CN105727751A - Application of high-dispersity hybridization antibacterial agent in aspect of ultrafiltration membrane improvement - Google Patents
Application of high-dispersity hybridization antibacterial agent in aspect of ultrafiltration membrane improvement Download PDFInfo
- Publication number
- CN105727751A CN105727751A CN201610263980.3A CN201610263980A CN105727751A CN 105727751 A CN105727751 A CN 105727751A CN 201610263980 A CN201610263980 A CN 201610263980A CN 105727751 A CN105727751 A CN 105727751A
- Authority
- CN
- China
- Prior art keywords
- application
- dispersity
- graphene oxide
- antibacterial agent
- ultrafiltration membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 11
- 238000009396 hybridization Methods 0.000 title abstract description 10
- 230000006872 improvement Effects 0.000 title abstract description 4
- 239000003242 anti bacterial agent Substances 0.000 title abstract 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 11
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005345 coagulation Methods 0.000 claims abstract description 6
- 230000015271 coagulation Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 241000446313 Lamella Species 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 239000002068 microbial inoculum Substances 0.000 claims description 3
- -1 sodium alkoxide Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000002033 PVDF binder Substances 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004873 anchoring Methods 0.000 abstract 1
- 238000000614 phase inversion technique Methods 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 230000009467 reduction Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 230000002070 germicidal effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 241000305071 Enterobacterales Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
Abstract
The invention discloses application of a high-dispersity hybridization antibacterial agent in aspect of ultrafiltration membrane improvement. The high-dispersity hybridization antibacterial agent is a nanometer hybridization material formed by anchoring silver nanoparticles to a graphene slice layer. The application of the high-dispersity hybridization antibacterial agent for ultrafiltration membrane improvement comprises the steps that firstly, the high-dispersity hybridization antibacterial agent is added into N,N dimethylacetamide or N,N dimethylformamide or dimethyl sulfoxide, ultrasonography is performed to obtain a uniform dispersion agent, polyvinylidene fluoride or polyether sulfone is added into the dispersion agent, stirring is performed at the temperature of 55-65 DEG C to obtain a uniform casting membrane solution, standing is performed for defoaming for 6-12 h, pure water is adopted as a coagulation bath, and an immerged phase-inversion method is adopted for preparing a modified ultrafiltration membrane. The high-dispersity hybridization antibacterial agent has the good dispersity in water and a solvent, the good compatibility of the high-dispersity hybridization antibacterial agent and a membrane matrix is achieved, the high-dispersity hybridization antibacterial agent can be applied to modifying the ultrafiltration membrane, the application method is simple, and the obtained modified ultrafiltration membrane is good in performance.
Description
Technical field
The invention belongs to nano material technology application, be specifically related to a kind of polymolecularity hydridization antibacterial modified at ultrafilter membrane
The application of aspect.
Background technology
The development of nanotechnology, opens the ground zero of nano silver antibacterial materials application.As a kind of emerging functional material,
The unique physico-chemical character that nanometer silver has.Preparing constitutionally stable nano silver composite material needs some with unique properties
Carrier, graphene oxide has bigger serface and a high chemical stability, can produce cooperative effect with nanometer silver again, improve
The overall fungistatic effect of composite, is preferable nano-silver loaded matrix.Additionally, Graphene has good bio-compatible
Property, biology will not be produced toxic and side effects as antibacterial.Graphene oxide is rich in a large amount of oxygen-content active groups, as receiving
Rice silver supporting matrix, can not only give full play to the cooperative effect of the two, and can become stabilizer and the Anchor Agent of nanoparticle,
It is suitable as biological antibiotic material.
Nanometer silver composite material can be used for functional adsorbent, and functional membrane is modified, but overwhelming majority nanometer additive system
Standby additional reducing agent and the stabilizer of being required for, to control the growth of Nano silver grain, seldom can adapt for concrete should being used as
Modification.
