CN104743549A - Non-layered cross-linked graphene oxide film as well as preparation method and application thereof - Google Patents
Non-layered cross-linked graphene oxide film as well as preparation method and application thereof Download PDFInfo
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- CN104743549A CN104743549A CN201510119617.XA CN201510119617A CN104743549A CN 104743549 A CN104743549 A CN 104743549A CN 201510119617 A CN201510119617 A CN 201510119617A CN 104743549 A CN104743549 A CN 104743549A
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Abstract
The invention discloses a preparation method of a non-layered cross-linked graphene oxide film. The preparation method comprises the following steps: firstly mixing poly-ammonia or an amino-terminated polymer with a graphene oxide water dispersion solution; uniformly dispersing to form graphene oxide sol; dropwise adding the graphene oxide sol into a substrate; and hermetically arranging at the temperature of 70 to 90 DEG C to obtain the non-layered cross-linked graphene oxide film. In the non-layered cross-linked graphene oxide film prepared by the method disclosed by the invention, a graphene oxide nanometer plate layer is formed by crosslinking the poly-ammonia and the amino-terminated polymer and is in irregular disordered orientation; the non-layered cross-linked graphene oxide film has super-hydrophilic properties and super-oleophobic properties underwater, high throughput and good pollution resistance and is suitable for separation of oil and water emulsion at normal pressure.
Description
Technical field
The present invention relates to the preparation field of film, particularly relate to a kind of non-laminar crosslinking-oxidization graphene film and its preparation method and application.
Background technology
Along with the development of economic society, the process of oily(waste)water becomes a global problem threatening HUMAN HEALTH and ecotope day by day, traditional separation method has air flotation, coagulation, absorption etc., but the usual inefficiency of these methods, be not suitable for the separation of oil hydrosol yet.And embrane method progressively receives the concern of people as a kind of relatively novel separation method, but due in sepn process, oil droplet is easily adsorbed in film surface, causes serious fouling membrane, causes the sharply decline of flux, have impact on the practicality of this technology.Therefore the preparation of pollution-resistant membrane becomes a focus.
Graphene has caused the close attention of various countries scientific research personnel since occurring from 2004 at short notice, and therefore its discoverer Geim AK and Novoselov KS also obtains the Nobel prize in 2010.Graphene is the graphite of unimolecular layer, and due to physics, the chemical property of Graphene uniqueness, it is widely used in electricity, optical field.But because Van der Waals force strong between graphene sheet layer and π-π interact, the separation of graphene sheet layer is very difficult.In order to address this problem, graphite is converted into graphite oxide with chemical means by people.A large amount of oxygen-containing functional groups that graphite flake is modified reduce interlayer magnetism, therefore make graphite oxide can be separated into the graphite oxide of individual layer in aqueous completely, i.e. graphene oxide.
Recently, graphene oxide is also more and more studied in the application in chemical separating field.Such as absorption etc.Especially, due to film-forming properties, abundant surface functional group and good water dispersible that graphene oxide is good, its research in membrane sepn receives increasing concern, sees document (Li H, Song ZN, Zhang XJ, Huang Y, Li SG, Mao YT, et al.Ultrathin, Molecular-Sieving Graphene Oxide Membranes for Selective HydrogenSeparation.Science 2013,342:95-8; Han Y, Xu Z, Gao C.Ultrathin GrapheneNanofiltration Membrane for Water Purification.Adv.Funct.Mater.2013; 23:3693-700.).These researchs are all the graphene oxide films based on laminate structure, utilize the fluid channel between graphene oxide lamella to sieve target separation system.But because the evolving path in layered graphite oxide alkene is oversize, increase fluid resistance, make flux very little.Therefore need high-throughout application for some, such as oily water separation, layered graphite oxide alkene film cannot satisfy the demands.
Summary of the invention
The invention provides a kind of preparation method of non-laminar crosslinking-oxidization graphene film, be applicable to the separation of oil hydrosol, there is high-throughput and good antifouling property.
A preparation method for non-laminar crosslinking-oxidization graphene film, comprises the following steps:
(1) polynary ammonia or Amino End Group polymkeric substance are mixed with graphene oxide aqueous dispersions, be uniformly dispersed and form graphene oxide colloidal sol;
(2) be added drop-wise in substrate by graphene oxide colloidal sol prepared by step (1), 70 ~ 90 DEG C of lower seals obtain described non-laminar crosslinking-oxidization graphene film after placing.
