CN103212304B - Semipermeable membrane and use thereof - Google Patents
Semipermeable membrane and use thereof Download PDFInfo
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- CN103212304B CN103212304B CN201310113187.1A CN201310113187A CN103212304B CN 103212304 B CN103212304 B CN 103212304B CN 201310113187 A CN201310113187 A CN 201310113187A CN 103212304 B CN103212304 B CN 103212304B
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Abstract
The invention discloses a semipermeable membrane which is formed from graphene provided with nanopores. The semipermeable membrane provided by the invention has extremely strong mechanical performance (strength: 130GPa), good thermal stability (can bear high temperature of 2300 DEG C) and excellent chemical and electro-chemical stability, and can be effectively used as a selective pervious membrane in permeation.
Description
Technical field
The present invention relates to material science.Particularly, a kind of pellicle and uses thereof is related to.
Background technology
Along with the high speed development of human society, the dependency degree of the mankind to water resource is more and more higher, but situation of water resource but allows common people cause anxiety.The surface area of the earth 71% that we live is covered with water.But, this wherein 97.5% water be seawater, seawater is not only salty but also bitter, can not drink, and can not irrigate, also be difficult to use in industry, only has remaining 2.5% to be fresh water.And in fresh water, 70% being frozen in the ice sheet in the South Pole and Greenland nearly, remaining major part is moisture in soil or deep phreatic water, is difficult to exploit for the mankind.The water in the source such as rivers, lake, reservoir and phreatic water is comparatively easy to exploitation for the mankind directly, but 1% of its lazy weight world fresh water, account for 0.007% of whole water on the earth.Our freshwater resources are not only very short, and distribution is also extremely uneven.This uneven main manifestations over time and space.For China, the precipitation of China's most area mainly concentrates on summer.The Annual variations of precipitation is very large.From spatial distribution, there is Dong Duoxi few, the feature that Nan Duobei is few.China is populous, and everyone only has 1/4th of world average level at the water resource had.
If most seawater can be utilized in water resource, and will can greatly alleviate our current water crisis by the sewage and waste water in remanufacture life.Therefore desalinization and sewage reclaim is the important means solving current water resources crisis, and in desalinization, it is inverse osmosis technology that current method mainly contains the wherein popular water technologies such as the way of distillation, electroosmose process and hyperfiltration.Inverse osmosis technology is the membrane separation technique relying on reverse osmosis membrane to make the solvent in solution and solute carry out being separated under the effect of ambient pressure, and forward osmosis technology then relies on the hyperosmosis of extract self and the selective penetrated property of forward osmosis membrane to make the spontaneous new membrane isolation technics extracted from material liquid of water.Visible, be no matter use forward osmosis technology or inverse osmosis technology, a suitable permselectivity membrane is vital.
But current pellicle still haves much room for improvement.
Summary of the invention
The present invention one of is intended to solve the problems of the technologies described above at least to a certain extent or at least provides a kind of useful business to select.
For this reason, one object of the present invention is to propose a kind of pellicle.According to embodiments of the invention, this pellicle is formed by Graphene, and described Graphene is formed with nano-pore.According to embodiments of the invention, the average diameter of nano-pore is below 10nm, and the average diameter of preferred described nano-pore is 1nm.According to embodiments of the invention, the edge of described nano-pore can by chemical group modification, described chemical group be selected from-OH ,-H ,-F ,-C-O-C-and-COOH one of at least.The embodiment other according to the present invention, the thickness of described pellicle is monatomic thickness.
Generally speaking, for suitable permselectivity membrane, the following standard of demand fulfillment:
(1) good selective, namely refusing salt rate needs to be greater than 99.5%.It is according to being determined by the difference of salt content in the solution before and after film that term adopted in the present invention " refuses salt rate ", namely salt rate=(1-fluid salt content/feed liquor salt content) * 100% is refused, wherein, solution salt content can be measured by conductivity measuring instrument.
