CN116375009B - Preparation method of modified graphene - Google Patents
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- CN116375009B CN116375009B CN202211678972.7A CN202211678972A CN116375009B CN 116375009 B CN116375009 B CN 116375009B CN 202211678972 A CN202211678972 A CN 202211678972A CN 116375009 B CN116375009 B CN 116375009B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 69
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 55
- 239000010439 graphite Substances 0.000 claims abstract description 55
- DEGAKNSWVGKMLS-UHFFFAOYSA-N calcein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(O)=O)CC(O)=O)=C(O)C=C1OC1=C2C=C(CN(CC(O)=O)CC(=O)O)C(O)=C1 DEGAKNSWVGKMLS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229960002378 oftasceine Drugs 0.000 claims abstract description 34
- 238000004108 freeze drying Methods 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 238000012986 modification Methods 0.000 claims description 15
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- 229910021389 graphene Inorganic materials 0.000 abstract description 43
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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Classifications
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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
- C01B32/19—Preparation by exfoliation
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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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Abstract
The invention discloses a preparation method of modified graphene, which comprises the following steps: (1) Dispersing graphite and a modifier in water to prepare pretreated graphite dispersion liquid; (2) Stripping and modifying the pretreated graphite dispersion liquid obtained in the step (1) to prepare modified graphene dispersion liquid; (3) And (3) freeze-drying the modified graphene dispersion liquid obtained in the step (2) to obtain modified graphene. According to the method, graphite is used as a raw material, calcein is used as a stripping auxiliary agent and a modifier, the graphite is stripped into graphene by utilizing the effect of the ultrahigh shear rate of a micro-jet homogenizer, and the graphene is modified; the whole process takes water as a medium, does not add strong acid or strong oxidant, and is environment-friendly; the surface of the obtained graphene contains active groups and has high conductivity.
Description
Technical Field
The invention relates to the field of graphene modification, in particular to a method for preparing modified graphene by taking calcein as a modifier.
Background
Graphene is a two-dimensional sheet formed by stacking sp 2 hybridized carbon atom layers, integrates the characteristics of excellent theoretical surface area (2630 m 2·g-1), young modulus (1.0 TPa), thermal conductivity (5000 W.m -1·K-1), light transmittance (97.7%), electrical conductivity (10 6S·m-1), carrier mobility (200000 cm 2·V-1·s-1) and the like, and has a quantum Hall effect and a dual-polarized electric field effect. The characteristics lead the graphene to have wide research and application prospects in the fields of energy storage and conversion, nanocomposite materials, quantum physics, catalysis, nanoelectronics, photoelectric detectors, biological materials and the like. Therefore, it is very important to develop a simple and efficient preparation method of graphene.
In the practical application of graphene, the problem exists that in the process of dispersing the graphene, the complete graphene structure is composed of benzene rings, so that the chemical stability is strong, the surface is in an inert state, the interaction force with other media is weak, but strong pi-pi interaction exists between graphene layers, the stacking of sheets is extremely easy to cause, and the agglomeration in a solution is difficult to uniformly compound with other organic or inorganic materials. This phenomenon creates great difficulties for application and research of graphene.
The problem can be effectively solved by modifying the surface of the graphene. By introducing specific functional groups on the surface of the graphene, the properties of the graphene are changed. These changes include: the dispersibility of the graphene is improved, the re-stacking of graphene sheets is prevented, the surface activity of the graphene is improved, and the physical and chemical properties of the graphene are improved or new physical and chemical properties are endowed.
Currently, there are many methods for modifying graphene, which are mainly classified into two types, covalent bond modification and non-covalent bond modification. The covalent bond modification is realized by utilizing the characteristic that the edge or defect of the graphene has higher activity and connecting new functional groups at the positions by utilizing covalent bonds, thereby realizing the modification of the graphene. The traditional modification method is to treat graphene by utilizing chemical reaction, and manufacture certain defects on the surface to form graphene oxide, so that the surface of the graphene oxide is rich in active groups such as carboxyl, hydroxyl, epoxy and the like. The covalent bond modification of the graphene surface can be realized by utilizing the reaction of the active groups and other substances, but the defects are that strong acid and strong oxidant are used for damaging the intrinsic structure of the graphene during modification, the physical and chemical properties of the graphene are changed, impurities are easily introduced, waste liquid pollution is large, and the operation danger is easy to explode.
