CN117247577A - Preparation method of graphene/manganese ferrite/cellulose composite membrane - Google Patents
Preparation method of graphene/manganese ferrite/cellulose composite membrane Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 229920002678 cellulose Polymers 0.000 title claims abstract description 44
- 239000001913 cellulose Substances 0.000 title claims abstract description 44
- 239000012528 membrane Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910000859 α-Fe Inorganic materials 0.000 title claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052748 manganese Inorganic materials 0.000 title claims description 8
- 239000011572 manganese Substances 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 41
- 235000010980 cellulose Nutrition 0.000 claims description 39
- 229910002804 graphite Inorganic materials 0.000 claims description 31
- 239000010439 graphite Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000005457 ice water Substances 0.000 claims description 18
- 238000003760 magnetic stirring Methods 0.000 claims description 15
- 238000009830 intercalation Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 230000002687 intercalation Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000011162 core material Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 4
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
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- 238000001816 cooling Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000001007 puffing effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 150000002696 manganese Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229920001046 Nanocellulose Polymers 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 4
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- 230000005670 electromagnetic radiation Effects 0.000 abstract 1
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- 238000005485 electric heating Methods 0.000 description 2
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- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing graphene/MnFe 2 O 4 A simple, green and environment-friendly method for preparing the cellulose composite membrane. The composite film adopts graphene oxide as a substrate, and MnFe is prepared by a tape casting self-stacking process 2 O 4 And nanocrystalline cellulose to prepare a film. The method has the advantages of simple preparation process, low cost, high production efficiency and the like. When the material is used as an electromagnetic shielding material, electromagnetic radiation can be effectively absorbed, and harm to human bodies and equipment is reduced; as a heat conduction material, the high-efficiency heat transfer can be realized, and the heat conductivity of the material is improved; high sensitivity and rapid response can be achieved as sensor materials; can be used as water purification filtering material to remove organic and inorganic dirt in waterAnd the quality of the water is improved due to the dye. Such graphene/MnFe 2 O 4 The cellulose composite membrane has the potential of large-scale and safe production and has wide market application prospect.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to graphene/MnFe 2 O 4 Preparation method of cellulose composite membrane.
Background
Graphene as a two-dimensional crystalline material with monoatomic layers, which is formed by passing sp from carbon atoms 2 Hybridized close packed, exhibiting unique honeycomb structures and various novel properties. Therefore, the composite formed by graphene and other materials also shows superior performance. For example, the composite formed by the ferrite magnetic nano-particles has good electromagnetic shielding and wave absorbing properties. Compared with the traditional ferrite material, mnFe 2 O 4 The density is high, but the magnetic material has strong magnetic property and magnetic loss wave absorbing property. The graphene has excellent electrical, thermodynamic and mechanical properties, small density, strong thermal stability and higher dielectric loss. Thus, mnFe 2 O 4 The wave-absorbing material with more excellent performance can be obtained by compounding the graphene, so that the aims of reducing reflection loss and widening the wave-absorbing frequency range are fulfilled.
In addition, nanocellulose is a high-potential material, has high strength, high rigidity, biodegradability, light weight, transparency and other bio-based functions, and is receiving more and more attention. It can be used to prepare highly ordered graded composites as a solid and stable carrier, matrix or scaffold component for the preparation of functional materials. Nanocellulose can be extensively derivatized to form stable and strong rigid chain macromolecular structures that have hydrogel or film-forming properties. Therefore, the composite material can be compounded with nano cellulose to enhance the structural stability and mechanical property of the material, and can be applied to the fields of water purification and filtration materials and the like.
Thus, this graphene oxide/MnFe 2 O 4 The preparation method of the cellulose composite membrane has wide application potential, is simple in preparation process and environment-friendly, and can be used in the fields of high-dielectric capacitance materials, electromagnetic shielding materials, heat conducting materials, core materials of various sensors, water purifying and filtering materials and the like. There are many graphene film materials on the market at present, for example, the method described in patent CN106030497a is to mix graphene oxide with cellulose solution, and then freeze-dry and reduce to obtain a composite filmAnd patent CN105384943a describes a method for preparing a composite membrane by reacting beta-cyclodextrin and cellulose in an alkaline environment to form beta-cyclodextrin-cellulose, and then mixing with graphene oxide dispersion, drying, reducing, and the like. The composite membrane material has the capabilities of inclusion, slow release and catalysis, and can effectively remove dye molecules in wastewater. However, the technical methods only consider the compounding of graphene and cellulose, do not involve the addition of metal oxide, and have the defects of higher cost, poor mechanical property, difficult recovery and the like.
