CN105801918A - Cellulose/graphene oxide composite film and preparing method thereof - Google Patents
Cellulose/graphene oxide composite film and preparing method thereof Download PDFInfo
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- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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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
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
Abstract
The invention provides a cellulose/graphene oxide composite film and a preparing method thereof.The preparing method comprises the following steps that firstly, cellulose aerogel is dispersed in an amide solvent, and a mixed solution is obtained; secondly, the mixed solution and a graphene oxide aqueous solution are mixed, vacuum filtration is carried out, and the cellulose/graphene oxide composite film is obtained.Compared with the prior art, the amide solvent serves as a solvent, and the network structure of cellulose aerogel is smashed and dissolved to obtain small cellulose micro-network structure bodies; after the small cellulose micro-network structure bodies are mixed with the graphene oxide aqueous solution, the mass cellulose micro-network structure bodies are pressed into a two-dimensional plane network with air pressure in the vacuum filtration process, the two-dimensional plane network serves as a supporting framework for sedimentation and loading of graphene oxide nanosheet patch layers, the cellulose/graphene oxide composite film with high mechanical strength is obtained after multilayer assembling, and the by means of the preparing method, high-degree micro combination of cellulose and graphene oxide is achieved.
Description
Technical field
The invention belongs to technical field of composite materials, particularly relate to a kind of cellulose/graphene oxide composite membrane and preparation method thereof.
Background technology
Graphene be a kind of by carbon atom with sp2Hybrid orbital composition hexangle type is the flat film of honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness.Since within 2004, being found, the material of this uniqueness receives significant attention because of its multiple excellent properties.
Existing a little preparation about graphene oxide Yu bacteria cellulose composite membrane is broadly divided into In-situ reaction and two kinds of methods of dystopy compound.Graphene oxide is mainly directly appended in the culture fluid of Bacterial cellulose growth by In-situ reaction preparation, along with graphene oxide is directly wrapped in its three-dimensional network by the cellulosic process of micro-organisms.But the method preparation process regulates and controls more difficult, graphene oxide solution generally in acidity, change after interpolation culture fluid acid-base value can the activity of appreciable impact microorganism, thus affecting the production of Bacterial cellulose.In addition In-situ reaction prepares composite film thickness and surface smoothness are difficult to control to, and are difficult to obtain the thin film of surfacing when especially preparing relatively thin composite membrane in the process obtained by thin Bacterial cellulose-graphene oxide compound water congealing glued membrane convection drying.
Another kind of dystopy compound, it is common that bacteria cellulose aquagel block is broken into homogenate, then sucking filtration film forming after mixing with graphene oxide dispersion, or directly gel mass is immersed in graphene oxide solution；Even if the Bacterial cellulose in the method process breaks into homogenate, it remains the cellulose aggregate of a large-size, hydrogel structure is stable, and graphene oxide is difficult to penetrate into inside three-dimensional network so that its interior three-dimensional network structure cannot be fully utilized and realize the microcosmic compound of high level.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is in that to provide a kind of cellulose/graphene oxide composite membrane and preparation method thereof, and the mechanical strength of cellulose prepared by the method/graphene oxide composite membrane is higher.
The preparation method that the invention provides a kind of cellulose/graphene oxide composite membrane, comprises the following steps:
S1) cellulose aerogels is dispersed in amide solvent, obtains mixed solution；
S2) described mixed solution is mixed with graphene oxide water solution, vacuum filtration, obtain cellulose/graphene oxide composite membrane.
Preferably, described cellulose aerogels is Bacterial cellulose aeroge.
Preferably, described amide solvent is one or more in Methanamide, DMF and N,N-dimethylacetamide.
Preferably, in described mixed solution, the concentration of cellulose aerogels is 0.5～3mg/ml.
Preferably, described step S1) middle employing ultrasonic disperse；The time of described ultrasonic disperse is 1～5h.
Preferably, described cellulose aerogels is prepared according to following steps:
Cellulose aquagel is rubbed by physical mechanical, then lyophilization, obtain cellulose aerogels.
Preferably, described cellulose aerogels is 50:(0.5～2 with the mass ratio of graphene oxide).
Present invention also offers a kind of cellulose/graphene oxide composite membrane, with cellulose two dimensional surface network for support frame, on described cellulose two dimensional surface network, deposition has graphene oxide nanoscale twins.