In addition to covalent bond modification, graphene may be modified by non-covalent bond linkages, including: pi-pi interactions, ionic bonds, hydrogen bonds, and the like. Since graphene itself has a highly conjugated structure, pi-pi interactions are easily generated with other small molecules and polymers having the same conjugated structure or aromatic ring. The method has the advantages that the intrinsic structure of the graphene is not damaged in the modification process, the physical and chemical properties of the graphene are reserved, and other components (such as a surfactant) are introduced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of modified graphene, which is a non-covalent modification method of graphene. The preparation method has the advantages of green and low-carbon preparation process, low production cost, high efficiency, good product quality and wide application prospect.
The technical scheme of the invention is as follows:
A preparation method of modified graphene comprises the following steps of
(1) Dispersing graphite and a modifier in water to prepare pretreated graphite dispersion liquid;
(2) Stripping and modifying the pretreated graphite dispersion liquid obtained in the step (1) to prepare modified graphene dispersion liquid;
(3) And (3) freeze-drying the modified graphene dispersion liquid obtained in the step (2) to obtain modified graphene.
According to the implementation method of the invention, in the step (1), the modifier is calcein; the structural formula of the calcein is shown as follows.
According to an embodiment of the invention, in step (1), the concentration of the modifier is 1-20mg/mL, for example 5-14mg/mL, or 10-20mg/mL, or 1-12mg/mL. Exemplary are 1mg/mL, 2mg/mL, 4mg/mL, 5mg/mL, 6mg/mL, 8mg/mL, 10mg/mL, 12mg/mL, 14mg/mL, 15mg/mL, 16mg/mL, 18mg/mL, or 20mg/mL.
According to an embodiment of the present invention, in step (1), the raw material of graphite may be selected from at least one of natural crystalline flake graphite, expanded graphite, graphite powder, and the like. Further, the graphite is in the form of powder, for example, the graphite powder has a mesh number of 80 mesh to 5000 mesh.
According to an embodiment of the invention, in step (1), the concentration of graphite in the pre-treated graphite dispersion is in the range of 1-60mg/mL, for example 3-17mg/mL, or 15-40mg/mL. Illustratively 1mg/mL、3mg/mL、5mg/mL、6mg/mL、8mg/mL、10mg/mL、12mg/mL、14mg/mL、15mg/mL、17mg/mL、18mg/mL、20mg/mL、30mg/mL、35mg/mL、40mg/mL、50mg/mL or 60mg/mL.
According to an embodiment of the present invention, in the step (1), the dispersion may be shear-dispersed using a high shear dispersing emulsifying machine, or ultrasonic-dispersed, or stirred-dispersed.
According to an embodiment of the invention, in step (1), the dispersing time is for example 1 to 100min.
According to an embodiment of the present invention, the step (1) may specifically be: (1a) Adding graphite into water, adding a modifier, and shearing and dispersing by using a high-shearing dispersing emulsifying machine to obtain a pretreated graphite dispersion liquid.
According to an embodiment of the present invention, step (1) may further be: (1b) Adding graphite into water, adding a modifier, and performing ultrasonic treatment to obtain a pretreated graphite dispersion liquid.
According to an embodiment of the present invention, step (1) may further be: (1c) Adding graphite into water, adding a modifier, and stirring to obtain pretreated graphite dispersion liquid.
According to an embodiment of the invention, in step (1 a), the time of dispersion is between 1 and 100min, for example 15-50min, exemplary 15min, 30min, 50min, 100min; the rotational speed of the high shear dispersing emulsifier is 100-15000rpm, for example 500-10000rpm, and is exemplified by 1000rpm, 2500rpm, 5000rpm.
According to an embodiment of the invention, in step (1 b), the time of the ultrasonic treatment is 1 to 10 minutes; the power of the ultrasonic treatment is 80-200W.
According to an embodiment of the present invention, in the step (2), the peeling and the modification are performed by using a micro-jet homogenizer.
In the step (2), "peeling and modifying the pretreated graphite dispersion liquid" means that peeling and modifying the graphite dispersion liquid are performed simultaneously in one step, and the graphene is peeled into graphene and modified to obtain a modified graphene dispersion liquid.
