CN107261857A - Modified graphene film separated for monovalence with polyvalent metal ion and preparation method thereof - Google Patents
Modified graphene film separated for monovalence with polyvalent metal ion and preparation method thereof Download PDFInfo
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- CN107261857A CN107261857A CN201710325859.3A CN201710325859A CN107261857A CN 107261857 A CN107261857 A CN 107261857A CN 201710325859 A CN201710325859 A CN 201710325859A CN 107261857 A CN107261857 A CN 107261857A
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- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of modified graphene film separated for monovalence with polyvalent metal ion, its membrane material is the slight redox graphene of carbon oxygen mass ratio 1.2~1.4, and the two-dimensional nano mass transfer channel being made up of slight redox graphene lamella in film can be such that monovalent metallic ion is retained by, polyvalent metal ion.Modified graphene film can be prepared by the method comprised the following steps that：Slight redox graphene is dispersed in water and forms slight redox graphene casting solution；By casting solution base material membrane filtration, hygrometric state modified graphene film is formed on base material film；The hygrometric state modified graphene film is placed under normal temperature together with base material film and dried, is peeled off after drying from base material film and modified graphene film is made.
Description
Technical field
It is more particularly to a kind of for changing that monovalence is separated with polyvalent metal ion the invention belongs to graphene oxide membrane field
Property graphene film and preparation method thereof.
Background technology
The separation of monovalence/polyvalent metal ion is widely used in fields such as resource, environment, agricultural, life and healths.Monovalence gold
Category ion such as potassium, sodium, lithium ion are all the ions with positive effect of being lived to human being's production.Potassium ion is that human body and animal are thin
Primary metal ion in intracellular fluid, directly affects the health of human body and animal；Potassium ion is also three big nutrition of plant growth
One of element, the use of potash fertilizer can promote the maturation of crops.Sodium ion is the major metal in human body and the outer liquid of zooblast
Ion, adult needs to take in about 10 grams of salt to supplement the sodium chloride of needed by human body daily；The sodium such as sodium hydroxide and sodium chloride
Compound is also the highly important raw material of industry.Lithium ion is the minimum monovalent metallic ion of atomic weight, its as battery sun
Have very big energy density, be to prepare cleaning, the indispensable metal ion of efficient lithium ion battery.These monovalencies gold
Belong to ion resource to extract from the seawater or salt solution of nature mostly, but the higher multivalence of content is often mixed with seawater and salt solution
Metal ion, such as magnesium, calcium alkaline-earth metal ions, must be by multivalence gold during by purifying extraction monovalent metallic ion
Category ionic impurity is removed from monovalent metallic ion.
In addition, the multivalence such as lead, cadmium, chromium heavy metal ion can cause great infringement to the nervous system of human body and animal,
But it is indispensable raw material in many industrial productions, or often association is present, so in related industries waste discharge
In inevitably contain these heavy metal ion, polyvalent metal ion should strictly be removed in these wastewater treatments.Certainly,
Contained above-mentioned monovalent metallic ion is due to beneficial to animals and plants in waste water, without removing.Therefore monovalence and polyvalent metal are realized
The separation of ion, retains polyvalent metal ion, and monovalent metallic ion back to nature is turned into resource, to environmental protection and resource again
Circulation is significant.
Membrane separation technique is to separate monovalence and the important means of polyvalent metal ion.Up to the present, according to monovalence with it is many
Seperation film, can mainly be divided into (1) electrical charge rejection film and (2) size screening major class of film two by the mechanism of valence metal ion separation.
According to the southern effect in road, positively charged electrical charge rejection film is greater than monovalence to the electrostatic repulsion forces of polyvalent metal ion
Metal ion, the infiltration of polyvalent metal ion can be hindered significantly, embody the separation property to monovalence and polyvalent metal ion.These
Electrical charge rejection film combination electrodialytic technique, mass transfer, the synchronous infiltration for improving ion isolation and selectivity are promoted with electric field force.So
And, the positively charged functional layer of these films is prepared with weak electrostatic interaction, is easily destroyed by the change of electric current and pH value of solution, it is impossible to realized
Separation steady in a long-term.Moreover, its current limit density is too low, stability contorting is difficult in actual applications, is exceeded slightly, then can
Accessory substance is electrolysed out, membrane structure is destroyed, weakens separating property.
Based on dimensional effect, the separation to different size ions or molecule can be realized by building various sizes of fenestra.