Preferably, the thickness of described cellulose/graphene oxide composite membrane is 11～17 μm.
Preferably, the aperture of described cellulose/graphene oxide composite membrane is 0.3～1.2nm.
The invention provides a kind of cellulose/graphene oxide composite membrane and preparation method thereof, comprise the following steps: S1) cellulose aerogels is dispersed in amide solvent, obtain mixed solution；S2) described mixed solution is mixed with graphene oxide water solution, vacuum filtration, obtain cellulose/graphene oxide composite membrane.Compared with prior art, the present invention is with amide solvent for solvent, cellulose aerogels network structure is smashed dissolving and obtains less cellulose micronetwork structure, then after mixing with graphene oxide water solution, vacuum filtration process utilize air pressure numerous cellulose microstructured bodies are pressed into two dimensional surface network, as support frame for the deposition load of graphene oxide nanoscale twins, multilamellar obtains the cellulose/graphene oxide composite membrane of high mechanical properties after assembling, and this preparation method achieves the microcosmic compound of cellulose and graphene oxide high level.
Accompanying drawing explanation
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 different GO additions in the embodiment of the present invention；
Fig. 3 is the incident illumination of the present invention photo through the Bacterial cellulose aeroge aqueous solution after the mixed solution obtained in 1.1 after standing and standing；
Bacterial cellulose/graphene oxide composite membrane film formation time curve chart when Fig. 4 is different graphene oxide addition in the embodiment of the present invention 1；
The photo of Bacterial cellulose/graphene oxide composite membrane when Fig. 5 is different graphene oxide addition in the embodiment of the present invention 1；
Fig. 6 is the stability test figure of the Bacterial cellulose/graphene oxide composite membrane obtained in the embodiment of the present invention 1；
Fig. 7 is the Bacterial cellulose/graphene oxide composite membrane, pure zirconia graphene film and the pure bacteria cellulose film stress-strain curve that obtain in the embodiment of the present invention 1；
Fig. 8 is the Bacterial cellulose/graphene oxide composite membrane, pure zirconia graphene film and the pure bacteria cellulose film the maximum tensile strength change curve that obtain in the embodiment of the present invention 1；
Fig. 9 is the change curve of the Bacterial cellulose/graphene oxide composite membrane, pure zirconia graphene film and the pure Bacterial cellulose film toughness that obtain in the embodiment of the present invention 1；
Figure 10 is the permeability apparatus of test ion sieve performance；
Figure 11 is large scale rhodamine B (RhB) UV-visible ray spectrogram of supply solution and percolating solution intermediate ion before and after infiltration after the Bacterial cellulose/graphene oxide composite membrane (GO concentration is 0.3mg/mL (BC+GO-0.3)) obtained in the embodiment of the present invention 1 separates；
Figure 12 is rhodamine B (RhB) and KCl infiltration rate curve chart on Bacterial cellulose/graphene oxide composite membrane (GO concentration is 0.3mg/mL (BC+GO-0.3))；
Figure 13 is large scale rhodamine B (RhB) UV-visible ray spectrogram of supply solution and percolating solution intermediate ion before and after infiltration after pure Bacterial cellulose membrance separation.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
The invention provides a kind of cellulose/graphene oxide composite membrane, with cellulose two dimensional surface network for support frame, on described cellulose two dimensional surface network, deposition has graphene oxide nanoscale twins.
Described cellulose is cellulose well known to those skilled in the art, there is no special restriction, is preferably Bacterial cellulose in the present invention.
The thickness of described cellulose/graphene oxide composite membrane is preferably 11～17 μm, more preferably 12～15 μm；The aperture of described cellulose/graphene oxide composite membrane is preferably 0.3～1.2nm, more preferably 0.4～0.8nm.
The preparation method that present invention also offers a kind of above-mentioned cellulose/graphene oxide composite membrane, comprises the following steps: S1) cellulose aerogels is dispersed in amide solvent, obtain mixed solution；S2) described mixed solution is mixed with graphene oxide water solution, vacuum filtration, obtain cellulose/graphene oxide composite membrane.