According to an embodiment of the present invention, step (2) is specifically: and adding the pretreated graphite dispersion liquid into a micro-jet homogenizer for stripping and modification to obtain modified graphene dispersion liquid.
According to an embodiment of the present invention, in step (2), the peeling and modifying process of the pretreated graphite dispersion in a microfluidic homogenizer comprises: the pretreated graphite dispersion is circulated through a 150-400 μm (exemplary 150 μm, 200 μm, 250 μm, 300 μm, or 400 μm) nozzle 10-30 times (exemplary 10 times, 15 times, 20 times, or 30 times) at a pressure of 10000-30000psi (exemplary 10000psi, 20000psi, or 30000 psi).
According to an embodiment of the invention, in step (3), the temperature of the freeze-drying is between-50 and-70 ℃.
According to an embodiment of the invention, in step (3), the time of freeze-drying is 1 to 5 days.
The invention also provides the modified graphene prepared by the method.
According to the embodiment of the invention, the number of layers of the modified graphene obtained by the preparation method of the modified graphene is 1-10, and the transverse dimension is 1-10 mu m.
According to an embodiment of the invention, the conductivity of the modified graphene is 10000-40000 Ω/m, preferably 13000-30000 Ω/m.
The invention also provides a liquid phase modification system for preparing the modified graphene, which comprises graphite, a modifier and a dispersion medium, wherein the modifier is calcein.
In the present invention, the graphite, modifier and dispersion medium of the liquid phase modification system have the meanings as above.
The invention has the beneficial effects that:
(1) According to the method, graphite is used as a raw material, calcein is used as a stripping auxiliary agent and a modifier, the graphite is stripped into graphene by utilizing the effect of the ultrahigh shear rate of a micro-jet homogenizer, and the graphene is modified; the whole process uses water as a medium, does not add strong acid or strong oxidant, and is environment-friendly.
(2) The graphene surface obtained by the method contains active groups and has high conductivity.
(3) According to the invention, the number of layers of the required graphene sheets, conductivity and other characteristics can be regulated by regulating the addition amount of the modifier, the use amount of raw graphite, the stripping time and other conditions.
Drawings
Fig. 1 is a raman spectrum of the modified graphene prepared in example 1.
Fig. 2 is a transmission electron microscopic image of the modified graphene prepared in example 1.
Fig. 3 is an atomic force microscope image of the modified graphene prepared in example 1.
Fig. 4 is an infrared spectrum of graphene, calcein, and modified graphene in example 1.
FIG. 5 is a fluorescence spectrum of calcein and modified graphene in example 1.
Fig. 6 is a graph of modified graphene dispersion prepared in example 1 and comparative example 1.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
(1) Firstly, adding graphite powder and calcein into deionized water to prepare graphite powder/calcein dispersion liquid, wherein the concentration of the graphite powder is 50mg/mL, the concentration of the calcein is 1mg/mL, and treating the mixture for 15min by a high-shear dispersion emulsifying machine to obtain uniformly mixed graphite aqueous dispersion liquid;
(2) Adding the dispersion liquid into a micro-jet homogenizer, and circularly treating for 15 times at 20000psi through a 300 mu m nozzle to obtain a modified graphene dispersion liquid;
(3) And freeze-drying the modified graphene dispersion liquid, wherein the freeze-drying temperature is-70 ℃, and the freeze-drying time is 3 days, so as to obtain the modified graphene.
The raman diagram of the modified graphene is shown in fig. 1. The ratio of the D peak to the G peak of the modified graphene (namely calcein/graphene in the figure 1) prepared by the micro-jet homogenizer is 0.12, and the 2D peak is a sharp single peak, so that the number of layers of the prepared modified graphene can be judged to be between 5 and 7 layers, and the modified graphene has a good stripping effect. The transmission electron microscope diagram of the modified graphene is shown in fig. 2. The typical lamellar structure of the modified graphene is evident from fig. 2, and the phenomenon of wrinkling occurs. FIG. 3 is an atomic force microscope image of modified graphene having a thickness of about 1.4nm and about 2-5 layers.