The present invention passes through sol-gel method, chemical reaction and electrostatic interaction is utilized to carry out cross-linking modified to graphene oxide, the amino generation epoxy ring-opening reaction of the epoxy group(ing) on graphene oxide and polynary ammonia or Amino End Group polymkeric substance, and the amino generation electrostatic interaction on the carboxyl on graphene oxide and polynary ammonia or Amino End Group polymkeric substance, produce crosslinking structure, then prepare non-laminar graphene oxide film by sol-gel method.
As preferably, in step (1), in described graphene oxide aqueous dispersions, the mass concentration of graphene oxide is 5 ~ 10mg/mL.
As preferably, in step (1), described polynary ammonia is selected from least one in quadrol, propylene diamine, butanediamine, hexanediamine;
Described Amino End Group polymkeric substance is selected from least one in polymine, hyperbranched polyethyleneimine, chitosan, polymeric amide, ultrabranching polyamide; But be not limited in preferably above.
Further preferably, in step (1), the mass ratio of described polynary ammonia or Amino End Group polymkeric substance and graphene oxide is 0.1 ~ 1.
As preferably, when adding Amino End Group polymkeric substance, first the pH value of graphene oxide aqueous dispersions is adjusted to value and is adjusted to >10, prevent the follow-up Amino End Group polymkeric substance added from occurring flocculation in the reaction.
As preferably, the mass concentration of the aqueous solution of described polynary ammonia or Amino End Group polymkeric substance is 10 ~ 16mg/mL.
As preferably, in step (2), described substrate is selected from non-woven fabrics, microfiltration membrane.
As preferably, in step (2), sealing storage period is 5 ~ 10h.Further preferably, 80 DEG C of lower seals place 8h.
According in the non-laminar crosslinking-oxidization graphene film that aforesaid method prepares, stannic oxide/graphene nano lamella is got up by polynary ammonia or Amino End Group crosslinked polymer, and presents erratic disordered orientation, and this film has super hydrophilic, super thin oil properties under water.
The invention also discloses the application that described non-laminar crosslinking-oxidization graphene film is separated as oil hydrosol.
As preferably, described oil hydrosol is toluene/water emulsion, normal hexane/water miscible liquid, octane/water miscible liquid or Isopar G/ water miscible liquid, and profit volume ratio is 1:99.
Testing method is the filtration method under gravity condition, and utilizes TOC to analyze the cutoff performance of non-laminar crosslinking-oxidization graphene film for oil hydrosol.
Compared with prior art, tool of the present invention has the following advantages:
1, preparation method's technique of the present invention is simple, easy to operate;
2, the non-laminar crosslinking-oxidization graphene film surface that prepared by the present invention has a large amount of, interconnective stannic oxide/graphene nano Particle Cluster, but in lack of alignment, this makes film surface very coarse under microcosmic angle, and can observe the overshooting shape structure of more small nanoscale in these stannic oxide/graphene nano Particle Cluster; Therefore less compared with the water permeation resistance of lamellar graphite alkene film, at ambient pressure, the effective separation to multiple oil hydrosol can be realized;
3, the non-laminar crosslinking-oxidization graphene film prepared of the present invention, has satisfactory stability, can prevent stannic oxide/graphene nano particle from splitting away off from film under water surrounding; There is high water flux and rejection, also have very outstanding anti-fouling performance simultaneously, can reuse; And there is super hydrophilic, super thin oil properties under water.
Accompanying drawing explanation
Fig. 1 is the sectional view of non-laminar crosslinking-oxidization graphene film prepared by embodiment 1;
Fig. 2 is the exterior view of non-laminar crosslinking-oxidization graphene film prepared by embodiment 1;
Fig. 3 is water contact angle and the oily contact angle under water of non-laminar crosslinking-oxidization graphene film prepared by embodiment 1;
Fig. 4 is the separating effect of non-laminar crosslinking-oxidization graphene film prepared by embodiment 1.
