CN110877907A - Graphene material with regularly-arranged pore structure and preparation method thereof - Google Patents
Graphene material with regularly-arranged pore structure and preparation method thereof Download PDFInfo
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- CN110877907A CN110877907A CN201910918218.8A CN201910918218A CN110877907A CN 110877907 A CN110877907 A CN 110877907A CN 201910918218 A CN201910918218 A CN 201910918218A CN 110877907 A CN110877907 A CN 110877907A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention provides a graphene material with a regularly-arranged pore structure, which comprises: A) providing a template material with a regularly arranged pore structure; B) compounding a graphene material on the template material; C) preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode; D) and removing the template to obtain the graphene material with the regularly-arranged pore structure. According to the method, graphene is used as a raw material, a template with regularly-arranged pore structures is firstly prepared, then the template is covered on a graphene material, then the pore structures are formed on the graphene material in a chemical corrosion or laser processing mode, and finally the template is removed, so that the graphene material with the regularly-arranged pore structures is obtained. The preparation method has the advantages of simple preparation process, easy control of reaction process, simple required equipment, convenient operation and short required time.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a graphene material with a regularly-arranged pore structure and a preparation method thereof.
Background
The graphene material is a monolayer of graphite, each carbon atom is hybridized by sp2, and then a hexagonal two-dimensional carbon nano material in a honeycomb lattice is formed. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. The graphene is expected to be used for composite materials because the excellent mechanical and electrical properties are endowed by the flexibility of carbon atoms in the graphene and the abnormal uniformity of the surface electron density of the carbon atoms, and other functional groups are easily introduced into the carbon atoms and are bonded with other materials. In addition, since graphene is a large conjugated system, the conjugated structure of graphene in the graphene composite material can also be influenced with the electron system of other materials, so that the physicochemical properties of the graphene composite material are changed.
The compounding of graphene materials and other materials has been studied more, but there are few reports of graphene materials having regularly arranged pore structures. The material of the type is synthesized, the influence of the periodically changed conjugated structure on other composite materials can be researched, and the performance of the composite material is expected to be further improved
The graphene material with regularly arranged pore structures and the preparation method thereof are very necessary, and the porous graphene prepared by the in-growth method in the prior art is easy to agglomerate and is not easy to form an ordered pore structure.
Disclosure of Invention
In view of this, the invention provides a preparation method of a graphene material with a regularly arranged pore structure, and the graphene material prepared by the preparation method is not easy to agglomerate and is easy to form an ordered pore structure.
The invention provides a graphene material with a regularly-arranged pore structure, which comprises:
A) providing a template material with a regularly arranged pore structure;
B) compounding a graphene material on the template material;
C) preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode;
D) and removing the template to obtain the graphene material with the regularly-arranged pore structure.
Preferably, the template material is selected from one or more of an alumina template, a polymer template, a metal template, a silica template and a molecular sieve template.
Preferably, the aperture of the template material is 0.1 nm-100 nm; the arrangement mode of the template material is a regular matrix arrangement mode or a hexagonal grid structure.
Preferably, the template material is prepared by one or more methods selected from electrochemical deposition, chemical polymerization, direct spin coating, physical deposition and self-assembly.
Preferably, the compounding manner in the step B) is specifically as follows: graphene is dissolved by a solvent and then spin-coated on a template material.
Preferably, the rotation speed of the spin coating is 100-10000 r/min; the spin coating time is 10 s-100 s.
Preferably, the chemical etching in step C) is KMnO4Corrosion of the KMnO solution4The concentration of the solution is 0.01-1mol/L, and the corrosion treatment time is 0.1-100 min; the laser processing parameters are specifically as follows: the laser power is 0.01-100 w; the treatment time is 1-100 s.
Preferably, the method for removing the template in the step D) specifically comprises: ultrasonic treatment is carried out for 1-100 s or the solution is carried out for 1-100min by using 0.01-1mol/L acid.
The invention provides a graphene material with a regularly-arranged pore structure, which is prepared by the preparation method in any one of the technical schemes.
Preferably, the diameter of the pore channel of the graphene material is 0.1 nm-100 nm.
