CN104743549B - 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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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 thin film, particularly relate to a kind of non-laminar crosslinking-oxidization Graphene thin
Film and its preparation method and application.
Background technology
Along with the development of economic society, the process of oily waste water is increasingly becoming global threatening
Health and the problem of ecological environment, traditional separation method has air flotation, coagulation, absorption etc.,
But the usual inefficiency of these methods, is not suitable for the separation of oil hydrosol yet.And embrane method is as one
Kind of relatively new separation method is progressively paid close attention to by people, but due in separation process, film
Oil droplet is easily adsorbed on surface, causes serious fouling membrane, causes the drastically decline of flux, have impact on this skill
The practicality of art.Therefore the preparation of pollution-resistant membrane becomes a focus.
Graphene, since within 2004, occurring, has caused the close pass of various countries scientific research personnel at short notice
Note, the most therefore its finder Geim AK and Novoselov KS obtains Nobel Prize in 2010.Stone
Ink alkene is the graphite of monolayer, and due to physics, the chemical property of Graphene uniqueness, it is by widely
It is applied to electricity, optical field.But due to Van der Waals force strong between graphene sheet layer and π-π
Interacting, the separation of graphene sheet layer is extremely difficult.In order to solve this problem, people's chemistry
Graphite is converted into graphite oxide by means.The a large amount of oxygen-containing functional groups modified on graphite flake reduce interlayer
Captivation, hence in so that graphite oxide can be completely separated into the graphite oxide of monolayer in aqueous,
I.e. graphene oxide.
Recently, graphene oxide is the most more and more studied in the application in chemical separating field.Ratio
Such as absorption etc..Especially, due to the good film property of graphene oxide, abundant surface functional group with
And good water dispersible, its research in terms of membrance separation receives more and more attention, and sees document
(Li H,Song ZN,Zhang XJ,Huang Y,Li SG,Mao YT,et al.Ultrathin,
Molecular-Sieving Graphene Oxide Membranes for Selective Hydrogen
Separation.Science 2013,342:95-8；Han Y,Xu Z,Gao C.Ultrathin Graphene
Nanofiltration Membrane for Water Purification.Adv.Funct.Mater.
2013；23:3693-700.).These researchs are all based on the graphene oxide film of layer structure, utilize
Target separation system is sieved by the fluid channel between graphene oxide lamella.But due to stratiform oxygen
The evolving path in functionalized graphene is oversize, increases fluid resistance so that flux is the least.The most right
Needing high-throughout application, such as oil-water separation in some, layered graphite oxide alkene thin film cannot meet
Demand.
Summary of the invention
The invention provides the preparation method of a kind of non-laminar crosslinking-oxidization graphene film, be applicable to
The separation of oil hydrosol, has high flux and good antifouling property.
The preparation method of a kind of non-laminar crosslinking-oxidization graphene film, comprises the following steps:
(1) polynary ammonia or Amino End Group polymer being mixed with graphene oxide aqueous dispersions, dispersion is all
Even formation graphene oxide colloidal sol；
(2) graphene oxide colloidal sol prepared by step (1) is added drop-wise in substrate, at 70～90 DEG C
Seal after placing, obtain described non-laminar crosslinking-oxidization graphene film.
The present invention passes through sol-gal process, utilizes chemical reaction and electrostatic interaction to come graphite oxide
Alkene carries out cross-linking modified, epoxy radicals on graphene oxide and polynary ammonia or the amino of Amino End Group polymer
There is epoxy ring-opening reaction, and on carboxyl on graphene oxide and polynary ammonia or Amino End Group polymer
Amino generation electrostatic interaction, produce cross-linked structure, then prepare non-laminar by sol-gal process
Graphene oxide film.
As preferably, in step (1), graphene oxide in described graphene oxide aqueous dispersions
Mass concentration is 5～10mg/mL.
As preferably, in step (1), described polynary ammonia selected from ethylenediamine, propane diamine, butanediamine,
At least one in hexamethylene diamine；
Described Amino End Group polymer is selected from polymine, hyperbranched polyethyleneimine, chitosan, gathers
At least one in amide, ultrabranching polyamide；It is not limited to it is above preferred.
Further preferably, in step (1), described polynary ammonia or Amino End Group polymer and graphite oxide
The mass ratio of alkene is 0.1～1.