(2) in infiltration, there is high flux;
(3) excellent mechanics, calorifics, chemical stability, under Thief zone pressure reduction, Stability Analysis of Structures is not destroyed; Ensure that pellicle has a wide in range working range; Not because of thermal agitation, microorganism, electrochemical corrosion, and and other chemical substances between contact and lost efficacy;
(4) low concentration polarization.Usually, concentration polarization phenomenon is divided into external concentration polarization phenomenon and internal concentration polarization phenomenon.For positive process of osmosis, external concentration polarization phenomenon is because the extract concentration near pellicle is caused extract and material liquid valid density difference to reduce by dilution, reduces forward osmosis efficiency; For reverse osmosis process, external concentration polarization phenomenon is because the extract concentration near pellicle is greater than extract overall density, and when extract side impressed pressure is constant, this is equivalent to decrease effective pressure reduction, reduces inverse osmosis efficiency.External concentration polarization phenomenon can be alleviated by increasing stirring.Internal concentration polarization phenomenon is then relevant with structure to the character of membrane material itself, and internal concentration polarization phenomenon by poor for the valid density reduced between extract and material liquid, thus reduces osmotic efficiency.Membrane material is thinner in principle, and internal concentration polarization phenomenon is more weak.
(5) oneself's cleaning function.In process of osmosis, pollutant all stayed film outside and do not stick to film surface, with teaching display stand cleaning function, extending the service life of membrane component.
Graphene be a kind of by carbon atom with sp
2hybridized orbit composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Graphene is the thinnest in the world is at present the hardest nano material also, and it has extremely strong mechanical property (intensity 130GPa), good thermal stability (can bear the high temperature of 2300 degrees Celsius) and excellent chemistry, electrochemical stability.Inventor finds, the pellicle of grapheme material of the present invention, can be effective as the permselectivity membrane used in infiltration.
Relative to traditional polymer pellicle, the advantage of nano-pore structure Graphene pellicle of the present invention is embodied in the following aspects:
(1) optionally advantage: traditional pellicle is based on poromeric polymer pellicle, and it forms a large amount of interstitial spaces by being cross-linked with each other between polymer monomer, and these interstitial spaces are connected by the thermal fluctuation of polymer.The interstitial space of polymer, is similar to and can be regarded as pore structure.The crosslinking degree of polymer is directly related with the size in hole.Being cross-linked to a certain degree, can produce sizeable hole, and this ensures that polymer pellicle has the reason of selective penetrated property.Obviously, Kong Yue little, salt ion will more be difficult to pass through, and refusing salt rate will be higher, but too small hole can make water in the polymer originally unhappy transport velocity greatly slow down.Height refuses salt rate and high flux is difficult to take into account when adopting polymer pellicle simultaneously.And for Graphene pellicle of the present invention, owing to having the architectural characteristic of monatomic thickness, as long as ensure that aperture is suitable, just guarantee is high-throughout while, can keep high and refuse salt rate.According to embodiments of the invention, utilize according to pellicle of the present invention, can 100L/cm be reached
2the high flux (larger than thin polymer film more than 100 times) of more than Day, and refuse salt rate theory can reach 100%.Wherein, it should be noted that, the present invention is that the area by controlling etching controls aperture.Particularly, etch Graphene by UV-induced oxidation, and then by controlling the time of etching, control the size in the hole that etching produces.
(2) advantage of flux: in process of osmosis, hydrone enters the interstitial space in polymer pellicle, due to the warm-up movement of polymer, interstitial space is connected with each other logical, thus transporting of hydrone be accomplished, each step can only spread 0.3 nanometer, and is 100 nanometers through the yardstick of polymer pellicle.Obviously, this transport mechanism depending on polymer warm-up movement fluctuation is unusual poor efficiency.And the pellicle that the grapheme material with nano-pore structure of the present invention is formed, traditional polymer pellicle one or two order of magnitude large that its flow-rate ratio is current, and can keep high and refuse salt rate.
