metallic nickel powder dechlorination hydrogenation at present, thereby reaches degraded organochlorine for the object of thing.
Nano level metal iron particle has the advantages that particle size is little, specific area is large, reactivity is high, and organochlorine in water is obviously better than to common zeroth order reduced iron powder for the removal effect of thing.But because nano-sized metal particles easily occurs to reunite or the oxidized reactivity that causes reduces in preparation process, and it is retained in for a long time in suspension and is also unfavorable for recovery and reuse, and use cost is high.In order to improve reactivity, noble metal nano particles is loaded on zeroth order Fe nano particle.Quantity research shows greatly, and the bimetal nano particles being comprised of with iron noble metal is compared with pure iron nano particle, has the activity significantly improving.But noble metal-Fe nanometer particles exists reunion equally, and use cost is high, inconvenient operation, the defect such as is difficult for reusing.In order to improve the stability of nano particle and the convenience of use, noble metal-iron double metal nano particle is fixed on some carrier and becomes needs.Compare with homogeneous phase noble metal-Fe nanometer particles, the nano particle after load is easier to use, separation and is integrated in reactor apparatus, is also beneficial to the recovery and reuse of metal nanoparticle.At present, solid support thing that can dispersing nanometer particle mainly contains active carbon, metal oxide, zeolite or polymer etc.
Polymer film is the diffusion barrier with loose structure, and the specific area that it is high and a large amount of through-hole structures become desirable nanoparticulate carriers.If metal nanoparticle is loaded in fenestra, metal nanoparticle will have larger avtive spot and reactant molecule haptoreaction, improves reactivity; Meanwhile, product will more easily leave from nanoparticle surface, greatly reduces coated to avtive spot, improves reaction efficiency.
It is basement membrane that the present invention proposes to take polyacrylic acid (PAA) microgel/polyvinylidene fluoride flat film prepared by physical blending method, then utilizes metal ion to form the characteristic of complex compounds with polyelectrolyte and the principle of active metal displacement reaction is prepared hybridized film.In the introducing of the additive in the casting solution polymer film using polyacrylic acid microgel, improve membrane pore structure, improve fenestra volume, the scattering and permeating of intensified response thing, improves reaction rate.Utilize polyelectrolyte and intermetallic coordination, realize the high degree of dispersion of metal nanoparticle in basement membrane and fixing, overcome and assemble and loss defect.By electronation, iron and precious metal ion are replaced, the iron-noble metal nano particles obtaining has higher Activity and stabill.By controlling chargedization degree and the Fe of polyacrylic acid microgel
2+concentration can control the load capacity of Fe nano particle, and the load capacity of noble metal can realize by changing the concentration of time swap and precious metal ion.
Summary of the invention
The object of the invention is in order to solve existing Nanoscale Iron degraded organochlorine lowly for thing reactivity, reusability is poor, the problem that operating cost is large.The invention provides a kind of PVDF hybridized film that contains iron-noble metal nano particles and polyacrylic acid microgel, and the preparation method of above-mentioned hybridized film is provided.This film comprises PVDF, polyacrylic acid (PAA) microgel and iron-noble metal nano particles, and PAA gel and iron-noble metal nano particles are positioned at fenestra surface.
The technical scheme that the present invention solves described product preparation method technical problem is: the preparation method who designs a kind of Kynoar iron-precious metal nanoparticle hybrid film, the method is by Kynoar (PVDF) and polyacrylic acid (PAA) microgel physical blending masking, then utilize fenestra polyacrylic acid (PAA) microgel load iron-noble metal nano particles, comprise the steps:
(1). the preparation of polyacrylic acid microgel: by acrylic acid (AA) 8g, crosslinking agent N, N-methylene-bisacrylamide (MBAA) 0.1g, initiator potassium persulfate (K
2s
2o
4) 0.2g is dissolved in 100mL absolute ethyl alcohol, under nitrogen protection condition, 80 ℃ of isothermal reaction 8h, obtain PAA microgel;
(2) preparation of .PVDF flat sheet membrane:
(1) PAA microgel step 1 being obtained and Kynoar PVDF powder add in DMF DMF, disperse, and vacuum defoamation, makes the casting solution of transparent homogeneous;
(2) casting solution is poured on clean smooth glass plate, with glass bar, it is evenly scraped and makes liquid film, then immerse in distilled water, coagulation forming, obtains flat sheet membrane after soaking 12h in distilled water.