Embodiment
Embodiment 1
By 16mg graphene oxide (GO) 2ml deionized water for ultrasonic 1.5 hours, obtain uniform graphene oxide aqueous dispersions, add the sodium hydroxide solution of 4mol/L to pH=12.8, add hyperbranched polyethyleneimine (PEI) aqueous solution that 0.25ml concentration is 16mg/ml, vigorous stirring forms graphene oxide colloidal sol, afterwards graphene oxide colloidal sol is slowly added drop-wise to equably on the non-woven fabrics in culture dish, after culture dish being put into sealed can 80 DEG C process 8h, cleaning is filtered with a large amount of clear water, to remove remaining sodium hydroxide and unreacted hyperbranched polyethyleneimine, i.e. obtained non-laminar crosslinking-oxidization graphene film.
Fig. 1 and Fig. 2 is respectively sectional view and the exterior view of non-laminar crosslinking-oxidization graphene film prepared by the present embodiment, as known in the figure, the cross section of non-laminar crosslinking-oxidization graphene film presents the spongy structure of homogeneous, thickness is 250 μm, much larger than the general graphene oxide film prepared by vacuum filtration process, this is because in non-laminar crosslinking-oxidization graphene film, GO nanoparticle is not stacking mutually with horizontal direction but remains the state of lack of alignment.
Fig. 3 is water contact angle and the oily contact angle under water of non-laminar crosslinking-oxidization graphene film prepared by the present embodiment, and as known in the figure, the contact angle of water on film surface is 0 ° in atmosphere, and the contact angle of oil droplet on film surface is 160 ° under water.These results show Superhydrophilic and the super oleophobic property under water of non-laminar crosslinking-oxidization graphene film.
The non-laminar crosslinking-oxidization graphene film of preparation is placed in Suction filtration device and carries out oily water separation test.Experimentation is as follows: be first placed on the core of Suction filtration device by the film prepared, and face upward; Then filter bowl is buckled on film, fixes with clip; Then oil hydrosol is added in filter bowl and carry out oily water separation experiment.Calculate permeation flux by weighing method, raw material and penetrating fluid organic carbon content adopt TOC to analyze, and calculate permeation flux and the rejection of film accordingly.
Record non-laminar graphene oxide film that PEI is cross-linked to the rejection of toluene/water emulsion, normal hexane/water miscible liquid, octane/water miscible liquid and Isopar G/ water miscible liquid all more than 99.9%, permeation flux is respectively 634,688,672 and 644Lm
-2h
-1(see Fig. 4 (a)).
From Fig. 4 (b), for Isopar G/ water miscible liquid, the crosslinked non-laminar graphene oxide film of PEI is through circulating after 10 times, and the velocity of variation of permeation flux maintains 1%.
Result shows the non-laminar graphene oxide film that PEI prepared by the present embodiment is cross-linked and has good oily water separation performance.
Comparative example
By 16mg graphene oxide 2ml deionized water for ultrasonic 1.5 hours, obtain uniform graphene oxide aqueous dispersions, add the sodium hydroxide solution of 4mol/L to pH=12.8, add the ultrabranching polyamide aqueous solution that 0.5ml concentration is 16mg/ml, vigorous stirring forms graphene oxide colloidal sol, afterwards by graphene oxide colloidal sol vacuum filtration on ultra-filtration membrane, put into 80 DEG C, water process 8h afterwards, cleaning is filtered again with a large amount of clear water, to remove remaining sodium hydroxide and unreacted ultrabranching polyamide, i.e. obtained stratiform crosslinking-oxidization graphene film.
Record layered graphite oxide alkene film that this PEI is cross-linked to the rejection of toluene/water emulsion, normal hexane/water miscible liquid, octane/water miscible liquid and Isopar G/ water miscible liquid all more than 99.9%, permeation flux is respectively 0.05,0.05,0.04 and 0.05Lm
-2h
-1.
The data of comparative example 1 are known, and under normal pressure, the layered graphite oxide alkene film that common PEI is cross-linked does not have separating effect substantially to multiple oil hydrosol; The non-laminar graphene oxide film that the PEI that the application prepares is cross-linked then has excellent oily water separation performance.
Embodiment 2
By 16mg graphene oxide 2ml deionized water for ultrasonic 1.5 hours, obtain uniform graphene oxide aqueous dispersions, add the sodium hydroxide solution of 4mol/L to pH=12.8, add the ultrabranching polyamide aqueous solution that 0.5ml concentration is 16mg/ml, vigorous stirring forms graphene oxide colloidal sol, afterwards by graphene oxide the colloidal sol slowly uniform slow non-woven fabrics dripped in culture dish, after culture dish being put into sealed can 80 DEG C process 8h, cleaning is filtered with a large amount of clear water, to remove remaining sodium hydroxide and unreacted ultrabranching polyamide, i.e. obtained non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oily water separation test.Experimentation is identical with embodiment 1.
