CN105801918B - A kind of cellulose/graphene oxide composite membrane and preparation method thereof - Google Patents
A kind of cellulose/graphene oxide composite membrane and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Abstract
The present invention provides a kind of cellulose/graphene oxide composite membrane and preparation method thereof, comprise the following steps：S1) cellulose aerogels are dispersed in amide solvent, obtain mixed solution；S2) mixed solution is mixed with graphene oxide water solution, is filtered by vacuum, obtains cellulose/graphene oxide composite membrane.Compared with prior art, the present invention is using amide solvent as solvent, cellulose aerogels network structure is smashed into dissolving and obtains less cellulose micronetwork structure, then after being mixed with graphene oxide water solution, numerous a cellulose microstructured bodies are pressed into two dimensional surface network using air pressure during vacuum filtration, as support frame for the deposition load of graphene oxide nanoscale twins, cellulose/graphene oxide composite membrane of high mechanical properties is obtained after multilayer assembling, and the preparation method realizes the microcosmic compound of cellulose and graphene oxide high level.
Description
Technical field
The invention belongs to technical field of composite materials, more particularly to a kind of cellulose/graphene oxide composite membrane and its system
Preparation Method.
Background technology
Graphene be one kind by carbon atom with sp2Hybridized orbit composition hexangle type is in the flat film of honeycomb lattice, only
The two-dimensional material of one carbon atom thickness.Since 2004 are found, this unique material because its a variety of excellent properties by
To extensive concern.
The existing preparation a little on graphene oxide and bacteria cellulose composite membrane is broadly divided into In-situ reaction and dystopy
Compound two methods.In-situ reaction prepares the nutrient solution that graphene oxide is mainly directly appended to bacteria cellulose growth
In, graphene oxide is directly wrapped in its three-dimensional network with the process of micro-organisms cellulose.But this method
It is more difficult to regulate and control in preparation process, and for graphene oxide solution usually in acidity, the acid-base value for changing nutrient solution after addition can notable shadow
The activity of microorganism is rung, so as to influence the production of bacteria cellulose.In addition the composite film thickness and table that In-situ reaction is prepared
Surface evenness is difficult to control, by thin bacteria cellulose-graphene oxide composite hydrogel when especially preparing relatively thin composite membrane
Film convection drying is difficult to the film for obtaining surfacing during obtaining.
Another dystopy is compound, bacteria cellulose aquagel block typically is broken into homogenate, then divide with graphene oxide
Film forming is filtered after dispersion liquid mixing, or directly gel mass is immersed in graphene oxide solution；It is thin during this method
Even if fungin breaks into homogenate, it is still the cellulose aggregate of a large-size, and hydrogel structure is stablized, and aoxidizes stone
Black alkene is difficult to penetrate into inside three-dimensional network so that its interior three-dimensional network structure can not be fully utilized and realize high level
It is microcosmic compound.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of cellulose/graphene oxide composite membrane and
Its preparation method, the mechanical strength of cellulose/graphene oxide composite membrane prepared by this method are higher.
The present invention provides a kind of preparation method of cellulose/graphene oxide composite membrane, comprise the following steps：
S1) cellulose aerogels are dispersed in amide solvent, obtain mixed solution；
S2) mixed solution is mixed with graphene oxide water solution, is filtered by vacuum, obtains cellulose/graphite oxide
Alkene composite membrane.
Preferably, the cellulose aerogels are bacteria cellulose aeroge.
Preferably, the amide solvent is in formamide, n,N-Dimethylformamide and n,N-dimethylacetamide
It is one or more.
Preferably, the concentration of cellulose aerogels is 0.5~3mg/ml in the mixed solution.
Preferably, the step S1) in use ultrasonic disperse；The time of the ultrasonic disperse is 1~5h.
Preferably, the cellulose aerogels follow the steps below preparation：
Cellulose aquagel is rubbed by physical mechanical, is then freeze-dried, obtains cellulose aerogels.
Preferably, the mass ratio of the cellulose aerogels and graphene oxide is 50：(0.5~2).
Present invention also offers a kind of cellulose/graphene oxide composite membrane, using cellulose two dimensional surface network as support
Skeleton, deposition has graphene oxide nanoscale twins on the cellulose two dimensional surface network.