(3). iron-noble metal nano particles/PVDF hybridized film preparation: the dull and stereotyped basement membrane that step (2) is made immerses in the NaOH solution that concentration is 0.1～1.0mol/L and soaks 4h, then in distilled water, soak 2 hours, in pH value, be 2 again, the FeCl that concentration is 0.01～10mol/L
2in the aqueous solution, soak 4～12h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metallic; There is the flat sheet membrane of Fe metallic to put into the ethanol solution that concentration is 5～30mmol/L precious metal salt load, make Fe react 2h with precious metal ion, wash away impurity in anaerobic distilled water after, obtain iron-noble metal nano particles/PVDF hybridized film, room temperature preservation is in absolute ethyl alcohol.
The technical scheme that the present invention solves described product technology problem is: design a kind of PVDF flat sheet membrane, it is characterized in that this flat sheet membrane is by Kynoar and PAA microgel physical blending gained, then loads to iron-noble metal nano particles on fenestra PAA microgel.Physical blending and iron-noble metal nano particles carrying method are by preparation method's defined of the present invention.
Iron-noble metal nano particles of the present invention/PVDF hybridized film, PAA microgel is positioned at fenestra surface, iron-noble metal nano particles is positioned on fenestra gel, realizes the adjusting of and reactivity big or small to fenestra by the variation of PAA gel self structure, can environment pH value be changed and be responded.Outstanding advantages of the present invention is that PAA microgel and iron-noble metal nano particles are fixed in fenestra, thereby make the response function of iron-noble metal nano particles, the pH response function of PAA microgel, the filtering function of separation membrane ideally combines, by regulating the structure of PAA microgel in fenestra, regulating easily fenestra size, thereby regulate its reaction and filtering feature, is a kind of novel separation membrane.
Iron-noble metal nano particles of the present invention/PVDF hybridized film is prepared gained at normal temperature, there is process simple, operating cost is low, energy consumption is little, treating capacity is large, catalytic activity is high, the advantages such as repeat performance is good, and reproducibility is good, have wide using value at the organochlorine of degradation water middle and high concentration difficult degradation for object space face.
The specific embodiment
The present invention is a kind of iron-noble metal nano particles/PVDF hybridized film and preparation method thereof.This film is to select Kynoar (PVDF) as film forming main material, by PAA microgel and its physical blending, adopts the method for solution phase conversion film to make.Its design principle is that Kynoar (PVDF) and incompatible PAA microgel are formed to concentrated solution, and the mutual entanglement in solution phase conversion film process between macromolecule is fixed to PAA microgel in Kynoar; Simultaneously, incompatiblely between Kynoar and PAA microgel cause them in film forming procedure, to be separated, form the polyvinylidene fluoride separation membrane that PAA microgel is positioned at fenestra surface, then utilize carboxyl in PAA microgel and Fe effect to form the hybridized film of load Fe nano particle, further utilize precious metal ion and Fe
0reaction form iron-precious metal nanoparticle hybrid film.Preparation method of the present invention specifically selects polyacrylic acid microgel and Kynoar physical blending inversion of phases film forming, prepares Kynoar (PVDF) diffusion barrier, then by with Fe
2+complexing, through NaBH
4be reduced into the Fe nano particle being positioned on hybridized film fenestra microgel, further this film and precious metal salt effect obtained to iron-precious metal nanoparticle hybrid film subsequently.Because iron-noble metal nano particles is in fenestra high degree of dispersion, it can show high catalytic reaction activity; Meanwhile, the membrane material of through-hole structure makes nano particle catalysis efficiency high, easy to use, and recycling and reproducibility are good.In addition, owing to being positioned at the polyacrylic acid of fenestra, there is pH sensitiveness, the aperture of prepared film can change and change along with extraneous pH, can regulate by the variation of external condition the aperture of fenestra, thereby regulate the flux of film, film the performance such as hold back, be a kind of new Kynoar (PVDF) separation membrane.
In iron-noble metal nano particles of the present invention/PVDF hybridized film preservation process, will be immersed in absolute ethyl alcohol, object is to prevent that Zero-valent Iron nano particle is oxidized.
Although the method that the present invention narrates is preferentially selected Kynoar (PVDF) flat sheet membrane, but it is equally applicable to the film of other form, comprise tubular membrane, other form such as hollow-fibre membrane, and prepare corresponding iron-noble metal nano particles/PVDF hybridized film with this.
