CN112604510B - Graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane - Google Patents
Graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane Download PDFInfo
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- CN112604510B CN112604510B CN202011630901.0A CN202011630901A CN112604510B CN 112604510 B CN112604510 B CN 112604510B CN 202011630901 A CN202011630901 A CN 202011630901A CN 112604510 B CN112604510 B CN 112604510B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a graphene oxide-carbon quantum dot composite hydrophilic and oleophobic membrane and a preparation method thereof, and belongs to the technical field of material preparation. According to the invention, graphene oxide and carbon quantum dots are effectively compounded under a certain condition to obtain a stably dispersed graphene oxide-carbon quantum dot composite sheet, and the composite sheet is prepared into a thin film material with hydrophilic and oleophobic properties through suction filtration. The composite membrane combines the hydrophilic and oleophobic properties of the graphene oxide and the carbon quantum dots, has high self-cleaning property, is simple in preparation method, cheap and easily available in raw materials, easy to adjust and beneficial to large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a graphene oxide-carbon quantum dot composite hydrophilic and oleophobic membrane and a preparation method thereof.
Background
The leakage of crude oil in the process of mining, transporting and storing, the discharge of industrial and domestic oily sewage and the like bring great harm to the environment and ecological balance, and the purification of the oily sewage leads the oil-water separation technology to be more and more concerned by people.
The hydrophilic oleophobic material can effectively reduce the adhesion of oil drops on the surface, is beneficial to the recovery and enrichment of oil, and has positive effect on the pollution resistance of the substrate material. The graphene and the derivatives thereof have good film-forming property, and can form thin film coating materials on the surfaces of different substrates; meanwhile, the special surface properties of the carbon-based nanosheets also show excellent performance in the aspect of designing and preparing the amphiphobic interface material. As a derivative material of graphene, the graphene oxide has abundant functional groups on the surface, so that the material has excellent hydrophilic performance; however, these surface functional groups have poor stability and are easily reduced by external influences. The benzene ring structure recovered by reduction endows graphene oxide with certain oleophylic property, which brings limitation to the application of using graphene oxide as a thin film coating material in the aspects of hydrophily and lipophobicity.
The surface modification not only can stabilize the graphene oxide, but also can reasonably modify the surface property by introducing the specific functional material. However, in most of the current researches, the surface modification of graphene oxide, such as grafting organic small molecules, loading inorganic nanoparticles, and the like, easily causes the agglomeration of the composite material, which provides a great obstacle for the effective processing of the graphene oxide-based thin film coating structure. Therefore, a suitable surface modification material is selected to prepare a relatively stable composite dispersion system, and the preparation method is very important for constructing the graphene oxide film with the oleophobic property.
Disclosure of Invention
The invention aims to provide a graphene oxide-carbon quantum dot composite hydrophilic and oleophobic membrane and a preparation method thereof, which combine the properties of graphene oxide and carbon quantum dots, have good hydrophilic and oleophobic characteristics, are simple in preparation method, cheap and easily available in raw materials, are beneficial to large-scale industrial production, and have remarkable economic and social benefits.
In order to realize the purpose, the invention adopts the following technical scheme:
a graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) dispersing graphene oxide and carbon quantum dots in water according to a certain proportion to form a composite suspension;
(2) adjusting the pH value of the composite suspension to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and carrying out suction filtration to form the graphene oxide-quantum dot composite membrane.
Wherein the mass ratio of the graphene oxide to the carbon quantum dots used in the step (1) is 1: 0.4-1: 2.
And (3) adjusting the pH value of the suspension liquid to 9-12 in the step (2).
When in suction filtration in the step (3), controlling the content of graphene oxide in the carbon quantum dot-graphene oxide composite sheet suspension poured in per square filtration area to be 0.1-2.0 g; the pressure during the suction filtration is preferably above 50 mbar.
The contact angle of the obtained composite hydrophilic oleophobic membrane to water is less than 40 degrees, the contact angle to oil is greater than 120 degrees, and the composite hydrophilic oleophobic membrane has obvious hydrophilic oleophobic performance.
The invention has the beneficial effects that:
(1) the thin film material constructed by the graphene oxide-carbon quantum dot composite sheet has good hydrophilic and oleophobic properties, and can achieve a good oil-water separation effect.
(2) The invention adjusts the structure and performance of the composite membrane material by simply adjusting the proportion of the graphene oxide and the carbon quantum dots, the pH value and the using amount of the composite sheet during suction filtration, is favorable for large-scale industrial production, and has very high practical value and application prospect.
