CN110316727B - Preparation method of double-sided asymmetric modified graphene - Google Patents
Preparation method of double-sided asymmetric modified graphene Download PDFInfo
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- CN110316727B CN110316727B CN201910537972.7A CN201910537972A CN110316727B CN 110316727 B CN110316727 B CN 110316727B CN 201910537972 A CN201910537972 A CN 201910537972A CN 110316727 B CN110316727 B CN 110316727B
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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
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses a preparation method of double-sided asymmetric modified graphene. The preparation method comprises the step of sequentially modifying two sides of the layered graphene to obtain the double-side asymmetrically modified graphene. The method starts from graphene, and the modified graphene with two asymmetric modification surfaces is prepared.
Description
Technical Field
The application relates to a preparation method of double-sided asymmetric modified graphene, and belongs to the technical field of carbon materials.
Background
Graphene materials are the hottest new materials in recent years, and the discovery of graphene materials is awarded with the nobel prize in physics in less than 10 years. Graphene, as a two-dimensional carbon material, has a thickness of only 0.335 nm and has extremely excellent electrical conductivity, thermal conductivity, mechanical strength and other characteristics, so that graphene and its derivative materials have potential applications in various fields such as electronic devices, sensors, batteries, environments and the like, and some application fields have already been industrialized.
Graphene materials are pure two-dimensional carbon materials, and the planes of carbon groups do not have any groups, so that the solubility and dispersibility of graphene in water and other matrixes are poor. The intermediate product graphene oxide for preparing graphene by the graphite oxidation-reduction method has good dispersibility in water due to rich oxygen-containing groups on a carbon-based plane, and the groups on the surface bring many possibilities for material modification. And modifying one surface of the graphene oxide to obtain the graphene nanosheet material with two different surfaces. The graphene nanosheet material with the two sides modified asymmetrically has wide application prospect in the fields of novel oil displacement agents, environment-friendly surfactants, oil stain treatment and the like.
For example, application No. 201810141755.1 discloses that a graphene oxide material with two different modified surfaces is obtained by using silica microspheres as a template, performing single-side modification on graphene oxide, reacting silanized ethylene diamine tetraacetic acid (EDTA-Silane) with oxygen-containing groups on the surface of the graphene oxide, removing the silica template, and then modifying the other surface of the graphene oxide material with alkylamine.
The existing preparation method of the double-sided asymmetric modified graphene starts from graphene oxide, and due to the fact that the delocalized large pi-shaped bond is damaged by the access of oxygen atoms, the original ultrahigh electron conductivity of the graphene is lost, and the problems of low modification efficiency and the like exist. In addition, the existing graphene oxide starting process needs to prepare graphene oxide by using an oxidation stripping method, so that the source of raw materials is greatly limited.
Disclosure of Invention
According to one aspect of the application, a preparation method of double-sided asymmetrically modified graphene is provided, and the method starts from graphene and prepares double-sided asymmetrically modified graphene. The original ultrahigh electron conductivity of graphene is reserved, and the modification efficiency is higher
A preparation method of double-sided asymmetrically modified graphene is characterized in that double sides of layered graphene are sequentially modified on a substrate, and the double-sided asymmetrically modified graphene can be obtained.
Optionally, the preparation method at least comprises the following steps:
a) obtaining graphene attached to a substrate I;
b) modifying the exposed surface of the graphene in the step a) to obtain single-surface modified graphene;
c) transferring the single-sided modified graphene to a substrate II;
d) and modifying the other side of the single-side modified graphene to obtain the double-side asymmetrically modified graphene.
In step a), obtaining graphene attached to the substrate i may be a method well known to those skilled in the art. For example, graphene is grown on the substrate i by a chemical vapor deposition method or applied to the substrate i by a drop-wise spin coating method.
Optionally, in the step a), the substrate i is selected from any one of copper foil, silicon wafer, glass, quartz, sapphire, SiC, ITO glass and FTO glass.
Optionally, step b) comprises: and heating the mixture containing the graphene and the modifier I, and initiating hydrocarbyl chain grafting on one surface of the graphene to obtain the single-surface modified graphene.
Specifically, an initiator is added to initiate the grafting of the hydrocarbyl chain on one side of the graphene. The initiator may be any one of benzoyl peroxide BPO, lauroyl peroxide LPO, tert-butyl peroxybenzoate BPB, 2-di (tert-butylperoxy) butane DBPB.
