CN116554556A - Cellulose nanocrystalline-reduced graphene oxide composite membrane and preparation method and application thereof - Google Patents
Cellulose nanocrystalline-reduced graphene oxide composite membrane and preparation method and application thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 168
- 229920002678 cellulose Polymers 0.000 title claims abstract description 145
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- 239000002131 composite material Substances 0.000 title claims abstract description 120
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000012528 membrane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002159 nanocrystal Substances 0.000 claims abstract description 30
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- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 230000008020 evaporation Effects 0.000 claims abstract description 17
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 238000010612 desalination reaction Methods 0.000 claims abstract description 4
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
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- 239000002064 nanoplatelet Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 abstract description 6
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- 238000012360 testing method Methods 0.000 description 13
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- 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
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
Abstract
The invention discloses a cellulose nanocrystalline-reduced graphene oxide composite membrane, and a preparation method and application thereof. The cellulose nanocrystalline-reduced graphene oxide composite film comprises a reduced graphene oxide layer and a cellulose nanocrystalline self-assembly layer which are alternately stacked, wherein the reduced graphene oxide layer comprises reduced graphene oxide nano sheets, and the cellulose nanocrystalline self-assembly layer comprises cellulose nanocrystals which are arranged in an oriented manner. The cellulose nanocrystalline-reduced graphene oxide composite film has the advantages of high photo-thermal conversion efficiency, high strength, high toughness, low cost and the like, and the preparation method is simple and environment-friendly, and has wide application prospect in the field of solar energy interface evaporation sea water desalination.
Description
Technical Field
The invention relates to the technical field of graphene-based composite materials, in particular to a cellulose nanocrystalline-reduced graphene oxide composite film, and a preparation method and application thereof.
Background
Graphene is a kind of graphene which passes sp 2 The carbon nanomaterial with the hexagonal grid structure formed by hybridization has high specific surface area, high mechanical strength, high optical absorption performance and excellent electric conduction and heat conduction performance, and has great application potential in the fields of adsorption, energy sources, photo-thermal conversion, electronic materials and the like. However, the inherent conjugated structure of graphene makes it prone to aggregation, not only not easy to blend with other materials, but also reduces its specific surface area. Graphene Oxide (GO) is a derivative of graphene, contains a large number of oxygen-containing functional groups on the surface, has hydrophilicity, and can form chemical combination with various materials, but the graphene oxide has more defects, so that the mechanical property, the electric conductivity and the heat conductivity of a graphene sheet are seriously influenced. The Reduced Graphene Oxide (RGO) not only maintains partial oxygen-containing functional groups, but also has excellent performance of graphene and better application prospect. However, most of the existing graphene-based composite materials have the problems of uneven distribution of the graphene-based materials, poor mechanical properties, complex preparation process, high cost and the like, and the application is greatly limited.
Therefore, the development of the graphene-based composite material which has the advantages of uniform distribution of the graphene-based material, excellent mechanical property, simple preparation process and low cost has very important significance.
Disclosure of Invention
The invention aims to provide a cellulose nanocrystalline-reduced graphene oxide composite membrane, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a cellulose nanocrystalline-reduced graphene oxide composite film comprises a reduced graphene oxide layer and a cellulose nanocrystalline self-assembly layer which are alternately stacked; the composition of the reduced graphene oxide layer comprises reduced graphene oxide nanoplatelets; the composition of the cellulose nanocrystalline self-assembled layer comprises cellulose nanocrystalline arranged in an orientation.
Preferably, the mass ratio of the reduced graphene oxide nano-sheets to the cellulose nano-crystals is 0.05-0.3:1.
Preferably, the sheet diameter of the reduced graphene oxide nano sheet is 50 nm-200 nm.
Preferably, the length of the cellulose nanocrystalline is 100 nm-500 nm, and the diameter is 5 nm-20 nm.