The present invention is with amide solvent for solvent, cellulose aerogels network structure is smashed dissolving and obtains less cellulose micronetwork structure, then after mixing with graphene oxide water solution, vacuum filtration process utilize air pressure numerous cellulose microstructured bodies are pressed into two dimensional surface network, as support frame for the deposition load of graphene oxide nanoscale twins, multilamellar obtains the cellulose/graphene oxide composite membrane of high mechanical properties after assembling, and this preparation method achieves the microcosmic compound of cellulose and graphene oxide high level.
The restriction that the present invention is not special to the source of all raw materials, for commercially available or self-control.Described cellulose aerogels is cellulose aerogels well known to those skilled in the art, there is no special restriction, is preferably Bacterial cellulose aeroge in the present invention；Described cellulose aerogels is preferably prepared according to following steps: rubbed by physical mechanical by cellulose aquagel, then lyophilization, obtains cellulose aerogels.
Wherein, described cellulose aquagel is preferably first purified, and removes the protein and other microorganism secretion things that wherein adulterate, then rubs again through physical mechanical.The method of described purification is method well known to those skilled in the art, there is no special restriction, and preferably according to following steps purification in the present invention: be immersed in alkaline solution by cellulose aquagel, heating processes, and is finally washed till neutrality with deionized water.Wherein, described alkaline solution is alkaline solution well known to those skilled in the art, there is no special restriction, the present invention is preferably sodium hydroxide solution, it is more preferably the sodium hydroxide solution of 1%～4% (w/v), is further preferably the sodium hydroxide solution of 2%～3% (w/v)；The temperature of described heating is preferably 40 DEG C～80 DEG C, more preferably 50 DEG C～70 DEG C, is further preferably 55 DEG C～65 DEG C, it is most preferred that be 60 DEG C；The time of described process is preferably 20～30h, more preferably 22～26h, is further preferably 23～25h, it is most preferred that for 24h.
Being rubbed by physical mechanical by cellulose aquagel after purification, then moisture is removed in lyophilization, obtains cellulose aerogels.
Cellulose aerogels is dispersed in amide solvent, it is preferable that first cellulose aerogels is mixed with amide solvent, then ultrasonic disperse, obtain mixed solution.Wherein, described amide solvent is amide solvent well known to those skilled in the art, there is no special restriction, the amide solvent that preferably can dissolve each other with water in the present invention, be more preferably in Methanamide, DMF and N,N-dimethylacetamide one or more；The time of described ultrasonic disperse is preferably 1～5h, more preferably 1～4h, is further preferably 1～3h, is further preferably 1.5～2.5h, it is most preferred that for 2h；Cellulose and amide solvent can dissolve each other, but amide solvent is a kind of waste by the too low cellulose aerogels amide-type solution of configuration concentration, and cellulose aerogels excessive concentration is difficult to fully dispersed when can cause ultrasonic, therefore in described mixed solution, the concentration of cellulose aerogels is preferably 0.5～3mg/ml, it is more preferably 0.5～2.5mg/ml, it is further preferably 1～2mg/ml, it is most preferred that be 1～1.5mg/ml.
The present invention selects amide solvent that cellulose is prepared into stable colloidal sol, on the one hand, this solvent can dissolve cellulose and stabilize it dispersion；On the other hand, this solvent can also dissolve each other with water, because needing to be sufficiently mixed with graphene oxide water solution in follow-up recombination process.Although cellulose contains abundant hydrophilic hydroxy group group, but because of very strong hydrogen bond action between its nano-cellulose, make the cellulose network structure produced sufficiently stable, it is difficult to be dissolved by common solvent obtain single scattered cellulose solution, including aqueous solvent (although the water-holding capacity of cellulose gel is significantly high, but water insoluble).The present invention selects to form the amide solvent of more strong hydrogen bonding as solvent with hydroxyl, breaks cellulose hydrogen bond action each other, obtain under ultrasonic wave added can long-time stable exist cellulose sol.The cellulose obtained of course through this process is still unable to reach single scattered state, but the cellulose aggregate that machinery of comparing is smashed is much smaller, can promote its being fully contacted and highly microcosmic compound with graphene oxide.