The hydrated diameter scope of monovalent metallic ion is in 0.658-0.764nm, and the hydrated diameter scope of polyvalent metal ion is in 0.802-
0.950nm, therefore it is optimal to the separating effect of monovalence and polyvalent metal ion to build 0.8nm or so homogeneous fenestra or passage.
At present, following method prepares fenestra：(1) entered using macromolecules such as TMC/MPD (three formyl chlorides of 1,3,5- benzene/1,3- phenylenediamines)
Row interfacial polymerization builds nanofiltration fenestra；(2) using heavy ions in PET (polyethylene terephthalate) film, graphene
Punched on film；(3) punched using electric pulse on graphene film；(4) using graphene oxide, Ti3C2Tx(two-dimentional transition metal
Carbide or carbonitride) etc. two-dimensional material build two-dimensional nano passage, can construct the different fenestra/passage of size is used for
The mass transfer of lewis' acid is with separating.However, macromolecular nano filtering membrane pore size distribution range is too wide (0.4-2.0nm), fenestra is not advised
It is whole homogeneous, it is impossible to realize being precisely separated for monovalence and polyvalent metal ion.PET and graphene fenestra prepared by heavy ions method
Footpath size distribution is in 0.4-0.6nm, but these film punch densities are relatively low, cause the permeation flux of ion isolation smaller.And electric arteries and veins
Charge and attack graphene film aperture prepared by hole method larger (2-20nm), it is virtually impossible to separate all monovalence and polyvalent metal ion.
It can be designed that height can be adjusted in 0.64-0.98nm using the method for physics confinement stannic oxide/graphene nano lamella
Two-dimensional nano passage, infiltration rate of the bivalent metal ion in passage will be far below monovalent metallic ion, but this nanometer
Passage length is longer, and mass transfer is distant, causes ion permeation flux relatively low.In addition, Ti3C2TxTwo-dimensional nano channel height can
Expand/reduce with the change of metal ion price by Coulomb repulsion/sucking action between ion and nanoscale twins, but
In the case that monovalence and polyvalent metal ion coexist, its two-dimensional nanostructure is in the mixing collective effect of Coulomb repulsion and attraction
In, it is difficult to realize that monovalence and polyvalent metal ion are efficiently separated.Two-dimensional nano channel height constructed by graphene oxide
For 0.9nm, it is impossible to which separating most hydrated diameter is less than 0.9nm monovalence and polyvalent metal ion.To reduction two-dimensional nano
Channel height, it usually needs eliminate the oxide group as support on a certain amount of nanoscale twins, leads to so as to reduce two-dimensional nano
The interlamellar spacing in road.So far, eliminate oxide group common method mainly by graphene oxide is carried out (1) thermal reduction and
(2) two methods of electronation.But, thermal reduction can destroy the structure of stannic oxide/graphene nano lamella, formed a large amount of defects and
Hole, is unfavorable for being precisely separated for ion and molecule.Electronation under high temperature hydrothermal condition can cause a lying fold for lamella,
Constructed nanostructured out-of-flatness is caused, the homogeneity of two-dimensional nano channel height is influenceed.These methods can not all be prepared
It is adapted to the two-dimensional nano lamella of monovalence/polyvalent metal ion separation.
The above method can not realize that efficient, accurate monovalence is separated with polyvalent metal ion well.At present, it is how real
This existing target, it is still one big to build the regular nanometer fenestra that homogeneous, resistance to mass tranfer is low, separation accuracy is good of size or nanochannel
Challenge.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of flat regular, lamella of two-dimensional nano passage
Homogeneous modified graphene film of spacing and preparation method thereof, to realize, essence efficient to monovalent metallic ion and polyvalent metal ion
Really separation.
The basic thought of the present invention is to control graphene two-dimensional nano piece spacing layer by layer by adjusting graphene modification degree,
0.8nm or so two-dimensional nano mass transfer channel is designed, polyvalent metal ion and the hydration for being more than 0.8nm to hydrated diameter is realized
Diameter is less than the accurate screening of 0.8nm monovalent metallic ion.
The modified graphene film separated provided by the present invention for monovalence with polyvalent metal ion, its membrane material is carbon oxygen matter
The two-dimensional nano being made up of slight redox graphene lamella in the slight redox graphene than 1.2~1.4, film is measured to pass
Matter passage can be such that monovalent metallic ion is retained by, polyvalent metal ion.
In the technical scheme of above-mentioned modified graphene film, the slight redox graphene of two-dimensional nano mass transfer channel is constituted
Piece interlamellar spacing is 0.765nm~0.801nm.
