CN111204751A - Three-dimensional graphene macroscopic material and preparation method and application thereof - Google Patents
Three-dimensional graphene macroscopic material and preparation method and application thereof Download PDFInfo
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- CN111204751A CN111204751A CN201911152133.XA CN201911152133A CN111204751A CN 111204751 A CN111204751 A CN 111204751A CN 201911152133 A CN201911152133 A CN 201911152133A CN 111204751 A CN111204751 A CN 111204751A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 117
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 29
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000000017 hydrogel Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 description 5
- 239000004964 aerogel Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B2204/22—Electronic properties
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a three-dimensional graphene macroscopic body material and a preparation method and application thereof, and specifically comprises the following steps: uniformly mixing graphene oxide and heteropoly acid solution, then adding hydrazine hydrate, uniformly mixing, and standing at room temperature to obtain the graphene macroscopic body with the three-dimensional cross-linked porous network. Compared with the prior art, the preparation method of the three-dimensional graphene macroscopic material only needs room temperature and does not need heating; the method is simple and convenient to operate, convenient and quick, low in energy consumption and high in efficiency, and is a method capable of preparing the three-dimensional graphene macroscopic body in a large scale.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a method for quickly preparing a graphene/heteropoly acid composite three-dimensional graphene macroscopic body at room temperature.
Background
The three-dimensional graphene macroscopic material has the characteristics of low density, porosity, high specific surface area and the like, can be used as an excellent electrode, adsorption and heat dissipation material, and has wide application prospect. At present, methods for constructing a three-dimensional graphene macroscopic body mainly include a template method and a self-assembly method. The template method mainly uses a chemical vapor deposition method, and the surface of the three-dimensional graphene macroscopic body prepared by the method is always strong in hydrophobicity and very limited in application; in addition, the chemical vapor deposition method has high preparation cost and is difficult to realize large-scale preparation. The self-assembly method mainly comprises a sol-gel method, a hydrothermal/solvothermal method, chemical reduction self-assembly and the like, but the reaction temperature of the existing self-assembly process is mostly higher than 90 ℃, the energy consumption is high, a hydrothermal kettle is needed, the large-scale production is not easy, and the practical application of the self-assembly method is greatly limited. Therefore, the development of a method which is simple in process, low in energy consumption and capable of preparing the high-performance three-dimensional graphene macroscopic material in a large scale can greatly promote the development and practical application of the three-dimensional graphene macroscopic material in the fields of electrode materials and the like.
Disclosure of Invention
In order to overcome the defect that the macroscopical preparation method of the three-dimensional graphene is embodied, the invention aims to develop a method for quickly, efficiently and massively preparing a macroscopical three-dimensional graphene body at room temperature.
The invention provides a graphene/heteropoly acid composite three-dimensional graphene macroscopic body material, wherein the graphene/heteropoly acid composite three-dimensional graphene macroscopic body consists of graphene and heteropoly acid, and the density of the graphene/heteropoly acid composite three-dimensional graphene macroscopic body is 0.02-1.5g/cm3The content of heteropoly acid is 5-30 wt%, and the specific surface area is 100-800cm2The electrical conductivity is 10-100S/m.
The invention provides a preparation method of a graphene/heteropoly acid composite three-dimensional graphene macroscopic material, which specifically comprises the following steps:
(1) uniformly mixing graphene oxide and a heteropoly acid aqueous solution to obtain a mixed solution; wherein the mass ratio of the graphene oxide to the heteropoly acid is 0.1-20: 1. The lateral dimension of the graphene oxide is 0.5-200 μm, and the preferable range is 1-100 μm; the concentration of the graphene oxide is 0.1-20mg/mL, and the preferable range is 0.5-10 mg/mL.
(2) Uniformly dispersing hydrazine hydrate in the mixed solution obtained in the step (1), and standing at room temperature to obtain graphene/heteropoly acid composite three-dimensional graphene hydrogel;
(3) and (3) drying the graphene/heteropoly acid composite three-dimensional graphene hydrogel obtained in the step (2) to obtain the three-dimensional graphene macroscopic material.
The three-dimensional graphene macroscopic body is a graphene/heteropoly acid composite three-dimensional graphene macroscopic body.
The heteropoly acid in the step (1) comprises one or more of phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid, phosphotungstic acid, silicotungstic acid, germanium tungstic acid and the like.
The concentration of the heteropoly acid in the step (1) is 0.1-50mmol/L, and the preferable range is 0.5-30 mmol/L.