Record non-laminar graphene oxide membrane that this PEI is cross-linked to the rejection of toluene/water emulsion, normal hexane/water miscible liquid, octane/water miscible liquid and Isopar G/ water miscible liquid all more than 99.9%, permeation flux is respectively 621,632,654 and 649Lm
-2h
-1.
Embodiment 3
By 20mg graphene oxide 2ml deionized water for ultrasonic 1.5 hours, obtain uniform graphene oxide aqueous dispersions, add the butanediamine aqueous solution that 0.25ml concentration is 16mg/ml, vigorous stirring forms graphene oxide colloidal sol, afterwards graphene oxide colloidal sol is delayed on the uniform slow non-woven fabrics dripped in culture dish, after culture dish being put into sealed can 80 DEG C process 8h, filter cleaning with a large amount of clear water, to remove unreacted butanediamine, i.e. obtained non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oily water separation test.Experimentation is identical with embodiment 1.
Record non-laminar graphene oxide membrane that this PEI is cross-linked to the rejection of toluene/water emulsion, normal hexane/water miscible liquid, octane/water miscible liquid and Isopar G/ water miscible liquid all more than 99.9%, permeation flux is respectively 566,576,557 and 541Lm
-2h
-1.
In dispersion liquid, graphene oxide concentration is 5 ~ 10mg/ml.The mass ratio of polynary ammonia or Amino End Group polymkeric substance and graphene oxide is 0.1 ~ 1.
Embodiment 4
By 10mg graphene oxide 2ml deionized water for ultrasonic 1.5 hours, obtain uniform graphene oxide aqueous dispersions, add the chitosan aqueous solution that 1ml concentration is 10mg/ml, vigorous stirring 30min, ultrasonic 15min under 200kHz, adds 0.06g medicine afterwards, stir 30min, ultrasonic 15min under 200kHz afterwards, is stirred in suction filtration 18h in CA microfiltration membrane, i.e. the crosslinking-oxidization graphene film of obtained medicine carrying.
By 10mg graphene oxide 2ml deionized water for ultrasonic 1.5 hours, obtain uniform graphene oxide aqueous dispersions, add the chitosan aqueous solution that 1ml concentration is 10mg/ml, vigorous stirring forms graphene oxide colloidal sol, afterwards graphene oxide colloidal sol is delayed on the uniform slow non-woven fabrics dripped in culture dish, after culture dish being put into sealed can 80 DEG C process 8h, filter cleaning with a large amount of clear water, to remove unreacted chitosan, i.e. obtained non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oily water separation test.Experimentation is identical with embodiment 1.
Record non-laminar graphene oxide membrane that this PEI is cross-linked to the rejection of toluene/water emulsion, normal hexane/water miscible liquid, octane/water miscible liquid and Isopar G/ water miscible liquid all more than 99.9%, permeation flux is respectively 586,596,597 and 641Lm
-2h
-1.
Embodiment 5
By 18mg graphene oxide 2ml deionized water for ultrasonic 1.5 hours, obtain uniform graphene oxide aqueous dispersions, add the sodium hydroxide solution of 4mol/L to pH=12.8, add the ethylenediamine solution that 0.5ml concentration is 16mg/ml, vigorous stirring forms graphene oxide colloidal sol, afterwards graphene oxide colloidal sol is delayed on the uniform slow non-woven fabrics dripped in culture dish, after culture dish being put into sealed can 80 DEG C process 8h, cleaning is filtered with a large amount of clear water, to remove remaining sodium hydroxide and unreacted quadrol, i.e. obtained non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oily water separation test.Experimentation is identical with embodiment 1.
Record non-laminar graphene oxide membrane that this PEI is cross-linked to the rejection of toluene/water emulsion, normal hexane/water miscible liquid, octane/water miscible liquid and Isopar G/ water miscible liquid all more than 99.9%, permeation flux is respectively 641,672,654 and 659Lm
-2h
-1.
Claims (10)
1. a preparation method for non-laminar crosslinking-oxidization graphene film, is characterized in that, comprises the following steps:
(1) polynary ammonia or Amino End Group polymkeric substance are mixed with graphene oxide aqueous dispersions, be uniformly dispersed and form graphene oxide colloidal sol;
(2) be added drop-wise in substrate by graphene oxide colloidal sol prepared by step (1), 70 ~ 90 DEG C of lower seals obtain described non-laminar crosslinking-oxidization graphene film after placing.