Compared with the prior art, the invention provides a graphene material with a regularly-arranged pore structure, which comprises the following components: A) providing a template material with a regularly arranged pore structure; B) compounding a graphene material on the template material; C) preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode; D) and removing the template to obtain the graphene material with the regularly-arranged pore structure. According to the method, graphene is used as a raw material, a template with regularly-arranged pore structures is firstly prepared, then the template is covered on a graphene material, then the pore structures are formed on the graphene material in a chemical corrosion or laser processing mode, and finally the template is removed, so that the graphene material with the regularly-arranged pore structures is obtained. The preparation method has the advantages of simple preparation process, easy control of reaction process, simple required equipment, convenient operation and short required time.
Drawings
FIG. 1 is a schematic view of the preparation process of the present invention.
Detailed Description
The invention provides a graphene material with a regularly-arranged pore structure and a preparation method thereof, and a person skilled in the art can use the contents to appropriately improve process parameters for realization. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a graphene material with a regularly-arranged pore structure, which comprises:
A) providing a template material with a regularly arranged pore structure;
B) compounding a graphene material on the template material;
C) preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode;
D) and removing the template to obtain the graphene material with the regularly-arranged pore structure.
The invention firstly provides a template material with a regularly arranged pore structure. Wherein, the template material is preferably selected from one or more of an alumina template, a polymer template, a metal template, a silicon dioxide template and a molecular sieve template.
The polymer template can be polystyrene, polyacrylate, etc.
The metal template may be Au, Al, Cu, etc.
The aperture of the template material is preferably 0.1 nm-100 nm; more preferably 1nm to 100 nm; most preferably 10nm to 100 nm; the arrangement mode of the template material is a regular matrix arrangement mode or a hexagonal grid structure; other regular arrangements are also possible, which are not limited by the present invention.
The source of the template material is not limited in the present invention, and the template material may be commercially available or may be prepared in a manner known to those skilled in the art.
According to the present invention, the template material is prepared by one or more methods selected from electrochemical deposition, chemical polymerization, direct spin coating, physical deposition and self-assembly. The present invention is not limited to the above-described embodiments, and those skilled in the art will be familiar with the present invention.
Compounding a graphene material on the template material; the compounding mode is specifically as follows: graphene is dissolved by a solvent and then spin-coated on a template material.
According to the invention, the solvent is preferably ethanol; the ratio of graphene to ethanol is 1 g: 1-1000mL, wherein the rotation speed of the spin coating is preferably 100-10000 r/min; more preferably 500 to 9000 r/min; most preferably 1000-8000 r/min; the time for the spin coating is preferably 10s to 100 s; more preferably 20s to 80 s; most preferably 30s to 70 s.
The thickness of the spin-on graphene material is preferably 1-100 micrometers; more preferably 10-90 microns
And obtaining a template material layer and a graphene layer arranged on the template material layer after compounding.
Preparing a regularly-arranged pore structure on the graphene material by adopting a chemical corrosion or laser processing mode.
Specifically, a regularly-arranged pore structure equal to the pore diameter of the template is prepared on the graphene material by using the pores of the template as a reference and adopting a chemical corrosion or laser processing mode.
Wherein the chemical corrosion is KMnO4Corrosion of the KMnO solution4The concentration of the solution is 0.01-1mol/L, and the corrosion treatment time is 0.1-100 min; the laser processing parameters are specifically as follows: the laser power is preferably 0.01-100 w; more preferably 1-90 w; most preferably 10-80 w; the treatment time is preferably 1-100 s; more preferably 10-90 s; most preferably 20 to 80 seconds.
And removing the template to obtain the graphene material with the regularly-arranged pore structure.
The template removing method specifically comprises the following steps: preferably performing ultrasonic treatment on the treated material for 1-100 s; more preferably, the ultrasonic treatment is carried out for 10-90 s;
or:
dissolving the treated material by 0.01-1mol/L acid for 1-100min to remove the acid; more preferably, 0.1-0.9 mol/L acid is adopted for dissolving for 10-90 min for removal; wherein the acid is preferably an organic acid; for example, oxalic acid, citric acid, acetic acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.; the concentration of the acid is preferably 0.1-1 mol/L; more preferably 0.4 to 0.8 mol/L; most preferably 0.5 to 0.7 mol/L.