Described mixed solution is mixed with graphene oxide water solution, wherein, graphene oxide is graphene oxide well known to those skilled in the art, there is no special restriction, the present invention is preferably and adopts the Hummers method improved to prepare graphene oxide, be more preferably prepared according to following steps: A) graphite pre-oxidation: by crystalline flake graphite, K2S2O8、P2O5With concentrated sulphuric acid hybrid reaction, obtain pre-oxidation graphite；B) by described pre-oxidation graphite and NaNO3Join in the concentrated sulphuric acid of pre-cooling, be slowly added to KMnO4And react under condition of ice bath, it is then transferred in 35 DEG C of water-baths and reacts；It is slowly added deionized water again and is transferred to 98 DEG C of water-baths and reacts；Again add deionized water, after cooling, add 30%H2O2, obtain graphite oxide；C) with hydrochloric acid solution, described graphite oxide is washed to without SO4 2-Detection (uses BaCl2Detection)；Ultrasonic, centrifugal subsequently, it is from the suspension not got off and peels off the graphene oxide obtained, precipitate discards；GO solution is contained in bag filter and dialyses, namely obtain the graphene oxide after finally cleaning.
Described mixed solution is mixed with graphene aqueous solution, it is preferred to use ultrasonic mix；The described ultrasonic time is preferably 5～30min, more preferably 10～20min, is further preferably 10～15min.
After mixing, carry out vacuum filtration, it is preferable that after natural air drying, obtain cellulose/graphene oxide composite membrane.
The present invention mainly adopts the method for dystopy compound, cellulose aquagel block first breaks into homogenate and removes moisture by lyophilization, and what obtain is still the cellulose 3D collection of network body of large-size；Select suitable solvent that this network structure is smashed dissolving further subsequently and obtain less cellulose micronetwork structure；After mixing with graphene oxide water solution, vacuum filtration process utilize air pressure numerous cellulose microstructured bodies are pressed into two dimensional surface network, as support frame for the deposition load of GO nanoscale twins, it assembles schematic diagram as shown in Figure 1, wherein A is cellulose two dimensional surface network, B is graphene oxide, and C is cellulose/graphene oxide composite membrane；Multilamellar obtains the cellulose/graphene oxide composite membrane in the present invention with high mechanical properties after assembling.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of cellulose/graphene oxide composite membrane provided by the invention and preparation method thereof is described in detail.
Reagent used in following example is commercially available.
Embodiment 1
The purification of 1.1 Bacterial cellulose (BC) and dissolving:
BC purification: BC aquagel membrane is immersed in 2% (w/v) NaOH aqueous solution, heat treated 24h at 60 DEG C；Clean to neutral with deionized water subsequently.
BC aeroge: the BC aquagel membrane after purification is rubbed by physical mechanical, and lyophilization removal moisture, obtain BC aeroge.
BC dissolves: 50mgBC aeroge is added in 50ml formamide solution, with ultrasonic cell disintegration instrument (under 400W power) ultrasonic 2h, makes BC be well dispersed in formamide solution, prepares the mixed solution of 1mg/ml.
The preparation (adopting the Hummers method improved) of 1.2 graphene oxides (GO):
Graphite pre-oxidation: 9g crystalline flake graphite (80 μm) and 7.5gK2S2O8、7.5gP2O5, the dense H of 36ml2SO4Water-bath magnetic agitation 4h at 80 DEG C；It is then slowly added to 750ml deionized water；Filter and clean 2～3 times to neutral with deionized water；Forced air drying at 80 DEG C, obtains pre-oxidation graphite.
Prepared by graphite oxide: pre-oxidation graphite and 4.5gNaNO3Join the dense H of 210ml of pre-cooling (< 4 DEG C)2SO4In；It is slowly added to 27gKMnO4And in ice bath, carry out 30min；It is subsequently transferred in 35 DEG C of water-baths and reacts 2h；It is slowly added 420ml deionized water again and is transferred to 98 DEG C of water-bath 15min；Again add 420ml deionized water, after cooling, add 60ml30%H2O2。
GO preparation and cleaning: with 10%HCl solution to the washing of above-mentioned graphite oxide to without SO4 2-detection (uses BaCl2Detection)；Ultrasonic 1h subsequently, centrifugal under 8000rpm, it is from the suspension not got off and peels off the GO obtained, precipitate discards；GO solution is contained in bag filter and dialyses 2 weeks, namely obtain the GO solution after finally cleaning；And determine concentration.