Introduce specific embodiments of the invention below:
Embodiment 1
A) preparation of polyacrylic acid microgel: by AA8g, crosslinking agent MBAA0.1g, initator K
2s
2o
40.2g is dissolved in 100mL absolute ethyl alcohol, and under nitrogen protection condition, 80 ℃ of isothermal reaction 8h carry out radical polymerization, obtain PAA microgel;
B) preparation of casting solution: the PAA microgel that step a) is made is 5% by PAA microgel mass fraction, 10%, 15%, 20%, 30%, 40% ratio and PVDF powder mix, then be dispersed in DMF, at 60 ℃, stir, standing and defoaming 2h under vacuum condition, obtaining mass concentration is the casting solution 10g of the transparent homogeneous of 15wt%;
C) preparation of the dull and stereotyped basement membrane of PVDF: by step b) gained casting solution is poured on clean smooth glass plate, with glass bar, it is evenly scraped and makes liquid film, then glass plate is immersed in distilled water, be frozen into flat sheet membrane, in distilled water, soak 12h, except residual solvent in striping;
D) 20cm Au-Fe nano particle/PVDF hybridized film preparation: by step c) making
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 0.1mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 1mol/L
2in the aqueous solution, soak 4h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 5mmol/L chlorauride (HAuCl
4) ethanol solution in, make Fe and Au
3+ionic reaction 2h, obtains Au-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 2
A) with embodiment 1
B) preparation of casting solution: the PAA microgel that step a) is made is 5% by PAA microgel mass fraction, 10%, 15%, 20%, 30%, 40% ratio and PVDF powder mix, then be dispersed in DMF, at 60 ℃, stir, standing and defoaming 2h under vacuum condition, obtaining mass concentration is the casting solution 10g of the transparent homogeneous of 20wt%;
C) with embodiment 1
D) with embodiment 1
Embodiment 3
A) with embodiment 1
B) the PAA microgel that the preparation of casting solution a) makes step is 5% by PAA microgel mass fraction, 10%, 15%, 20%, 30%, 40% ratio and PVDF powder mix, then be dispersed in DMF, at 60 ℃, stir, standing and defoaming 2h under vacuum condition, obtaining mass concentration is the casting solution 10g of the transparent homogeneous of 25wt%;
C) with embodiment 1
D) with embodiment 1
Embodiment 4
A) with embodiment 1
B) with embodiment 1
C) with embodiment 1
D) 20cm Au-Fe nano particle/PVDF hybridized film preparation: by step c) making
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 0.5mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 5mol/L
2in the aqueous solution, soak 8h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 10mmol/L HAuCl
4ethanol solution in, make Fe and Au
3+ionic reaction 2h, obtains Au-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 5
A) with embodiment 1
B) with embodiment 2
C) with embodiment 1
D) 20cm Au-Fe nano particle/PVDF hybridized film preparation: by step c) making
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 0.5mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 5mol/L
2in the aqueous solution, soak 8h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 15mmol/L HAuCl
4ethanol solution in, make Fe and Au
3+ionic reaction 2h, obtains Au-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 6
A) with embodiment 1
B) with embodiment 3
C) with embodiment 1
D) 20cm Au-Fe nano particle/PVDF hybridized film preparation: by step c) making
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 1mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 10mol/L
2in the aqueous solution, soak 12h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 20mmol/L chlorauride HAuCl
4ethanol solution in, make Fe and Au
3+ionic reaction 2h, obtains Au-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 7
A) with embodiment 1
B) with embodiment 1
C) with embodiment 1
D) Au-Fe nano particle/PVDF hybridized film preparation: by step c) make 20cm
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 1mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 10mol/L
2in the aqueous solution, soak 12h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 30mmol/L chlorauride HAuCl
4ethanol solution in, make Fe and Au
3+ionic reaction 2h, obtains Au-Fe nano particle PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 8
A) with embodiment 1
B) with embodiment 2
C) with embodiment 1
D) Au-Fe nano particle/PVDF hybridized film preparation: by step c) make 20cm
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 1mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 10mol/L
2in the aqueous solution, soak 12h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 25mmol/L chlorauride HAuCl
4ethanol solution in, make Fe and Au
3+ionic reaction 2h, obtains Au-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 9
A) with embodiment 1
B) with embodiment 3
C) with embodiment 1