In the technical scheme of above-mentioned modified graphene film, the film thickness of modified graphene film can be 0.5 μm~5.0 μm；It is excellent
It is 1.5 μm~2.5 μm to select film thickness.
In the technical scheme of above-mentioned modified graphene film, modified graphene film is preferably by slight redox graphene sheet
Body is formed by suction filtration layer upon layer.The slight redox graphene is to change under normal temperature (10 DEG C~25 DEG C) temperature conditionss
Learn prepared by redox graphene.The modification degree of slight modified graphene refers to the degree of its reduction-oxidation, depending on normal
The warm lower redox reaction time, characterized with its carbon oxygen mass ratio.The carbon oxygen mass ratio of common graphene oxide is
0.86~0.91.
Above-mentioned modified graphene film, can be prepared by the method comprised the following steps that：
(1) slight redox graphene is dispersed in water and forms slight redox graphene concentration and be
0.20mg/mL~0.30mg/mL casting solution；
(2) by casting solution base material membrane filtration obtained by step (1), hygrometric state modified graphene film is formed on base material film；
(3) the hygrometric state modified graphene film is placed under normal temperature (10 DEG C~25 DEG C) together with base material film and done
It is dry, then dried modified graphene film is peeled off from base material film, that is, modified graphene film is made.
Modified graphene film is prepared using the above method, can by selection at normal temperatures the appropriate recovery time produce it is slight
Redox graphene, that is, select the slight redox graphene of different carbon oxygen mass ratioes, can adjust modified graphene oxide
The effective interlamellar spacing of hygrometric state of film, the effective interlamellar spacing of hygrometric state is adjusted to 0.8nm or so.
In above-mentioned modified graphene membrane preparation technology scheme, the base material film preferentially from average pore size be 200nm~
230nm organic film.Further preferentially from the circular organic substrate films of a diameter of 45mm~50mm.Organic substrate Mo Weikecong cities
The commercial organic substrate film of direct acquisition on field.
In above-mentioned modified graphene membrane preparation technology scheme, the consumption of casting solution is that can form the modified graphite of design thickness
Alkene film；For the circular organic substrate films of a diameter of 45mm~50mm, casting solution consumption is 38mL~42mL.
Graphene oxide can be bought from market, or be prepared with reference to existing method, for example：Preparing graphene oxide can join
Examine document (1) Y.Xu, H.Bai, G.Lu, C.Li, G.Shi, J.Am.Chem.Soc.2008,130,5856-5857；(2)
W.S.Hummers,R.E.Offeman,J.Am.Chem.Soc.1958,80,1339-1339；The slight reduction-oxidation graphite
Alkene can be according to, to the demand of reducing degree, graphene oxide slightly being reduced in a mild condition and is made in practical application.Prepare
Method refers to document：D.Li,M.B.Muller,S.Gilje,R.B.Kaner,G.G.Wallace,Nature
Nanotechnol.2008,3,101-105。
Why the present invention can realize the separation of accurate, efficient, stable monovalence and polyvalent metal ion, and its principle exists
In：Slight redox graphene is to changing that graphene progress partial reduction oxidation is obtained using gentle chemical reduction conditions
Property graphene, eliminates the partial oxidation group of its sheet surfaces so that modified graphene lamella interlamellar spacing can be by different
Reducing degree is adjusted, while gentle temperature conditionss avoid the thermal fluctuation fold of lamella so that modified graphene film
Two-dimensional nano passage is very flat regular, it is hereby achieved that two-dimensional nano mass transfer of the height of size uniformity in 0.8nm or so
Passage, based on size sieve effect, can be accurately separated monovalent metallic ion of the hydrated diameter scope in 0.658-0.764nm
With hydrated diameter scope in 0.802-0.950nm polyvalent metal ion, segregational stability and reproducible.
Compared with prior art, the invention has the advantages that：
1. the invention provides a kind of new modified graphene oxide film, prepared by slight redox graphene.By
In the oxide group on slight redox graphene nanoscale twins for general graphene oxide it is less, supporter subtracts
It is few, therefore interlamellar spacing can be reduced, it is less than 0.9nm, by adjusting reducing degree, it is possible to achieve for monovalence, polyvalent metal
Structure of the height of ion isolation in 0.8nm or so two-dimensional nano mass transfer channel.