The mixing time of the graphene oxide and the heteropoly acid solution in the step (1) is 0.5-5h, and the preferred range is 1-3 h.
The mass ratio of hydrazine hydrate to heteropoly acid in the step (2) is 0.5-5: 1.
The preparation temperature of the graphene oxide/heteropoly acid composite three-dimensional graphene macroscopic body in the step (2) is 10-35 ℃. The preferred range is 20-30 ℃.
And (3) adding hydrazine hydrate in the step (2) into the mixed solution obtained in the step (1), uniformly mixing, and standing for 0.1-20 h.
And (3) drying the three-dimensional graphene macroscopic body in the step (3) in a drying mode including room temperature drying, forced air drying, vacuum drying and freeze drying.
The graphene/heteropoly acid composite three-dimensional graphene macroscopic material disclosed by the invention is used as an electrode material of a super capacitor, an organic solvent and an adsorbent of heavy metal.
The three-dimensional graphene macroscopic body is a graphene/heteropoly acid composite three-dimensional graphene macroscopic body and is prepared by taking a graphene oxide solution and a heteropoly acid solution as raw materials.
The invention has the following advantages:
1. the invention provides a method for quickly, efficiently and massively preparing a three-dimensional graphene macroscopic body at room temperature, which is simple to operate, low in energy consumption and high in efficiency, and has no special requirements on containers and equipment (heating and reaction kettles are not needed) in the preparation process;
2. the three-dimensional graphene macroscopic body consists of graphene and heteropoly acid, and the graphene and the heteropoly acid are connected through chemical bonds, so that the three-dimensional graphene macroscopic body has better stability;
3. heteropoly acid with excellent electrochemical performance and catalytic performance is introduced into the graphene, so that the application field of the graphene assembly is widened.
Drawings
Fig. 1 is a photograph of a graphene/heteropoly acid three-dimensional macroscopic material prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of a graphene/heteropoly acid three-dimensional graphene macroscopic body prepared in example 2 of the present invention.
Detailed Description
The method of the present invention will be described in detail with reference to specific examples, which are carried out on the premise of the technical solution of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Uniformly mixing 10mL of graphene oxide with the concentration of 5mg/mL and the transverse dimension of 10-50 μm with 5mL of 5mmol/L phosphomolybdic acid solution, then adding 100 μ L of 80% hydrazine hydrate, uniformly mixing, and standing at 20 ℃ for 2h to obtain the three-dimensional graphene macroscopic body hydrogel (as shown in figure 1). Obtaining a compact three-dimensional graphene macroscopic body through vacuum drying, wherein the mass density is 1.25g/cm3Specific surface area of 58cm2The specific mass capacity of the material is 360F/g.
Example 2
Uniformly mixing 8mL of graphene oxide with the concentration of 0.1mg/mL and the transverse dimension of 1-50 μm with 5mL of phosphotungstic acid solution with the transverse dimension of 0.1mmol/L, then adding 10 μ L of 50% hydrazine hydrate, uniformly mixing, and standing at 25 ℃ for 0.1h to obtain the three-dimensional graphene macroscopic body hydrogel. Drying at room temperature to obtain compact three-dimensional graphene macroscopic body with mass density of 1.5g/cm3The specific surface area is 380cm2The specific mass capacity of the electrode material is 230F/g.
Example 3
Uniformly mixing 20mL of graphene oxide with the concentration of 20mg/mL and the transverse dimension of 10-50 μm with 1mL of phosphomolybdic acid solution with the transverse dimension of 50mmol/L, then adding 200 μ L of 80% hydrazine hydrate, uniformly mixing, and standing at 25 ℃ for 20h to obtain the three-dimensional graphene macroscopic body hydrogel. Freeze drying to obtain three-dimensional graphene macroscopic body aerogel (shown as figure 2), with mass density of 1.5g/cm3The specific surface area is 0.03cm2The specific conductivity is 1000S/m, and the specific adsorption capacity is 130 times of the volume of the adsorbent applied to the organic solvent.
Example 4
30mL of the oxidized stone with the concentration of 20mg/mL and the transverse dimension of 50-200 mu mUniformly mixing the graphene with 1mL of 25mmol/L silicomolybdic acid solution, then adding 100 mu L of 60% hydrazine hydrate, uniformly mixing, and standing at 27 ℃ for 8h to obtain the three-dimensional graphene macroscopic body. Obtaining the three-dimensional graphene macroscopic body aerogel through air blast drying, wherein the mass density is 0.45g/cm3The specific surface area is 0.03cm2The specific surface area per gram (mg/g) and the conductivity is 750S/m, and the specific surface area per gram (mg/g) is 450mg/g when the adsorbent is applied to an adsorbent for heavy metal lead ions.
