CN107651675B - Three-dimensional fold reduced graphene oxide and preparation method thereof - Google Patents
Three-dimensional fold reduced graphene oxide and preparation method thereof Download PDFInfo
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- CN107651675B CN107651675B CN201711104334.3A CN201711104334A CN107651675B CN 107651675 B CN107651675 B CN 107651675B CN 201711104334 A CN201711104334 A CN 201711104334A CN 107651675 B CN107651675 B CN 107651675B
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Abstract
The invention provides a preparation method of three-dimensional fold reduced graphene oxide, which specifically comprises the following steps: A) preparing three-dimensional porous tubular graphene by using a sponge template method, and reducing the three-dimensional porous tubular graphene to obtain three-dimensional porous tubular reduced graphene oxide; the sponge of the sponge template method is melamine sponge; B) carrying out hydrothermal treatment on the three-dimensional porous tubular reduced graphene oxide in a supercritical water environment, and then carrying out freeze drying to obtain the three-dimensional folded reduced graphene oxide. The invention firstly proposes the work of designing the graphene three-dimensional scale fold by using a template collapse method, and successfully realizes the synthesis of the three-dimensional scale fold structure by using a special thermoplastic collapse process of thermosetting melamine sponge under a hydrothermal condition. The three-dimensional folded graphene material prepared by the invention has practical value in the field of sensor research, has the characteristics of high sensing sensitivity, wide testable range and the like, and has extremely high guiding effect on a macroscopic self-assembly method of nano elements.
Description
Technical Field
The invention relates to the field of nano material macroscopic assembly, in particular to three-dimensional folded reduced graphene oxide and a preparation method thereof.
Background
The corrugation comprises bending corrugation of the two-dimensional nano-sheet, bending deflection of the nano-wire and ripple-shaped structure of the surface of the one-dimensional nano-ball. The fold structure not only can improve the specific surface area of the nano material, but also can obviously improve the mechanical property of the nano material.
In recent years, the research on wrinkle morphology is increasingly hot in the fields of energy storage, sensing, stretchable devices, self-assembly materials and the like. For example, the journal of Science (Science,2010,329: 1637) in the united states reports that a graphene nanoplatelet is formed on the surface of a metal nanoparticle, which can significantly improve the energy storage capacity of an electric double layer capacitor, and due to the special zigzag structure, the graphene nanoplatelet not only can reduce the device step, but also can be beneficial to ion conduction, thereby reducing the filtering effect. British self-heating nanotechnology (Naturenatotechnology, 2011,6:788.) utilizes one-dimensional carbon nanotubes to prepare transparent bionic skin with pressure and stress response, and a pre-stretching biaxial shrinkage process based on a flexible substrate enables the formed spring-shaped carbon nanotubes to have excellent stretchability. English Natural materials 2013,12(4): 321) utilizes a prestretching template of Polydimethylsiloxane (PDMS) to successfully synthesize a graphene nanosheet with a two-dimensional folded structure, and the folded structure improves the stretchability of the graphene nanosheet and has a remarkable effect on the hydrophilicity and hydrophobicity of the graphene nanosheet. However, these reports are all based on the synthesis of wrinkle morphology at low latitudes, which is relatively easy to implement for forming stress templates. At present, no report about three-dimensional wrinkle morphology exists, which is mainly caused by the fact that the stress shrinkage process formed by three-dimensional scale is relatively complex and difficult to realize.
At present, a lot of reports are provided on the assembly method of the graphene folded structure, the assembly method of the zero-dimensional nano-sphere particles based on the graphene material mainly comprises a spray drying method and a core-shell soft sphere shrinkage method, the method is relatively simple to operate, and the application range is relatively limited. For example, U.S. nanometer Kuaiji (Nano letters,2011,12(1): 486-; the shrinkage process of this spherical surface shell was simulated by the dry shrinkage of peas in the U.S. Physical review letters,2011,106(23):234301. The method for assembling the bending wire based on the one-dimensional nano material mainly comprises a pre-stretching shrinkage method and a template printing method, and the method has wide application range but lower controllability on an assembly structure. For example, U.S. Advanced Materials (2015, 27(18): 2866-.