Fig. 4 is an infrared spectrogram of graphene (i.e., graphite powder), calcein and modified graphene, wherein no obvious characteristic peak appears in the graphene, the characteristic peak of the modified graphene mainly comes from calcein, and the characteristic peak example of the modified graphene is obviously blue-shifted, which indicates that the surface of the modified graphene contains calcein. FIG. 5 is a fluorescence spectrum of modified graphene, after calcein is excited, a characteristic fluorescence peak is shown, the absorption peak is blue-shifted in the modified graphene, and meanwhile, the peak intensity is greatly reduced, which indicates pi-pi interaction exists between calcein and graphene.
The photograph of the appearance of the modified graphene dispersion is shown on the right side of fig. 6. The modified graphene shows good dispersibility and excellent stability in a dispersion liquid.
Example 2
(1) Firstly, adding expanded graphite and calcein into deionized water to prepare an expanded graphite/calcein dispersion liquid, wherein the concentration of the expanded graphite is 50mg/mL, the concentration of the calcein is 2mg/mL, and treating the mixture for 15min by a high-shear dispersion emulsifying machine to obtain a uniformly mixed graphite aqueous dispersion liquid;
(2) Adding the dispersion liquid into a micro-jet homogenizer, and circularly treating for 15 times at 20000psi through a 300 mu m nozzle to obtain a modified graphene dispersion liquid;
(3) And freeze-drying the modified graphene dispersion liquid, wherein the freeze-drying temperature is-70 ℃, and the freeze-drying time is 5 days, so as to obtain the modified graphene.
Example 3
(1) Firstly, adding graphite powder and calcein into deionized water to prepare graphite powder/calcein dispersion liquid, wherein the concentration of the graphite powder is 50mg/mL, the concentration of the calcein is 4mg/mL, and carrying out ultrasonic dispersion for 30min to obtain uniformly mixed graphite aqueous dispersion liquid;
(2) Adding the dispersion liquid into a micro-jet homogenizer, and circularly treating for 30 times at 10000psi through a 200 μm nozzle to obtain modified graphene dispersion liquid;
(3) And freeze-drying the modified graphene dispersion liquid, wherein the freeze-drying temperature is-60 ℃, and the freeze-drying time is 2 days, so that the modified graphene is obtained.
Example 4
(1) Firstly, adding natural crystalline flake graphite and calcein into water to prepare natural crystalline flake graphite/calcein dispersion liquid, wherein the concentration of the natural crystalline flake graphite is 50mg/mL, the concentration of the calcein is 8mg/mL, and stirring until the system is uniform to obtain natural crystalline flake graphite dispersion liquid;
(2) Adding the dispersion liquid into a micro-jet homogenizer, circulating for 20 times through a nozzle with the diameter of 300 mu m and the pressure of 3000psi to obtain modified graphene dispersion liquid;
(3) And freeze-drying the modified graphene dispersion liquid, wherein the freeze-drying temperature is-50 ℃, and the freeze-drying time is 3 days, so as to obtain the modified graphene.
Example 5
(1) Firstly, adding graphite powder and calcein into water to prepare graphite powder/calcein dispersion liquid, wherein the concentration of the graphite powder is 50mg/mL, the concentration of the calcein is 12mg/mL, and stirring until the system is uniform to obtain graphite dispersion liquid;
(2) Adding the dispersion liquid into a micro-jet homogenizer, and circularly treating for 10 times at 20000psi through a nozzle with the diameter of 400 mu m to obtain modified graphene dispersion liquid;
(3) And freeze-drying the modified graphene dispersion liquid, wherein the freeze-drying temperature is-70 ℃, and the freeze-drying time is 5 days, so as to obtain the modified graphene.
Comparative example 1
(1) Firstly, adding expanded graphite and 3',6' -dichlorofluorescein into ethanol to prepare an expanded graphite/3 ',6' -dichlorofluorescein dispersion liquid, wherein the concentration of the expanded graphite is 50mg/mL, the concentration of the 3',6' -dichlorofluorescein is 2mg/mL, and stirring until the system is uniform, and the structural formula of the 3',6' -dichlorofluorescein is shown as follows;
(2) Adding the dispersion liquid into a high-shear dispersion emulsifying machine, shearing and mixing the dispersion liquid for 15min at a rotating speed of 1000rpm to obtain a modified graphene dispersion liquid, wherein the appearance photo of the modified graphene dispersion liquid is shown as the left side of fig. 6;
(3) And freeze-drying the modified graphene dispersion liquid, wherein the freeze-drying temperature is-70 ℃, and the freeze-drying time is 21 days, so as to obtain the modified graphene.