2. because modified graphene of the present invention is to carry out electronation oxidation stone using the temperature conditionss of normal temperature
Black alkene, it is to avoid hot conditions, therefore obtained slight redox graphene lamella is very smooth, be not in hydrothermal condition
Caused thermal fluctuation, very homogeneous regular as the nanostructured of the modified graphene oxide film prepared by it, this structure is favourable
In the structure of the two-dimensional nanostructure for accurately sieving ion.
3. due to the oxide regions on slight redox graphene lamella for graphene oxide less, and oxygen
The aquation of lamella and hydrone can be reduced by changing the reduction in region, while can reduce interlamellar spacing makes to produce π-π between lamella
Effect, so as to be effectively increased stability of the modified graphene film in water, in acid solution or aqueous slkali, is conducive to film in acidity
Under ion isolation field application.Experiment shows that modified graphene film prepared by the present invention is steady in ion isolation application
It is qualitative good, the stable separation property of film was still kept more than 6 months.There is good repeatability simultaneously, be conducive to it long-term
Stable operation during ion isolation, industrial applications and development beneficial to the technology.
4. the modified graphene oxide film that the present invention is provided is in monovalence and polyvalent metal ion separation process, without addition
Ambient pressure or electric field, need to can only obtain higher ion permeation flux, and keep good ion point using osmotic pressure
From performance, this energy conservation characteristic is conducive to the further industrial applications of the technology.
Brief description of the drawings
Fig. 1 is the x-ray photoelectron energy spectrum diagram of 12 hours modified graphenes prepared by embodiment 1；
Fig. 2 is the atomic force microscopy diagram of 12 hours modified graphenes prepared by embodiment 1；
Fig. 3 is the profile scanning electron microscope of 12 hours modified graphene films prepared by embodiment 1；
Fig. 4 is the elementary analysis C/O ratio graphs of film prepared by comparative example 1 and embodiment 1~3；
Fig. 5 is film effective interlamellar spacing curve that X-ray diffraction is tested under hygrometric state prepared by comparative example 1 and embodiment 1~3
Figure；
Fig. 6 is the x-ray photoelectron energy spectrum diagram of 24 hours modified graphenes prepared by embodiment 2；
Fig. 7 is the atomic force microscopy diagram of 24 hours modified graphenes prepared by embodiment 2；
Fig. 8 is the profile scanning electron microscope of 24 hours modified graphene films prepared by embodiment 2；
Fig. 9 is the x-ray photoelectron energy spectrum diagram of 48 hours modified graphenes prepared by embodiment 3；
Figure 10 is the atomic force microscopy diagram of 48 hours modified graphenes prepared by embodiment 3；
Figure 11 is the profile scanning electron microscope of 48 hours modified graphene films prepared by embodiment 3；
Figure 12 is the profile scanning electron microscope of modified graphene film prepared by comparative example 1；
Figure 13 is X-ray diffraction energy spectrum diagram of the high temperature reduction graphene oxide membrane of the preparation of comparative example 2~3 under hygrometric state；
Figure 14 is that graphene oxide membrane prepared by comparative example 1 soaks difference in pure water, hydrochloric acid solution, sodium hydroxide solution
The photo of time；
Figure 15 is the 24 hours modified graphene films prepared in embodiment 2 in pure water, hydrochloric acid solution, sodium hydroxide solution
Soak the photo of different time；
Figure 16 is the 48 hours modified graphene films prepared in embodiment 3 in pure water, hydrochloric acid solution, sodium hydroxide solution
Soak the photo of different time；
Figure 17 is comparative example 1 and the graphene oxide membrane and the stress of modified graphene film-should that are prepared in embodiment 1~3
Varied curve；
Figure 18 is that monovalence separates H type schematic devices used in test with polyvalent metal ion；
Figure 19 is the separation permeability of 24 hours modified graphene films preparing in embodiment 2 to 9 kinds of hybrid metal ions
Performance map；
Figure 20 be 24 hours modified graphene oxide films preparing in embodiment 2, comparative example 2, comparative example 3 and 50%,
The separation permeability properties figure of 80% high temperature reduction graphene oxide membrane respectively to 3 kinds of hybrid metal ions；
Figure 21 is that 24 hours modified graphene films prepared by embodiment 2 and high temperature reduction graphene oxide membrane are mixed to 9 kinds
The stable reperformance test performance map of the separation of metal ion；
Embodiment
By the following examples to the modified graphene oxide of the present invention separated for monovalence with polyvalent metal ion
Film and preparation method thereof is described further.