The above work on three-dimensional pleating is merely to create creases in two dimensions and only thickness stacking in the other dimension, not strictly three-dimensional pleating material, which does not fully embody the advantages of pleating morphology. The preparation method of the three-dimensional wrinkle shape mainly comprises an ice template method and a poor solvent collapse method. For example, natural communications,2016,7,12920 in the uk reports that a three-dimensional arched graphene structure is prepared by using an ice template method, and due to the introduction of an ordered arched structure in the three-dimensional structure, the material has excellent sensing characteristics. In the us, ACS nano (ACS nano,2017,11(8):8092), a graphene wrinkled structure is reported, and firstly, graphene dissolved in a good solvent is transferred to a poor solvent, so that the stretched graphene shrinks, and the three-dimensional wrinkled graphene is formed by layer-by-layer assembly through a top-down method. However, there has been no report of the formation of wrinkle features in three dimensions, mainly because there has been no suitable driving force to produce shrinkage in three dimensions.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of three-dimensional folded reduced graphene oxide, and the preparation method provided by the application can be used for preparing the reduced graphene oxide with three-dimensional folded dimensions.
In view of this, the present application provides a method for preparing three-dimensional folded reduced graphene oxide, including the following steps:
A) preparing three-dimensional porous tubular graphene by a sponge template method, and reducing the three-dimensional porous tubular graphene to obtain three-dimensional porous tubular reduced graphene oxide; the sponge of the sponge template method is melamine sponge;
B) carrying out hydrothermal treatment on the three-dimensional porous tubular reduced graphene oxide in a supercritical water environment, and then carrying out freeze drying to obtain the three-dimensional folded reduced graphene oxide.
Preferably, the freeze-drying method further comprises the following steps:
and (3) carrying out high-temperature heat treatment on the three-dimensional folded reduced graphene oxide obtained by freeze drying.
Preferably, the temperature of the hydrothermal treatment in the step B) is 60-180 ℃, and the time is 60-180 min.
Preferably, the freeze-drying process specifically comprises:
and pre-freezing the graphene subjected to the hydrothermal treatment by adopting liquid nitrogen, and then drying.
Preferably, the preparation process of the three-dimensional porous tubular graphene specifically comprises the following steps:
and soaking melamine sponge in the graphene solution, and performing vacuum treatment to obtain the three-dimensional porous tubular graphene.
Preferably, the reducing agent is hydroiodic acid.
Preferably, the temperature of the high-temperature heat treatment is 200-250 ℃ and the time is 1-2 h.
The application also provides a three-dimensional fold reduced graphene oxide, which shrinks in the same proportion in the radial direction and the tangential direction of the reduced graphene oxide.
Preferably, the shrinkage scale of the three-dimensional folded reduced graphene oxide is 0-70%.
Preferably, the wrinkle dimension of the three-dimensional wrinkle reduced graphene oxide is 0.2-5 μm.
The application provides a preparation method of three-dimensional fold reduced graphene oxide, which comprises the steps of firstly preparing three-dimensional porous tubular graphene by a sponge template method, reducing the three-dimensional porous tubular graphene to obtain the three-dimensional porous tubular reduced graphene oxide, then carrying out hydrothermal treatment on the three-dimensional porous tubular reduced graphene oxide in a supercritical water environment, and carrying out freeze drying to obtain the three-dimensional fold reduced graphene oxide. In the process of preparing the three-dimensional folded reduced graphene oxide, melamine sponge is used as a template, a sponge template method is used for carrying out macroscopic assembly on graphene, a graphene nanotube skeleton structure with a porous structure is synthesized, reduction is carried out to improve the conductivity of the graphene, then the sponge template is subjected to hydrothermal treatment to collapse, the graphene wrapped on the surface layer is subjected to stress contraction, and the three-dimensional porous graphene has a micro-ordered multi-stage folded structure due to the special isometric contraction effect of the sponge template; the final freeze drying maintains the folded structure of the graphene.