D) Au-Fe nano particle/PVDF hybridized film preparation: by step c) make 20cm
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 1mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 10mol/L
2in the aqueous solution, soak 12h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 30mmol/L chlorauride HAuCl
4ethanol solution in, make Fe and Au
3+ionic reaction 2h, obtains Au-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 10
A) with embodiment 1
B) with embodiment 2
C) with embodiment 1
D) Ag-Fe nano particle/PVDF hybridized film preparation: by step c) make 20cm
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 0.1-1mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 5-15mol/L
2in the aqueous solution, soak 4-8h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 5-30mmol/LAgNO
3ethanol solution in, under lucifuge condition, make Fe and Ag
+ionic reaction 2h, obtains Ag-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
Embodiment 11
A) with embodiment 1
B) with embodiment 3
C) with embodiment 1
D) 20cm Pd-Fe nano particle/PVDF hybridized film preparation: by step c) making
2dull and stereotyped basement membrane immerse in the NaOH solution that 50ml concentration is 0.1-1mol/L and soak 4h, then in distilled water, soak 2 hours, in pH value, be then 2, the 50mL FeCl that concentration is 5-10mol/L
2in the aqueous solution, soak 4-12h, after the dull and stereotyped basement membrane after processing is fully cleaned with distilled water, put into the NaBH that 50mL concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into 50mL concentration load is 20mmol/L PdCl
2ethanol solution in, make Fe and pd
2+ionic reaction 2h, obtains Pd-Fe nano particle/PVDF hybridized film; The hybridized film making is washed away to impurity in anaerobic distilled water, and then room temperature preservation is in absolute ethyl alcohol.
After testing, the polyacrylic acid microgel that prepared hydridization fenestra contains 100～300nm, the particle diameter that contains dispersion on microgel is 10～30nm iron-noble metal nano particles, Fe is 20:1-5:1 with the element ratio of another kind of metal, fenestra aperture is 25～300nm, at 0.10MPa, under 20 ℃ of conditions, pure water flux is 30～500L/m
2h, and fenestra aperture and water flux and bovine serum albumin hold back with aqueous solution pH and change and change, and has pH sensitiveness.At 0.10MPa, the cross-flow mode of take at 20 ℃ is carried out catalytic performance test to the 40mL aqueous solution of trichloro-ethylene (concentration is 40mg/L), found that all 20cm
2film is within the processing time of 6h, and the dechlorination rate of trichloro-ethylene reaches 100%, shows that catalytic membrane has very high reactivity.In addition,, through repeating 5 tests, film does not have obvious activity decreased.Through long-time use lose activity after, the sour water that is 2 with pH by film processing, after method load iron-noble metal nano particles of describing in then according to the present invention, the reactivity of film can be recovered.In addition, under identical experiment condition, use the chlorinatedorganics such as all right catalysis monochloroacetic acid of this catalytic membrane, chlorophenesic acid, tetrachloromethane and Polychlorinated biphenyls, dechlorination rate reaches 83.2～100%.
Iron-noble metal nano particles/PVDF hybridized film that the present invention proposes and preparation method thereof, by embodiment, be described, person skilled obviously can change content as herein described or suitably change with combination and realize the present invention within not departing from content of the present invention, spirit and scope.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are all deemed to be included in spirit of the present invention, scope and content.
Claims (9)
1. iron-noble metal nano particles/PVDF hybridized film, is characterized in that this film is by iron-noble metal nano particles, and polyacrylic acid microgel and PVDF form.
2. iron-noble metal nano particles according to claim 1/PVDF hybridized film, is characterized in that polyacrylic acid microgel is positioned at fenestra surface, and particle diameter is 100～300nm.
3. iron-noble metal nano particles according to claim 1/PVDF hybridized film, is characterized in that Au-Fe bimetal nano particles is positioned on the microgel of fenestra, and particle size is 10-30nm.
4. iron-noble metal nano particles according to claim 1/PVDF hybridized film, is characterized in that Fe and the element ratio of another kind of metal are 20:1-5:1.
5. iron-noble metal nano particles according to claim 1/PVDF hybridized film, is characterized in that described noble metal is for gold, silver and palladium.
6. iron-noble metal nano particles according to claim 1/PVDF hybridized film, is characterized in that fenestra aperture is 25～300nm.