In following each embodiments and comparative example, the flaky graphite purchase Nanjing Xian Feng nanosecond science and technology Co., Ltd, the concentrated sulfuric acid,
Potassium peroxydisulfate, sodium hydroxide, hydrogen chloride are purchased from Chengdu Ke Long chemical reagents factory, and phosphorus pentoxide, potassium permanganate are purchased from Chengdu
Long March chemical reagent Co., Ltd, hydrazine hydrate and ammoniacal liquor are purchased from Chengdu Ke Long chemical reagents factory, and cellulose mixture film is purchased from Hangzhoupro
State (torch) Xidoumen Membrane Industrial Co., Ltd, anodic alumina films (AAO films) be purchased from Whatman companies of Britain, it is described go from
Sub- aquatic products is in Millipore pure water systems.
Embodiment 1
In the present embodiment, the preparation method of slight redox graphene lamella and modified graphene film is as follows：
(1) graphene oxide is prepared using improvement Hummer methods
1. by 3g flaky graphite graphite, the 12mL concentrated sulfuric acids, 2.5g potassium peroxydisulfates, 2.5g phosphorus pentoxides add single-necked flask
In, 4.5h is reacted in 80 DEG C under agitation, gained reaction solution is cooled to room temperature, 500mL deionized waters are added, it is stirred
At night, then filter, elute filter cake with 1500mL deionized waters, dry in the air 24h to remove the moisture in filter cake in room temperature, that is, complete graphite
Pretreatment；
2. 120mL temperature is added in conical flask for 0 DEG C of the concentrated sulfuric acid, then adds the stone 1. pre-processed by step
Ink, adds 15g potassium permanganate, the adding speed of control potassium permanganate try one's best it is slow so that the temperature of mixture in conical flask not
More than 20 DEG C, after potassium permanganate addition is finished, 2h is reacted at 35 DEG C, gained reaction solution is added in 250mL deionized waters and carried out
Temperature is controlled to be no more than 50 DEG C by ice bath in dilution, dilution, dilution is added after starting stirring, stirring 2h after finishing
700mL deionized waters, then add the hydrogen peroxide that 20mL concentration is 30wt%, now have a large amount of bubble formations in solution, treat nothing
During bubble formation, resulting solution is centrifuged with 8000r/min rotating speed, gained solid 10wt% salt acid elution will be centrifuged,
The operation 3 times of the centrifugation-washing is repeated, gained solid is dispersed in 500mL deionizations and loads molecular cut off is
In~14000 bag filter, dialyse 10 days in deionized water.
3. the graphene oxide solution 20mL that 2. step obtains is taken, is diluted with 980mL deionized waters, is in power
0.5h is handled under 100W ultrasound condition, is then centrifuged with 3000r/min rotating speed, unstripped graphite particle is removed, finally
The graphene oxide water solution that graphene oxide concentration is 0.5mg/mL is obtained with deionized water dilution；
(2) slight redox graphene is prepared
1. graphene oxide water solution 70mL obtained by step (1) is taken, 70mL deionized waters, 48 μ L hydrazine hydrates are added
((51.2wt%) and 550 μ L ammoniacal liquor (25wt%) react 12 hours in 25 DEG C under agitation.
2. after reaction terminates, solution is used into HCl solution titration regulation pH to 7 or so.
3. by resulting solution using deionized water centrifuge washing three times, centrifugal condition is 20000 revs/min, 20 minutes, 20
℃.Sediment after being centrifuged to last time adds deionized water and adjusted to slight redox graphene concentration therein
0.25mg/mL, produces the 12 hours slight redox graphene aqueous solution.
12 hours slight redox graphene samples prepared by step (2) carry out x-ray photoelectron power spectrum (XPS) inspection
Survey, as shown in Figure 1；Step (2) prepare 12 hours slight redox graphenes atomic force microscopy diagram as shown in Fig. 2
As shown in Figure 2, the slight redox graphene nanoscale twins thickness is about 1nm.
(3) modified graphene oxide film casting solution is handled
The slight redox graphene aqueous solution 40mL for taking step (2) to prepare, in power under 100W ultrasound condition
0.5h is handled, that is, obtains slight modified graphene oxide film casting solution.
(4) 12 hours modified graphene oxide films are prepared
Cellulose mixture film (CN-CA films) by 220nm of average pore size is as base material film, by casting film obtained by step (3)
Liquid base material membrane filtration, hygrometric state modified graphene oxide film is formed on base material film, and the hygrometric state 12 hours is modified oxidized
Graphene film is together with 12h is dried under base material film normal temperature, by dried 12 hours modified graphene oxide films from base material film
It is upper to peel off, produce 12 hours modified graphene oxide films that thickness is about 2 μm.