Preferably, the thickness of the cellulose/graphene oxide composite membrane is 11~17 μm.
Preferably, the aperture of the cellulose/graphene oxide composite membrane is 0.3~1.2nm.
The present invention provides a kind of cellulose/graphene oxide composite membrane and preparation method thereof, comprise the following steps：S1)
Cellulose aerogels are dispersed in amide solvent, obtain mixed solution；S2) by the mixed solution and graphene oxide water
Solution mixes, and vacuum filtration, obtains cellulose/graphene oxide composite membrane.Compared with prior art, the present invention is molten with amide-type
Agent is solvent, and cellulose aerogels network structure is smashed dissolving obtains less cellulose micronetwork structure, then with oxygen
After the mixing of graphite aqueous solution, numerous a cellulose microstructured bodies are pressed into two using air pressure during vacuum filtration
Dimensional plane network, as support frame for the deposition load of graphene oxide nanoscale twins, high mechanical properties are obtained after multilayer assembling
Cellulose/graphene oxide composite membrane, and the preparation method realizes the microcosmic multiple of cellulose and graphene oxide high level
Close.
Brief description of the drawings
Fig. 1 is the assembling schematic diagram of cellulose of the present invention/graphene oxide composite membrane；
Fig. 2 is composite film thickness variation diagram under difference GO additive amounts in the embodiment of the present invention；
Fig. 3 is incident light of the present invention through the bacteria cellulose after the mixed solution and standing obtained in 1.1 after standing
The photo of airsetting glue solution；
Bacteria cellulose/graphene oxide composite membrane when Fig. 4 is different graphene oxide additive amounts in the embodiment of the present invention 1
Film formation time curve map；
Bacteria cellulose/graphene oxide composite membrane when Fig. 5 is different graphene oxide additive amounts in the embodiment of the present invention 1
Photo；
Fig. 6 is the stability test figure of the bacteria cellulose/graphene oxide composite membrane obtained in the embodiment of the present invention 1；
Fig. 7 is bacteria cellulose/graphene oxide composite membrane, the pure zirconia graphene film obtained in the embodiment of the present invention 1
With pure bacteria cellulose film stress-strain curve；
Fig. 8 is bacteria cellulose/graphene oxide composite membrane, the pure zirconia graphene film obtained in the embodiment of the present invention 1
With pure bacteria cellulose film the maximum tensile strength change curve；
Fig. 9 is bacteria cellulose/graphene oxide composite membrane, the pure zirconia graphene film obtained in the embodiment of the present invention 1
With the change curve of pure bacteria cellulose film toughness；
Figure 10 is the permeability apparatus of test ion sieve performance；
Figure 11 is that (GO concentration is 0.3mg/ for bacteria cellulose/graphene oxide composite membrane for being obtained in the embodiment of the present invention 1
ML (BC+GO-0.3)) large scale rhodamine B (RhB) supplies the UV- of solution and percolating solution intermediate ion before and after infiltration after separation
Visible ray spectrogram；
Figure 12 is that in bacteria cellulose/graphene oxide composite membrane, (GO concentration is 0.3mg/mL to rhodamine B (RhB) with KCl
(BC+GO-0.3)) the infiltration rate curve map on；
Figure 13 supplies solution and infiltration for large scale rhodamine B (RhB) after pure bacteria cellulose UF membrane before and after infiltration
The UV- visible ray spectrograms of effects of ion.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained without making creative work, all
Belong to the scope of protection of the invention.
The present invention provides a kind of cellulose/graphene oxide composite membrane, using cellulose two dimensional surface network as support rib
Frame, deposition has graphene oxide nanoscale twins on the cellulose two dimensional surface network.
The cellulose is cellulose well known to those skilled in the art, has no special limitation, excellent in of the invention
Elect bacteria cellulose as.
The thickness of the cellulose/graphene oxide composite membrane is preferably 11~17 μm, more preferably 12~15 μm；It is described
The aperture of cellulose/graphene oxide composite membrane is preferably 0.3~1.2nm, more preferably 0.4~0.8nm.
Present invention also offers a kind of preparation method of above-mentioned cellulose/graphene oxide composite membrane, comprise the following steps：
S1) cellulose aerogels are dispersed in amide solvent, obtain mixed solution；S2) by the mixed solution and graphite oxide
Aqueous solution mixes, and vacuum filtration, obtains cellulose/graphene oxide composite membrane.