Chinese patent (Authorization Notice No.: CN102125056 B) discloses the system of a kind of silver/graphene antimicrobial composite material
Preparation Method, with reduced form graphene oxide-polystyrene sulphuric acid sodium as nanoparticulate carriers with reducing agent, polystyrene sulphuric acid sodium
As water soluble dispersing agent, AgNO3For reduction presoma, the silver/graphite alkene by reflux heat reduction preparation bio-safety is antibacterial
Composite, but the early stage of the method needs strong reductant hydrazine hydrate reduction graphene oxide, and experiment condition controls strict,
Requiring height, process is complicated, and for being applied to separate film, process is loaded down with trivial details.
Sun et al. is with sodium citrate as reducing agent, and graphene oxide is nanoparticulate carriers, and AgNO3 is reduction presoma,
By high-temperature hot reduction preparation GO-AgNPs, then with GO-AgNPs suspension as filtrate, will by the method filtered
GO-AgNPs is deposited on CA micro-filtration membrane surface, resisting microbial contamination for CA film modified (X.-F.Sun, et al.,
Graphene oxide–silver nanoparticle membrane for biofouling control and water purification,
Chemical Engineering Journal,281(2015)53-59.).GO-AgNPs prepared by this additional reducing agent at water
Middle good dispersion, but it is directly deposited film surface, in water separates application, active component is easy to run off.
Vatanpour et al. is with sodium citrate for thermal reduction agent, and graphene oxide hydrogel is nanoparticulate carriers, AgNO3
For reduction presoma, by the high-temperature hot reduction preparation nano combined additive of GO/Ag, then this additive is joined
In PES/DMAc/PVP hybrid system, by phase separation prepare antibacterial film (V.Vatanpour, et al.,
Fabrication and characterization of anti-fouling and anti-bacterial Ag-loaded graphene
oxide/polyethersulfone mixed matrix membrane,Journal of Industrial and Engineering
Chemistry,30(2015)342-352.).Modified Membrane prepared by the method, anti-microbial property has and largely improves, the parent of film
Aqueous improves.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of polymolecularity hydridization antibacterial at ultrafilter membrane
Application in terms of Gai Xing.The hydridization antibacterial of the present invention and has good dispersibility in solvent in water, has very well with membrane matrix
The compatibility, can be applicable to modified ultrafiltration membrane.
Technical scheme is specifically described as follows.
The present invention provides the application in terms of modified ultrafiltration membrane of a kind of polymolecularity hydridization antibacterial, and described polymolecularity hydridization resists
In microbial inoculum, Nano silver grain is stably anchored on graphene oxide lamella, forms sandwich structure or nucleocapsid structure, silver nanoparticle
The particle diameter of particle is between 50-150nm.
In the present invention, apply the application process at modified ultrafiltration membrane as follows polymolecularity hydridization antibacterial:
Polymolecularity hydridization antibacterial is joined N, in N dimethyl acetamide, DMF or dimethyl sulfoxide,
Ultrasonic 1～3h obtains uniform dispersion liquid, then adds Kynoar or polyether sulfone in dispersion liquid, stirs at a temperature of 55-65 DEG C
Mix the 6～14h uniform casting solutions of acquisition, stand froth breaking 6～12h, then with pure water as coagulation bath, immersion precipitation phase inversion process system
For obtaining modified ultrafiltration membrane；Wherein: in casting solution, the mass percentage concentration of polymolecularity hydridization antibacterial is 0.05～2%,
The mass percent concentration of polyether sulfone is 15～20%.
In the present invention, the preparation method of described polymolecularity hydridization antibacterial is specific as follows:
(1) first use airtight oxidizing process oxidation expanded graphite to obtain graphite oxide, then gained graphite oxide is joined nothing
In water-ethanol, ultrasonic stripping 1.5～2.5h, obtains homodisperse graphene oxide/alcohol dispersion liquid；Washing is dried again, uses water
Graphene oxide/the aqueous dispersions of preparation high degree of dispersion；
(2) in graphene oxide/aqueous dispersions, AgNO is added3Solution, ultrasonic 0.5～2h, add water and be diluted to 2～5 times,
It is subsequently adding dispersant and aqueous slkali, reacts 0.5～3h after adding at a temperature of 60～120 DEG C, treat that solution colour is become by brown brown
After yellowish-brown, continuing insulation 4～8h, be finally centrifuged, wash and be dried, i.e. secure satisfactory grades scattered property hydridization antibacterial.
