CN105860153A - Composite membrane doped with graphene oxide quantum dots and preparation method thereof - Google Patents
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Abstract
The invention discloses a composite membrane doped with graphene oxide quantum dots and a preparation method thereof, wherein the composite membrane has the principal raw materials of chitosan, sodium alginate and graphene oxide quantum dots, and the preparation method comprises the following steps: (1) preparing a graphene oxide quantum dot suspension; (2) adding sodium alginate powder to the graphene oxide quantum dot suspension, carrying out ultrasonic stirring uniformly; (3) dropwise adding an acetic acid solution of chitosan into the graphene oxide quantum dot solution with the sodium alginate, stirring the solution to obtain blended sol; and (4) pouring the blended sol solution into a template, standing for a period of time, and carrying out calcium chloride cross-linking treatment to obtain the composite membrane doped with the graphene oxide quantum dots. The composite membrane and preparation method have the advantages of simple preparation process, easy availability of raw materials and mild conditions, and the prepared composite membrane has good hydrophilicity, mechanical property and biocompatibility and is applicable to water separation, adsorption filtration, surgical dressing and the like in the biomedical field.
Description
Technical field
The present invention relates to membrance separation field, particularly relate to composite membrane of a kind of graphene oxide quantum dot that adulterates and preparation method thereof.
Background technology
Macromolecular-inorganic hybrid membrane can comprehensively macromolecule and the advantage of inorganic material film, overcome polymeric membrane poor stability and inorganic film quality is crisp, be difficult to processing shortcoming, and there is the new advantage such as derivative high control accuracy and high regulation and control degree of freedom after hydridization, the most progressively become film and the forward position in membrane process field.
Chitosan, also known as chitosan, is that the chitin being widely present by nature obtains through deacetylation.From 1859, after first Frenchman Rouget obtains chitosan, the premium properties such as the biological functionality of this natural polymer and the compatibility, blood compatibility, safety, microbic resolvability are achieved major progress by all trades and professions extensive concern, the applied research at numerous areas such as medicine, food, chemical industry, cosmetics, water process, METAL EXTRACTION and recovery, biochemistry and biomedical engineerings.
Sodium alginate is a kind of natural polysaccharide carbohydrate extracted the Thallus Laminariae (Thallus Eckloniae) from Brown algae or Alga Sgrgassi Enerves, strand is made up of beta-D-mannuronic acid (M section) and α-L-guluronic acid (G section), formation gel can be crosslinked in divalent salts solion, sodium alginate has that thickening property is good, good film-forming property, gel strength advantages of higher, but owing to specific surface area is relatively low, usually through carrying out compound to improve absorption property with nano material.
Graphene oxide (GO) is powdered graphite product after chemical stripping, is the most emerging a kind of Two-dimensional Carbon material, has single atomic layer, and its surface has more hydroxyl, carboxyl and epoxy-functional；Meanwhile, GO itself also has preferable chemical stability, hydrophilic, antifouling property, biocompatibility and mechanical performance.Graphene oxide quantum dot (GOQDs) is the nano material of quasi-zero dimension, and the motion in all directions of its internal electron is all restricted, so quantum confinement effect is obvious especially, has a lot of unique character.Derivant as graphene oxide composite material, while having taken into account graphene oxide good characteristic, rely on again quantum confined effect and boundary effect to possess the character not available for the graphene oxides such as luminescence generated by light, and also have preferably performance at the aspect such as cytotoxicity, biocompatibility；In fields such as biology, medical science, material, semiconductor devices, there is important potential application.Therefore, graphene oxide quantum dot is carried out sodium alginate modification and can optimize macromolecule-inorganic interface configuration, and improve the absorbability to hydrone, have good application prospect at aspects such as water separation, biological medicines.
Summary of the invention
It is an object of the invention to provide composite membrane of a kind of graphene oxide quantum dot that adulterates and preparation method thereof.Preparation process of the present invention is simple, raw material is easy to get, mild condition, and the composite membrane of the doping graphene oxide quantum dot of preparation has preferable hydrophilic and mechanical performance, and biocompatibility, for bio-medical fields such as water separation, adsorption filtration, medical dressing.
For achieving the above object, the present invention adopts the following technical scheme that
The primary raw material of the composite membrane of a kind of graphene oxide quantum dot that adulterates is chitosan, sodium alginate and graphene oxide quantum dot, and its preparation method comprises the following steps:
(1) joining in 50ml deionized water by 0.01-0.05g graphene oxide quantum dot, 200W sonic oscillation processes 2h, obtains graphene oxide quantum dot dispersion liquid；
(2) being joined by 0.4-0.8g sodium alginate in the graphene oxide quantum dot dispersion liquid that step (1) obtains, magnetic agitation processes, and whipping temp is 25-35 DEG C, and mixing time is 20-28h；
(3) 0.1-0.8g chitosan is joined (pH is 1.4-2.0) in acetic acid solution, after room temperature magnetic agitation 2-5h, obtains uniform chitosan solution；
(4) step (3) stirring gained chitosan solution is added dropwise in the solution that step (2) obtains, room temperature magnetic agitation 5-10h, obtains colloidal sol is blended；
(5) step (4) stirring gained being blended colloidal sol and stand degassing process 1 day, pour in 20 × 10 × 0.5cm plastic formwork, room temperature hangs 20-28h；
(6) template is all immersed in the calcium chloride solution of 3mM-8mM process 8-12min, and washing 3 times, dry naturally afterwards.