Cellulose aerogels network structure is smashed dissolving and obtains less fiber by the present invention using amide solvent as solvent
Plain micronetwork structure, after then being mixed with graphene oxide water solution, utilizes air pressure by crowd during vacuum filtration
Multiple cellulose microstructured bodies are pressed into two dimensional surface network, are loaded as support frame for graphene oxide nanoscale twins deposition,
Obtain cellulose/graphene oxide composite membrane of high mechanical properties after multilayer assembling, and the preparation method realize cellulose with
Graphene oxide high level it is microcosmic compound.
The present invention is not particularly limited the source of all raw materials, for commercially available or self-control.The cellulose gas
Gel is cellulose aerogels well known to those skilled in the art, has no special limitation, is preferably bacterium in the present invention
Cellulose aerogels；The cellulose aerogels are preferably prepared according to following steps：Cellulose aquagel is passed through into physical mechanical
Rub, be then freeze-dried, obtain cellulose aerogels.
Wherein, the cellulose aquagel is preferably first purified, and removes the protein wherein adulterated and other microorganisms
Secretion, is then rubbed by physical mechanical again.The method of the purifying is method well known to those skilled in the art, and
Without special limitation, preferably purified in the present invention according to following steps：Cellulose aquagel is immersed in alkaline solution, is heated
Handled, be finally washed with deionized water to neutrality.Wherein, the alkaline solution is molten for alkalescence well known to those skilled in the art
Liquid, has no special limitation, is preferably the hydrogen-oxygen of sodium hydroxide solution, more preferably 1%~4% (w/v) in the present invention
Change sodium solution, be further preferably the sodium hydroxide solution of 2%~3% (w/v)；The temperature of the heating is preferably 40 DEG C~80 DEG C,
More preferably 50 DEG C~70 DEG C, be further preferably 55 DEG C~65 DEG C, is most preferably 60 DEG C；The time of the processing is preferably 20~
30h, more preferably 22~26h, are further preferably 23~25h, are most preferably 24h.
Cellulose aquagel after purification is rubbed by physical mechanical, moisture removal is removed in then freeze-drying, obtains fiber
Plain aeroge.
Cellulose aerogels are dispersed in amide solvent, are preferably first mixed cellulose aerogels and amide solvent
Close, then ultrasonic disperse, obtain mixed solution.Wherein, the amide solvent is molten for amide-type well known to those skilled in the art
Agent, has no special limitation, be preferably in the present invention can be miscible with water amide solvent, more preferably formamide, N,
Dinethylformamide and the one or more in DMAC N,N' dimethyl acetamide；The time of the ultrasonic disperse is preferably 1~5h,
More preferably 1~4h, is further preferably 1~3h, is further preferably 1.5~2.5h, is most preferably 2h；Cellulose can with amide solvent
Dissolve each other, but the too low cellulose aerogels amide-type solution of configuration concentration is a kind of waste to amide solvent, and cellulose gas
Gel strength it is excessive and can cause to be difficult to during ultrasound it is fully dispersed, therefore in the mixed solution cellulose aerogels concentration it is excellent
Elect 0.5~3mg/ml as, more preferably 0.5~2.5mg/ml, be further preferably 1~2mg/ml, be most preferably 1~1.5mg/ml.
Cellulose is prepared into stable colloidal sol by present invention selection amide solvent, on the one hand, the solvent can dissolve fibre
Dimension element stabilizes it scattered；On the other hand, which can also be miscible with water, because being needed in follow-up recombination process and oxygen
Graphite aqueous solution is sufficiently mixed.Although cellulose contains abundant hydrophilic hydroxy group group, between its nano-cellulose
Because of very strong hydrogen bond action so that the cellulose network structure of generation is sufficiently stable, it is difficult to dissolves to obtain by common solvent single
Scattered cellulose solution, including solvent-water (although the water-holding capacity of cellulose gel is very high, not soluble in water).Present invention choosing
The amide solvent that more strong hydrogen bonding can be formed with hydroxyl is selected as solvent, to break the mutual hydrogen bond action of cellulose,
Being obtained under ultrasonic wave added can cellulose sol existing for long-time stable.Certainly the cellulose obtained by the process still can not
Reach single scattered state, but it is much smaller compared to the more mechanical cellulose aggregate smashed, itself and graphite oxide can be promoted
Alkene come into full contact with and it is highly microcosmic compound.