The preparation method of the cellulose nanocrystalline-reduced graphene oxide composite membrane comprises the following steps:
1) Mixing the cellulose nanocrystalline suspension and the graphene oxide nanosheet dispersion to obtain a cellulose nanocrystalline-graphene oxide mixed dispersion;
2) Forming a film from the cellulose nanocrystalline-graphene oxide mixed dispersion liquid to obtain a cellulose nanocrystalline-graphene oxide composite film;
3) And (3) soaking the cellulose nanocrystalline-graphene oxide composite membrane in NaOH solution, and taking out and drying to obtain the cellulose nanocrystalline-reduced graphene oxide composite membrane.
Preferably, in the step 1), the mass ratio of the Cellulose Nanocrystals (CNC) in the cellulose nanocrystal suspension to the graphene oxide nanoplatelets in the Graphene Oxide (GO) nanoplatelet dispersion is 1:0.05-0.3.
Preferably, the mass fraction of the cellulose nanocrystals in the suspension of the cellulose nanocrystals in the step 1) is 0.8% -1.2%.
Preferably, the concentration of the graphene oxide nano-sheets in the graphene oxide nano-sheet dispersion liquid in the step 1) is 1.8 mg/mL-2.2 mg/mL.
Preferably, the mixing in step 1) is carried out by ultrasonic dispersion.
Preferably, the ultrasonic dispersion is performed in an ice-water bath.
Preferably, the film forming mode in the step 2) is suction filtration.
Preferably, the pore size of the filter membrane used for suction filtration is 0.2-0.3 μm.
Preferably, the mass fraction of the NaOH solution in the step 3) is 16% -20%.
Preferably, the soaking time in the step 3) is 9-12 hours.
A solar energy interface evaporation sea water desalination device comprises the cellulose nanocrystalline-reduced graphene oxide composite membrane.
The beneficial effects of the invention are as follows: the cellulose nanocrystalline-reduced graphene oxide composite film has the advantages of high photo-thermal conversion efficiency, high strength, high toughness, low cost and the like, and the preparation method is simple and environment-friendly, and has wide application prospect in the field of solar energy interface evaporation sea water desalination.
Specifically:
1) The cellulose nanocrystalline-reduced graphene oxide composite film is composed of the reduced graphene oxide layers and the cellulose nanocrystalline self-assembly layers which are alternately stacked, the original graphene oxide nano-sheets in the reduced graphene oxide layers are orderly embedded into the cellulose nanocrystalline self-assembly layers formed by the self-assembly orientation arrangement of the cellulose nanocrystalline, a highly orderly layered stacked structure is formed, the excellent performance of the reduced graphene oxide can be fully exerted, the structure enables incident light to be reflected in a large amount between graphene layers which are arranged in parallel, and refraction is carried out in a large amount between cellulose nanocrystalline layers, so that the light absorption performance of the composite film is improved, in addition, an amorphous region can be formed between the cellulose nanocrystalline by NaOH solution soaking treatment, covalent bond bonding can be formed between the region and the cellulose nanocrystalline (the amorphous region plays a role similar to an adhesive), and therefore the strength, toughness and stability of the composite film can be remarkably improved;
2) The preparation process of the cellulose nanocrystalline-reduced graphene oxide composite membrane is simple and environment-friendly, economical and safe, low in cost and short in period, and is suitable for large-scale industrial production.
Drawings
Fig. 1 is a schematic structural view of a cellulose nanocrystalline-reduced graphene oxide composite membrane of the present invention.
Fig. 2 is an SEM image of a cross section of the cellulose nanocrystal-reduced graphene oxide composite membrane in example 1 and the cellulose nanocrystal-graphene oxide composite membrane in comparative example.
Fig. 3 is an XPS diagram of the cellulose nanocrystal-reduced graphene oxide composite film in example 1 and the cellulose nanocrystal-graphene oxide composite film in the comparative example.
Fig. 4 is a C1s spectrum of the cellulose nanocrystal-reduced graphene oxide composite film in example 1 and the cellulose nanocrystal-graphene oxide composite film in comparative example.
Fig. 5 is an FTIR diagram of the cellulose nanocrystal-reduced graphene oxide composite film in example 1 and the cellulose nanocrystal-graphene oxide composite film in the comparative example.