Drawings
Fig. 1 is a schematic diagram of a synthesis of a three-dimensional porous corrugated graphene tubular structure prepared according to an embodiment of the present invention;
FIG. 2 is a pictorial view and SEM image of a sponge;
FIG. 3 is a pictorial view and SEM image of graphene oxide coated sponge;
FIG. 4 is a pictorial and SEM image of a reduced graphene oxide coated sponge;
fig. 5 is a pictorial view and SEM image of a three-dimensional porous pleated graphene tubular structure;
FIG. 6 is a graph showing the relationship between the shrinkage rate of a reduced graphene oxide coated sponge after hydrothermal treatment and the treatment time;
FIG. 7 is a Raman plot of sponge, graphene oxide, reduced graphene oxide, and wrinkled graphene before and after hydrothermal treatment;
FIG. 8 is a diagram of a tubular structure of three-dimensional porous corrugated graphene with different shrinkage rates;
fig. 9 is an SEM image of a three-dimensional porous corrugated graphene tubular structure at different shrinkage rates;
FIG. 10 is a graph showing the variation of fiber length and aspect ratio during the shrinkage process of melamine sponge;
FIG. 11 is a graph showing the thermal infrared absorption of the hydrothermal decomposition product of melamine sponge;
FIG. 12 is a graph comparing dry and wet strength of melamine sponges;
FIG. 13 is a thermogravimetric analysis of melamine sponge after hydrothermal treatment;
FIG. 14 is a BET pore size analysis plot of a melamine sponge after hydrothermal treatment;
FIG. 15 is a graph of melamine sponge samples at different shrinkages after different hydrothermal treatments;
fig. 16 is an SEM image of melamine sponges with different shrinkage rates after different hydrothermal time treatments.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the fact that the wrinkles have the effect of improving the stretchability of the nanomaterial, but no suitable template is available at present for a three-dimensional wrinkle structure, and the current wrinkle technology is limited to a two-dimensional scale, the invention provides a graphene material with a three-dimensional wrinkle structure in a three-dimensional direction. Specifically, the melamine sponge template capable of being subjected to stress contraction in three dimensions has a negative Poisson ratio characteristic and can be used for synthesizing materials with a three-dimensional direction wrinkle structure. As shown in fig. 1, fig. 1 is a schematic diagram of the preparation of three-dimensional porous wrinkled reduced graphene oxide according to the present invention. Specifically, the invention provides a preparation method of three-dimensional folded reduced graphene oxide, which comprises the following steps:
A) preparing three-dimensional porous tubular graphene by a sponge template method, and reducing the three-dimensional porous tubular graphene to obtain three-dimensional porous tubular reduced graphene oxide; the sponge of the sponge template method is melamine sponge;
B) carrying out hydrothermal treatment on the three-dimensional porous tubular reduced graphene oxide in a supercritical water environment, and then carrying out freeze drying to obtain the three-dimensional folded reduced graphene oxide.
In the process of preparing the three-dimensional folded reduced graphene oxide, firstly, a sponge template is utilized to carry out macroscopic assembly on graphene nano-sheets to synthesize a graphene nanotube skeleton structure with a porous structure, specifically, melamine sponge is used as the template, graphene is used as a shrinkage material, and a sponge template method is utilized to synthesize three-dimensional porous tubular graphene, namely graphene oxide wrapped melamine sponge. Specifically, the preparation process of the three-dimensional porous tubular graphene comprises the following steps:
the melamine sponge is soaked in the graphene solution, gas inside the sponge is removed through vacuum treatment, the thickness of the wrapped graphene is more uniform, and the adsorbed redundant graphene is removed through centrifugation.
In the process, three-dimensional porous graphene tubular structures with different thicknesses can be synthesized due to different graphene concentrations. The source of the graphene and melamine sponge is not particularly limited in the present application, and may be obtained in a manner well known to those skilled in the art.
Melamine sponge is a thermosetting resin which does not have the thermoplastic shrinkage characteristic under normal conditions; in a hydrothermal environment, due to the reversible hydrolysis process of the melamine sponge, molecular chains are reconstructed under the action of internal polymerization, and further the thermal shrinkage characteristic is generated. The process is different from the thermal shrinkage process of common thermoplastic materials, and because partial molecular chains are dissolved after being hydrolyzed in a hydrothermal environment, the mass of the material is reduced, the total volume is reduced, and therefore the material can be shrunk in the three-dimensional direction, and the shrinkage characteristic with a negative Poisson ratio is formed. Therefore, the preparation of the template method for really realizing the three-dimensional multistage fold morphology can be realized by using the melamine sponge with the three-dimensional porous structure as the template and using the special thermoplastic negative Poisson's ratio shrinkage process under the hydrothermal condition.