Drawings
Fig. 1 is a contact angle test chart of the graphene oxide-carbon quantum dot composite hydrophilic and oleophobic membrane prepared in example 5 for water (a) and oil (B).
Detailed Description
A graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) adding graphene oxide and carbon quantum dots into water according to the mass ratio of 1: 0.4-1: 2, and dispersing the graphene oxide and the carbon quantum dots by stirring, ultrasonic and other methods to form flocculent composite suspension;
(2) adjusting the pH value of the composite suspension to 9-12 by adding alkali to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and (3) padding a filter membrane in the filter, and performing suction filtration on the composite sheet suspension according to the amount of adding the composite sheet suspension containing 0.1-2.0 g of graphene oxide per square meter of filter area to form the graphene oxide-quantum dot composite membrane.
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
A graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) adding graphene oxide and carbon quantum dots into water according to the mass ratio of 1:0.4, and performing ultrasonic treatment to form a flocculent composite suspension;
(2) ammonia water or sodium hydroxide is added to adjust the pH value of the composite suspension to 10, so as to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and (3) padding a filter membrane in the filter, adding the amount of the composite sheet suspension containing 0.1 g of graphene oxide per square meter of filter area, and performing suction filtration on the composite sheet suspension to form the graphene oxide-quantum dot composite membrane.
And testing the contact angle of the obtained graphene oxide-quantum dot particle composite membrane on water and oil by using a contact angle instrument. The contact angle of the obtained graphene oxide-quantum dot particle composite membrane to water is 32 degrees, the contact angle to oil is 128 degrees, and the graphene oxide-quantum dot particle composite membrane is proved to have good hydrophilic and oleophobic performances.
Example 2
A graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) adding graphene oxide and carbon quantum dots into water according to the mass ratio of 1:0.5, and performing ultrasonic treatment to form a flocculent composite suspension;
(2) adjusting the pH value of the composite suspension to 11 by adding ammonia water or sodium hydroxide to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and (3) padding a filter membrane in the filter, adding the amount of the composite sheet suspension containing 0.5 g of graphene oxide per square meter of filter area, and performing suction filtration on the composite sheet suspension to form the graphene oxide-quantum dot composite membrane.
And testing the contact angle of the obtained graphene oxide-quantum dot particle composite membrane on water and oil by using a contact angle instrument. The contact angle of the obtained graphene oxide-quantum dot particle composite membrane to water is 37 degrees, the contact angle to oil is 138 degrees, and the graphene oxide-quantum dot particle composite membrane is proved to have good hydrophilic and oleophobic performances.
Example 3
A graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) adding graphene oxide and carbon quantum dots into water according to the mass ratio of 1:1, and performing ultrasonic treatment to form a flocculent composite suspension;
(2) adjusting the pH value of the composite suspension to 9 by adding ammonia water or sodium hydroxide to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and (3) padding a filter membrane in the filter, adding the amount of the composite sheet suspension containing 1.0 g of graphene oxide according to the filtering area per square meter, and performing suction filtration on the composite sheet suspension to form the graphene oxide-quantum dot composite membrane.
And testing the contact angle of the obtained graphene oxide-quantum dot particle composite membrane on water and the contact angle on oil by using a contact angle instrument. The contact angle of the obtained graphene oxide-quantum dot particle composite membrane to water is 30 degrees, the contact angle to oil is 142 degrees, and the graphene oxide-quantum dot particle composite membrane is proved to have good hydrophilic and oleophobic performances.
Example 4
A graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) adding graphene oxide and carbon quantum dots into water according to the mass ratio of 1:1.5, and performing ultrasonic treatment to form a flocculent composite suspension;
(2) adjusting the pH value of the composite suspension to 10 by adding ammonia water or sodium hydroxide to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and (3) padding a filter membrane in the filter, adding the amount of the composite sheet suspension containing 2.0 g of graphene oxide per square meter of filter area, and performing suction filtration on the composite sheet suspension to form the graphene oxide-quantum dot composite membrane.
And testing the contact angle of the obtained graphene oxide-quantum dot particle composite membrane on water and the contact angle on oil by using a contact angle instrument. The contact angle of the obtained graphene oxide-quantum dot particle composite membrane to water is 28 degrees, the contact angle to oil is 144 degrees, and the graphene oxide-quantum dot particle composite membrane is proved to have good hydrophilic and oleophobic performances.