Claims (13)
1. A graphene/heteropoly acid composite three-dimensional graphene macroscopic body material is characterized in that: the graphene/heteropoly acid composite three-dimensional graphene macroscopic body consists of graphene and heteropoly acid, and the density of the graphene/heteropoly acid composite three-dimensional graphene macroscopic body is 0.02-1.5g/cm3The content of heteropoly acid is 5-30 wt%, and the specific surface area is 10-800cm2The electrical conductivity is 10-1000S/m.
2. A preparation method of a graphene/heteropoly acid composite three-dimensional graphene macroscopic body material is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) uniformly mixing graphene oxide and a heteropoly acid aqueous solution to obtain a mixed solution;
(2) uniformly dispersing hydrazine hydrate in the mixed solution obtained in the step (1), and standing at room temperature to obtain graphene/heteropoly acid composite three-dimensional graphene hydrogel;
(3) and (3) drying the graphene/heteropoly acid composite three-dimensional graphene hydrogel obtained in the step (2) to obtain the three-dimensional graphene macroscopic material.
3. The preparation method of the graphene/heteropoly acid composite three-dimensional graphene macroscopic material according to claim 2, which is characterized in that: the three-dimensional graphene macroscopic body is a graphene/heteropoly acid composite three-dimensional graphene macroscopic body.
4. The preparation method of the graphene/heteropoly acid composite three-dimensional graphene macroscopic material according to claim 2, which is characterized in that: the mass ratio of the graphene oxide to the heteropoly acid in the step (1) is 0.1-20: 1.
5. The preparation method of the graphene/heteropoly acid composite three-dimensional graphene macroscopic material according to claim 2, which is characterized in that: in the step (1), the transverse size of the graphene oxide is 0.5-200 μm, and the concentration is 0.1-20 mg/mL.
6. The preparation method of the graphene/heteropoly acid composite three-dimensional graphene macroscopic material according to claim 2, which is characterized in that: the heteropoly acid in the step (1) comprises one or more of phosphomolybdic acid, silicomolybdic acid, germanium molybdic acid, phosphotungstic acid, silicotungstic acid, germanium tungstic acid and the like.
7. The preparation method of the graphene/heteropoly acid composite three-dimensional graphene macroscopic material according to claim 2, which is characterized in that: the concentration of the heteropoly acid in the step (1) is 0.1-50 mmol/L.
8. The method for preparing the graphene/heteropoly acid composite three-dimensional graphene macroscopic body according to claim 2, wherein the method comprises the following steps: and (2) mixing the graphene oxide and the heteropoly acid solution in the step (1) for 0.5-5 h.
9. The method for preparing the graphene/heteropoly acid composite three-dimensional graphene macroscopic body according to claim 2, wherein the method comprises the following steps: the mass ratio of hydrazine hydrate to heteropoly acid in the step (2) is 0.5-5: 1.
10. The method for preparing the graphene/heteropoly acid composite three-dimensional graphene macroscopic body according to claim 2, wherein the method comprises the following steps: the preparation temperature of the graphene oxide/heteropoly acid composite three-dimensional graphene macroscopic body in the step (2) is 10-35 ℃.
11. The method for preparing the graphene/heteropoly acid composite three-dimensional graphene macroscopic body according to claim 2, wherein the method comprises the following steps: and (3) adding hydrazine hydrate in the step (2) into the mixed solution obtained in the step (1), uniformly mixing, and standing for 0.1-20 h.
12. The method for preparing the graphene/heteropoly acid composite three-dimensional graphene macroscopic body according to claim 2, wherein the method comprises the following steps: and (3) drying the three-dimensional graphene macroscopic body in the step (3) in a drying mode including room temperature drying, forced air drying, vacuum drying and freeze drying.
13. The application of the graphene/heteropoly acid composite three-dimensional graphene macroscopic material of claim 1, which is characterized in that: the graphene/heteropoly acid composite three-dimensional graphene macroscopic material is used as an electrode material of a super capacitor, an organic solvent and an adsorbent of heavy metal.
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Application publication date: 20200529 |