12 hours modified graphene oxide films manufactured in the present embodiment can be peeled off intactly from base material film, described 12 hours
The scanning electron microscope (SEM) photograph of modified graphene oxide film section is as shown in figure 3, from the figure 3, it may be seen that 12 hours modified graphene oxide films
With good layer upon layer structure.
12 hours modified graphene oxide membrane samples for taking 5 parts of steps (4) to prepare carry out elementary analysis (EA) detection, such as scheme
4, as a result show that the carbon-to-oxygen ratio that the step prepares 12 hours modified graphene oxide films is 1.219~1.251.Hygrometric state sample is entered
Row X-ray diffraction (XRD) is tested, and such as Fig. 5, the average hygrometric state of 12 hours modified graphene oxide films manufactured in the present embodiment is effective
Interlamellar spacing is 0.8933nm.
Embodiment 2
In the present embodiment, the operation of the preparation method and embodiment 1 of modified graphene oxide film is essentially identical, difference
It is only that：The normal-temperature reaction time in step (2) is 24 hours.24 hours modified graphene oxide films manufactured in the present embodiment
Carbon-to-oxygen ratio is 1.206~1.285, and the effective interlamellar spacing of average hygrometric state is 0.7736nm.
Embodiment 3
In the present embodiment, the operation of the preparation method and embodiment 1 of modified graphene oxide film is essentially identical, difference
It is only that：The normal temperature table reaction time in step (2) is 48 hours.48 hours modified graphene oxide films manufactured in the present embodiment
Carbon-to-oxygen ratio be 1.346~1.403, the average effective interlamellar spacing of hygrometric state is 0.7340nm.
Comparative example 1
In the present embodiment, the preparation method of graphene oxide layer and graphene oxide membrane is as follows：
(1) casting solution is prepared
The graphene oxide water solution 20mL prepared in the step of Example 1 (1), in power under 100W ultrasound condition
0.5h is handled, that is, obtains casting solution.
(2) anodic alumina films (AAO films) by 220nm of average pore size are as base material film, by casting film obtained by step (1)
Liquid base material membrane filtration, forms hygrometric state graphene oxide membrane, by the hygrometric state graphene oxide membrane together with base on base material film
Material film is placed under normal temperature together dries 12h, dried graphene oxide membrane is peeled off from base material film, it is about 2 μ to produce thickness
M graphene oxide membrane.
Graphene oxide membrane prepared by this comparative example can be peeled off intactly from base material film, the graphene oxide membrane section
Scanning electron microscope (SEM) photograph as shown in figure 12, as shown in Figure 12, the graphene oxide membrane has good layer upon layer structure.Such as Fig. 5,
The effective interlamellar spacing of average hygrometric state of graphene oxide membrane prepared by this comparative example is 1.073nm.
Comparative example 2
In the present embodiment, the preparation method of high temperature reduction graphene oxide layer and 50% high temperature reduction graphene oxide membrane
It is as follows：
(1) graphene oxide of high temperature reduction is prepared
Gained graphene oxide water solution 70mL in the step of Example 1 (1), adds 70mL deionized waters, 48 μ L hydrations
((51.2wt%) and 550 μ L ammoniacal liquor (25wt%) react 20 minutes hydrazine in 65 DEG C under agitation.
(2) casting solution is prepared
Take high temperature reduction graphene oxide water solution 20mL prepared by step (1) and the oxygen of step (1) preparation in embodiment 1
Graphite aqueous solution 10mL is mixed, and is handled 0.5h in the case where power is 100W ultrasound condition, that is, is obtained casting solution.
(3) cellulose mixture film (CN-CA films) by 220nm of average pore size will be cast as base material film obtained by step (2)
Film liquid base material membrane filtration, forms the high temperature reduction graphene oxide membrane of hygrometric state 50%, by the hygrometric state 50% on base material film
High temperature reduction graphene oxide membrane is placed under normal temperature together with base material film and dries 12h, by dried 50% high temperature reduction oxygen
Graphite alkene film is peeled off from base material film, produces the 50% high temperature reduction graphene oxide membrane that thickness is about 2 μm.Such as Figure 13, this
The effective interlamellar spacing of average hygrometric state of 50% high temperature reduction graphene oxide membrane prepared by comparative example is 0.763nm.