The mixed solution is mixed with graphene oxide water solution, wherein, graphene oxide is those skilled in the art
Well known graphene oxide, has no special limitation, is preferably to be prepared using improved Hummers methods in the present invention
Graphene oxide, more preferably follows the steps below preparation：A) graphite pre-oxidizes：By crystalline flake graphite, K2S2O8、P2O5With dense sulphur
Sour hybrid reaction, obtains pre-oxidation graphite；B) by the pre-oxidation graphite and NaNO3It is added in the concentrated sulfuric acid of precooling, slow
It is slow to add KMnO4And reacted under condition of ice bath, it is then transferred into 35 DEG C of water-baths and is reacted；Deionized water is slowly added again
And it is transferred to 98 DEG C of water-baths and is reacted；Deionized water is added again, and 30%H is added after cooling2O2, obtain graphite oxide；C) use
Hydrochloric acid solution washs the graphite oxide to no SO4 2-Detection (uses BaCl2Detection)；Then ultrasound, centrifugation, from what is do not got off
Suspension as peels off obtained graphene oxide, and sediment discards；GO solution is mounted in bag filter and is dialysed, that is, is obtained final clear
Graphene oxide after washing.
The mixed solution is mixed with graphene aqueous solution, it is preferred to use ultrasound is mixed；The ultrasonic time
Preferably 5~30min, more preferably 10~20min, are further preferably 10~15min.
After mixing, it is filtered by vacuum, preferably after natural air drying, obtains cellulose/graphene oxide composite membrane.
Cellulose aquagel block mainly using the compound method of dystopy, is first broken into homogenate and is done by freezing by the present invention
Dry to remove moisture removal, what is obtained is still the cellulose 3D collection of network bodies of large-size；Appropriate solvent is then selected by the network
Structure further smashes dissolving and obtains less cellulose micronetwork structure；After being mixed with graphene oxide water solution, true
Numerous a cellulose microstructured bodies are pressed into two dimensional surface network using air pressure during sky suction filtration, are supplied as support frame
The deposition load of GO nanoscale twins, for its assembling schematic diagram as shown in Figure 1, wherein A is cellulose two dimensional surface network, B is oxidation stone
Black alkene, C are cellulose/graphene oxide composite membrane；Multilayer assembling after obtain in the present invention with high mechanical properties cellulose/
Graphene oxide composite membrane.
In order to further illustrate the present invention, with reference to embodiments to a kind of cellulose/graphite oxide provided by the invention
Alkene composite membrane and preparation method thereof is described in detail.
Reagent used is commercially available in following embodiments.
Embodiment 1
The purifying and dissolving of 1.1 bacteria celluloses (BC)：
BC is purified：BC aquagel membranes are immersed in 2% (w/v) NaOH aqueous solutions, heat 24h at 60 DEG C；With
Cleaned afterwards with deionized water to neutrality.
BC aeroges：BC aquagel membranes after purification are rubbed by physical mechanical, and are freeze-dried and are removed moisture removal, obtain BC
Aeroge.
BC dissolves：50mg BC aeroges are added in 50ml formamide solutions, with ultrasonic cell disintegration instrument (400W power
Under) ultrasound 2h, BC is well dispersed in formamide solution, the mixed solution of 1mg/ml is prepared.
The preparation (using improved Hummers methods) of 1.2 graphene oxides (GO)：
Graphite pre-oxidizes：9g crystalline flake graphites (80 μm) and 7.5g K2S2O8、7.5g P2O5, the dense H of 36ml2SO4At 80 DEG C
Water-bath magnetic agitation 4h；It is then slowly added to 750ml deionized waters；Filter and clean 2~3 times to neutrality with deionized water；
Forced air drying at 80 DEG C, obtains pre-oxidation graphite.