Fig. 6 is a stress-strain relationship curve of the cellulose nanocrystal-reduced graphene oxide composite film in examples 1 to 2 and the cellulose nanocrystal-graphene oxide composite film in comparative example.
Fig. 7 is a graph showing the results of water evaporation test of the cellulose nanocrystal-reduced graphene oxide composite film in examples 1 to 2 and the cellulose nanocrystal-graphene oxide composite film in comparative example.
Fig. 8 is a graph showing the surface temperature-time relationship of the cellulose nanocrystal-reduced graphene oxide composite film in examples 1 to 2 and the cellulose nanocrystal-graphene oxide composite film in comparative example.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1:
the preparation method of the cellulose nanocrystalline-reduced graphene oxide composite membrane comprises the following steps:
1) Mixing 15mL of a cellulose nano-crystal (Gui Linji macro-tech Co., ltd., length of 100-500 nm, diameter of 5-20 nm) suspension with 22.5mL of a graphene oxide nano-sheet dispersion (monolayer graphene oxide dispersion of Jiangsu Xianfeng nano-material Co., ltd., sheet diameter of 50-200 nm) with a concentration of 2mg/mL, stirring at 600rpm at room temperature for 12h, then placing in an ice-water bath for ultrasonic dispersion for 30min, and ultrasonic power of 150W to obtain a cellulose nano-crystal-graphene oxide mixed dispersion (the mass ratio of CNC and GO is 1:0.3);
2) Filtering the cellulose nanocrystalline-graphene oxide mixed dispersion liquid in vacuum to form a film, wherein a filter membrane adopted in vacuum filtering is a hydrophilic nylon filter membrane, the pore diameter is 0.22 mu m, the diameter is 50mm, and drying is carried out at room temperature to obtain a cellulose nanocrystalline-graphene oxide composite membrane;
3) And (3) putting the cellulose nanocrystalline-graphene oxide composite membrane into a NaOH solution with the mass fraction of 16% for soaking for 9 hours, taking out and alternately soaking with deionized water and absolute ethyl alcohol until phenolphthalein does not turn red after dripping into a washing liquid (indicating that NaOH is cleaned), and naturally drying at room temperature to obtain the cellulose nanocrystalline-reduced graphene oxide composite membrane (the structural schematic diagram is shown in figure 1).
Example 2:
the preparation method of the cellulose nanocrystalline-reduced graphene oxide composite membrane comprises the following steps:
1) Mixing 15mL of cellulose nano-crystal (Gui Linji macro-tech Co., ltd., 100 nm-500 nm, diameter 5 nm-20 nm) suspension with 7.5mL of graphene oxide nano-sheet dispersion (monolayer graphene oxide dispersion of Jiangsu Xianfeng nano-material Co., ltd., sheet diameter of graphene oxide nano-sheet 50 nm-200 nm) with concentration of 2mg/mL, stirring at 600rpm for 12h at room temperature, then placing in an ice-water bath for ultrasonic dispersion for 30min, and ultrasonic power being 150W to obtain cellulose nano-crystal-graphene oxide mixed dispersion (the mass ratio of CNC and GO is 1:0.1);
2) Filtering the cellulose nanocrystalline-graphene oxide mixed dispersion liquid in vacuum to form a film, wherein a filter membrane adopted in vacuum filtering is a hydrophilic nylon filter membrane, the pore diameter is 0.22 mu m, the diameter is 50mm, and drying is carried out at room temperature to obtain a cellulose nanocrystalline-graphene oxide composite membrane;
3) And (3) putting the cellulose nanocrystalline-graphene oxide composite membrane into a NaOH solution with the mass fraction of 16% for soaking for 9 hours, taking out and alternately soaking with deionized water and absolute ethyl alcohol until phenolphthalein does not turn red after dripping into a washing liquid, and naturally drying at room temperature to obtain the cellulose nanocrystalline-reduced graphene oxide composite membrane (the structural schematic diagram is shown in figure 1).