Comparative example 3
In this comparative example, the operation of the preparation method and comparative example 2 of 80% high temperature reduction graphene oxide membrane is essentially identical,
It the difference is that only：Casting solution in step (2) is by high temperature reduction graphene oxide water solution 32mL and step in embodiment 1
(1) the graphene oxide water solution 4mL prepared is obtained by mixing.Such as Figure 13,80% high temperature reduction oxidation stone prepared by this comparative example
The effective interlamellar spacing of average hygrometric state of black alkene film is 0.758nm.
Performance test
(1) graphene oxide membrane and modified graphene oxide film are steady in pure water, hydrochloric acid solution and sodium hydroxide solution
It is qualitative
1. by the graphene oxide membrane in comparative example 1 respectively in pure water (pH=6.8), hydrochloric acid solution (pH=1.2) and hydrogen
Immersion 1 minute~1 week in sodium hydroxide solution (pH=13.2), the situation of film is as shown in figure 14, as seen from the figure, graphene oxide membrane
Static soak 1 week in pure water, film does not occur breakage, but static soak 1 day in hydrochloric acid solution and sodium hydroxide solution
Afterwards, film occurs in that dissolution phenomena.Although illustrating stability of the graphene oxide membrane in pure water preferably, in acid solution or
Less stable in aqueous slkali.
2. 24 hours modified graphene oxide films prepared by embodiment 2 are respectively in pure water (pH=6.8), hydrochloric acid solution
(pH=1.2) and in sodium hydroxide solution (pH=13.2) soak 1 day~1 month, the situation of film is as shown in figure 15.It is real by scheming
24 hours modified graphene oxide films for applying the preparation of example 2 can guarantee that prolonged stabilization under three circumstances, embody preferably
Stability.
3. 48 hours modified graphene oxide films prepared by embodiment 3 are respectively in pure water (pH=6.8), hydrochloric acid solution
(pH=1.2) and in sodium hydroxide solution (pH=13.2) soak 1 day~1 month, the situation of film is as shown in figure 16.It is real by scheming
48 hours modified graphene oxide films for applying the preparation of example 3 can guarantee that prolonged stabilization under three circumstances, embody preferably
Stability.
(2) load-deformation curve
The load-deformation curve for the film that comparative example 1, embodiment 1, embodiment 2 are prepared with embodiment 3 is as shown in figure 17, by
Figure 17 is understood, compared to the graphene oxide membrane of the preparation of comparative example 1, embodiment 1, embodiment 2 and the modification oxygen of the preparation of embodiment 3
The fracture strength of graphite alkene film has obtained a certain degree of lifting, with more preferable mechanical strength.
(3) monovalence is tested with polyvalent metal ion separating effect
1st, monovalence is carried out using the device shown in Figure 18 and test is separated with polyvalent metal ion.From made in embodiment 2
24 hours standby modified graphene oxide films are sandwiched to be tested in H type devices.Supply side solution is that 9 kinds of hybrid metal ions are molten
Liquid, respectively potassium nitrate, sodium nitrate, lithium nitrate, plumbi nitras, copper nitrate, magnesium nitrate, cadmium nitrate, ferric nitrate, aluminum nitrate, concentration
It is 0.1mol/L, per-meate side is deionized water, and both sides solution is all 200mL, and both sides are constantly in stirring.By difference
Time of penetration, take per-meate side solution carry out ICP-OES (inductively coupled plasma spectrometry) test and handle.Can by Figure 19
Know, modified graphene oxide film has higher permeation flux to monovalent metallic ion within 24 hours, and polyvalent metal ion is oozed
Thoroughly relatively low, the separation factor of kalium ion and natrium ion and most of polyvalent metal ions can reach more than 100.
2nd, the film from gained in embodiment 2, comparative example 2, comparative example 3, which is sandwiched in H type devices, carries out test comparison.Supply
Side solution is 3 kinds of mixed ion solutions, respectively potassium nitrate, magnesium nitrate, chromic nitrate, and concentration is 0.1mol/L, and per-meate side is
Deionized water, both sides solution is all 200mL, and both sides are constantly in stirring.By different times of penetration, per-meate side is taken
Solution carries out ICP-OES (inductively coupled plasma spectrometry) and tests and handle.As shown in Figure 20,24 hours in embodiment 2
Modified graphene oxide film has higher separation property to monovalence/polyvalent metal ion, and obtained in comparative example 2,3 50%,
The separation property of 80% high temperature reduction graphene oxide membrane its monovalence/polyvalent metal ion is poor.This is due to that high temperature reduction have impact on
The planarization of graphene oxide layer so that the two-dimensional nanostructure of high temperature reduction graphene oxide membrane is more modified oxidized than 24 hours
Graphene film is irregular, more chaotic, and XRD peak values are less obvious, therefore to monovalence and the separation property of polyvalent metal ion just
It is not accurate enough.