The preparation of 1.3 Bacterial cellulose/graphene oxide composite membrane:
GO solution is made into the weak solution of a series of concentration: 0.1mg/ml, 0.2mg/ml, 0.3mg/ml, 0.4mg/ml, 0.5mg/mL.
Being added to by the GO aqueous solution (a certain concentration) of 5ml in the BC mixed solution (1mg/ml) obtained in the 1.1 of 15mL, ultrasonic 10min is so as to be sufficiently mixed；By Vacuum filtration device, 20ml mixed solution is made the composite membrane of BC Yu GO；After natural air drying, the self-supported membrane of BC+GO just can be easy to peel from the basement membrane of Suction filtration device.Therefore Bacterial cellulose/graphene oxide the composite membrane of a series of different GO content can be prepared, the thickness of film is 11～17 μm, as shown in Figure 2, Fig. 2 is composite film thickness variation diagram under different GO addition, wherein A is Bacterial cellulose/graphene oxide composite membrane that 0.1mg/mlGO aqueous solution prepares, B is Bacterial cellulose/graphene oxide composite membrane that 0.2mg/mlGO aqueous solution prepares, C is Bacterial cellulose/graphene oxide composite membrane that 0.3mg/mlGO aqueous solution prepares, as shown in Figure 2, the thickness of the more big film of the addition of GO also strengthens therewith.
Fig. 3 is the photo of the Bacterial cellulose aeroge aqueous solution after the mixed solution obtained in 1.1 after incident illumination passes through standing and standing, and wherein A is the Bacterial cellulose aeroge aqueous solution after standing, and B is the mixed solution obtained in 1.1 after standing；From the figure 3, it may be seen that Bacterial cellulose cannot stable dispersion exist in aqueous, again can reunite together, and the Bacterial cellulose in formamide solution all exists with stable colloidal form, presents more consistent Tyndall phenomenon.
Can the ratio of Bacterial cellulose and graphene oxide there is no impact for the Bacterial cellulose/graphene oxide composite membrane that prepare, but all has impact in various degree for preparation process, the pattern of composite membrane and final film properties.
Bacterial cellulose/graphene oxide composite membrane film formation time curve chart when Fig. 4 is different graphene oxide addition, as shown in Figure 4, increase along with graphene oxide addition, Bacterial cellulose and graphene oxide liquid mixture time needed for film forming in vacuum filtration process then can be multiplied, when ensureing that volume ratio is constant, when graphene oxide concentration increases to 0.4mg/ml, the time of mixed solution film forming reaches more than 5h, this for after amplifying filming technology required time long.
When Fig. 5 is different graphene oxide addition, the photo of Bacterial cellulose/graphene oxide composite membrane, increases successively for graphene oxide addition from left to right.As shown in Figure 5, increase along with graphene oxide addition, the transparency of the Bacterial cellulose prepared/graphene oxide composite membrane weakens gradually, by pure Bacterial cellulose prepare for white translucent thin film, after adding small amounts Graphene (0.1mg/ml), become brown color translucent, gradually become sepia and reduced transparency subsequently.
In addition, the addition meeting appreciable impact of graphene oxide finally prepares the performance of Bacterial cellulose/graphene oxide composite membrane, on the one hand, graphene oxide addition is more high, the mechanical strength of the Bacterial cellulose obtained/graphene oxide composite membrane is more high, including tensile strength and toughness；nullOn the other hand，When the addition of graphene oxide is too low，When Bacterial cellulose/graphene oxide the composite membrane prepared is as permeable membrane, ion rejection ability is too poor，As when in 1.3, graphene oxide water solution concentration is 0.1mg/ml，The selectivity of the Bacterial cellulose prepared/graphene oxide composite membrane ion permeable is poor，The film prepared with pure Bacterial cellulose is similar，In solution, various sizes of ion/molecular is both transparent for cellulose crosslinked bigger network hole，Only when the addition of graphene oxide increases to a certain degree，The graphene oxide lamella stacking hole being enough to cover cellulose network on Bacterial cellulose skeleton，The selective penetrated property of ion/molecular just can be played further with the spacing between stacking graphene oxide lamella and lamella，Graphene oxide addition is more big，The screening of ion/molecular is more thin and transmission rates is more slow，Can according to the actual requirements (such as mechanical strength、Penetrating power etc.) select suitable Bacterial cellulose and graphene oxide ratio to prepare Bacterial cellulose/graphene oxide composite membrane.