7. iron-noble metal nano particles according to claim 1/PVDF hybridized film, is characterized in that this film has the dechlorination degradation function to monochloroacetic acid, chlorophenesic acid, trichloro-ethylene, tetrachloromethane and Polychlorinated biphenyls.
8. iron-noble metal nano particles according to claim 1/PVDF hybridized film, is characterized in that this film has pH response.
9. iron-noble metal nano particles according to claim 1/PVDF hybridized film preparation method, is characterized in that the step preparation by the following method of this film:
(1). the preparation of polyacrylic acid microgel: by acrylic acid 8g, crosslinking agent N, N-methylene-bisacrylamide 0.1g, initiator potassium persulfate 0.2g is dissolved in 100mL absolute ethyl alcohol, and under nitrogen protection condition, 80 ℃ of isothermal reaction 8h, obtain PAA microgel;
(2) preparation of the dull and stereotyped basement membrane of .PVDF: the PAA microgel 1. step 1 being obtained and PVDF powder are scattered in DMF DMF, dissolve, and vacuum defoamation, makes casting solution; 2. casting solution is poured on clean smooth glass plate, with glass bar, it is evenly scraped and makes liquid film, then immerse in distilled water, coagulation forming, puts into distilled water and soaks 12h, obtains flat sheet membrane.
(3). iron-noble metal nano particles/PVDF hybridized film preparation: the flat sheet membrane that step (2) is made immerses in the NaOH solution that concentration is 0.1～1.0mol/L and soaks 4h, then in distilled water, soak 2 hours, in pH value, be 2 again, the FeCl that concentration is 0.01～10mol/L
2in the aqueous solution, soak 4～12h, after the flat sheet membrane after processing is fully cleaned with distilled water, put into the NaBH that concentration is 1.5g/L
4in the aqueous solution, reduce 30min, then put into the fully rinsing of anaerobic distilled water, obtain the flat sheet membrane of load Fe metal nanoparticle; Having the flat sheet membrane of Fe metal nanoparticle to put into concentration load is 5～30mmol/L HAuCl
4or AgNO
3or PdCl
2ethanol solution in, make Fe and Au
3+or Ag
+or Pd
2+reaction 2h, obtains iron-noble metal nano particles/PVDF hybridized film after washing away impurity in anaerobic distilled water.
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| CN103878028A (en) * | 2014-03-24 | 2014-06-25 | 哈尔滨师范大学 | Nanometer Pd/Fe/PVDF catalyst modified by means of in-situ polymerization and application of catalyst |
| CN107082889A (en) * | 2017-04-26 | 2017-08-22 | 华中科技大学 | A kind of Centimeter Level, intergranular are away from adjustable polymer grafting golden nanometer particle composite single layer film and preparation method thereof |
| CN108380222A (en) * | 2018-03-08 | 2018-08-10 | 大连大学 | A kind of method and its application of fixed noble metal catalyst active component |
| CN111672335A (en) * | 2020-06-03 | 2020-09-18 | 兰州大学 | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane |
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| CN103878028A (en) * | 2014-03-24 | 2014-06-25 | 哈尔滨师范大学 | Nanometer Pd/Fe/PVDF catalyst modified by means of in-situ polymerization and application of catalyst |
| CN107082889A (en) * | 2017-04-26 | 2017-08-22 | 华中科技大学 | A kind of Centimeter Level, intergranular are away from adjustable polymer grafting golden nanometer particle composite single layer film and preparation method thereof |
| CN107082889B (en) * | 2017-04-26 | 2019-06-18 | 华中科技大学 | A kind of Centimeter Level, grain polymer grafting gold nanoparticle composite single layer film adjustable in pitch and preparation method thereof |
| CN108380222A (en) * | 2018-03-08 | 2018-08-10 | 大连大学 | A kind of method and its application of fixed noble metal catalyst active component |
| CN108380222B (en) * | 2018-03-08 | 2020-10-09 | 大连大学 | Method for fixing active component of noble metal catalyst and application thereof |
| CN111672335A (en) * | 2020-06-03 | 2020-09-18 | 兰州大学 | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane |
| CN111672335B (en) * | 2020-06-03 | 2021-09-10 | 兰州大学 | Preparation method and application of CuO @ CuS/PVDF water treatment composite membrane |
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