In order to solve these problems, the present invention proposes a method for preparing a composite film by combining magnetically lossy MnFe 2 O 4 The nano particles and the graphene oxide are compounded, and nano cellulose is added to enhance the film forming property and mechanical property of the composite. The composite film not only can realize effective absorption of electromagnetic waves, but also has good electric heating performance, and can be used for preparing efficient wave-absorbing materials and electric heating devices. Compared with the existing graphene composite material, the composite film material has more excellent performance and wide application prospect.
Disclosure of Invention
The invention aims to provide graphene/MnFe 2 O 4 The preparation method of the cellulose composite membrane is simple and environment-friendly in preparation process, and can be used for high-dielectric capacitance materials, electromagnetic shielding materials, heat conducting materials, core materials of various sensors and water purifying and filtering materials.
In order to achieve the above object, the present invention provides the following technical solutions: graphene/MnFe 2 O 4 The preparation method of the cellulose composite membrane comprises the following specific steps of selecting a natural crystalline flake graphite, adopting a modified Hummers method to prepare Graphene Oxide (GO), and preparing the graphene oxide according to the following specific steps:
step one, low-temperature intercalation puffing to form separation between graphite layers:
a. 1g of sodium nitrate powder was dissolved in 60ml of concentrated sulfuric acid (98%) and placed in an open beaker followed by magnetic stirring in an ice water bath for 15-30min;
b. slowly adding 2g of graphite powder at a rate of 1g/min, and maintaining magnetic stirring (speed 600 rpm/min) and ice water bath for 30min;
step two, intercalation oxidation at normal temperature is carried out so as to enable intercalation oxidation between graphite layers:
c. slowly adding 10g of potassium permanganate powder into the graphite mixed solution at a rate of 1g/min, and maintaining magnetic stirring for 1.5h;
d. removing the open beaker from the ice water bath, naturally heating the reaction system to about 35 ℃ due to intercalation oxidation heat release of concentrated sulfuric acid on graphite, maintaining the magnetic stirring speed at 1000rpm/min, keeping the temperature, gradually changing the color of the solution into black and green, and taking the color on the wall of the beaker as the reference;
e. the self-intercalation oxidation reaction of the reaction system is kept for about 8 hours, so that the color of the mixed solution is changed into dark brown;
step three, high-temperature hydrolysis and reduction are terminated to prepare expanded graphite oxide:
f. adding 90ml deionized ice water slowly and uniformly into the graphite oxide mixed solution, adjusting the mechanical stirring speed to 400rpm/min to prevent the temperature rise and sputtering of severe reaction, and maintaining the self-reaction state for 15min when the reaction system is self-heated to 85 ℃;
g. 1000ml of deionized water is added into the mixed solution, and then 30% hydrogen peroxide is dropwise added until the mixed solution is bright yellow;
h. standing the solution, precipitating, removing supernatant, adding 100ml of 10% diluted hydrochloric acid, magnetically stirring for 5min, replacing sulfate radical with hydrochloric acid radical, standing for 5h, pouring out supernatant, repeating the pickling step for 3 times, centrifuging with deionized water, washing with water to remove diluted hydrochloric acid, and repeating the centrifuging water washing until the pH value of supernatant is greater than 5 to obtain near neutral graphite oxide liquid with dark brown color;
step four, GO/MnFe 2 O 4 Preparing a composite solution: a proper amount of ferric salt solution is dripped into the graphite oxide liquid and is continuously stirred, so as to form graphene oxide/manganese ferrite (GO/MnFe) 2 O 4 ) A solution;
step five, GO/MnFe 2 O 4 Preparation of cellulose composite film:
i. placing 14ml (7%wt) sodium hydroxide solution, 24ml (12%wt) urea solution and 162ml deionized water in an open beaker, pre-cooling to about-12 ℃, adding 1g microcrystalline cellulose and rapidly stirring for 5min until the solution is transparent;
j. taking GO/MnFe 2 O 4 Placing 15ml of the composite solution and 10ml of the cellulose solution in an open beaker, and carrying out ultrasonic treatment for 10min to obtain a mixed solution;
k. pouring the composite solution into a polytetrafluoroethylene dish, standing at room temperature for 6-24 h, depositing, evaporating, solidifying and forming, then placing into a vacuum drying oven, and drying at 60 ℃ for 4h to obtain GO/MnFe 2 O 4 Cellulose composite membrane.