Preferably, in step (2), graphene oxide and AgNO3Mass ratio be 4:1～1:1.
Preferably, in step (2), the mass ratio of graphene oxide, dispersant and alkali is 1:(0.05～0.5): (0.5～1).
Preferably, in step (2), described dispersant is PVP, and alkali is KOH, NaOH or sodium alkoxide.
Preferably, the concentration of graphene oxide/aqueous dispersions is 0.5～2.5mg/mL, AgNO3The concentration of solution is
1～10mmol/L.
Further, the present invention also provides for the application in terms of preparation Modified Membrane of the above-mentioned polymolecularity hydridization antibacterial.Preferably,
Application process is as follows:
Polymolecularity hydridization antibacterial is joined N, N dimethyl acetamide (DMAC) or N, N-dimethylformamide
(DMF), in dimethyl sulfoxide (DMSO), ultrasonic 1～3h obtains uniform dispersion liquid, then adds poly-in dispersion liquid
Vinylidene or polyether sulfone, the stirring 6～14h uniform casting solutions of acquisition at a temperature of 55-65 DEG C, standing froth breaking 6～12h, then with
Pure water is coagulation bath, immersion precipitation phase inversion process film forming, wherein: in casting solution, and the quality hundred of polymolecularity hydridization antibacterial
Point concentration is 0.05～2%, and the mass percent concentration of polyether sulfone is 15～20%.
Preferably, in immersion precipitation phase inversion process, coagulation bath temperature 20～40 DEG C.
Compared to the prior art, beneficial effects of the present invention is as follows:
Doing dispersant with PVP in the present invention, GO does reducing agent and Anchor Agent, and under the conditions of alkalescence, local reduction way is prepared for height
It is modified that scattered composite nano germicide is applied to ultrafilter membrane；The polymolecularity hydridization antibacterial of the present invention, uses alkali to be used as
On the one hand the pretreating agent of GO in GO-Ag preparation process, is that the hydroxyl on graphene oxide lamella is activated under the conditions of alkalescence
Changing into semiquinone and have reproducibility, on the other hand on graphene oxide, other oxy radicals are not destroyed, and are Ag+Stablize
Agent, moreover it is possible to keeping the dispersibility of Graphene, good dispersibility is conducive to its application in terms of membrane modifying.The high score of the present invention
Dissipate property hydridization antibacterial and and solvent has good dispersibility in water, have the good compatibility with membrane matrix, it is possible to for dividing
Modified preparation from film.Meanwhile, the Modified Membrane function admirable prepared.
Accompanying drawing explanation
Fig. 1 is the XRD figure of embodiment 1 gained GO, GO-Ag.
Fig. 2 is the infared spectrum of embodiment 1-4 gained GO, GO-Ag.
Fig. 3 is the SEM figure of the dispersion liquid of embodiment 3,4 gained GO, GO-Ag；Wherein: a is GO dispersion liquid, b
For the SEM figure of the dispersion liquid of embodiment 3 gained GO-Ag, c and d is the dispersion liquid of embodiment 4 gained GO-Ag
SEM schemes.
Fig. 4 is the SEM figure of Application Example gained antibacterial film, a and b is the surface SEM figure of gained antibacterial film, c and d
Cross section SEM for gained antibacterial film schemes.
Detailed description of the invention
The present invention is further described below in conjunction with the accompanying drawings.Technical solution of the present invention is not limited to being embodied as of act set forth below
Mode, also includes the combination in any between each detailed description of the invention.