The stable reperformance test that (four) 24 hours modified graphene films are separated to monovalence with polyvalent metal ion
Ion isolation test is carried out using the device shown in Figure 18.It is modified oxidized from 24 hours of gained in embodiment 2
Graphene film is sandwiched to be tested in H type devices.Supply side solution is 9 kinds of mixed ion solutions, respectively potassium nitrate, nitric acid
Sodium, lithium nitrate, plumbi nitras, copper nitrate, magnesium nitrate, cadmium nitrate, ferric nitrate, aluminum nitrate, concentration are 0.1mol/L, and per-meate side is
Deionized water, both sides solution is all 200mL, and both sides are constantly in stirring.By the time of penetration of 1 day, per-meate side is taken
Solution carries out ICP-OES (inductively coupled plasma spectrometry) and tests and handle.It is careful to rinse the cup of both sides, and use deionization
Water logging bulb apparatus both sides, both sides are still kept stirring for state.After 15 days, above-mentioned mixed solution is poured into again, is permeated 1 day, and sampling is surveyed
Examination.Repeat to rinse, immersion, after 15 days, retest again.In three monovalence/polyvalent metal ion separation tests, same 24
The hour ion isolation performance of modified graphene oxide film is as shown in figure 21.Modified graphene oxide film is up to 6 within 24 hours
In the time of the moon, the separation property held stationary of its monovalence and polyvalent metal ion, and it is reproducible, be conducive to industrialization extensive
Production application.
Claims (10)
1. a kind of modified graphene film separated for monovalence with polyvalent metal ion, it is characterised in that membrane material is carbon oxygen matter
The two-dimensional nano being made up of slight redox graphene lamella in the slight redox graphene than 1.2~1.4, film is measured to pass
Matter passage can be such that monovalent metallic ion is retained by, polyvalent metal ion.
2. it is used for the modified graphene film that monovalence is separated with polyvalent metal ion according to claim 1, it is characterised in that light
Micro- redox graphene piece interlamellar spacing is 0.765nm~0.801nm.
3. it is used for the modified graphene film that monovalence is separated with polyvalent metal ion according to claim 1, it is characterised in that change
Property graphene film film thickness be 0.5 μm~5.0 μm.
4. it is used for the modified graphene film that monovalence is separated with polyvalent metal ion according to claim 3, it is characterised in that change
Property graphene film film thickness be 1.5 μm~2.5 μm.
5. it is used for the modified graphene film that monovalence is separated with polyvalent metal ion, its feature according to one of Claims 1-4
It is, is formed by slight redox graphene plates by suction filtration layer upon layer, slight redox graphene is normal
Under warm temperature conditionss prepared by electronation graphene oxide.
6. preparing is used for the method for the modified graphene film that monovalence is separated with polyvalent metal ion described in one of claim 1 to 5,
It is characterised in that it includes following processing step：
(1) slight redox graphene is dispersed in water and forms slight redox graphene concentration for 0.20mg/
ML~0.30mg/mL casting solution；
(2) by casting solution base material membrane filtration obtained by step (1), hygrometric state modified graphene film is formed on base material film；
(3) the hygrometric state modified graphene film is placed under normal temperature together with base material film and be dried, then will be dried
Modified graphene film is peeled off from base material film, that is, modified graphene film is made.
7. the method for the modified graphene film separated for monovalence with polyvalent metal ion is prepared according to claim 6, its
It is characterised by, the base material film is organic film, and the average pore size of base material film is 200nm~230nm.
8. the method for the modified graphene film separated for monovalence with polyvalent metal ion is prepared according to claim 7, its
It is characterised by, organic substrate film is circular membrane, a diameter of 45mm~50mm of film.
9. according to one of claim 6 to 8 modified graphene film for being separated for monovalence with polyvalent metal ion of preparing
Method, it is characterised in that the consumption of casting solution is that can form the modified graphene film of design thickness.
10. the method for the modified graphene film separated for monovalence with polyvalent metal ion is prepared according to claim 9, its
It is characterised by, the casting solution consumption by base material membrane filtration casting film is 38mL~42mL.
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