The stability of the Bacterial cellulose/graphene oxide composite membrane obtained in 1.3 is analyzed, itself and pure zirconia graphene film are individually positioned in aqueous solution, both steadiness in water environment of test, as shown in Figure 6.As shown in Figure 6, pure zirconia graphene film just starts water suction at just contact aqueous solution (3min) soon and breaks, thorough ladder after 1h, therefore the thin film that prepared by pure zirconia Graphene is difficult to apply and operate in reality is permeated, in contrast, Bacterial cellulose prepared by the present invention/graphene oxide composite membrane still keeps complete membrane structure and available tweezers to pick up after soaking 1h in aqueous, still without damaged after experience 3h aqueous solution soaking in testing even at follow-up permeance property, illustrate that Bacterial cellulose/graphene oxide composite membrane prepared by the present invention has higher water stability, it is applicable to actual process of osmosis.
The mechanical performance of the Bacterial cellulose/graphene oxide composite membrane obtained in 1.3 is tested, with pure zirconia graphene film and pure bacteria cellulose film, it is carried out mechanical performance compare, obtain the stress-strain curve of three, as shown in Figure 7, obtain the change curve of Bacterial cellulose/graphene oxide composite membrane, the pure zirconia graphene film the maximum tensile strength with pure bacteria cellulose film and toughness, as shown in Fig. 8 and Fig. 9.As shown in Figure 7, the tensile strength of pure zirconia graphene film is the most weak, then greatly improve after itself and Bacterial cellulose compound, and graphene oxide addition is more big in Bacterial cellulose/graphene oxide composite membrane, tensile strength is more high, when graphene oxide addition is 0.3mg/ml, the tensile strength of composite membrane close to 60MPa, can fully meet the infiltration applications of reality；Same, along with the addition of graphene oxide increases, the toughness of Bacterial cellulose/graphene oxide composite membrane also strengthens successively.The lifting of the mechanical performance index such as tensile strength and toughness all illustrates that Bacterial cellulose/graphene oxide composite membrane prepared by the present invention has the application advantage of material itself in actual process of osmosis.
The ion sieve performance of the Bacterial cellulose/graphene oxide composite membrane obtained in 1.3 is tested, and Figure 10 is the permeability apparatus of test ion sieve performance, and wherein A is percolating solution, and B is supply solution, and C is Bacterial cellulose/graphene oxide composite membrane；Figure 11 is large scale rhodamine B (RhB) UV-visible ray spectrogram of supply solution and percolating solution intermediate ion before and after infiltration after Bacterial cellulose/graphene oxide composite membrane separates, as shown in Figure 11, after the process of osmosis of experience 3h, supply solution concentration remains unchanged, percolating solution also there is no the detection of RhB simultaneously, this illustrates that Bacterial cellulose/graphene oxide composite membrane prepared by the present invention can retain large scale ion, stops it to penetrate；Figure 12 is rhodamine B (RhB) and KCl infiltration rate curve chart on Bacterial cellulose/graphene oxide composite membrane, as shown in Figure 12, when having large scale rhodamine B and small size ion KCl exists simultaneously, in the percolating solution on the left side, electrical conductivity elapses in time and is continuously increased (KCl is contributed), and the concentration of RhB remains unchanged and also can't detect passing through of RhB in percolating solution in the supply solution on the right, this illustrates that the Bacterial cellulose/graphene oxide composite membrane of present invention synthesis can function well as sieving actoion for various sizes of ion, can pass through small size ion and retain the effect of large scale ion；Figure 13 is large scale rhodamine B (RhB) UV-visible ray spectrogram of supply solution and percolating solution intermediate ion before and after infiltration after pure Bacterial cellulose membrance separation, as shown in Figure 13, there is no the sterically hindered crown_interception of graphene oxide, macroion RhB can quickly through middle thin film, just through 1h can substantially observe in percolating solution or detect RhB, and elapse over time, the RhB ion in supply solution is constantly through pure bacteria cellulose film.