Comparative example:
the preparation method of the cellulose nanocrystalline-graphene oxide composite film comprises the following steps:
1) Mixing 15mL of cellulose nano-crystal (Gui Linji macro-tech Co., ltd., 100 nm-500 nm, diameter 5 nm-20 nm) suspension with 22.5mL of graphene oxide nano-sheet dispersion with concentration of 2mg/mL (monolayer graphene oxide dispersion of Jiangsu Xianfeng nano-material Co., ltd., sheet diameter of graphene oxide nano-sheet 50 nm-200 nm), stirring at 600rpm for 12h at room temperature, then placing in an ice-water bath for ultrasonic dispersion for 30min, and ultrasonic power being 150W to obtain cellulose nano-crystal-graphene oxide mixed dispersion (the mass ratio of CNC and GO is 1:0.3);
2) And (3) performing vacuum filtration on the cellulose nanocrystalline-graphene oxide mixed dispersion liquid to form a film, wherein a filter membrane adopted in the vacuum filtration is a hydrophilic nylon filter membrane, the pore diameter is 0.22 mu m, the diameter is 50mm, and drying is performed at room temperature to obtain the cellulose nanocrystalline-graphene oxide composite membrane.
Performance test:
1) Scanning Electron Microscopy (SEM) images of the cross sections of the cellulose nanocrystal-reduced graphene oxide composite film in example 1 and the cellulose nanocrystal-graphene oxide composite film in the comparative example are shown in fig. 2 (a 1 is an SEM image of a stepped cross section formed by tearing of the cellulose nanocrystal-graphene oxide composite film in the comparative example, a2 is an SEM image of a cross section formed by brittle fracture of the cellulose nanocrystal-graphene oxide composite film in the comparative example with liquid nitrogen, b1 is an SEM image of a stepped cross section formed by tearing of the cellulose nanocrystal-reduced graphene oxide composite film in example 1, and b2 is an SEM image of a cross section formed by brittle fracture of the cellulose nanocrystal-reduced graphene oxide composite film in example 1 with liquid nitrogen).
As can be seen from fig. 2:
a) The cellulose nanocrystalline-graphene oxide composite film still maintains an ordered layered stack structure after being soaked in NaOH solution (comparison of a1 and b 1); after the cellulose nanocrystalline-graphene oxide composite film is soaked in NaOH solution, CNCs in the cellulose nanocrystalline-graphene oxide composite film are mutually aggregated, and a crystallization area dissolved by the NaOH solution is converted into an amorphous area between layers, so that the section of the composite film is smoother (compared with a2 and b 2);
b) The cellulose nanocrystal-reduced graphene oxide composite film in example 1 is composed of a reduced graphene oxide layer and a cellulose nanocrystal self-assembled layer which are alternately stacked, and the reduced graphene oxide nanoplatelets (with a sheet diameter of 50nm to 200 nm) in the reduced graphene oxide layer are orderly embedded into the cellulose nanocrystal self-assembled layer formed by the self-assembled orientation arrangement of the cellulose nanocrystals, so that a highly ordered layered stack structure is formed.
2) The photoelectron spectroscopy (XPS) patterns of the cellulose nanocrystal-reduced graphene oxide composite film in example 1 and the cellulose nanocrystal-graphene oxide composite film in the comparative example are shown in fig. 3, and the C1s pattern is shown in fig. 4 (a is the cellulose nanocrystal-graphene oxide composite film, and b is the cellulose nanocrystal-reduced graphene oxide composite film).
As can be seen from fig. 3 and 4: the content of oxygen element is obviously reduced after the cellulose nanocrystalline-graphene oxide composite film is soaked in NaOH solution, and the content of oxygen-containing functional groups is reduced, which indicates that GO is reduced.
3) An infrared spectrum (FTIR) diagram of the cellulose nanocrystal-reduced graphene oxide composite film in example 1 and the cellulose nanocrystal-graphene oxide composite film in the comparative example is shown in fig. 5.