After the three-dimensional porous tubular graphene is obtained, the three-dimensional porous tubular graphene is reduced to improve the conductivity of the graphene. The reducing agent is hydroiodic acid. The reduction process specifically comprises the following steps:
adding hydriodic acid and water into a beaker according to the volume ratio of 1:1, heating the mixture to 90 ℃ in an oil bath, dipping the three-dimensional porous tubular graphene into the mixed solution for 5-10 s, and cleaning the reduced sample by using an ethanol solution to obtain the three-dimensional porous tubular reduced graphene oxide.
The three-dimensional porous tubular reduced graphene oxide is subjected to hydrothermal treatment in a supercritical water environment, the sponge collapses and contracts in the water environment in the process, the contraction process is in the same proportion of radial and tangential direction contraction, and the graphene tubular structure on the surface layer is driven by stress to contract in the sponge template collapse process to form a wrinkle appearance. Test results show that the macroscopic shrinkage scale of the sponge template is 0-70%, and the wrinkle scale of graphene is 0.2-5 microns. In the hydrothermal treatment process, the temperature of the hydrothermal treatment is 60-180 ℃, and the time is 60-180 min; in a specific embodiment, the temperature of the hydrothermal treatment is 120-180 ℃.
According to the invention, finally, the product after the hydrothermal treatment is subjected to freeze drying, so that the folded structure of the graphene is not damaged in the drying process of the product. The freeze-drying process of the present application specifically comprises:
after the product after the hydrothermal treatment is cleaned, liquid nitrogen is used for pre-freezing, and a freeze drying technology is used for drying.
The above lyophilization was carried out at-45 ℃.
In order to further improve the performance of the three-dimensional folded reduced graphene oxide, the obtained three-dimensional folded reduced graphene oxide is preferably subjected to high-temperature heat treatment, so that the deformation of a sponge framework can be avoided, and the folded graphene obtained after the hydrothermal treatment can be reduced to the maximum extent. The temperature of the high-temperature heat treatment is 200-250 ℃, and the time is 1-2 h.
The present application thus also provides a three-dimensional folded reduced graphene oxide that shrinks the same proportion in both the radial and tangential directions of the reduced graphene oxide.
Experimental results show that the shrinkage scale of the three-dimensional folded reduced graphene oxide is 0-70%, and the folding scale is 0.2-5 mu m.
The invention provides a template collapse method for synthesizing a macroscopically ordered three-dimensional graphene wrinkle structure; the method is characterized in that under special conditions, the self-assembly process of the three-dimensional multilevel fold morphology of the nano-material graphene is realized by utilizing the collapse of a three-dimensional porous material melamine sponge with the negative Poisson's ratio shrinkage characteristic. Specifically, firstly, a sponge template method is utilized to carry out macroscopic assembly on graphene nano sheets, and a graphene nanotube skeleton structure with a porous structure is synthesized; then, thermally reducing the oxidized graphene by using hydroiodic acid to improve the conductivity of the graphene; and then, the process of sinking the hydrothermal sponge template is utilized to lead the graphene wrapped on the surface layer to carry out stress shrinkage, and the three-dimensional porous graphene has a microcosmic ordered multi-stage fold structure due to the special isometric shrinkage effect of the sponge template. And finally, the fold structure of the graphene is kept by utilizing a freeze drying technology, and the graphene is further reduced by utilizing high-temperature heat treatment, so that the functional strength of the graphene is improved.
The innovation point of the invention is that the work of designing the three-dimensional scale fold by utilizing the template collapse method is firstly provided, and the synthesis of the three-dimensional scale fold structure is successfully realized due to the special thermoplastic collapse process of the thermosetting melamine sponge under the hydrothermal condition. The three-dimensional folded graphene material prepared by the invention has practical value in the field of sensor research, has the characteristics of high sensing sensitivity, wide testable range and the like, and has extremely high guiding effect on the assembly method of nano elements.