Optionally, in step b), the heating conditions are: the temperature is 100-200 ℃, and the time is 10-100 hours.
Specifically, the upper limit of the heating temperature in step b) is selected from 170 ℃, 190 ℃, 200 ℃; the lower limit of the heating temperature is selected from 100 deg.C, 170 deg.C, and 190 deg.C.
The upper limit of the heating time is selected from 24h and 100 h; the lower limit of the heating time is selected from 10h and 24 h.
Optionally, in the step b), the mass ratio of the graphene to the modifier i is 1: 0.5-1: 10.
Optionally, step c) comprises: and coating the modified surface of the single-surface modified graphene by using a substrate II, and then removing the substrate I.
Specifically, the graphene subjected to single-sided modification is transferred from a substrate I to a substrate II, and the transfer method comprises coating transfer and the like. And combining the modified surface of the graphene with the substrate II, and exposing the other surface (the unmodified graphene layer surface) in an etching and stripping manner, so as to modify the other surface.
Optionally, in step c), the substrate ii is selected from a polymeric film substrate;
the polymer film substrate includes any one of a polymethyl methacrylate substrate, a polyvinyl alcohol substrate, a polyimide substrate, a polyethylene terephthalate substrate, and a polyvinyl phenol (PVP) substrate.
Specifically, the polymer film substrate includes any one of a polymethyl methacrylate (PMMA) substrate, a polyvinyl alcohol (PVA) substrate, a Polyimide (PI) substrate, a polyethylene terephthalate (PET) substrate, and a polyvinyl phenol (PVP) substrate.
Optionally, step d) comprises: and heating the mixture containing the single-sided modified graphene and the modifier II, initiating hydrocarbyl chain grafting on the other side of the graphene, and removing the substrate II to obtain the double-sided asymmetric modified graphene.
Specifically, an initiator is added to initiate hydrocarbon-based chain grafting on the other side of the graphene. The initiator may be any one of benzoyl peroxide BPO, lauroyl peroxide LPO, tert-butyl peroxybenzoate BPB, 2-di (tert-butylperoxy) butane DBPB.
Optionally, in step d), the heating conditions are: the temperature is 100-150 ℃, and the time is 10-100 hours.
Specifically, the upper limit of the heating temperature in step d) is selected from 120 ℃, 150 ℃; the lower limit of the heating temperature is selected from 100 ℃ and 120 ℃.
The upper limit of the heating time is selected from 24h and 100 h; the lower limit of the heating time is selected from 10h and 24 h.
Optionally, the mass ratio of the single-sided modified graphene to the modifier II is 1: 0.5-1: 10.
Optionally, the modifier I and the modifier II are independently selected from at least one compound with a structural formula shown in a formula I;
RX formula I
Wherein R represents an organic group;
the organic group comprises any one of alkyl, substituted alkyl and heteroalkyl;
x is selected from any one of halogens.
Optionally, the substituted alkyl is selected from any one of groups with structural formulas shown as formulas II and III;
HO-R' -formula II
Ar-R' formula III
Wherein R ', R' are independently selected from C4～C20Any one of the alkyl groups of (a);
ar represents a nitrogen-or sulfur-containing heteroaryl group.
For example, the modification I or the modification II may be independently selected from any one of n-chlorohexane, n-heptane bromide, hexadecane iodide, cetylpyridinium chloride, 6-chloro-1-hexanol, 2-bromo-3-hexylthiophene, 2-bromoethylsulfide, isopropyl-2-bromoethyl ether.
Specifically, alkyl chain grafting is initiated by thermal decomposition.
Alternatively, the alkyl group is selected from C4～C20An alkyl group;
the heteroalkyl group is selected from C4～C20Oxygen-containing alkyl radical, C4～C20Nitrogen-containing alkyl group, C4～C20Any of sulfoalkyl groups.
On the other hand, the double-sided asymmetrically modified graphene obtained by the preparation method comprises a carbon-based plane and an organic group, wherein the organic group is asymmetrically grafted on the two sides of the carbon-based plane.