It is prepared by graphite oxide：Pre-oxidize graphite and 4.5g NaNO3Be added to precooling (<4 DEG C) the dense H of 210ml2SO4In；It is slow
It is slow to add 27g KMnO4And 30min is carried out in ice bath；It is subsequently transferred to react 2h in 35 DEG C of water-baths；420ml is slowly added again
Deionized water is simultaneously transferred to 98 DEG C of water-bath 15min；420ml deionized waters are added again, and 60ml 30% is added after cooling
H2O2。
GO is prepared and cleaning：Above-mentioned graphite oxide is washed to no SO with 10%HCl solution4 2- detection (uses BaCl2Inspection
Survey)；Subsequent ultrasound 1h, centrifuges under 8000rpm, obtained GO is as peeled off from the suspension not got off, sediment discards；By GO
Solution is mounted in bag filter and dialyses 2 weeks, i.e., the GO solution after finally being cleaned；And determine concentration.
The preparation of 1.3 bacteria celluloses/graphene oxide composite membrane：
GO solution is made into a series of weak solution of concentration：0.1mg/ml、0.2mg/ml、0.3mg/ml、0.4mg/ml、
0.5mg/mL。
The GO aqueous solutions (a certain concentration) of 5ml are added in the BC mixed solutions (1mg/ml) obtained in the 1.1 of 15mL,
Ultrasonic 10min is allowed to be sufficiently mixed；20ml mixed solutions are made to the composite membrane of a BC and GO with Vacuum filtration device；It is natural
After air-drying, the self-supported membrane of BC+GO can be easy to peel from the basilar memebrane of Suction filtration device.Therefore can prepare it is a series of not
With bacteria cellulose/graphene oxide composite membrane of GO contents, the thickness of film is 11~17 μm, as shown in Fig. 2, Fig. 2 is difference
Composite film thickness variation diagram under GO additive amounts, wherein A are bacteria cellulose/oxidation that 0.1mg/ml GO aqueous solutions are prepared
Graphene composite film, B are bacteria cellulose/graphene oxide composite membrane that 0.2mg/ml GO aqueous solutions are prepared, and C is
The bacteria cellulose that 0.3mg/ml GO aqueous solutions are prepared/graphene oxide composite membrane, as shown in Figure 2, the additive amount of GO is got over
The thickness of big film also increases therewith.
Fig. 3 is incident light through the bacteria cellulose aeroge after the mixed solution and standing obtained in 1.1 after standing
The photo of aqueous solution, wherein A are the bacteria cellulose airsetting glue solution after standing, B be after standing 1.1 in obtained mixing
Solution；From the figure 3, it may be seen that in aqueous bacteria cellulose can not stable dispersion exist, can reunite together again, and in formyl
Bacteria cellulose in amine aqueous solution exists with stable colloidal form, and more consistent Tyndall phenomenon is presented.
Can the ratio of bacteria cellulose and graphene oxide multiple for the bacteria cellulose/graphene oxide that be prepared
Close film and have no influence, but pattern for preparation process, composite membrane and final film properties have different degrees of influence.
Bacteria cellulose/graphene oxide composite membrane film formation time curve map when Fig. 4 is different graphene oxide additive amounts,
As shown in Figure 4, as the increase of graphene oxide additive amount, bacteria cellulose had been filtered by vacuum with graphene oxide liquid mixture
Required time that forms a film in journey can then be multiplied, in the case where ensureing that volume ratio is constant, when graphene oxide concentration increases
When adding to 0.4mg/ml, the time of mixed solution film forming reaches more than 5h, the time required to this is for filming technology after amplification
It is long.
The photo of bacteria cellulose/graphene oxide composite membrane when Fig. 5 is different graphene oxide additive amounts, from left to right
It is sequentially increased for graphene oxide additive amount.As shown in Figure 5, with the increase of graphene oxide additive amount, what is be prepared is thin
The transparency of fungin/graphene oxide composite membrane gradually weakens, by pure bacteria cellulose be prepared for white it is semi-transparent
Bright film, after addition small amounts graphene (0.1mg/ml), it is translucent to be changed into brown color, then gradually becomes sepia and thoroughly
Lightness weakens.