For further understanding of the present invention, the following provides a detailed description of the method for preparing three-dimensionally folded reduced graphene oxide according to the present invention with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Weighing 10g of graphite flake and 7.5g of sodium nitrate, uniformly mixing in a 2L beaker, slowly adding 300mL of concentrated sulfuric acid, slowly adding 40g of potassium permanganate, stirring to be viscous, standing for stripping for 5 days, slowly adding 1L of deionized water and 60mL of H2O2Centrifuging at 8000r/min for 10min each time, taking a viscous yellow middle layer, putting the centrifuged product into a dialysis bag, and dialyzing for 7 days to remove impurities such as manganese in the dialyzed product to obtain graphene;
soaking the cleaned melamine sponge in 3mg/mL graphene solution, removing gas in the sponge by vacuum treatment to make the thickness of the wrapped graphene more uniform, and removing the adsorbed excessive graphene at a centrifugal rate of 3500r/min to obtain the graphene-wrapped melamine sponge, wherein the structure of the graphene-wrapped melamine sponge is macroscopically yellow, and the wrapping amount is about 0.1mg/cm3. A sponge template method is utilized to wrap the two-dimensional graphene material, and three-dimensional porous graphene tubular structures with different thicknesses can be synthesized according to different graphene concentrations. FIG. 2 is a pictorial view and SEM image of a sponge; FIG. 3 is a pictorial view and SEM image of graphene oxide coated sponge;
adding hydroiodic acid and deionized water into a baked cake according to the volume ratio of 1:1, heating the baked cake to 90 ℃ in an oil bath, soaking the graphene-coated melamine sponge in a hydriodic acid hot solution for reducing for 5 to 10 seconds, taking out a reduced sample, soaking and cleaning the reduced sample in an ethanol solution, and removing iodine residues to obtain reduced graphene oxide-coated melamine sponge which is black in macroscopic view; FIG. 4 is a pictorial and SEM image of a reduced graphene oxide coated sponge;
carrying out hydrothermal treatment on a sponge wrapped by reduced graphene oxide in a supercritical water environment to ensure that the sponge collapses and contracts in the water environment, wherein the contraction process is in the same proportion in the radial direction and the tangential direction, the macroscopic contraction scale is between 0% and 70%, the graphene tubular structure on the surface layer is driven by stress to contract in the sponge template collapse process to form a wrinkle shape, the wrinkle scale is between 0.2 and 5 micrometers, the temperature of the hydrothermal treatment is 160 ℃, and the time is 60 to 180 min; freezing the obtained sample by liquid nitrogen in advance, and then freezing and drying at minus 45 ℃; and finally, carrying out high-temperature heat treatment at 200 ℃ for 2h, so that the sponge framework can be prevented from being denatured, and folded graphene obtained after hydrothermal treatment can be reduced to the maximum extent, so that three-dimensional folded reduced graphene oxide is obtained. Fig. 5 is a physical diagram and an SEM diagram of a three-dimensional porous corrugated graphene tubular structure.
Example 2
Taking 7 blocks of reduced graphene oxide coated melamine sponge prepared in example 1, cutting the blocks into 6 x 2cm, putting the blocks into a 50mL reaction kettle, adding 40mL deionized water, putting the reaction kettle into a 160 ℃ oven, performing hydrothermal treatment for 60, 80, 100, 120, 140, 160 and 180min respectively, naturally cooling to room temperature after the reaction is finished, carrying out about 5h, transferring the obtained sample from the reaction kettle to deionized water, and soaking and cleaning; and pre-freezing the obtained sample by using liquid nitrogen, and then drying the sample by using a freeze drying technology to obtain the three-dimensional folded reduced graphene oxide with different shrinkage rates.