In one particular embodiment:
(1) graphene coating of the substrate: growing graphene on the substrate I by a chemical vapor deposition method or dropwise and spin-coating the graphene on the substrate I; the substrate I is selected from copper foil, silicon wafer, glass or quartz and other materials;
(2) single-sided modification of graphene: adding an initiator benzoyl peroxide, and initiating grafting of an alkyl chain through thermal decomposition, as shown in figure 2;
(3) substrate transfer: transferring the single-face modified graphene from the CVD substrate to a substrate II; the substrate II can be a polymer film substrate such as PMMA, PVA and the like; the transfer method comprises spin coating, etching and the like;
(4) and (3) modifying the other surface: performing single-side modification on the graphene material obtained in the step three again; the modification method comprises thermal decomposition to initiate the grafting of alkyl chains, as shown in FIG. 3;
(5) removing the substrate II: and removing the substrate II from the double-sided modified graphene obtained in the step four and the substrate II through an organic solvent such as acetone.
In the present application, "alkyl" refers to a group formed by the loss of any one hydrogen atom from the molecule of an alkane compound.
C4～C20The subscripts in (a) each represent the carbon contained in the groupAtomic number. For example, C4～C20The alkyl group represents an alkyl group having 4 to 20 carbon atoms, C4～C20The oxygen-containing alkyl group represents an oxygen-containing alkyl group having 4 to 20 carbon atoms.
"substituted alkyl" refers to a group resulting from the substitution of at least one hydrogen atom in an alkyl group with a substituent;
"heteroalkyl" refers to a group consisting of a heteroatom including, but not limited to O, N, S and an alkyl group.
The beneficial effects that this application can produce include:
1) the preparation method of the double-sided asymmetrically modified graphene provided by the application starts from graphene, obtains the double-sided asymmetrically modified graphene material through two-step single-sided modification, and overcomes the defect that the double-sided asymmetrically modified graphene is prepared from graphene oxide in the prior art.
2) The double-sided asymmetric modified graphene provided by the application reserves the original ultrahigh electron conductivity of graphene, and is higher in modification efficiency.
Drawings
Fig. 1 is a flowchart of a method for preparing double-sided asymmetrically modified graphene according to an embodiment of the present disclosure;
fig. 2 is a schematic diagram of single-sided modification of graphene according to an embodiment of the present disclosure;
FIG. 3 is a schematic view of FIG. 2 with another side modified.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Example 1
(1) Graphene coating of the substrate: growing graphene on the copper foil by a chemical vapor deposition method; the carbon source was methane at 1000 deg.C under 10kPa and the carrier gas was hydrogen for 15 minutes. And cooling and taking out the graphene deposited copper foil. And weighing before and after deposition to obtain the graphene mass.
(2) Single-sided modification of graphene: the copper foil deposited with 0.1 g of graphene is soaked in a solvent dimethyl sulfoxide (DMSO), 1g of iodohexadecane and 0.05 g of an initiator benzoyl peroxide are added, the mixture is heated to 190 ℃ and refluxed for 24 hours, and the mixture is taken out after cooling, so that the single-side modified graphene copper foil is obtained.
(3) Substrate transfer: dissolving polymethyl methacrylate (PMMA) in diethyl ether according to the mass ratio of 1:10, fully and uniformly stirring, and standing for 2 hours; spin-coating a PMMA/ether solution on the single-sided modified graphene copper foil, uniformly coating the whole surface, drying, and evaporating ether to obtain a solid PMMA-coated copper foil; placing the PMMA-coated copper foil on the surface of a ferric trichloride solution with the coating surface upward, standing for 4 hours to completely dissolve the copper foil substrate, fishing out the single-side modified graphene PMMA film, heating to 60 ℃, and drying for 2 hours.
(4) And (3) modifying the other surface: soaking a single-sided modified graphene PMMA film (wherein the mass of the single-sided modified graphene is 0.2g) in a solvent toluene, adding 2g of 6-chloro-1-hexanol and 0.05 g of an initiator Lauroyl Peroxide (LPO), heating to 120 ℃, refluxing for 24 hours, cooling, and taking out the PMMA film to obtain a double-sided asymmetric modified graphene PMMA film;
(5) removing the substrate II: soaking the double-sided asymmetric modified graphene PMMA film in acetone, standing for 10 hours to enable the PMMA film to be completely dissolved, filtering to obtain a filter cake, heating to 50 ℃, and drying for 2 hours to obtain the double-sided asymmetric modified graphene.
Example 2
(1) Graphene coating of the substrate: the graphene is coated on the silicon wafer by a spin coating method.