As can be seen from fig. 5: 1000cm -1 ～1800cm -1 Peaks in the range are peaks related to oxygen-containing functional groups, and the peaks almost disappear after the cellulose nanocrystalline-graphene oxide composite film is soaked in NaOH solution, which indicates that GO is reduced to RGO.
4) Stress-strain relationship curves of the cellulose nanocrystal-reduced graphene oxide composite film in examples 1 to 2 and the cellulose nanocrystal-graphene oxide composite film in comparative example are shown in fig. 6.
As can be seen from fig. 6: the tensile strength of the cellulose nanocrystalline-reduced graphene oxide composite film in example 1 is 84.12MPa, the elongation at break is 7.63%, and 220.73% and 1062.67% are respectively improved compared with the cellulose nanocrystalline-graphene oxide composite film in comparative example, which indicates that the strength of the cellulose nanocrystalline-graphene oxide composite film is greatly improved after the cellulose nanocrystalline-graphene oxide composite film is soaked in NaOH solution.
5) Water evaporation test (test performed at room temperature): placing a polylactic acid frame printed in 3D on a plastic cup mouth filled with deionized water, placing a non-woven fabric on the polylactic acid frame, placing a composite film test sample on the top of the non-woven fabric, constructing a simple interface evaporation device (the non-woven fabric is used as a supporting layer, water can be transmitted to the composite film sample, the direct contact of the composite film sample and a water body is avoided, and heat energy is prevented from being lost into the water), placing the device on an electronic analytical balance, and recording the power of the device at 1kW/m 2 The xenon lamp simulates the weight change under sunlight, and the water evaporation test results of the cellulose nanocrystalline-reduced graphene oxide composite films in examples 1 and 2 and the cellulose nanocrystalline-graphene oxide composite film in comparative example obtained by the test are shown in fig. 7.
As can be seen from fig. 7: the water evaporation rate of the cellulose nanocrystalline-graphene oxide composite membrane (CNC and GO mass ratio 1:0.3) in the comparative example was 1.58kg·m -2 ·h -1 Whereas the water evaporation rate of the cellulose nanocrystalline-reduced graphene oxide composite membrane in example 1 (mass ratio of CNC and RGO 1:0.3) was 1.85 kg.m -2 ·h -1 The improvement of 17% indicates that the NaOH solution treatment is helpful to improve the water evaporation efficiency of the composite membrane; the water evaporation rate of the cellulose nanocrystalline-reduced graphene oxide composite membrane (mass ratio of CNC and RGO 1:0.1) in example 2 was 1.53kg·m -2 ·h -1 It is explained that the water evaporation rate of the composite film increases with increasing content of reduced graphene oxide in the composite film.
Note that:
the calculation formula of the water evaporation rate is as follows: v=dm/(s×dt), where dm is the mass of evaporated water (unit: kg), and S is the composite membrane area (unit: m) 2 ) Dt is the evaporation time (unit：h)。
6) Temperature rise test (test performed at room temperature): spreading the composite film sample on a glass plate, placing a frame printed by polylactic acid on the composite film sample (preventing the composite film sample from being bent when heated), placing the glass plate on two wood blocks which are consistent in height and wrapped by a reflective adhesive tape (taking the wood blocks as supports, separating the composite film sample from a tabletop, facilitating normal heat dissipation of the material, thereby enabling the result to be more accurate), and recording the power of the composite film sample at 1kW/m by using an infrared camera (FLIR E6) 2 The xenon lamp simulates the change of the surface temperature under sunlight with time, and the surface temperature-time relationship curves of the cellulose nanocrystalline-reduced graphene oxide composite films in examples 1 and 2 and the cellulose nanocrystalline-graphene oxide composite film in comparative example obtained by testing are shown in fig. 8.