Performing macroscopic size measurement, scanning electron microscope observation and Raman characterization on the obtained samples with different shrinkage rates, and performing infrared spectrum analysis on the decomposition product of the hydrothermal melamine sponge, as shown in fig. 6 and 7, wherein fig. 6 is a graph showing the relationship between the shrinkage rate of the sponge wrapped by the reduced graphene oxide after hydrothermal treatment and the treatment time; fig. 7 is a raman plot of sponge, graphene oxide, reduced graphene oxide, and wrinkled graphene before and after hydrothermal treatment.
Example 3
The hydrothermal temperature in the embodiment 2 is changed to 120-180 ℃, and the hydrothermal time is controlled to 40-200 min respectively, so that the purpose of collapsing the reduced graphene oxide coated melamine sponge to different degrees can be achieved. As shown in fig. 8 and 9, fig. 8 is a real object diagram of a three-dimensional porous corrugated graphene tubular structure with different shrinkage rates; fig. 9 is an SEM image of three-dimensional porous corrugated graphene tubular structures of different shrinkage rates.
Comparative example 1
Taking 7 cleaned melamine sponges, cutting into 6 x 2cm pieces, putting the pieces into a 50mL reaction kettle, adding 40mL deionized water, putting the pieces into drying ovens with the temperature of 120-180 ℃, performing hydrothermal treatment for 60-180 min, naturally cooling to room temperature after the reaction is finished, cooling for about 5h, and transferring the samples from the reaction kettle to deionized water for dipping and cleaning; the samples were pre-frozen with liquid nitrogen and then dried using freeze-drying techniques.
Performing macroscopic size characterization, scanning electron microscope observation, tensile strength measurement, thermogravimetric analysis and BET void analysis on the melamine sponge before and after hydrothermal treatment, and performing infrared spectrum analysis on the decomposition product of the hydrothermal melamine sponge, as shown in FIGS. 10-14; FIG. 10 is a graph of the change in fiber length to aspect ratio during shrinkage of a melamine sponge; FIG. 11 is a graph showing the thermal infrared absorption of the hydrothermal decomposition product of melamine sponge; FIG. 12 is a graph comparing dry and wet strength of melamine sponges; FIG. 13 is a thermogravimetric analysis of melamine sponge after hydrothermal treatment; fig. 14 is a BET pore size analysis chart of the melamine sponge after the hydrothermal treatment.
Comparative example 2
The hydrothermal temperature in the embodiment 1 is changed to 120-180 ℃, and the purpose of collapsing the melamine sponge in different degrees can be achieved by respectively controlling the hydrothermal time to be 40-200 min. As shown in fig. 15 and 16, fig. 15 is a graph of melamine sponges with different shrinkage rates after different hydrothermal time treatments; fig. 16 is an SEM image of melamine sponges with different shrinkage rates after different hydrothermal time treatments.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A preparation method of three-dimensional folded reduced graphene oxide comprises the following steps:
A) preparing three-dimensional porous tubular graphene by a sponge template method, and reducing the three-dimensional porous tubular graphene to obtain three-dimensional porous tubular reduced graphene oxide; the sponge of the sponge template method is melamine sponge;
B) carrying out hydrothermal treatment on the three-dimensional porous tubular reduced graphene oxide in a supercritical water environment, and then carrying out freeze drying to obtain the three-dimensional folded reduced graphene oxide.
2. The method of claim 1, further comprising, after freeze-drying:
and (3) carrying out high-temperature heat treatment on the three-dimensional folded reduced graphene oxide obtained by freeze drying.
3. The method according to claim 1 or 2, wherein the temperature of the hydrothermal treatment in step B) is 60 to 180 ℃ and the time is 60 to 180 min.
4. The method according to claim 1 or 2, wherein the freeze-drying process is specifically:
and pre-freezing the graphene subjected to the hydrothermal treatment by adopting liquid nitrogen, and then drying.
5. The preparation method according to claim 1 or 2, wherein the preparation process of the three-dimensional porous tubular graphene is specifically as follows:
and soaking melamine sponge in the graphene solution, and performing vacuum treatment to obtain the three-dimensional porous tubular graphene.
6. The method according to claim 1 or 2, wherein the reducing agent is hydroiodic acid.
7. The method according to claim 2, wherein the high temperature heat treatment is performed at a temperature of 200 to 250 ℃ for 1 to 2 hours.
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