As preferably, when adding Amino End Group polymer, first by the pH value of graphene oxide aqueous dispersions
Regulation is to value regulation extremely > 10, prevent the Amino End Group polymer of follow-up addition from flocculation occurring in the reaction.
As preferably, the mass concentration of the aqueous solution of described polynary ammonia or Amino End Group polymer is
10～16mg/mL.
As preferably, in step (2), described substrate is selected from non-woven fabrics, micro-filtration membrane.
As preferably, in step (2), sealing standing time is 5～10h.Further preferably, 80 DEG C
Lower seal places 8h.
According in the non-laminar crosslinking-oxidization graphene film that said method prepares, graphene oxide
Nanoscale twins is got up by polynary ammonia or Amino End Group crosslinked polymer, and presents erratic unordered take
To, this thin film has super hydrophilic, the most superoleophobic character.
The invention also discloses described non-laminar crosslinking-oxidization graphene film to separate as oil hydrosol
Application.
As preferably, described oil hydrosol is toluene/water emulsion, normal hexane/aqueous emulsion, normal octane/water
Emulsion or Isopar G/ aqueous emulsion, profit volume ratio is 1:99.
Method of testing is the Filtration under the conditions of gravity, and utilizes TOC to analyze non-laminar crosslinking-oxidization stone
Ink alkene film is for the cutoff performance of oil hydrosol.
Compared with prior art, present invention have the advantage that
1, the preparation method technique of the present invention is simple and convenient to operate；
2, the non-laminar crosslinking-oxidization graphene film surface that prepared by the present invention has in a large number, interconnects mutually
The stannic oxide/graphene nano Particle Cluster connect, but in lack of alignment, this makes film surface at microcosmic angle
Under degree the most coarse, and it is observed that more small in these stannic oxide/graphene nano Particle Cluster
The overshooting shape structure of nanoscale；Therefore less compared with the water penetration resistance of lamellar graphite alkene thin film, often
Pressure, can realize efficiently separating multiple oil hydrosol；
3, the non-laminar crosslinking-oxidization graphene film that prepared by the present invention, has good under water environment
Stability, it is possible to prevent stannic oxide/graphene nano particle from splitting away off from film；There is high water
Flux and rejection, also have very prominent anti-fouling performance, it is possible to reuse simultaneously；And have
Super hydrophilic, the most superoleophobic character.
Accompanying drawing explanation
Fig. 1 is the sectional view of the non-laminar crosslinking-oxidization graphene film of embodiment 1 preparation；
Fig. 2 is the exterior view of the non-laminar crosslinking-oxidization graphene film of embodiment 1 preparation；
Fig. 3 be embodiment 1 preparation non-laminar crosslinking-oxidization graphene film water contact angle and under water oil connect
Feeler；
Fig. 4 is the separating effect of the non-laminar crosslinking-oxidization graphene film of embodiment 1 preparation.
Detailed description of the invention
Embodiment 1
By 16mg graphene oxide (GO) in 2ml deionized water ultrasonic 1.5 hours, obtain uniformly
Graphene oxide aqueous dispersions, add the sodium hydroxide solution of 4mol/L to pH=12.8, add
0.25ml concentration is hyperbranched polyethyleneimine (PEI) aqueous solution of 16mg/ml, is stirred vigorously formation
Graphene oxide colloidal sol, the nothing afterwards graphene oxide colloidal sol being added drop-wise in culture dish the most equably
Spin on cloth, culture dish is put in hermetically sealed can 80 DEG C process 8h after, filter cleaning with a large amount of clear water,
To remove remaining sodium hydroxide and unreacted hyperbranched polyethyleneimine, i.e. prepare non-laminar crosslinking
Graphene oxide film.
The cross section of non-laminar crosslinking-oxidization graphene film prepared by Fig. 1 and Fig. 2 respectively the present embodiment
Figure and exterior view, it can be seen that the cross section of non-laminar crosslinking-oxidization graphene film presents homogenizing
Spongiosis, thickness is 250 μm, much larger than the graphite oxide typically prepared by vacuum filtration process
Alkene thin film, this is because in non-laminar crosslinking-oxidization graphene film, GO nanoparticle be not with
Horizontal direction stacks mutually but remains the state of lack of alignment.