As can be seen from fig. 8: the surface temperature of the composite film sample is rapidly increased under short-time illumination, which indicates that the composite film sample has excellent photo-thermal conversion performance; the cellulose nanocrystalline-graphene oxide composite film (CNC to GO mass ratio 1:0.3) in the comparative example rapidly increased from 28.0 ℃ to about 55.8 ℃ after 60s of illumination, thereafter, up to 68.1 ℃ and remained constant, whereas the cellulose nanocrystalline-reduced graphene oxide composite film (CNC to RGO mass ratio 1:0.3) in example 1 rapidly increased from 28.0 ℃ to about 60.0 ℃ after 60s of illumination, thereafter, up to 69.8 ℃ and remained constant, indicating that the NaOH solution treatment increased the surface temperature of the composite film faster, and the composite film had more excellent photo-thermal conversion properties; the cellulose nanocrystalline-reduced graphene oxide composite film in example 2 (CNC and RGO mass ratio 1:0.1) rapidly increased from 28.0 ℃ to about 43.3 ℃ after 60s of illumination, thereafter increased up to 56.8 ℃ and remained constant, and the higher the surface temperature of example 1 compared to example 2 by about 8 ℃, demonstrated that the higher the reduced graphene oxide content in the composite film, the stronger the photo-thermal conversion performance of the composite film.
Example 3:
the preparation method of the cellulose nanocrystalline-reduced graphene oxide composite membrane comprises the following steps:
1) Mixing 15mL of cellulose nano-crystal (Gui Linji macro-tech Co., ltd., 100 nm-500 nm, diameter 5 nm-20 nm) suspension with 15mL of graphene oxide nano-sheet dispersion with concentration of 2mg/mL (monolayer graphene oxide dispersion of Jiangsu Xianfeng nano-material Co., ltd., sheet diameter of graphene oxide nano-sheet 50 nm-200 nm), stirring at 600rpm for 12h at room temperature, then placing in an ice water bath for ultrasonic dispersion for 30min, and ultrasonic power of 150W to obtain cellulose nano-crystal-graphene oxide mixed dispersion (the mass ratio of CNC and GO is 1:0.2);
2) Filtering the cellulose nanocrystalline-graphene oxide mixed dispersion liquid in vacuum to form a film, wherein a filter membrane adopted in vacuum filtering is a hydrophilic nylon filter membrane, the pore diameter is 0.22 mu m, the diameter is 50mm, and drying is carried out at room temperature to obtain a cellulose nanocrystalline-graphene oxide composite membrane;
3) And (3) putting the cellulose nanocrystalline-graphene oxide composite membrane into a NaOH solution with the mass fraction of 16% for soaking for 9 hours, taking out and alternately soaking with deionized water and absolute ethyl alcohol until phenolphthalein does not turn red after dripping into a washing liquid, and naturally drying at room temperature to obtain the cellulose nanocrystalline-reduced graphene oxide composite membrane (the structural schematic diagram is shown in figure 1).
Through testing (the testing method is the same as that above), the microstructure and the composition of the cellulose nanocrystalline-reduced graphene oxide composite film in the embodiment are highly similar to those of the cellulose nanocrystalline-reduced graphene oxide composite film in the embodiment 1, the tensile strength is 63.38MPa, the elongation at break is 7.3%, the temperature in simulated solar illumination for 60s is rapidly increased to 50.3 ℃, the temperature is then increased to 61.5 ℃ at most and kept constant, and the water evaporation rate after illumination for 1h is 1.63 kg.m -2 ·h -1 。
Example 4:
the preparation method of the cellulose nanocrystalline-reduced graphene oxide composite membrane comprises the following steps:
1) Mixing 15mL of cellulose nano-crystal (Gui Linji macro-tech Co., ltd., 100 nm-500 nm, diameter 5 nm-20 nm) suspension with 7.5mL of graphene oxide nano-sheet dispersion (monolayer graphene oxide dispersion of Jiangsu Xianfeng nano-material Co., ltd., sheet diameter of graphene oxide nano-sheet 50 nm-200 nm) with concentration of 2mg/mL, stirring at 600rpm for 12h at room temperature, then placing in an ice-water bath for ultrasonic dispersion for 30min, and ultrasonic power being 150W to obtain cellulose nano-crystal-graphene oxide mixed dispersion (the mass ratio of CNC and GO is 1:0.1);
2) Filtering the cellulose nanocrystalline-graphene oxide mixed dispersion liquid in vacuum to form a film, wherein a filter membrane adopted in vacuum filtering is a hydrophilic nylon filter membrane, the pore diameter is 0.22 mu m, the diameter is 50mm, and drying is carried out at room temperature to obtain a cellulose nanocrystalline-graphene oxide composite membrane;
3) And (3) putting the cellulose nanocrystalline-graphene oxide composite membrane into a NaOH solution with the mass fraction of 16% for soaking for 9 hours, taking out and alternately soaking with deionized water and absolute ethyl alcohol until phenolphthalein does not turn red after dripping into a washing liquid, and naturally drying at room temperature to obtain the cellulose nanocrystalline-reduced graphene oxide composite membrane (the structural schematic diagram is shown in figure 1).