(3) advantage of mechanical stability: traditional polymer pellicle, due to the restriction of self mechanical strength, often needs to adopt thick polymer support.And the increase of thickness sharply can increase internal concentration polarization phenomenon, reduce osmotic efficiency.And Graphene pellicle of the present invention, only need very thin mechanical support, even do not need to add mechanical support.Thus, relative to traditional polymer pellicle, adopt Graphene pellicle of the present invention to permeate, osmotic efficiency can significantly improve.
The advantage of chemical/electrochemical stability: polymeric film material is as cellulose acetate, easily be subject to the corrosion of microorganism and complicated solution environment, and under the grapheme material normal temperature that pellicle of the present invention adopts chemistry and electrochemical properties very stable, can not lose efficacy because of microbial decomposition.
(4) concentration polarization: polymer itself, as organic macromolecule, also has other some defects.For the polyamide film composite of application main in current counter-infiltration market, in counter-infiltration during embody rule, it is mainly divided into three layers: polyester network as mechanical support, thick 120 to 150 microns; Micropore intermediate course, as transition, thick about 40 microns; Barrier layer, at the selective middle performance Main Function of infiltration, thick about 0.2 micron.Thickness is altogether about 200 microns, and such structure can cause serious concentration polarization phenomenon in actual applications.Concentration polarization is divided into two kinds, internal concentration polarization and external concentration polarization.External concentration polarization refer to when water through film and retain salt time, a low-down boundary layer of flow velocity can be formed on film surface, salinity in concentration polarization boundary layer is higher than water inlet bulk solution salinity, and the phenomenon that this salinity increases on film surface is called concentration polarization.Concentration polarization can make actual permeant flux lower than theoretical assessment, significantly can reduce the efficiency of infiltration.External concentration polarization phenomenon can be alleviated by increasing stirring.Internal concentration polarization phenomenon, mainly occurs in film inside, relevant with structure to the character of membrane material itself.Pellicle of the present invention just can eliminate internal concentration polarization phenomenon from principle because of the ultrathin (monatomic thickness) of adopted grapheme material self.
(5) graphene nano pore structure and modification thereof.Grapheme material can obtain pore structure by ion beam etching method, in addition, by using chemical reagent can obtain different chemical modifications flexibly, under the prerequisite not changing other good natures of grapheme material, improves the osmotic efficiency of Graphene pellicle.Polymeric material is then difficult to carry out the chemical modification favourable to osmotic efficiency.Those skilled in the art can carry out modification by conventional chemical treatment method to Graphene graphene nano bore edges.According to embodiments of the invention, the edge of nano-pore by chemical group modification, described chemical group be selected from-OH ,-H ,-F ,-C-O-C-and-COOH one of at least.Particularly, according to embodiments of the invention, for graphene nano bore edges adds the modification of hydroxyl (-OH), can be realized by the nano-pore edge of graphene oxide, such as Graphene with holes can be placed in the solution (as concentrated nitric acid solution) of oxidisability, if not easily reaction or speed are slowly, means of catalysis (as heating) catalysis can be used.According to embodiments of the invention, modify for graphene nano bore edges adds hydrogen (-H), can be realized by the nano-pore edge of reduced graphene, such as, Graphene with holes can be placed in the environment of reproducibility (as NaNH
2in environment or at H
2etch under ion atmosphere), apply suitable means of catalysis accelerated reaction.
(6) oneself's cleaning function: traditional polymer pellicle prolonged application is in the process of infiltration, because aperture, polymer surfaces gap is not of uniform size, pollutant can be constantly had to enter polymer film inside, blocking membrane channels, sharply reduce osmotic efficiency, finally cause pellicle to lose efficacy.And because polymer surfaces is uneven, easily make pollutant adhered thereto, after the use of a period of time, just need carry out extra cleaning.And pellicle of the present invention adopts grapheme material, because Graphene is a material only having monatomic thickness, surface is very smooth, thus pollutant can directly be kept off at film outside, and then greatly can extend the service life of Graphene pellicle.