Fig. 3 is the water contact angle and under water of non-laminar crosslinking-oxidization graphene film prepared by the present embodiment
Oil contact angle, it can be seen that the water contact angle on film surface is 0 ° in atmosphere, oil droplet under water
Contact angle on film surface is 160 °.These results show non-laminar crosslinking-oxidization graphene film
Superhydrophilic and the most superoleophobic property.
The non-laminar crosslinking-oxidization graphene film of preparation is placed in Suction filtration device and carries out oil-water separation
Test.Experimentation is as follows: be first placed on the core of Suction filtration device by the thin film prepared, face
Upward；Then filter bowl is buckled on thin film, fixes with clip；Then oil hydrosol is added in filter bowl
Carry out oil-water separation experiment.Permeation flux, raw material and penetrating fluid organic carbon content is calculated by weighing method
Use TOC to analyze, be calculated permeation flux and the rejection of thin film accordingly.
Record the non-laminar graphene oxide film of PEI crosslinking to toluene/water emulsion, normal hexane/water and milk
The rejection of liquid, normal octane/aqueous emulsion and Isopar G/ aqueous emulsion is all more than 99.9%, and permeation flux divides
It is not 634,688,672 and 644Lm-2h-1(see Fig. 4 (a)).
From Fig. 4 (b), as a example by Isopar G/ aqueous emulsion, the non-laminar oxidation stone of PEI crosslinking
Ink alkene thin film is after circulation 10 times, and the rate of change of permeation flux maintains 1%.
Result shows that the non-laminar graphene oxide film that PEI prepared by the present embodiment cross-links has well
Oil-water separation performance.
Comparative example
By 16mg graphene oxide in 2ml deionized water ultrasonic 1.5 hours, aoxidized stone uniformly
Ink alkene aqueous dispersions, the sodium hydroxide solution adding 4mol/L to pH=12.8, addition 0.5ml concentration is
The ultrabranching polyamide aqueous solution of 16mg/ml, is stirred vigorously formation graphene oxide colloidal sol, afterwards will
Graphene oxide colloidal sol vacuum filtration on ultrafilter membrane, puts into 80 DEG C of process 8h in water afterwards, then with big
Amount clear water filters and cleans, and to remove remaining sodium hydroxide and unreacted ultrabranching polyamide, i.e. makes
Obtain stratiform crosslinking-oxidization graphene film.
Record this PEI crosslinking layered graphite oxide alkene film to toluene/water emulsion, normal hexane/aqueous emulsion,
The rejection of normal octane/aqueous emulsion and Isopar G/ aqueous emulsion is all more than 99.9%, and permeation flux is respectively
0.05,0.05,0.04 and 0.05Lm-2h-1。
The data of comparative example 1 understand, under normal pressure, and the layered graphite oxide alkene of common PEI crosslinking
Film does not has separating effect substantially to multiple oil hydrosol；And the PEI crosslinking that the application prepares is non-
Layered graphite oxide alkene thin film then has the oil-water separation performance of excellence.
Embodiment 2
By 16mg graphene oxide in 2ml deionized water ultrasonic 1.5 hours, aoxidized stone uniformly
Ink alkene aqueous dispersions, the sodium hydroxide solution adding 4mol/L to pH=12.8, addition 0.5ml concentration is
The ultrabranching polyamide aqueous solution of 16mg/ml, is stirred vigorously formation graphene oxide colloidal sol, afterwards will
On non-woven fabrics in graphene oxide colloidal sol slowly uniform slow dropping culture dish, culture dish is put into close
In sealed cans, 80 DEG C process after 8h, filter with a large amount of clear water and clean, with remove remaining sodium hydroxide with
Unreacted ultrabranching polyamide, i.e. prepares non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oil-water separation
Test.Experimentation is same as in Example 1.