In addition, the additive amount of graphene oxide can significantly affect finally obtained bacteria cellulose/graphene oxide composite membrane
Performance, on the one hand, graphene oxide additive amount is higher, and the machinery of obtained bacteria cellulose/graphene oxide composite membrane is strong
Degree is higher, including tensile strength and toughness；On the other hand, when the additive amount of graphene oxide is too low, obtained bacteria cellulose/
Ion rejection ability is too poor when graphene oxide composite membrane is as permeable membrane, as graphene oxide water solution concentration is in 1.3
During 0.1mg/ml, the selectivity for the bacteria cellulose/graphene oxide composite membrane ion permeable being prepared is poor, with pure bacterium
Film prepared by cellulose is similar, and various sizes of ion/molecular is both transparent for the cellulose crosslinked larger net formed in solution
Network hole, only when graphene oxide additive amount increase to a certain extent, graphene oxide layer is in bacteria cellulose skeleton
On stacking be enough the hole for covering cellulose network, just can further using stack graphene oxide layer and lamella between
Spacing play the selective penetrated property of ion/molecular, graphene oxide additive amount is bigger, and the screening of ion/molecular is thinner and saturating
It is slower to cross speed, (such as mechanical strength, penetrating power) suitable bacteria cellulose and oxidation stone can be selected according to the actual requirements
Black alkene ratio prepares bacteria cellulose/graphene oxide composite membrane.
The stability of bacteria cellulose/graphene oxide composite membrane to obtaining in 1.3 is analyzed, by itself and pure zirconia
Graphene film is individually positioned in aqueous solution, steadiness of both tests in water environment, as shown in Figure 6.Can by Fig. 6
Know, pure zirconia graphene film in rigid connection touches aqueous solution, and (3min) just starts water suction rupture, the thorough ladder after 1h, therefore pure soon
Film prepared by graphene oxide is difficult to apply and operates in actually permeating, in contrast, bacterial fibers prepared by the present invention
Element/graphene oxide composite membrane still keeps complete membrane structure after soaking 1h in aqueous and can be picked up with tweezers, or even
Illustrate bacteria cellulose/oxygen prepared by the present invention still without breakage after experience 3h aqueous solution soakings in follow-up permeance property test
Graphite alkene composite membrane has higher water stability, suitable for actual process of osmosis.
The mechanical performance of bacteria cellulose/graphene oxide composite membrane to obtaining in 1.3 is tested, by itself and pure oxygen
Graphite alkene film and pure bacteria cellulose film carry out mechanical performance comparison, the stress-strain curve of three are obtained, such as Fig. 7 institutes
Show, it is strong to obtain bacteria cellulose/graphene oxide composite membrane, pure zirconia graphene film and the maximum tension of pure bacteria cellulose film
Degree and the change curve of toughness, as shown in Fig. 8 and Fig. 9.As shown in Figure 7, the tensile strength of pure zirconia graphene film is most weak, by it
With bacteria cellulose it is compound after then greatly improve, and in bacteria cellulose/graphene oxide composite membrane graphene oxide add
Amount is bigger, and tensile strength is higher, and when graphene oxide additive amount is 0.3mg/ml, the tensile strength of composite membrane is close to
60MPa, has fully met actual infiltration applications；Likewise, increase with the additive amount of graphene oxide, bacteria cellulose/
The toughness of graphene oxide composite membrane also strengthens successively.The lifting of the mechanical performance index such as tensile strength and toughness illustrates this hair
The bacteria cellulose of bright preparation/graphene oxide composite membrane has the application advantage of material in itself in actual process of osmosis.
The ion sieve performance of bacteria cellulose/graphene oxide composite membrane to obtaining in 1.3 is tested, Tu10Wei
The permeability apparatus of test ion sieve performance, wherein A are percolating solution, and B is supply solution, and C is bacteria cellulose/graphite oxide
Alkene composite membrane；Figure 11 is large scale rhodamine B (RhB) after the compound UF membrane of bacteria cellulose/graphene oxide before and after infiltration
The UV- visible ray spectrograms of solution and percolating solution intermediate ion are supplied, as shown in Figure 11, after the process of osmosis of experience 3h, supply
Solution concentration remains unchanged, while the detection of RhB is also had no in percolating solution, and bacteria cellulose prepared by this explanation present invention/
Graphene oxide composite membrane can retain large scale ion, prevent it from penetrating；Figure 12 is fine in bacterium with KCl for rhodamine B (RhB)
The infiltration rate curve map on element/graphene oxide composite membrane is tieed up, as shown in Figure 12, when having large scale rhodamine B and small size
Ion KCl at the same time in the presence of, electrical conductivity is continuously increased (KCl is contributed) over time in the percolating solution on the left side, and the right
Supply solution in the concentration of RhB remain unchanged and also can't detect the transmission of RhB in percolating solution, this explanation present invention closes
Into bacteria cellulose/graphene oxide composite membrane can function well as sieving actoion for various sizes of ion, can be saturating
Too small size ions and retain the effect of large scale ion；Figure 13 is large scale rhodamine B after pure bacteria cellulose UF membrane
(RhB) the UV- visible ray spectrograms of solution and percolating solution intermediate ion are supplied before and after infiltration, as shown in Figure 13, do not aoxidize stone
The steric hindrance crown_interception of black alkene, macroion RhB just be able to can permeate quickly through middle film by 1h
Substantially observe in solution or detect RhB, and as the time elapses, the RhB ions supplied in solution constantly pass through pure bacterium
Cellulose membrane.