The beneficial effects of the present invention is:
(1) primary raw materials of graphene oxide quantum dot is graphite, raw material sources extensively, be easy to get, with low cost；
(2) graphene oxide quantum dot of zero dimension is except having the biggest specific surface area of the intrinsic advantage of Graphene itself, good heat, chemical stability and environmentally friendly etc., owing to its size is at 10 nm
Hereinafter show higher quantum confined effect and boundary effect, thus show more new physicochemical properties；
(3) present invention process is simple, mild condition, environmental protection；
(4) composite membrane of the doping graphene oxide quantum dot of gained of the present invention has good hydrophilic, mechanical performance, and biocompatibility, can be used for separating the biological fields such as absorption, biological dressing.
Accompanying drawing explanation
Fig. 1 adulterates the composite membrane of graphene oxide quantum dot；
Fig. 2 adulterates the contact angle determination of composite membrane of graphene oxide quantum dot.
Detailed description of the invention
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention is not limited only to this.
Embodiment
1
1) joining in 50ml deionized water by 0.01g graphene oxide quantum dot, sonic oscillation processes 2h, obtains graphene oxide quantum dot dispersion liquid；
2) being joined by 0.4g sodium alginate in the graphene oxide quantum dot dispersion liquid that step 1) obtains, at a temperature of 25 DEG C, magnetic agitation processes 20h；
3) 0.2g chitosan is joined in 20ml acetic acid solution, after room temperature magnetic agitation 2h processes, obtain uniform chitosan solution；
4) being added dropwise in the solution that step (2) obtains by step (3) stirring gained chitosan solution, room temperature magnetic agitation processes 5h, obtains colloidal sol is blended；
5) step 4) stirring gained colloidal sol standing degassing process 1 day is blended, pour in 20 × 10 × 0.5cm plastic formwork, room temperature hangs 20h；
6) template is put into process 8min in 3mM calcium chloride solution, and washing 3 times, dry naturally afterwards.
Embodiment
2
1) joining in 50ml deionized water by 0.02g graphene oxide quantum dot, sonic oscillation processes 2h, obtains graphene oxide quantum dot dispersion liquid；
2) being joined by 0.5g sodium alginate in the graphene oxide quantum dot dispersion liquid that step 1) obtains, at a temperature of 28 DEG C, magnetic agitation processes 22h；
3) 0.4g chitosan is joined in 20ml acetic acid solution, after room temperature magnetic agitation 3h processes, obtain uniform chitosan solution；
4) being added dropwise in the solution that step (2) obtains by step (3) stirring gained chitosan solution, room temperature magnetic agitation processes 10h, obtains colloidal sol is blended；
5) step 4) stirring gained colloidal sol standing degassing process 1 day is blended, pour in 20 × 10 × 0.5cm plastic formwork, room temperature hangs 24h；
6) template being put into 9min in 4mM calcium chloride solution, washing 3 times, dry naturally afterwards.
Embodiment
3
1) joining in 50ml deionized water by 0.03g graphene oxide quantum dot, sonic oscillation processes 2h, obtains graphene oxide quantum dot dispersion liquid；
2) being joined by 0.6g sodium alginate in the graphene oxide quantum dot dispersion liquid that step 1) obtains, at a temperature of 30 DEG C, magnetic agitation processes 24h；
3) 0.6g chitosan is joined in 20ml acetic acid solution, after room temperature magnetic agitation 4h processes, obtain uniform chitosan solution；
4) being added dropwise in the solution that step (2) obtains by step (3) stirring gained chitosan solution, room temperature magnetic agitation processes 7h, obtains colloidal sol is blended；
5) step 4) stirring gained colloidal sol standing degassing process 1 day is blended, pour in 20 × 10 × 0.5cm plastic formwork, room temperature hangs 26h；
6) template being put into 10min in 6mM calcium chloride solution, washing 3 times, dry naturally afterwards.