Embodiment 1
Take 50mL, the 1mg/mL ultrasonic 0.5h of graphene oxide/aqueous dispersions, in this dispersion liquid, then add 50mL,
2×10-3The AgNO of mol/L3Solution, is diluted with water to 250mL after ultrasonic 0.5h, then by 5mL, 0.1mol/L's
KOH solution adds above-mentioned mixed liquor, and magnetic agitation lower 90 DEG C of oil baths reaction 2h, solution colour is become after yellowish-brown from brown
It is incubated a period of time at 60 DEG C.Gained solution centrifugal, washing, i.e. obtain composite nano germicide GO-Ag after drying.Fig. 1 is
The XRD figure of embodiment 1 gained GO, GO-Ag, the graphene oxide of preparation and being divided by X-ray diffraction of GO-Ag
Analysis characteristic diffraction peak crystalline substance picture composition, sweep limits is 2 θ=0～70 °, and the XRD of GO occurs (001) crystalline substance about 2 θ=10 °
Region feature peak, the XRD of GO in 2 θ=37 °, 45 °, 57 ° of (111) (200) (220) crystal face features that nanometer silver occurs
Peak.Prove prepared by the success of nanometer silver.In Fig. 2, GO-Ag1 curve is the infrared spectrogram of the material that embodiment 1 obtains.
Embodiment 2
Implement step with embodiment 1, AgNO3The amount of solution is 100mL, 2 × 10-3Mol/L, ultrasonic time 1.5h,
The amount of KOH solution is 7mL, 0.1mol/L.In Fig. 2, GO-Ag2 curve is the infrared spectrum of the material that embodiment 2 obtains
Figure.
Embodiment 3
Implement step with embodiment 1, AgNO3The amount of solution is 100mL, 2 × 10-3Mol/L, the amount of KOH solution is
7mL, 0.1mol/L, 100 DEG C of oil bath reaction 1.5h.In Fig. 2, GO-Ag3 curve is the infrared of the material that obtains of embodiment 3
Spectrogram.
Embodiment 4
Implement step with embodiment 1, AgNO3The amount of solution is 100mL, 2 × 10-3Mol/L, adds in mixed liquor
10wt%PVP, the amount of KOH solution is 7mL, 0.1mol/L.In Fig. 2, GO-Ag4 curve is the material that embodiment 4 obtains
The infrared spectrogram of material.
Application Example 1
Adding in DMAC by the antibacterial GO-Ag obtained in embodiment, ultrasonic 4h obtains uniform dispersion, to dividing
Dissipating and add PES in liquid, at 60 DEG C, mechanical agitation 8h obtains uniform casting solution, after standing froth breaking 8h, and immersion precipitation inversion of phases
Method film forming, wherein GO-Ag Yu PES accounts for the mass percentage concentration of total casting solution and is respectively 0～0.70wt% and 18wt%.
Application Example 2
Adding in DMF by obtaining antibacterial GO-Ag in embodiment, ultrasonic 2h obtains uniform dispersion, to dispersion liquid
Middle addition PVDF, at 60 DEG C, mechanical agitation 10h obtains uniform casting solution, after standing froth breaking 12h, immersion precipitation inversion of phases
Method film forming, wherein GO-Ag Yu PVDF accounts for the mass percentage concentration of total casting solution and is respectively 0～0.70wt% and 18wt%.
Antibacterial henchnmrk test
(1) dispersibility analysis experiment: the GO-Ag antibacterial of preparation in 0.05g embodiment is dissolved in 20mL deionized water respectively,
Dehydrated alcohol, N,N-dimethylacetamide, DMF, in dimethyl sulfoxide, ultrasonic a period of time observes GO-Ag
Dispersion effect.
(2) antibacterial contact experiment: GO-Ag antibacterial embodiment prepared is used for modified separation film, by separating the antibacterial of film
Effect evaluates the antibacterial effect of antibacterial.The Modified Membrane of different antimicrobial levels is measured Modified Membrane pair by inhibition zone algoscopy
Colibacillary antibacterial effect.