Record the non-laminar graphene oxide membrane of this PEI crosslinking to toluene/water emulsion, normal hexane/water and milk
The rejection of liquid, normal octane/aqueous emulsion and Isopar G/ aqueous emulsion is all more than 99.9%, and permeation flux divides
It is not 621,632,654 and 649Lm-2h-1。
Embodiment 3
By 20mg graphene oxide in 2ml deionized water ultrasonic 1.5 hours, aoxidized stone uniformly
Ink alkene aqueous dispersions, adds the butanediamine aqueous solution that 0.25ml concentration is 16mg/ml, is stirred vigorously shape
Become graphene oxide colloidal sol, afterwards by the nothing in slow for graphene oxide colloidal sol uniform slow dropping culture dish
Spin on cloth, culture dish is put in hermetically sealed can 80 DEG C process 8h after, filter cleaning with a large amount of clear water,
To remove unreacted butanediamine, i.e. prepare non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oil-water separation
Test.Experimentation is same as in Example 1.
Record the non-laminar graphene oxide membrane of this PEI crosslinking to toluene/water emulsion, normal hexane/water and milk
The rejection of liquid, normal octane/aqueous emulsion and Isopar G/ aqueous emulsion is all more than 99.9%, and permeation flux divides
It is not 566,576,557 and 541Lm-2h-1。
In dispersion liquid, graphene oxide concentration is 5～10mg/ml.Polynary ammonia or Amino End Group polymer and oxygen
The mass ratio of functionalized graphene is 0.1～1.
Embodiment 4
By 10mg graphene oxide in 2ml deionized water ultrasonic 1.5 hours, aoxidized stone uniformly
Ink alkene aqueous dispersions, adding 1ml concentration is the chitosan aqueous solution of 10mg/ml, is stirred vigorously 30min,
Ultrasonic 15min under 200kHz afterwards, adds 0.06g medicine, stirs 30min, afterwards at 200kHz
Under ultrasonic 15min, stirring in CA micro-filtration membrane sucking filtration 18h, i.e. prepare the crosslinking-oxidization graphite of medicine carrying
Alkene thin film.
By 10mg graphene oxide in 2ml deionized water ultrasonic 1.5 hours, aoxidized stone uniformly
Ink alkene aqueous dispersions, adding 1ml concentration is the chitosan aqueous solution of 10mg/ml, is stirred vigorously formation oxygen
Functionalized graphene colloidal sol, afterwards by the non-woven fabrics in slow for graphene oxide colloidal sol uniform slow dropping culture dish
On, culture dish is put in hermetically sealed can after 80 DEG C of process 8h, with the filtration cleaning of a large amount of clear water, to remove
Remove unreacted chitosan, i.e. prepare non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oil-water separation
Test.Experimentation is same as in Example 1.
Record the non-laminar graphene oxide membrane of this PEI crosslinking to toluene/water emulsion, normal hexane/water and milk
The rejection of liquid, normal octane/aqueous emulsion and Isopar G/ aqueous emulsion is all more than 99.9%, and permeation flux divides
It is not 586,596,597 and 641Lm-2h-1。
Embodiment 5
By 18mg graphene oxide in 2ml deionized water ultrasonic 1.5 hours, aoxidized stone uniformly
Ink alkene aqueous dispersions, the sodium hydroxide solution adding 4mol/L to pH=12.8, addition 0.5ml concentration is
The ethylenediamine solution of 16mg/ml, is stirred vigorously formation graphene oxide colloidal sol, will aoxidize stone afterwards
On non-woven fabrics in the slow uniform slow dropping culture dish of ink alkene colloidal sol, culture dish is put in hermetically sealed can
After 80 DEG C process 8h, filter with a large amount of clear water and clean, to remove remaining sodium hydroxide and unreacted
Ethylenediamine, i.e. prepare non-laminar crosslinking-oxidization graphene film.
Prepared non-laminar crosslinking-oxidization graphene film is placed in Suction filtration device and carries out oil-water separation
Test.Experimentation is same as in Example 1.
Record the non-laminar graphene oxide membrane of this PEI crosslinking to toluene/water emulsion, normal hexane/water and milk
The rejection of liquid, normal octane/aqueous emulsion and Isopar G/ aqueous emulsion is all more than 99.9%, and permeation flux divides
It is not 641,672,654 and 659Lm-2h-1。
Claims (8)
1. a non-laminar crosslinking-oxidization graphene film application in oil hydrosol separates, it is special
Levying and be, described oil hydrosol includes toluene/water emulsion, normal hexane/aqueous emulsion, normal octane/water and milk
Liquid or Isopar G/ aqueous emulsion；
The preparation method of described non-laminar crosslinking-oxidization graphene film comprises the following steps:
(1) polynary ammonia or Amino End Group polymer being mixed with graphene oxide aqueous dispersions, dispersion is all
Even formation graphene oxide colloidal sol；
(2) graphene oxide colloidal sol prepared by step (1) is added drop-wise in substrate, at 70～90 DEG C
Seal after placing, obtain described non-laminar crosslinking-oxidization graphene film.