Example 5
A graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) adding graphene oxide and carbon quantum dots into water according to the mass ratio of 1:0.5, and performing ultrasonic treatment to form a flocculent composite suspension;
(2) ammonia water or sodium hydroxide is added to adjust the pH value of the composite suspension to 12, so as to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and (3) padding a filter membrane in the filter, adding the amount of the composite sheet suspension containing 0.3 g of graphene oxide according to the filtering area per square meter, and performing suction filtration on the composite sheet suspension to form the graphene oxide-quantum dot particle composite membrane.
The contact angle of the obtained graphene oxide-quantum dot particle composite membrane on water and the contact angle on oil were measured by using a contact angle instrument, and the results are shown in fig. 1. As can be seen from figure 1, the contact angle of the obtained graphene oxide-quantum dot particle composite membrane to water is 33 degrees, and the contact angle to oil is 135 degrees, so that the graphene oxide-quantum dot particle composite membrane has good hydrophilic and oleophobic performances.
Example 6
A graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is prepared by the following steps:
(1) adding graphene oxide and carbon quantum dots into water according to the mass ratio of 1:1, and performing ultrasonic treatment to form a flocculent composite suspension;
(2) ammonia water or sodium hydroxide is added to adjust the pH value of the composite suspension to 10, so as to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) and (3) padding a filter membrane in the filter, adding the amount of the composite sheet suspension containing 0.3 g of graphene oxide per square meter of filter area, and performing suction filtration on the composite sheet suspension to form the graphene oxide-quantum dot composite membrane.
And testing the contact angle of the obtained graphene oxide-quantum dot particle composite membrane on water and the contact angle on oil by using a contact angle instrument. The contact angle of the obtained graphene oxide-quantum dot particle composite membrane to water is 29 degrees, and the contact angle to oil is 144 degrees, so that the graphene oxide-quantum dot particle composite membrane has good hydrophilic and oleophobic performances.
Comparative example
Graphene oxide and carbon quantum dots are added into water according to the mass ratio of 1:0.2 or 1:4, and an effective flocculent composite suspension cannot be formed by ultrasonic treatment, so that a membrane cannot be formed by suction filtration.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. A preparation method of a graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) dispersing graphene oxide and carbon quantum dots in water according to a certain proportion to form a composite suspension;
(2) adjusting the pH value of the composite suspension to form a stably dispersed carbon quantum dot-graphene oxide composite sheet suspension;
(3) carrying out suction filtration to form a graphene oxide-quantum dot composite film;
the mass ratio of the graphene oxide to the carbon quantum dots used in the step (1) is 1: 0.4-1: 2.
2. The preparation method of the graphene oxide-carbon quantum dot composite hydrophilic and oleophobic membrane of claim 1 is characterized in that: and (3) adjusting the pH value of the suspension liquid to 9-12 in the step (2).
3. The preparation method of the graphene oxide-carbon quantum dot composite hydrophilic oleophobic membrane of claim 1 is characterized in that: and (4) during suction filtration in the step (3), controlling the content of graphene oxide in the carbon quantum dot-graphene oxide composite sheet suspension poured in each square of the filtration area to be 0.1-2.0 g.
4. The graphene oxide-carbon quantum dot composite hydrophilic and oleophobic membrane prepared by the method of any one of claims 1-3, which is characterized in that: the contact angle of the obtained composite hydrophilic oleophobic membrane to water is less than 40 degrees, the contact angle to oil is greater than 120 degrees, and the composite hydrophilic oleophobic membrane has obvious hydrophilic oleophobic performance.
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| 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 |
| CN104789217A (en) * | 2015-04-28 | 2015-07-22 | 安徽大学 | Amphipathy carbon quantum dot and preparation method thereof |
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| US20190367368A1 (en) * | 2016-11-17 | 2019-12-05 | Research Institute Of Petroleum Industry | Formulation for the synthesis of thermal nanofluid based on carbon nanodots |
| GB201701406D0 (en) * | 2017-01-27 | 2017-03-15 | G20 Water Tech Ltd | Membrane |
| CN110304624B (en) * | 2019-07-05 | 2023-03-21 | 郑州大学 | Carbon quantum dot functionalized graphene oxide laminated membrane and preparation and application thereof |
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| 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 |
| CN104789217A (en) * | 2015-04-28 | 2015-07-22 | 安徽大学 | Amphipathy carbon quantum dot and preparation method thereof |
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