2. the preparation method of non-laminar crosslinking-oxidization graphene film according to claim 1, is characterized in that, in step (1), in described graphene oxide aqueous dispersions, the mass concentration of graphene oxide is 5 ~ 10mg/mL.
3. the preparation method of non-laminar crosslinking-oxidization graphene film according to claim 1, is characterized in that, in step (1), described polynary ammonia is selected from least one in quadrol, propylene diamine, butanediamine, hexanediamine;
Described Amino End Group polymkeric substance is selected from least one in polymine, hyperbranched polyethyleneimine, chitosan, polymeric amide, ultrabranching polyamide.
4. the preparation method of the non-laminar crosslinking-oxidization graphene film according to the arbitrary claim of claims 1 to 3, is characterized in that, in step (1), the mass ratio of described polynary ammonia or Amino End Group polymkeric substance and graphene oxide is 0.1 ~ 1.
5. the preparation method of non-laminar crosslinking-oxidization graphene film according to claim 4, is characterized in that, in step (1), first the pH value of graphene oxide aqueous dispersions is adjusted to >10.
6. the preparation method of non-laminar crosslinking-oxidization graphene film according to claim 1, is characterized in that, the mass concentration of the aqueous solution of described polynary ammonia or Amino End Group polymkeric substance is 10 ~ 16mg/mL.
7. the preparation method of non-laminar crosslinking-oxidization graphene film according to claim 1, is characterized in that, in step (2), described substrate is selected from non-woven fabrics or microfiltration membrane.
8. the preparation method of non-laminar crosslinking-oxidization graphene film according to claim 1, is characterized in that, in step (2), sealing storage period is 5 ~ 10h.
9. the non-laminar crosslinking-oxidization graphene film prepared of a method according to claim 1.
10. the application of a non-laminar crosslinking-oxidization graphene film according to claim 9 in oily water separation.
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| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
| CN107051229A (en) * | 2017-04-17 | 2017-08-18 | 江苏大学 | A kind of preparation method and its usage of graphene oxide/titanium dioxide stratiform composite membrane of polyethyleneimine crosslinking |
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| CN106744834A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of aqueous-dispersible conductive Graphene |
| CN107051229A (en) * | 2017-04-17 | 2017-08-18 | 江苏大学 | A kind of preparation method and its usage of graphene oxide/titanium dioxide stratiform composite membrane of polyethyleneimine crosslinking |
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| CN107737530B (en) * | 2017-11-15 | 2020-11-06 | 北京工业大学 | Modified graphene oxide/hyperbranched polymer composite membrane, preparation method and application |
| CN107737530A (en) * | 2017-11-15 | 2018-02-27 | 北京工业大学 | A kind of modified graphene oxide/dissaving polymer composite membrane, preparation method and application |
| CN110354696A (en) * | 2018-04-09 | 2019-10-22 | 天津大学 | A kind of flexible high-pass graphene oxide/silica composite films and preparation method thereof |
| CN110354696B (en) * | 2018-04-09 | 2021-11-23 | 天津大学 | Flexible high-flux graphene oxide/silicon dioxide composite membrane and preparation method thereof |
| CN108671764A (en) * | 2018-06-13 | 2018-10-19 | 洛阳纳诺环保科技有限公司 | A kind of method that one-step method prepares super hydrophilic/underwater superoleophobic water-oil separationg film |
| WO2019238119A1 (en) * | 2018-06-15 | 2019-12-19 | The University Of Hong Kong | Spiral-structured three dimensional porous graphene oxide-based membrane for stable ultrafast filtration |
| CN110743585A (en) * | 2019-11-20 | 2020-02-04 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
| CN113318597A (en) * | 2020-02-28 | 2021-08-31 | 天津大学 | Method for preparing graphene oxide membrane through covalent crosslinking of layer |
| WO2021194418A1 (en) * | 2020-03-24 | 2021-09-30 | National University Of Singapore | A semi-permeable membrane |
| CN112980083A (en) * | 2021-03-29 | 2021-06-18 | 鸡西瀚宇石墨烯科技有限公司 | Preparation method and preparation device of graphene antibacterial reinforced plastic |
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