Comparative example 2
(1) Firstly, adding expanded graphite and citric acid into ethanol to prepare an expanded graphite/citric acid dispersion liquid, wherein the concentration of the expanded graphite is 50mg/mL, the concentration of the citric acid is 2mg/mL, and stirring until the system is uniform, and the structural formula of the citric acid is shown as follows;
(2) Adding the dispersion liquid into a high-shear dispersion emulsifying machine, and shearing and mixing the dispersion liquid for 15min at a rotating speed of 1000rpm to obtain modified graphene dispersion liquid;
(3) And freeze-drying the modified graphene dispersion liquid, wherein the freeze-drying temperature is-70 ℃, and the freeze-drying time is 21 days, so as to obtain the modified graphene.
Table 1 shows the number of layers, lateral dimensions, and conductivity of the modified graphene sheets in examples 1-5 and comparative examples 1-2.
And testing the number of layers of the modified graphene sheet by adopting an atomic force microscope.
The transverse dimensions of the modified graphene sheets were tested using a transmission electron microscope.
And testing the conductivity of the modified graphene by adopting a four-probe method.
TABLE 1
* The peeling time is expressed by the use of a high shear dispersing emulsifying machine or an ultrasonic dispersing machine in the peeling operation.
In Table 1, the modifier used in examples 1-5 was calcein; the modifier used in comparative example 1 was 3',6' -dichlorofluorescein; the modifier used in comparative example 2 was citric acid.
The number of layers of the modified graphene sheet obtained by the preparation method provided by the invention is reduced along with the increase of the concentration of the modifier calcein, the stripping time and the cycle times, and the transverse dimension is increased along with the increase of the stripping time and the cycle times.
On the other hand, comparative examples 1 and 2 did not use calcein of the present invention as a modifier, but used 3',6' -dichlorofluorescein containing no hydroxyl group and carboxyl group and citric acid containing no benzene ring as a modifier. In comparative example 1, 3',6' -dichlorofluorescein containing no hydroxyl group and carboxyl group is used as a modifier, the number of layers and the size of the obtained modified graphene sheet are slightly increased, and the conductivity is greatly reduced. In comparative example 2, citric acid containing no hydroxyl group and carboxyl group and no benzene ring was used as a modifier, the number of layers and the size of the obtained modified graphene sheet were greatly increased, and the conductivity was also greatly reduced.
The embodiments of the present invention have been described above by way of example. The scope of the invention is not limited to the embodiments described above. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, are intended to be included within the scope of the present invention.
Claims (9)
1. The preparation method of the modified graphene is characterized by comprising the following steps of
(1) Dispersing graphite and a modifier in water to prepare pretreated graphite dispersion liquid;
(2) Stripping and modifying the pretreated graphite dispersion liquid obtained in the step (1) to prepare modified graphene dispersion liquid;
(3) Freeze-drying the modified graphene dispersion liquid obtained in the step (2) to obtain modified graphene;
In the step (1), the modifier is calcein; the structural formula of the calcein is shown as follows;
2. The method according to claim 1, wherein in the step (1), the dispersing means is at least one selected from the group consisting of high shear dispersing, emulsifying shear dispersing, ultrasonic dispersing and stirring dispersing.
3. The method of claim 1, wherein in step (1), the modifier is present at a concentration of 1-20mg/mL.
4. The method according to claim 1, wherein in the step (1), the raw material of graphite is at least one selected from the group consisting of natural crystalline flake graphite, expanded graphite, and graphite powder.
5. The method of claim 1, wherein in step (1), the concentration of graphite in the pretreated graphite dispersion is 1-60mg/mL.
6. The method according to claim 1, wherein in the step (2), the peeling and the modification are performed by using a micro-jet homogenizer.
7. A modified graphene prepared by the method of any one of claims 1-6.
8. The modified graphene of claim 7, wherein the number of layers of the modified graphene is 1-10 and the lateral dimension is 1-10 μm.
9. The modified graphene of claim 7, wherein the modified graphene has a conductivity of 10000 to 40000 Ω/m.
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