FIG. 1 is a schematic view of the preparation process of the present invention.
The invention provides a graphene material with a regularly-arranged pore structure, which is prepared by the preparation method in any one of the technical schemes.
According to the invention, the surface of the graphene material is provided with a plurality of pore channels, and the arrangement of the pore channels has certain regularity. The diameter of the pore canal is 0.1 nm-100 nm.
The invention provides a graphene material with a regularly-arranged pore structure, which comprises: A) providing a template material with a regularly arranged pore structure; B) compounding a graphene material on the template material; C) preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode; D) and removing the template to obtain the graphene material with the regularly-arranged pore structure. According to the method, graphene is used as a raw material, a template with regularly-arranged pore structures is firstly prepared, then the template is covered on a graphene material, then the pore structures are formed on the graphene material in a chemical corrosion or laser processing mode, and finally the template is removed, so that the graphene material with the regularly-arranged pore structures is obtained. The preparation method has the advantages of simple preparation process, easy control of reaction process, simple required equipment, convenient operation and short required time.
In order to further illustrate the present invention, the following describes in detail a graphene material with a regularly arranged pore structure and a preparation method thereof, which are provided by the present invention, with reference to examples.
Example 1
The preparation process of the graphene material with the regularly arranged pore structure comprises the following steps:
(1) directly selecting porous alumina template material with the aperture of 100 nm.
(2) Graphene was purified with ethanol according to a 1 g: diluting in a proportion of 100mL, dropwise adding a graphene material on a porous alumina template material, and spin-coating at a spin-coating speed of 1000 rpm for 20 s;
(3) and (3) processing the graphene for 10s by using 0.1W pulse laser, and preparing a pore structure with regular arrangement on the graphene.
(4) And (3) treating the graphene with 0.5mol/L oxalic acid solution for 5min to remove the porous alumina template, so as to obtain the graphene material with the regularly-arranged pore structure.
The graphene material obtained in the embodiment has no agglomeration, and forms an ordered hexagonal honeycomb-shaped pore channel structure.
Example 2
The preparation process of the graphene material with the regularly arranged pore structure comprises the following steps:
(1) directly selecting porous silica template material with pore diameter of 50nm, wherein the pore arrangement mode is hexagonal honeycomb
(2) Graphene was purified with ethanol according to a 1 g: diluting in a proportion of 100mL, dropwise adding a graphene material on the porous alumina template material, and spin-coating at a spin-coating speed of 2000 rpm for 30 s;
(3) and (3) processing the graphene for 20s by using 0.1W pulse laser, and preparing a pore structure with regular arrangement on the graphene.
(4) And (3) treating with 0.5mol/L hydrofluoric acid solution for 5min to remove the porous silicon dioxide template, thereby obtaining the graphene material with the regularly-arranged pore structure.
The graphene material obtained in the embodiment has no agglomeration, and forms an ordered hexagonal honeycomb-shaped pore channel structure.
Example 3
The preparation process of the graphene material with the regularly arranged pore structure comprises the following steps:
(1) directly selecting a molecular sieve template material with the aperture of 20nm, wherein the pore arrangement mode is a hexagonal honeycomb shape.
(2) Graphene was purified with ethanol according to a 1 g: diluting in a proportion of 100mL, dropwise adding a graphene material on the porous alumina template material, and spin-coating at a spin-coating speed of 500 rpm for 10 s;
(3) and (3) processing the graphene for 10s by using 0.1W pulse laser, and preparing a pore structure with regular arrangement on the graphene.
(4) And (3) treating the graphene material by using 0.3mol/L sulfuric acid solution for 10min to remove the molecular sieve template, thereby obtaining the graphene material with the regularly-arranged pore structure.
The graphene material obtained in the embodiment has no agglomeration, and forms an ordered hexagonal honeycomb-shaped pore channel structure.