Experimental result is as follows:
Equivalent GO-Ag at 20mL deionized water, dehydrated alcohol, N,N-dimethylacetamide, DMF,
Dimethyl sulfoxide is completely dispersed required time and is respectively 10min, 30min, 50min, 30min, 50min.
In Application Example 2 GO-Ag content be 0,0.05,0.15,0.45, the PVDF Modified Membrane of 0.60wt.% is to greatly
The inhibition zone of enterobacteria is respectively 0mm, 0.40mm, 0.80mm, 1.0mm, 1.4mm.
In Application Example, 2 compare the former film of PVDF, the minimum reduction of contact angle 10 °, and a small amount of additive is used for the modification of film,
Film surface hydrophilicity and antibacterial effect are obvious.
In sum, be can be seen that by the XRD figure of GO and GO-Ag that the XRD of GO (001) occurs about 2 θ=10 °
Crystal face characteristic peak, the XRD of GO is in 2 θ=37 °, and 45 °, 57 ° occur that (111) (200) (220) crystal face of nanometer silver is special
Levy peak, it was demonstrated that prepared by the success of nanometer silver.In Fig. 3, GO and GO-Ag dispersion liquid SEM schemes it is observed that Ag is uniform
It is embedded on GO lamella, and the GO-Ag adding dispersant PVP is embedded on lamella, more stable be conducive to into one
Step is applied for membrane modifying.The infared spectrum contrast of Fig. 2 embodiment 1-4 gained GO, GO-Ag, 3400cm-1Place's correspondence
The association absworption peak of hydroxyl, 1650cm-1Under corresponding carbonyl absorption peak, and different condition, carbonyl peak absorption intensity is different, it was demonstrated that
The reproducibility of GO is with reducing degree different.Surface and cross section SEM figure by film can be seen that the nano hybridization of preparation resists
Microbial inoculum is used for membrane modifying, can obtain the film pattern of uniform pore diameter, and the hydrophilic of film, flux and anti-microbial property are all improved.
The above is only the citing of embodiments of the present invention, it is noted that for those skilled in the art
For, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement and modification, these improve and modification
Also should be regarded as protection scope of the present invention.
Claims (8)
1. the polymolecularity hydridization antibacterial application in terms of ultrafilter membrane modification, it is characterised in that described polymolecularity hydridization resists
In microbial inoculum, Nano silver grain is stably anchored on graphene oxide lamella, forms sandwich structure or nucleocapsid structure, silver nanoparticle
The particle diameter of particle is between 50-150nm.
Application the most according to claim 1, it is characterised in that application process is as follows:
Polymolecularity hydridization antibacterial is joined N, in N dimethyl acetamide, DMF or dimethyl sulfoxide,
Ultrasonic 1～3h obtains uniform dispersion liquid, then adds Kynoar or polyether sulfone in dispersion liquid, stirs at a temperature of 55-65 DEG C
Mix the 6～14h uniform casting solutions of acquisition, stand froth breaking 6～12h, then with pure water as coagulation bath, immersion precipitation phase inversion process system
For obtaining modified ultrafiltration membrane；Wherein: in casting solution, the mass percentage concentration of polymolecularity hydridization antibacterial is 0.05～2%,
The mass percent concentration of polyether sulfone is 15～20%.
Application the most according to claim 1, it is characterised in that in immersion precipitation phase inversion process, coagulation bath temperature 20～40 DEG C.