The graphene/MnFe 2 O 4 The preparation method of the cellulose composite membrane is characterized in that the ratio of the concentrated sulfuric acid with the concentration of 98% to the sodium nitrate is 60:1; the ratio of the 98% concentrated sulfuric acid to the graphite is 30:1; the proportion of the potassium permanganate to the graphite is 5:1.
the graphene/MnFe 2 O 4 The preparation method of the cellulose composite film is characterized in that the ice water bath is a water bath with the temperature of 2-5 ℃.
The graphene/MnFe 2 O 4 The preparation method of the cellulose composite membrane is characterized in that the repeated centrifugal washing times are 4-10 times.
The graphene/MnFe 2 O 4 The preparation method of the cellulose composite film is characterized in that the thickness and the size of the composite film can be controlled by injecting the composite liquid into a mold and changing the area of the mold. The method can be applied to dies of different sizes and shapes to produce composite films of various specifications. In addition, the method can accurately control the components of the composite liquid in the preparation process so as to meet different application requirements.
The graphene/MnFe 2 O 4 A method for preparing cellulose, characterized in that the prepared composite film has a plurality of unique characteristics and can be used in various application fields. For example, the material can be used as core material of various sensors, including pressure sensor and humidity sensorSensors, chemical sensors, and the like. graphene/MnFe 2 O 4 The mass and safe production and utilization of the cellulose composite membrane are beneficial to the application and development of graphene composite membrane materials. The method can not only improve the preparation efficiency and quality of the composite membrane, but also reduce the production cost and environmental pollution.
Drawings
Fig. 1 is a macroscopic physical photograph of the prepared graphene/manganese ferrite/nano cellulose film.
Fig. 2 is an infrared spectrogram of the prepared graphene/manganese ferrite/nano-cellulose film.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1: graphene/MnFe 2 O 4 Cellulose composite membrane
The specific operation is as follows:
step one: a. 1g of sodium nitrate powder was dissolved in 60ml of concentrated sulfuric acid (98%) and placed in an open beaker followed by magnetic stirring in an ice water bath for 15-30min; b. 2g of graphite powder was slowly added at a rate of 1g/min, and magnetic stirring (speed 600 rpm/min) and ice-water bath were maintained for 30min.
Step two: c. slowly adding 10g of potassium permanganate powder into the graphite mixed solution at a rate of 1g/min, and maintaining magnetic stirring for 1.5h; d. removing the open beaker from the ice water bath, naturally heating the reaction system to about 35 ℃ due to intercalation oxidation heat release of concentrated sulfuric acid on graphite, maintaining the magnetic stirring speed at 1000rpm/min, keeping the temperature, gradually changing the color of the solution into black and green, and taking the color on the wall of the beaker as the reference; e. the reaction system is kept to perform the self-intercalation oxidation reaction for about 8 hours, so that the color of the mixed solution is changed into dark brown.
Step three: f. adding 90ml deionized ice water slowly and uniformly into the graphite oxide mixed solution, adjusting the mechanical stirring speed to 400rpm/min to prevent the temperature rise and sputtering of severe reaction, and maintaining the self-reaction state for 15min when the reaction system is self-heated to 85 ℃; g. 1000ml of deionized water is added into the mixed solution, and then 30% hydrogen peroxide is dropwise added until the mixed solution is bright yellow; h. standing the solution, precipitating, removing supernatant, adding 100ml of 10% diluted hydrochloric acid, magnetically stirring for 5min, replacing sulfate radical with hydrochloric acid radical, standing for 5h, pouring out supernatant, repeating the pickling step for 3 times, centrifuging with deionized water, washing with water to remove diluted hydrochloric acid, and repeating the centrifuging water washing until the pH value of supernatant is greater than 5 to obtain near neutral graphite oxide liquid with dark brown color.
Step four: a proper amount of ferric salt solution is dripped into the graphite oxide liquid and is continuously stirred, so as to form graphene oxide/manganese ferrite (GO/MnFe) 2 O 4 ) A solution.
Step five: i. taking 7ml (7%wt) of sodium hydroxide solution, 12ml (12%wt) of urea solution and 81ml of deionized water, placing in an open beaker, precooling to about-12 ℃, adding 0.5g of microcrystalline cellulose and rapidly stirring for 5min until the solution is in a transparent state; j. taking GO/MnFe 2 O 4 Placing 15ml of the composite solution and 10ml of the cellulose solution in an open beaker, and carrying out ultrasonic treatment for 10min to obtain a mixed solution; k. pouring the composite solution into a polytetrafluoroethylene dish, standing at room temperature for 12h, depositing, evaporating, solidifying and forming, then placing into a vacuum drying oven, and drying at 60 ℃ for 4h to obtain GO/MnFe 2 O 4 Cellulose composite membrane.