Non-laminar crosslinking-oxidization graphene film the most according to claim 1 divides at oil hydrosol
Application in from, it is characterised in that in step (1), oxygen in described graphene oxide aqueous dispersions
The mass concentration of functionalized graphene is 5～10mg/mL.
Non-laminar crosslinking-oxidization graphene film the most according to claim 1 divides at oil hydrosol
Application in from, it is characterised in that in step (1), described polynary ammonia selected from ethylenediamine, the third two
At least one in amine, butanediamine, hexamethylene diamine；
Described Amino End Group polymer is selected from polymine, hyperbranched polyethyleneimine, chitosan, gathers
At least one in amide, ultrabranching polyamide.
4. thin according to the non-laminar crosslinking-oxidization Graphene described in claims 1 to 3 any claim
Film oil hydrosol separate in application, it is characterised in that in step (1), described polynary ammonia or
Amino End Group polymer is 0.1～1 with the mass ratio of graphene oxide.
Non-laminar crosslinking-oxidization graphene film the most according to claim 4 divides at oil hydrosol
Application in from, it is characterised in that in step (1), first by the pH of graphene oxide aqueous dispersions
Value regulation is extremely > 10.
Non-laminar crosslinking-oxidization graphene film the most according to claim 1 divides at oil hydrosol
Application in from, it is characterised in that the quality of the aqueous solution of described polynary ammonia or Amino End Group polymer is dense
Degree is 10～16mg/mL.
Non-laminar crosslinking-oxidization graphene film the most according to claim 1 divides at oil hydrosol
Application in from, it is characterised in that in step (2), described substrate is selected from non-woven fabrics or microfiltration
Film.
Non-laminar crosslinking-oxidization graphene film the most according to claim 1 divides at oil hydrosol
Application in from, it is characterised in that in step (2), seal standing time be 5～10h.
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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 |
| CN107252635A (en) * | 2017-07-27 | 2017-10-17 | 徐州工程学院 | A kind of high stability graphene oxide membrane synthetic method |
| 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 |
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| 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 |
| CN112313169B (en) * | 2018-06-15 | 2021-12-21 | 港大科桥有限公司 | Three-dimensional porous graphene oxide-based membranes for stabilization of helical structures for ultrafast filtration |
| CN110743585B (en) * | 2019-11-20 | 2022-02-18 | 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 |
| US20230130300A1 (en) * | 2020-03-24 | 2023-04-27 | 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 |
| CN115245749A (en) * | 2021-12-10 | 2022-10-28 | 浙江理工大学 | Preparation method and application of super-hydrophilic-underwater super-oleophobic graphene hydrogel/stainless steel mesh composite oil-water separation membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948108A (en) * | 2010-10-02 | 2011-01-19 | 上海交通大学 | Optimized preparation method of oxidized graphite paper |
| CN103623709A (en) * | 2013-11-11 | 2014-03-12 | 华南理工大学 | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof |
| CN103736400A (en) * | 2014-01-06 | 2014-04-23 | 中国海洋大学 | Preparation method of graphene oxide composite nano filter membrane |
| CN104261392A (en) * | 2014-09-22 | 2015-01-07 | 东南大学 | Preparation method of borate ion crosslinked conductive graphene paper |
| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
-
2015
- 2015-03-18 CN CN201510119617.XA patent/CN104743549B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948108A (en) * | 2010-10-02 | 2011-01-19 | 上海交通大学 | Optimized preparation method of oxidized graphite paper |
| CN103623709A (en) * | 2013-11-11 | 2014-03-12 | 华南理工大学 | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof |
| CN103736400A (en) * | 2014-01-06 | 2014-04-23 | 中国海洋大学 | Preparation method of graphene oxide composite nano filter membrane |
| CN104261392A (en) * | 2014-09-22 | 2015-01-07 | 东南大学 | Preparation method of borate ion crosslinked conductive graphene paper |
| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
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