To sum up, the present invention takes full advantage of the superior character of grapheme material itself: extremely frivolous (only having monatomic thickness), there is extremely strong mechanical property (intensity 130GPa), good thermal stability (high temperature of 2300 degrees Celsius can be born), excellent chemical stability and outstanding self-cleaning function, the pellicle of the present invention that Graphene is formed is applied in process of osmosis as selective penetrated property film, thus, can guarantee high refuse salt rate (being greater than 99.5%) while, the flow of superelevation (being greater than traditional polymer film 1 to 2 order of magnitude) is provided.
Thus, in another aspect of this invention, the present invention proposes a kind of filter.According to embodiments of the invention, this filter is using foregoing pellicle as filter membrane.Obviously, this filter is provided with all advantages and the feature of pellicle noted earlier, does not repeat them here.In addition, it will be appreciated by persons skilled in the art that due to the extremely strong mechanical property of grapheme material itself, in order to improve osmotic efficiency, supporting construction can be selected flexibly according to the osmotic pressure in pellicle real work.And for the osmosis system of the positive process of osmosis of major part with some miniature scale, supporting construction can not be used, directly graphene film is integrated in membrane element.
Further, in still another aspect of the invention, the present invention proposes a kind of method of bodies for purifying fluids.According to embodiments of the invention, in the method for bodies for purifying fluids of the present invention, by fluid by foregoing filter.Obviously, the method for this bodies for purifying fluids is provided with all advantages and the feature of pellicle noted earlier and filter, does not repeat them here.According to embodiments of the invention, the type of the manageable fluid of the method is utilized to be not particularly limited, preferred liquid.Thus, the method of bodies for purifying fluids of the present invention can be applied to water treatment (desalinization, Water warfare, wastewater treatment etc.), the energy (permeable pressure head generating, fuel cell), life science (insoluble drug release, drug ingedient are collected), food industry (is separated beverage concentrate, food storing), and have very potential application in the field such as lifesaving and Military Application in the wild.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 shows the structural representation of traditional polymer pellicle;
Fig. 2 shows according to one embodiment of present invention, based on the pellicle schematic diagram of nano-pore structure Graphene;
Fig. 3 shows according to one embodiment of present invention, and nano-pore is by the structural representation of the Graphene pellicle of modification;
Fig. 4 shows according to one embodiment of present invention, prepares the schematic flow sheet of the method for nano-pore Graphene pellicle;
Fig. 5 shows according to one embodiment of present invention, the integrated structural representation of nano-pore Graphene supporting construction and Graphene with holes.
Detailed description of the invention
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Be exemplary below by the embodiment be described with reference to the drawings, be intended to for explaining the present invention, and can not limitation of the present invention be interpreted as.As nothing clearly states, material adopted in the examples below that is commercially available, and the method for involved non-specific explanations all can be carried out according to mode well known by persons skilled in the art.
Embodiment 1
With reference to figure 4, preparation has the Graphene selective penetrated property film of nano-pore structure through the following steps:
Utilizing UV-induced oxidation to etch Graphene, to obtain the Graphene with nano-pore structure, and by controlling the time of etching, controlling the size in the hole that etching produces.The obtained Graphene with nano-pore structure is placed in the middle of reproducibility or the environment of oxidisability, so that the edge of chemical modification modified Nano pore structure.
Be integrated on perforated substrate by the Graphene of the nano-pore structure through chemical modification, namely can be fixed by mechanics, restriction graphene film moves with fluid, ensures that it is not washed away by incoming flow.