Step six, graphene/MnFe 2 O 4 Preparation of cellulose composite film: reducing with hydriodic acid solution, and drying in 55 deg.C oven for 1 hr to obtain RGO/MnFe 2 O 4 Cellulose composite membrane.
Example 2: graphene/MnFe 2 O 4 Cellulose composite membrane
Step one: a. 0.5g of sodium nitrate powder was dissolved in 30ml of concentrated sulfuric acid (98%) and placed in an open beaker followed by magnetic stirring in an ice water bath for 15-30min; b. 1g of graphite powder was slowly added at a rate of 0.5g/min, and magnetic stirring (speed 600 rpm/min) and ice-water bath were maintained for 30min.
Step two: c. slowly adding 5g of potassium permanganate powder into the graphite mixed solution at a rate of 0.5g/min, and maintaining magnetic stirring for 1.5h; d. removing the open beaker from the ice water bath, naturally heating the reaction system to about 35 ℃ due to intercalation oxidation heat release of concentrated sulfuric acid on graphite, maintaining the magnetic stirring speed at 1000rpm/min, keeping the temperature, gradually changing the color of the solution into black and green, and taking the color on the wall of the beaker as the reference; e. the reaction system is kept to perform the self-intercalation oxidation reaction for about 8 hours, so that the color of the mixed solution is changed into dark brown.
Step three: f. adding 60ml deionized ice water slowly and uniformly into the graphite oxide mixed solution, adjusting the mechanical stirring speed to 400rpm/min to prevent the temperature rise and sputtering of severe reaction, and maintaining the self-reaction state for 15min when the reaction system is self-heated to 85 ℃; g. 500ml of deionized water is added into the mixed solution, and then 30% hydrogen peroxide is dropwise added until the mixed solution is bright yellow; h. standing the solution, precipitating, removing supernatant, adding 60ml of 5% diluted hydrochloric acid, magnetically stirring for 5min, replacing sulfate radical with hydrochloric acid radical, standing for 5h, pouring out supernatant, repeating the pickling step for 3 times, centrifuging with deionized water, washing with water to remove diluted hydrochloric acid, and repeating the centrifuging water washing until the pH value of supernatant is greater than 5 to obtain near neutral graphite oxide liquid with dark brown color.
Step four: a proper amount of ferric salt solution is dripped into the graphite oxide liquid and is continuously stirred, so as to form graphene oxide/manganese ferrite (GO/MnFe) 2 O 4 ) A solution.
Step five: i. placing 14ml (7%wt) sodium hydroxide solution, 24ml (12%wt) urea solution and 162ml deionized water in an open beaker, pre-cooling to about-12 ℃, adding 1g microcrystalline cellulose and rapidly stirring for 5min until the solution is transparent; j. taking GO/MnFe 2 O 4 Placing 15ml of the composite solution and 10ml of the cellulose solution in an open beaker, and carrying out ultrasonic treatment for 10min to obtain a mixed solution; k. pouring the composite solution into a polytetrafluoroethylene dish, standing at room temperature for 12h, depositing, evaporating, solidifying and forming, then placing into a vacuum drying oven, and drying at 60 ℃ for 4h to obtain GO/MnFe 2 O 4 Cellulose composite membrane.