Claims (10)
1. the preparation method of a kind of cellulose/graphene oxide composite membrane, it is characterised in that comprise the following steps：
S1) cellulose aerogels are dispersed in amide solvent, obtain mixed solution；
S2) mixed solution is mixed with graphene oxide water solution, is filtered by vacuum, it is multiple to obtain cellulose/graphene oxide
Close film.
2. preparation method according to claim 1, it is characterised in that the cellulose aerogels are bacteria cellulose airsetting
Glue.
3. preparation method according to claim 1, it is characterised in that the amide solvent is formamide, N, N- diformazans
Base formamide and the one or more in DMAC N,N' dimethyl acetamide.
4. preparation method according to claim 1, it is characterised in that the concentration of cellulose aerogels in the mixed solution
For 0.5~3mg/ml.
5. preparation method according to claim 1, it is characterised in that the step S1) in use ultrasonic disperse；It is described super
The time that sound disperses is 1~5h.
6. preparation method according to claim 1, it is characterised in that the cellulose aerogels follow the steps below
Prepare：
Cellulose aquagel is rubbed by physical mechanical, is then freeze-dried, obtains cellulose aerogels.
7. preparation method according to claim 1, it is characterised in that the cellulose aerogels and the matter of graphene oxide
Amount is than being 50：(0.5~2).
8. cellulose/graphene oxide composite membrane prepared by a kind of claim 1~7 any one, it is characterised in that with fibre
The plain two dimensional surface network of dimension is support frame, and being deposited on the cellulose two dimensional surface network has graphene oxide nanoscale twins.
9. cellulose according to claim 8/graphene oxide composite membrane, it is characterised in that the cellulose/oxidation stone
The thickness of black alkene composite membrane is 11~17 μm.
10. cellulose according to claim 8/graphene oxide composite membrane, it is characterised in that the cellulose/oxidation
The aperture of graphene composite film is 0.3~1.2nm.
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| CN106920700B (en) * | 2017-01-24 | 2019-01-15 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene oxide/bacteria cellulose/carbon nano-tube compound film preparation method and applications of functionalization |
| CN107321197B (en) * | 2017-08-18 | 2021-01-05 | 中国科学院宁波材料技术与工程研究所 | Composite nanofiltration membrane and preparation method thereof |
| CN107805319B (en) * | 2017-11-09 | 2020-05-08 | 陕西科技大学 | Preparation method of ultralight multifunctional composite sponge for reducing haze in air and product thereof |
| CN107973920A (en) * | 2017-11-15 | 2018-05-01 | 深圳大学 | A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof |
| CN108753262B (en) * | 2018-06-27 | 2021-01-22 | 中国科学院宁波材料技术与工程研究所 | Graphene-based heat-conducting composite material and preparation method thereof |
| CN109378110B (en) * | 2018-09-26 | 2020-01-21 | 浙江理工大学 | Preparation method of cellulose/graphene nanosheet flexible conductive composite material with piezoresistive sensing performance |
| CN110186600B (en) * | 2019-06-18 | 2021-06-18 | 福建师范大学 | Self-supporting film preparation method and pressure sensing actuator |
| CN112094420B (en) * | 2019-06-18 | 2022-07-15 | 中国科学技术大学 | Nanofiber multilayer structure plate and preparation method thereof |
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