Claims (10)
1. the preparation method of cellulose/graphene oxide composite membrane, it is characterised in that comprise the following steps:
S1) cellulose aerogels is dispersed in amide solvent, obtains mixed solution；
S2) described mixed solution is mixed with graphene oxide water solution, vacuum filtration, obtain cellulose/graphene oxide composite membrane.
2. preparation method according to claim 1, it is characterised in that described cellulose aerogels is Bacterial cellulose aeroge.
3. preparation method according to claim 1, it is characterised in that described amide solvent is one or more in Methanamide, DMF and N,N-dimethylacetamide.
4. preparation method according to claim 1, it is characterised in that in described mixed solution, the concentration of cellulose aerogels is 0.5～3mg/ml.
5. preparation method according to claim 1, it is characterised in that described step S1) middle employing ultrasonic disperse；The time of described ultrasonic disperse is 1～5h.
6. preparation method according to claim 1, it is characterised in that described cellulose aerogels is prepared according to following steps:
Cellulose aquagel is rubbed by physical mechanical, then lyophilization, obtain cellulose aerogels.
7. preparation method according to claim 1, it is characterised in that the mass ratio of described cellulose aerogels and graphene oxide is 50:(0.5～2).
8. cellulose/graphene oxide composite membrane, it is characterised in that with cellulose two dimensional surface network for support frame, on described cellulose two dimensional surface network, deposition has graphene oxide nanoscale twins.
9. cellulose according to claim 8/graphene oxide composite membrane, it is characterised in that the thickness of described cellulose/graphene oxide composite membrane is 11～17 μm.
10. cellulose according to claim 8/graphene oxide composite membrane, it is characterised in that the aperture of described cellulose/graphene oxide composite membrane is 0.3～1.2nm.
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| CN106920700A (en) * | 2017-01-24 | 2017-07-04 | 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 |
| CN107321197A (en) * | 2017-08-18 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of composite nanometer filtering film and preparation method thereof |
| CN107805319A (en) * | 2017-11-09 | 2018-03-16 | 陕西科技大学 | A kind of preparation method of ultralight multi-functional composite sponge for air drop haze and products 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 |
| CN108203090A (en) * | 2016-12-16 | 2018-06-26 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene |
| CN108753262A (en) * | 2018-06-27 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene-based heat-conductive composite material and preparation method thereof |
| CN109378110A (en) * | 2018-09-26 | 2019-02-22 | 浙江理工大学 | Cellulose with pressure drag sensitivity/graphene nanometer sheet flexible conductive composite material preparation method |
| CN110186600A (en) * | 2019-06-18 | 2019-08-30 | 福建师范大学 | Self-supporting film preparation method and pressure sensing actuator |
| CN112094420A (en) * | 2019-06-18 | 2020-12-18 | 中国科学技术大学 | Nanofiber multilayer structure plate and preparation method thereof |
| CN113956541A (en) * | 2021-07-30 | 2022-01-21 | 中国科学院宁波材料技术与工程研究所 | Cellulose/graphene oxide composite membrane |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108203090A (en) * | 2016-12-16 | 2018-06-26 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene |
| CN106920700A (en) * | 2017-01-24 | 2017-07-04 | 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 |
| 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 |
| CN107321197A (en) * | 2017-08-18 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of composite nanometer filtering film 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 |
| CN107805319A (en) * | 2017-11-09 | 2018-03-16 | 陕西科技大学 | A kind of preparation method of ultralight multi-functional composite sponge for air drop haze and products 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 |
| CN108753262A (en) * | 2018-06-27 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene-based heat-conductive 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 |
| CN109378110A (en) * | 2018-09-26 | 2019-02-22 | 浙江理工大学 | Cellulose with pressure drag sensitivity/graphene nanometer sheet flexible conductive composite material preparation method |
| CN110186600A (en) * | 2019-06-18 | 2019-08-30 | 福建师范大学 | Self-supporting film preparation method and pressure sensing actuator |
| CN112094420A (en) * | 2019-06-18 | 2020-12-18 | 中国科学技术大学 | Nanofiber multilayer structure plate and preparation method thereof |
| 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 |
| CN113956541A (en) * | 2021-07-30 | 2022-01-21 | 中国科学院宁波材料技术与工程研究所 | Cellulose/graphene oxide composite membrane |
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