Embodiment
4
1) joining in 50ml deionized water by 0.05g graphene oxide quantum dot, sonic oscillation processes 2h, obtains graphene oxide quantum dot dispersion liquid；
2) being joined by 0.8g sodium alginate in the graphene oxide quantum dot dispersion liquid that step 1) obtains, at a temperature of 35 DEG C, magnetic agitation processes 28h；
3) 0.8g chitosan is joined in 20ml acetic acid solution, after room temperature magnetic agitation 5h processes, obtain uniform chitosan solution；
4) being added dropwise in the solution that step (2) obtains by step (3) stirring gained chitosan solution, room temperature magnetic agitation processes 8h, obtains colloidal sol is blended；
5) step 4) stirring gained colloidal sol standing degassing process 1 day is blended, pour in 20 × 10 × 0.5cm plastic formwork, room temperature hangs 28h；
6) template is put into process 12min in 8mM calcium chloride solution, and washing 3 times, dry naturally afterwards.
Figure it is seen that the composite membrane of doping graphene oxide quantum dot has good hydrophilic performance, initial contact angle is 45 °；And prolongation over time, contact angle is gradually lowered, and when 180s, contact angle is reduced to 26 °, and i.e. prepared composite membrane has good hydrophilicity.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.
Claims (7)
1. the composite membrane of the graphene oxide quantum dot that adulterates, it is characterised in that: the primary raw material of described composite membrane is chitosan, sodium alginate and graphene oxide quantum dot.
2. the method for the composite membrane preparing doping graphene oxide quantum dot as claimed in claim 1, it is characterised in that: specifically include following steps:
(1) joining in 50ml deionized water by 0.01-0.05g graphene oxide quantum dot, 200W sonic oscillation processes 2h, obtains graphene oxide quantum dot dispersion liquid；
(2) being joined by 0.4-0.8g sodium alginate in the graphene oxide quantum dot dispersion liquid that step (1) obtains, magnetic agitation processes；
(3) 0.1-0.8g chitosan is joined in the acetic acid solution that pH is 1.4-2.0, after room temperature magnetic agitation processes, obtain uniform chitosan solution；
(4) being added dropwise in the solution that step (2) obtains by step (3) stirring gained chitosan solution, room temperature magnetic agitation processes, and obtains colloidal sol is blended；
(5) step (4) stirring gained being blended colloidal sol and stand degassing process 1 day, pour in 20 × 10 × 0.5cm plastic formwork, room temperature hangs；
(6) template being all immersed in calcium chloride solution and carry out crosslinking Treatment, washing 3 times, dry naturally afterwards.
The preparation method of the composite membrane of a kind of graphene oxide quantum dot that adulterates the most according to claim 2, it is characterised in that: in step (2), whipping temp is 25-35 DEG C, and mixing time is 20-28h.
The preparation method of the composite membrane of a kind of graphene oxide quantum dot that adulterates the most according to claim 2, it is characterised in that: in step (3), the magnetic agitation time is 2-5h.
The preparation method of the composite membrane of a kind of graphene oxide quantum dot that adulterates the most according to claim 2, it is characterised in that: in step (4), the magnetic agitation time is 5-10h.
The preparation method of the composite membrane of a kind of graphene oxide quantum dot that adulterates the most according to claim 2, it is characterised in that: in step (5), room temperature open assembly time is 20-28h.
The preparation method of the composite membrane of a kind of graphene oxide quantum dot that adulterates the most according to claim 2, it is characterised in that: in step (6), calcium chloride solution concentration is 3mM-8mM, and the process time is 8-12min.
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Cited By (9)
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| CN108172695A (en) * | 2018-01-11 | 2018-06-15 | 昆明物理研究所 | The preparation method of flexible support chlorine doped graphene quantum dot film |
| CN108425245A (en) * | 2018-04-08 | 2018-08-21 | 赵建平 | A kind of preparation method of flame retardant type cotton fiber |
| WO2018183609A1 (en) * | 2017-03-29 | 2018-10-04 | Miao Yu | Graphene oxide coated porous hollow fibrous substrates for carbon dioxide capture |
| CN109276738A (en) * | 2018-11-12 | 2019-01-29 | 张小伏 | A kind of high ventilative, antiphlogistic antibacterial bandage preparation method |
| CN109603750A (en) * | 2018-12-27 | 2019-04-12 | 曲阜师范大学 | One kind includes Fe3O4The preparation method of the plural gel adsorbed film of-GQDs |
| CN113980295A (en) * | 2021-11-12 | 2022-01-28 | 中国石油大学(华东) | Chitosan/sodium alginate hydrogel and preparation method and use method thereof |
| CN115444782A (en) * | 2022-09-08 | 2022-12-09 | 浙江科技学院 | Rapid film-forming liquid smearing mask, preparation method and use method |
| CN115612337A (en) * | 2022-11-21 | 2023-01-17 | 上海巨峰化工有限公司 | Fluorine modified organic silicon defoaming agent and preparation process thereof |
| CN116199973A (en) * | 2023-02-20 | 2023-06-02 | 河北同福健康产业有限公司 | Packaging material and packaging bag for prolonging shelf life of steamed bread |
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