Application the most according to claim 1 and 2, it is characterised in that the preparation method of described polymolecularity hydridization antibacterial
Specific as follows:
(1) first use airtight oxidizing process oxidation expanded graphite to obtain graphite oxide, then gained graphite oxide is joined nothing
In water-ethanol, ultrasonic stripping 1.5～2.5h, obtains homodisperse graphene oxide/alcohol dispersion liquid；Washing is dried again, uses water
Graphene oxide/the aqueous dispersions of preparation high degree of dispersion；
(2) in graphene oxide/aqueous dispersions, AgNO is added3Solution, ultrasonic 0.5～2h, add water and be diluted to 2～5 times, so
Rear addition dispersant and aqueous slkali, react 0.5～3h, treat that solution colour is become from brown brown at a temperature of 60～120 DEG C after adding
After yellowish-brown, continuing insulation 4～8h, be finally centrifuged, wash and be dried, i.e. secure satisfactory grades scattered property hydridization antibacterial.
Application the most according to claim 4, it is characterised in that in step (2), graphene oxide and AgNO3Matter
Amount ratio is 4:1～1:1.
Application the most according to claim 4, it is characterised in that in step (2), graphene oxide, dispersant and alkali
Mass ratio is 1:(0.05～0.5): (0.5～1).
Application the most according to claim 4, it is characterised in that in step (2), described dispersant is PVP, and alkali is
KOH, NaOH or sodium alkoxide.
Application the most according to claim 4, it is characterised in that the concentration of graphene oxide/aqueous dispersions is
0.5～2.5mg/mL, AgNO3The concentration of solution is 1～10mmol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610263980.3A CN105727751B (en) | 2016-04-26 | 2016-04-26 | A kind of application of polymolecularity hydridization antibacterial agent in terms of ultrafiltration membrane modifying |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610263980.3A CN105727751B (en) | 2016-04-26 | 2016-04-26 | A kind of application of polymolecularity hydridization antibacterial agent in terms of ultrafiltration membrane modifying |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105727751A true CN105727751A (en) | 2016-07-06 |
| CN105727751B CN105727751B (en) | 2019-07-23 |
Family
ID=56285587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610263980.3A Expired - Fee Related CN105727751B (en) | 2016-04-26 | 2016-04-26 | A kind of application of polymolecularity hydridization antibacterial agent in terms of ultrafiltration membrane modifying |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105727751B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111450635A (en) * | 2020-04-09 | 2020-07-28 | 中科第三极(安徽)技术研究院有限公司 | Multilayer antibacterial nanofiber air purification filter membrane and preparation process thereof |
| CN114832643A (en) * | 2022-05-14 | 2022-08-02 | 阿克菲姆膜材(嘉兴)有限公司 | Preparation method of high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05148116A (en) * | 1991-09-27 | 1993-06-15 | Sumitomo Cement Co Ltd | Antibacterial mildew-proofing composition and its production |
| CN105214502A (en) * | 2015-09-18 | 2016-01-06 | 浙江工商大学 | A kind of Nano Silver/Graphene/polyvinyl alcohol mixing matrix membrane and preparation method thereof |
| CN105233706A (en) * | 2015-09-23 | 2016-01-13 | 三达膜科技（厦门）有限公司 | Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof |
-
2016
- 2016-04-26 CN CN201610263980.3A patent/CN105727751B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05148116A (en) * | 1991-09-27 | 1993-06-15 | Sumitomo Cement Co Ltd | Antibacterial mildew-proofing composition and its production |
| CN105214502A (en) * | 2015-09-18 | 2016-01-06 | 浙江工商大学 | A kind of Nano Silver/Graphene/polyvinyl alcohol mixing matrix membrane and preparation method thereof |
| CN105233706A (en) * | 2015-09-23 | 2016-01-13 | 三达膜科技（厦门）有限公司 | Oxidized graphene metal/metallic oxide nanoparticle modified hollow fiber ultrafiltration membrane, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JINGQI TIAN ET AL: "Environmentally Friendly, One-Pot Synthesis of Ag Nanoparticle-Decorated Reduced Graphene Oxide Composites and Their Application to Photocurrent Generation", 《INORGANIC CHEMISTRY》 * |