Step (a)Six, graphene/MnFe 2 O 4 Preparation of cellulose composite film: reducing the material with hydrazine hydrate steam, and drying the material at room temperature for 1h to obtain RGO/MnFe 2 O 4 Cellulose composite membrane.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (6)
1. graphene/MnFe 2 O 4 The cellulose composite membrane and the preparation method thereof adopt an improved Hummers method for preparing Graphene Oxide (GO), and are characterized in that the method comprises the following specific steps:
(1) Low temperature intercalation puffing to form separation between graphite layers: sodium nitrate powder is dissolved in concentrated sulfuric acid (98%) and placed in an open beaker, and then magnetically stirred in an ice water bath for 15-30min; slowly adding graphite powder at a rate below 1g/min, and maintaining magnetic stirring (speed 600 rpm/min) and ice water bath for 30min;
(2) Intercalation oxidation at normal temperature to oxidize intercalation between graphite layers: slowly adding potassium permanganate powder into the graphite mixed solution at a rate of less than 1g/min, and maintaining magnetic stirring for more than 1.5 hours; removing the open beaker from the ice water bath, naturally heating the reaction system to about 35 ℃ due to intercalation oxidation heat release of concentrated sulfuric acid on graphite, maintaining the magnetic stirring speed at 1000rpm/min, keeping the temperature, gradually changing the color of the solution into black and green, and taking the color on the wall of the beaker as the reference; e. the self-intercalation oxidation reaction of the reaction system is maintained for more than 8 hours,
the color of the mixed solution turns dark brown;
(3) High-temperature hydrolysis and reduction are terminated, and the puffed graphite oxide is prepared: adding deionized ice water slowly and uniformly into the graphite oxide mixed solution, adjusting the mechanical stirring speed to 400rpm/min to prevent the temperature rise and sputtering of severe reaction, and maintaining the self-reaction state for 15min from the temperature rise to about 85 ℃; 1000ml of deionized water is added into the mixed solution, and then 30% hydrogen peroxide is dropwise added until the mixed solution is bright yellow; standing the solution, precipitating, removing supernatant, adding 10% diluted hydrochloric acid, stirring uniformly by magnetic force, replacing sulfate radical with hydrochloric acid radical, standing for 5 hours, pouring out supernatant, repeating the pickling step for 3 times, centrifuging with deionized water, washing with water to remove diluted hydrochloric acid, and repeating the centrifuging water washing until the pH value of the supernatant is greater than 5 to obtain near neutral graphite oxide liquid with dark brown color;
(4)GO/MnFe 2 O 4 preparing a composite solution: proper ferric salt and manganese salt solution are dropwise added into the graphite oxide liquid, and the mixture is continuously stirred and ultrasonically treated to form graphene oxide/manganese ferrite (GO/MnFe) with laminated coating structure 2 O 4 ) A solution;
(5)GO/MnFe 2 O 4 preparation of cellulose composite film: placing sodium hydroxide solution, 12 wt% urea solution and deionized water in an open beaker, pre-cooling to about-12 ℃, adding microcrystalline cellulose, and rapidly stirring for 5min until the solution is transparent; taking GO/MnFe 2 O 4 Placing 15ml of the composite solution and 10ml of the cellulose solution in an open beaker, and carrying out ultrasonic treatment for 10min to obtain a mixed solution; k. pouring the composite solution into a polytetrafluoroethylene dish, standing at room temperature for 6-24 h, depositing, evaporating, solidifying and forming, then placing into a vacuum drying oven, and drying at 60 ℃ for 4h to obtain GO/MnFe 2 O 4 Cellulose composite membrane.
(6) graphene/MnFe 2 O 4 Preparation of cellulose composite film: reducing the material with hydrazine hydrate steam, and drying the material at room temperature for 1h to obtain RGO/MnFe 2 O 4 Cellulose composite membrane.
2. A graphene/MnFe according to claim 1 2 O 4 The preparation method of the cellulose composite membrane is characterized in that the ratio of the concentrated sulfuric acid with the concentration of 98% to the sodium nitrate is 60:1; the ratio of the 98% concentrated sulfuric acid to the graphite is 30:1; the ratio of the potassium permanganate to the graphite is 5:1.
3. According to claim1 graphene/MnFe 2 O 4 The preparation method of the cellulose composite film is characterized in that the ice water bath is a water bath with the temperature of 2-5 ℃.
4. A graphene/MnFe according to claim 1 2 O 4 The preparation method of the cellulose composite membrane is characterized in that the repeated centrifugal washing times are 4-10 times.
5. A graphene/MnFe according to claim 1 2 O 4 The preparation method of the cellulose composite film is characterized in that the thickness and the size of the composite film can be controlled by injecting the composite liquid into a mold and changing the area of the mold. The method can be applied to dies of different sizes and shapes to produce composite films of various specifications. In addition, the method can accurately control the components of the composite liquid in the preparation process so as to meet different application requirements.
6. A graphene/MnFe according to claim 1 2 O 4 The preparation method of the cellulose composite film is characterized in that the prepared composite film has a plurality of unique characteristics and can be used in various application fields. Such as core materials for various sensors including pressure sensors, humidity sensors, chemical sensors, and the like. graphene/MnFe 2 O 4 The mass and safe production and utilization of the cellulose composite membrane are beneficial to the application and development of graphene composite membrane materials. The method can not only improve the preparation efficiency and quality of the composite membrane, but also reduce the production cost and environmental pollution.
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