Example 4
The preparation process of the graphene material with the regularly arranged pore structure comprises the following steps:
(1) directly selecting metal template material with 80nm aperture, wherein the aperture is arranged in matrix type
(2) Graphene was purified with ethanol according to a 1 g: diluting in a proportion of 100mL, dropwise adding a graphene material on a porous alumina template material, and spin-coating at a spin-coating speed of 5000 rpm for 50 s;
(3) and (3) processing the graphene for 40s by using 0.1W pulse laser, and preparing a pore structure with regular arrangement on the graphene.
(4) And (3) treating with 0.8mol/L hydrochloric acid solution for 50min to remove the metal template, thereby obtaining the graphene material with the regularly-arranged pore structure.
The graphene material obtained in the embodiment has no agglomeration, and forms an ordered matrix-type arrangement pore channel structure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A graphene material with a regularly-arranged pore structure is characterized by comprising:
A) providing a template material with a regularly arranged pore structure;
B) compounding a graphene material on the template material;
C) preparing a regularly-arranged pore structure on a graphene material by adopting a chemical corrosion or laser treatment mode;
D) and removing the template to obtain the graphene material with the regularly-arranged pore structure.
2. The preparation method according to claim 1, wherein the template material is selected from one or more of an alumina template, a polymer template, a metal template, a silica template and a molecular sieve template.
3. The method according to claim 1, wherein the pore size of the template material is 0.1nm to 100 nm; the arrangement mode of the template material is a regular matrix arrangement mode or a hexagonal grid structure.
4. The method of claim 1, wherein the template material is prepared by one or more methods selected from electrochemical deposition, chemical polymerization, direct spin coating, physical deposition, and self-assembly.
5. The preparation method according to claim 1, wherein the compounding manner in step B) is specifically: graphene is dissolved by a solvent and then spin-coated on a template material.
6. The preparation method according to claim 5, wherein the spin coating is performed at a rotation speed of 100 to 10000 r/min; the spin coating time is 10 s-100 s.
7. The method as claimed in claim 1, wherein the chemical etching in step C) is KMnO4Corrosion of the KMnO solution4The concentration of the solution is 0.01-1mol/L, and the corrosion treatment time is 0.1-100 min;
the laser processing parameters are specifically as follows: the laser power is 0.01-100 w; the treatment time is 1-100 s.
8. The method according to claim 1, wherein the step D) of removing the template is specifically: ultrasonic treatment is carried out for 1-100 s or the solution is carried out for 1-100min by using 0.01-1mol/L acid.
9. A graphene material with a regularly-arranged pore structure is characterized by being prepared by the preparation method of any one of claims 1-9.
10. The graphene material with the regularly-arranged pore structure according to claim 9, wherein the diameter of the pore channel of the graphene material is 0.1 nm-100 nm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013028826A2 (en) * | 2011-08-25 | 2013-02-28 | Wisconsin Alumni Research Foundation | Barrier guided growth of microstructured and nanostructured graphene and graphite |
| CN104649253A (en) * | 2013-11-18 | 2015-05-27 | 国家纳米科学中心 | Preparing methods of porous graphene and porous graphene film |
| CN107200317A (en) * | 2017-04-14 | 2017-09-26 | 北京航空航天大学 | A kind of method that loose structure graphene is prepared based on laser |
| CN108507719A (en) * | 2018-03-26 | 2018-09-07 | 合肥工业大学 | A method of referance leak is made based on graphene self-defect |
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- 2019-09-26 CN CN201910918218.8A patent/CN110877907A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013028826A2 (en) * | 2011-08-25 | 2013-02-28 | Wisconsin Alumni Research Foundation | Barrier guided growth of microstructured and nanostructured graphene and graphite |
| CN104649253A (en) * | 2013-11-18 | 2015-05-27 | 国家纳米科学中心 | Preparing methods of porous graphene and porous graphene film |
| CN107200317A (en) * | 2017-04-14 | 2017-09-26 | 北京航空航天大学 | A kind of method that loose structure graphene is prepared based on laser |
| CN108507719A (en) * | 2018-03-26 | 2018-09-07 | 合肥工业大学 | A method of referance leak is made based on graphene self-defect |
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Application publication date: 20200313 |