Through testing (the testing method is the same as the above), the microstructure and the composition of the cellulose nanocrystalline-reduced graphene oxide composite film in the implementation are highly similar to those of the cellulose nanocrystalline-reduced graphene oxide composite film in the example 1, the tensile strength is 55.17MPa, the elongation at break is 12.28%, the temperature in simulated solar illumination for 60s is rapidly increased from 28 ℃ to 46.6 ℃, and then the temperature is increased to 58.9 ℃ at most and kept stable, and the water evaporation rate after illumination for 1h is 1.59 kg.m -2 ·h -1 。
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The cellulose nanocrystalline-reduced graphene oxide composite film is characterized by comprising reduced graphene oxide layers and cellulose nanocrystalline self-assembly layers which are alternately stacked; the composition of the reduced graphene oxide layer comprises reduced graphene oxide nanoplatelets; the composition of the cellulose nanocrystalline self-assembled layer comprises cellulose nanocrystalline arranged in an orientation.
2. The cellulose nanocrystalline-reduced graphene oxide composite membrane according to claim 1, characterized in that: the mass ratio of the reduced graphene oxide nano-sheets to the cellulose nano-crystals is 0.05-0.3:1.
3. The cellulose nanocrystalline-reduced graphene oxide composite membrane according to claim 1 or 2, characterized in that: the sheet diameter of the reduced graphene oxide nano sheet is 50 nm-200 nm.
4. The cellulose nanocrystalline-reduced graphene oxide composite membrane according to claim 1 or 2, characterized in that: the length of the cellulose nanocrystalline is 100 nm-500 nm, and the diameter is 5 nm-20 nm.
5. A method for producing a cellulose nanocrystalline-reduced graphene oxide composite membrane according to any one of claims 1 to 4, comprising the steps of:
1) Mixing the cellulose nanocrystalline suspension and the graphene oxide nanosheet dispersion to obtain a cellulose nanocrystalline-graphene oxide mixed dispersion;
2) Forming a film from the cellulose nanocrystalline-graphene oxide mixed dispersion liquid to obtain a cellulose nanocrystalline-graphene oxide composite film;
3) And (3) soaking the cellulose nanocrystalline-graphene oxide composite membrane in NaOH solution, and taking out and drying to obtain the cellulose nanocrystalline-reduced graphene oxide composite membrane.
6. The method of manufacturing according to claim 5, wherein: the mass ratio of the cellulose nanocrystalline in the cellulose nanocrystalline suspension to the graphene oxide nanosheets in the graphene oxide nanosheet dispersion liquid in the step 1) is 1:0.05-0.3.
7. The method of manufacturing according to claim 5 or 6, characterized in that: the mixing mode in the step 1) is ultrasonic dispersion;
and step 2), the film forming mode is suction filtration.
8. The method of manufacturing according to claim 5, wherein: and 3) the mass fraction of the NaOH solution is 16% -20%.
9. The preparation method according to claim 5 or 8, characterized in that: the soaking time in the step 3) is 9-12 h.
10. A solar energy interface evaporation sea water desalination device, characterized by comprising the cellulose nanocrystalline-reduced graphene oxide composite membrane according to any one of claims 1 to 4.
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