| VAHID VATANPOUR,ET AL.: "Fabrication and characterization of anti-fouling and anti-bacterial Ag-loaded graphene oxide/polyethersulfone mixed matrix membrane", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111450635A (en) * | 2020-04-09 | 2020-07-28 | 中科第三极(安徽)技术研究院有限公司 | Multilayer antibacterial nanofiber air purification filter membrane and preparation process thereof |
| CN114832643A (en) * | 2022-05-14 | 2022-08-02 | 阿克菲姆膜材(嘉兴)有限公司 | Preparation method of high-strength long-acting antioxidant polyvinylidene fluoride hollow fiber membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105727751B (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nasrollahi et al. | Preparation and characterization of a novel polyethersulfone (PES) ultrafiltration membrane modified with a CuO/ZnO nanocomposite to improve permeability and antifouling properties | |
| Ayyaru et al. | Application of sulfonic acid group functionalized graphene oxide to improve hydrophilicity, permeability, and antifouling of PVDF nanocomposite ultrafiltration membranes | |
| Pang et al. | Preparation and characterization of ZrO2/PES hybrid ultrafiltration membrane with uniform ZrO2 nanoparticles | |
| Dong et al. | Antifouling enhancement of poly (vinylidene fluoride) microfiltration membrane by adding Mg (OH) 2 nanoparticles | |
| Zhao et al. | Improving permeability and antifouling performance of polyethersulfone ultrafiltration membrane by incorporation of ZnO-DMF dispersion containing nano-ZnO and polyvinylpyrrolidone | |
| Irfan et al. | Surface modification and performance enhancement of nano-hybrid f-MWCNT/PVP90/PES hemodialysis membranes | |
| Rahimpour et al. | Novel functionalized carbon nanotubes for improving the surface properties and performance of polyethersulfone (PES) membrane | |
| CN102743983B (en) | Nano-grade porous ceramic composite nano-filtration membrane and preparation method thereof | |
| Li et al. | Effect of TiO2 nanoparticles on the surface morphology and performance of microporous PES membrane | |
| Hwang et al. | The properties and filtration efficiency of activated carbon polymer composite membranes for the removal of humic acid | |
| CN102743984B (en) | Nano porous ceramics composite reverse osmosis membrane and preparation method | |
| Liao et al. | Synthesis and characterization of low content of different SiO2 materials composite poly (vinylidene fluoride) ultrafiltration membranes | |
| CN105457504A (en) | Novel titanium dioxide nano-particle/polymer hybrid membrane and preparation method thereof | |
| Liu et al. | A novel PES-TiO2 hollow fiber hybrid membrane prepared via sol-gel process assisted reverse thermally induced phase separation (RTIPS) method | |
| CN109019745A (en) | A kind of preparation method improving multi-functional hybridized film particulate load amount | |
| Zhang et al. | Development of phosphorylated silica nanotubes (PSNTs)/polyvinylidene fluoride (PVDF) composite membranes for wastewater treatment | |
| CN102068925B (en) | Preparation method of polyaniline nano composite film | |
| CN106031847B (en) | A kind of preparation method for adulterating inorganic/organic nano particle forward osmosis membrane | |
| Pang et al. | In situ preparation of Al-containing PVDF ultrafiltration membrane via sol–gel process | |
| CN102728240A (en) | Novel polyvinylidene fluoride film as well as preparation method and application thereof | |
| CN103801201A (en) | Method for preparing organic-inorganic nano-composite membranes by using layered inorganic nano particles | |
| CN110141975A (en) | A kind of multi-walled carbon nanotube-polyacrylonitrile (MWCNT-PAN) composite hyperfiltration membrane and preparation method thereof | |
| CN107051208B (en) | Doping Kynoar mixed-matrix ultrafiltration membrane and its preparation is blended in three-dimensional structure nano-complex | |
| Ma et al. | Hydrophilic PAA-g-MWCNT/TiO2@ PES nano-matrix composite membranes: Anti-fouling, antibacterial and photocatalytic | |
| CN107362698A (en) | A kind of preparation method and applications of durable hydrophilic property polyvinylidene fluoride film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190723 |