Wherein, the actual conditions of chemical modification modification is:
(1). hydroxyl (-OH) modify: the Graphene with nano-pore structure is inserted in ozone environment, then again with NaBH
4reaction, obtains the Graphene of the nano-pore structure of hydroxyl modified.
(2). fluorine (-F) is modified: the Graphene with nano-pore structure is inserted fluorine gas (F
2) in environment, be heated to 150.C, obtains the Graphene of the nano-pore structure that fluorine is modified.
(3). carboxyl (-COOH) is modified: the Graphene with nano-pore structure is inserted nitric acid (HNO
3) in, heating, obtains the Graphene of the nano-pore structure of carboxyl modified.
(4). hydrogen (-H) is modified: NaNH
2in environment or at H
2etch under ion atmosphere, obtain the Graphene of the nano-pore structure that hydrogen is modified.
The structure display of the pellicle of final acquisition in Figure 5.Through measuring, (area is less than 2nm to nano-pore structure
2) the biaxial stretch-formed intensity of graphene film can reach more than 40GPa.Because grapheme material can stand the high temperature of 2600K, thus the operating temperature of graphene film is very wide, and heat endurance is fabulous.The salt rate of refusing of this pellicle maintains 1nm at hole area
2time, can 100% be reached.The chemical stability of this Graphene pellicle is good, and the pH value that can work, between 2 ~ 9, is not subject to biological corrosion.Already described before the feature of high flow capacity, can 100L/cm be reached
2more than Day, than large more than 100 times of tradition positive osmopolymer film.
In the description of this description, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention when not departing from principle of the present invention and aim, revising, replacing and modification.
Claims (7)
1. a pellicle, it is formed by Graphene, and described Graphene is formed with nano-pore, wherein, the edge of described nano-pore by chemical group modification, described chemical group be selected from-OH ,-H ,-F ,-C-O-C-and-COOH one of at least.
2. pellicle according to claim 1, is characterized in that, the average diameter of described nano-pore is below 10nm.
3. pellicle according to claim 1, is characterized in that, the average diameter of described nano-pore is 1nm.
4. pellicle according to claim 1, is characterized in that, the thickness of described pellicle is monatomic thickness.
5. a filter, is characterized in that, using the pellicle described in any one of Claims 1 to 4 as filter membrane.
6. a method for bodies for purifying fluids, is characterized in that, by fluid by filter according to claim 5.
7. method according to claim 6, is characterized in that, described fluid is liquid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4095096A1 (en) * | 2021-05-24 | 2022-11-30 | Sgraphene | Method for forming graphene nanoholes using detachable functional groups, and graphene sheet having graphene nanoholes formed thereby |
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| CN103603706A (en) * | 2013-11-25 | 2014-02-26 | 广西玉柴机器股份有限公司 | Engine crankcase oil-gas separator |
| JP2017500195A (en) * | 2013-12-10 | 2017-01-05 | ユニバーシティー オブ サウス カロライナ | Ultra-thin graphene-based films for water treatment and their formation and use |
| CN107218685A (en) * | 2016-03-21 | 2017-09-29 | 中山市创思泰新材料科技股份有限公司 | A kind of membrane type molecule humidifier |
| CN107158967B (en) * | 2017-06-16 | 2020-04-14 | 上海海事大学 | Carbon-containing composite semipermeable membrane for light evaporation of water, preparation method and application thereof |
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| EP0227299A3 (en) * | 1985-12-20 | 1987-10-07 | The Standard Oil Company | Polymer/liquid crystal composite semipermeable membranes and process for the use thereof |
| EP3196645B1 (en) * | 2009-09-18 | 2019-06-19 | President and Fellows of Harvard College | Bare single-layer graphene membrane having a nanopore enabling high-sensitivity molecular detection and analysis |
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| EP4095096A1 (en) * | 2021-05-24 | 2022-11-30 | Sgraphene | Method for forming graphene nanoholes using detachable functional groups, and graphene sheet having graphene nanoholes formed thereby |
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