(2) Single-sided modification of graphene: soaking the silicon wafer coated with 1g of graphene in a solvent Dimethylacetamide (DMAC), adding 1g of bromo-n-heptane and 0.05 g of an initiator Lauroyl Peroxide (LPO), heating to 170 ℃, refluxing for 24 hours, cooling, and taking out to obtain a single-side modified graphene silicon wafer;
(3) substrate transfer: dissolving Polyimide (PI) in dimethyl formamide DMF (dimethyl formamide) according to the mass ratio of 1:10, fully and uniformly stirring, and standing for 2 hours; spin-coating a PI/DMF solution on a single-side modified graphene silicon wafer, uniformly coating the whole surface, and drying to obtain a solid PI-coated silicon wafer; soaking the PI-coated silicon wafer in 0.1mol/L diluted hydrochloric acid, standing for 4 hours, fishing out the single-side modified graphene PI film after the silicon wafer is completely stripped from graphene, washing with water, and heating to 60 ℃ for drying.
(4) And (3) modifying the other surface: soaking a single-sided modified graphene PI film (wherein the mass of the single-sided modified graphene is 2g) in a solvent toluene, adding 1g of chlorohexadecyl pyridine and 0.05 g of initiator Benzoyl Peroxide (BPO), heating to 120 ℃, refluxing for 24 hours, cooling, and taking out the PI film to obtain a double-sided asymmetric modified graphene PI film;
(5) removing the substrate II: soaking the double-sided asymmetrically-modified graphene PI film in Dimethylacetamide (DMAC), standing for 10 hours to completely dissolve PI, filtering to obtain a filter cake, heating to 50 ℃, and drying for 2 hours to obtain the double-sided asymmetrically-modified graphene.
Example 3
(1) Graphene coating of the substrate: the graphene is coated on the glass sheet by a spin coating method.
(2) Single-sided modification of graphene: soaking the glass sheet coated with 0.1 g of graphene in a solvent of Dimethylacetamide (DMAC), adding 1g of bromo-n-heptane and 0.05 g of initiator tert-Butyl Peroxybenzoate (BPB), heating to 170 ℃, refluxing for 24 hours, cooling, and taking out to obtain a single-side modified graphene glass sheet;
(3) substrate transfer: dissolving polyethylene terephthalate (PET) in dimethyl formamide DMF (dimethyl formamide) according to the mass ratio of 1:10, fully and uniformly stirring, and standing for 2 hours; spin-coating a PET/DMF solution on a single-side modified graphene glass sheet, uniformly coating the whole surface, and drying to obtain a solid PET-coated glass sheet; soaking the PET-coated glass sheet in 0.1mol/L diluted hydrochloric acid, standing for 4 hours, taking out the single-side modified graphene PET film after the glass sheet is completely stripped from graphene, washing with water, and heating to 60 ℃ for drying.
(4) And (3) modifying the other surface: soaking a single-sided modified graphene PET film (wherein the mass of the single-sided modified graphene is 1g) in a solvent toluene, adding 2g of chlorohexadecyl pyridine and 0.05 g of initiator Benzoyl Peroxide (BPO), heating to 120 ℃, refluxing for 24 hours, cooling, and taking out a PI film to obtain a double-sided asymmetric modified graphene PET film;
(5) removing the substrate II: soaking the double-sided asymmetric modified graphene PET film in Dimethylacetamide (DMAC), standing for 10 hours to completely dissolve the PET, filtering to obtain a filter cake, heating to 50 ℃, and drying for 2 hours to obtain the double-sided asymmetric modified graphene.
Example 4
Replacing the iodohexadecane in example 1 with 2-bromo-3-hexylthiophene; the remaining conditions were the same as in example 1.
Example 5
The n-heptane bromide in example 2 was replaced with 2-bromoethyl sulfide; the remaining conditions were the same as in example 2.
Example 6
The n-heptane bromide in example 2 was replaced with isopropyl-2-bromoethyl ether; the remaining conditions were the same as in example 2.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (9)
1. A preparation method of double-sided asymmetrically modified graphene is characterized in that double sides of layered graphene are sequentially modified on a substrate, so that the double-sided asymmetrically modified graphene can be obtained;
at least comprises the following steps:
a) obtaining graphene attached to a substrate I;
b) heating a mixture containing the graphene obtained in the step a) and a modifier I in the presence of an initiator I, and initiating hydrocarbyl chain grafting on one surface of the graphene to obtain single-surface modified graphene; wherein the heating conditions are as follows: the temperature is 100-200 ℃, and the time is 10-100 hours;
c) transferring the single-side modified graphene from the substrate I to the substrate II, removing the substrate I, and exposing the unmodified graphene layer on the other side;
d) in the presence of an initiator II, heating a mixture containing the single-sided modified graphene and a modifier II, initiating hydrocarbyl chain grafting on the other side of the graphene, and then removing the substrate II to obtain the double-sided asymmetric modified graphene; wherein the heating conditions are as follows: the temperature is 100-150 ℃, and the time is 10-100 hours;
wherein, the modifier I and the modifier II are independently selected from at least one compound with a structural formula shown in a formula I;
RX formula I
Wherein R represents an organic group;
the organic group comprises any one of alkyl, substituted alkyl and heteroalkyl;
x is selected from any one of halogens;
the initiator I is selected from any one of benzoyl peroxide BPO, lauroyl peroxide LPO, tert-butyl peroxybenzoate BPB and 2, 2-di (tert-butylperoxy) butane DBPB;
the initiator II is selected from any one of benzoyl peroxide BPO, lauroyl peroxide LPO, tert-butyl peroxybenzoate BPB and 2, 2-di (tert-butylperoxy) butane DBPB.
2. The method according to claim 1, wherein in step a), the substrate I is selected from any one of copper foil, silicon wafer, glass, quartz, sapphire, SiC, ITO glass and FTO glass.
3. The preparation method of claim 1, wherein in the step b), the mass ratio of the graphene to the modifier I is 1: 0.5-1: 10.
4. The method of claim 1, wherein step c) comprises: and coating the modified surface of the single-surface modified graphene by using a substrate II, and then removing the substrate I.
5. The method according to claim 1, wherein in step c), the substrate II is selected from a polymeric film substrate;
the polymer film substrate includes any one of a polymethyl methacrylate substrate, a polyvinyl alcohol substrate, a polyimide substrate, a polyethylene terephthalate substrate, and a polyvinyl phenol substrate.
6. The preparation method according to claim 1, wherein the mass ratio of the single-side modified graphene to the modifier II is 1: 0.5-1: 10.
7. The method according to claim 1, wherein the substituted alkyl group is selected from any one of groups having structural formulas shown in formulas II and III;
HO-R' -formula II
Ar-R' formula III
Wherein R ', R' are independently selected from C4～C20Any one of the alkyl groups of (a);
ar represents a nitrogen-or sulfur-containing heteroaryl group.
8. The method of claim 1, wherein the alkyl group is selected from C4～C20An alkyl group;
the heteroalkyl group is selected from C4～C20Oxygen-containing alkyl radical, C4～C20Nitrogen-containing alkyl group, C4～C20Any of sulfoalkyl groups.
9. The double-sided asymmetric modified graphene obtained by the preparation method according to any one of claims 1 to 8, wherein the double-sided asymmetric modified graphene comprises a carbon-based plane and organic groups, and the organic groups are asymmetrically grafted on both sides of the carbon-based plane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849732A (en) * | 2012-09-18 | 2013-01-02 | 北京大学 | Method for realizing double-surface asymmetric modification of single-layer graphene |
| CN103796766A (en) * | 2011-09-14 | 2014-05-14 | 威廉马歇莱思大学 | Solvent-based methods for production of graphene nanoribbons |
| CN105731431A (en) * | 2016-01-14 | 2016-07-06 | 哈尔滨工业大学 | Chemical modification method of surface graphene on basis of solid-phase thermochemical reaction |
-
2019
- 2019-06-20 CN CN201910537972.7A patent/CN110316727B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103796766A (en) * | 2011-09-14 | 2014-05-14 | 威廉马歇莱思大学 | Solvent-based methods for production of graphene nanoribbons |
| CN102849732A (en) * | 2012-09-18 | 2013-01-02 | 北京大学 | Method for realizing double-surface asymmetric modification of single-layer graphene |
| CN105731431A (en) * | 2016-01-14 | 2016-07-06 | 哈尔滨工业大学 | Chemical modification method of surface graphene on basis of solid-phase thermochemical reaction |
Non-Patent Citations (2)
| Title |
|---|
| Functionalized Low Defect Graphene Nanoribbons and Polyurethane Composite Film for Improved Gas Barrier and Mechanical Performances;Changsheng Xiang et al.;《ACS Nano》;20131008;第7卷(第11期);第10380-10386页 * |
| 石墨烯的光化学修饰;周琳等;《化学学报》;20141231;第72卷;第292页"3 石墨烯的光甲基化加成反应" * |
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