CN110668429A - Ultrathin graphene and preparation method thereof - Google Patents
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention relates to graphene, in particular to graphene and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing a solid organic matter composed of glucose, citric acid and fructose and a molten salt composed of sodium chloride, potassium chloride and calcium chloride according to a weight part ratio of 1: 5-100 to obtain a mixture; and (3) in an inert gas environment with the flow rate of 100-800 mL/min, heating to 1000-1400 ℃ at the heating rate of 1-10 ℃/min, and preserving heat for 3-10 h, and performing high-temperature thermal polymerization to generate the ultrathin graphene. The invention provides a simple method for generating ultrathin and ultralight graphene materials by taking solid organic matters as raw materials for synthesizing graphene and taking a molten state of mixed metal chlorides at high temperature as a solvent to inhibit stacking among carbon sheet layers and finally volatilizing.
Description
Technical Field
The invention relates to graphene, in particular to graphene and a preparation method thereof.
Background
Graphene is a two-dimensional nano-sheet carbon material with a honeycomb lattice structure, and sp is formed by C atoms in the plane2The hybridized forms are connected into two-dimensional conjugate planes, and adjacent layers are tightly gathered together through van der Waals interaction between large pi bonds. Due to the unique two-dimensional lamellar structure and excellent photoelectric property, the material quickly becomes a current research hotspot, is gradually applied to a plurality of fields such as adsorbing materials, photo-thermal materials, batteries, capacitor materials and the like, and shows a huge application prospect. Therefore, the controllable synthesis of graphene is very important.
At present, the preparation method of graphene has two strategies of top-down and bottom-up. In the "top-down" strategy, the graphene material with few or single layers is obtained mainly by delaminating graphite powder. In this strategy, the earliest method, the tape tearing method, continuously delaminates the graphite sheets. Since then, researchers have developed several delamination methods, such as an electrolytic method (described in patent application No. CN 102465309A), a freezing-heating expansion method (described in patent application No. CN 106809818A), a plasma delamination method (described in patent application No. CN 108821270A), and a redox delamination method (described in patent application nos. CN109607526A and CN 105217621A), which, however, are susceptible to damage of their own crystal structure and breakage of graphene into smaller pieces during delamination; meanwhile, the yield is low, the time consumption of the process flow is long, and products with uniform sizes are difficult to obtain.
In the strategy of 'bottom-up', a graphene sheet layer material is obtained by polymerizing some organic small molecule gases on the surface of a certain metal catalyst at high temperature. A commonly used method is a (thermal catalysis or microwave plasma) Chemical Vapor Deposition (CVD) method, which uses organic small molecules such as methane and ethylene as reaction gases to generate single-layer or double-layer wafer-level graphene (CN109852944A, CN109485035A, CN109852944A) on the surface of a metal (copper or nickel) foil or SiC under high temperature and low pressure conditions. Although the CVD method can synthesize graphene with complete crystal form, large lamella and atomic level, the process flow needs high-end experimental equipment, a fine experimental flow and expensive raw materials, the yield is low, and the method is not suitable for batch preparation. In addition, patents CN109319765A and CN109319764A utilize lignin or biomass to burn under metal (magnesium, calcium or aluminum) and a certain atmosphere, and the graphene is obtained by catalytic reduction under a high temperature environment. The method has high resource utilization rate and high yield, but the prepared graphene material has low quality and thicker lamella. The process flow is complex, the used simple substance metal has certain danger, and can not be recycled, and the mass production is not suitable; the size is not uniform, and the sheet layer is thicker.
Disclosure of Invention
Technical problem to be solved
In order to solve the above problems in the prior art, the present invention provides a simple method for producing an ultra-thin and ultra-light graphene material by using a solid organic material as a raw material for synthesizing graphene and using a molten state of a mixed metal chloride at a high temperature as a solvent to inhibit stacking between carbon sheet layers and finally volatilize.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
the invention provides a preparation method of ultrathin graphene, which comprises the following steps:
s1 mixing raw materials: uniformly mixing the solid organic matter and the molten salt to obtain a mixture;
s2 thermal polymerization: and carrying out thermal polymerization reaction on the obtained mixture in an inert gas environment to generate the ultrathin graphene.
According to the preferable scheme of the preparation method, in the step S1, the solid organic matter and the molten salt are mixed according to the weight part ratio of 1: 5-100.
In the preferable scheme of the preparation method, the solid organic matter is one or the mixture of more than two of glucose, citric acid or fructose. The solid organic matters are the most common biomass organic matters, are cheap and easily available, and are safe and nontoxic.
In the preferable scheme of the preparation method, the molten salt is a metal chloride formed by combining one or more than two of sodium chloride, potassium chloride and calcium chloride. The selected metal chlorides are the most common raw materials in chemical industry, are cheap and easily available, and are safe and nontoxic.
The scheme takes common metal chloride as a high-temperature solvent and changes into a molten state at high temperature. The high-temperature solvent can be used as a good solvent for carbon polymerization reaction, enhances the mass transfer effect of raw materials, reduces the polymerization energy and reaction time, can be used as a polar medium, inhibits the stacking of carbon sheet layers at high temperature, and is beneficial to the generation of ultrathin graphene. And as the temperature rises to the highest point, the metal chloride is gradually evaporated and removed from the product along with the inert atmosphere, so that the ultrathin and ultralight graphene material is obtained in one step. The mixed salt which is evaporated and then cooled and precipitated can be recycled after being collected.
In the preferable scheme of the preparation method, the inert gas is one or the combination of more than two of nitrogen, argon and helium.
According to the preferable scheme of the preparation method, the flow of the inert gas is 100-800 mL/min.
According to the preferable scheme of the preparation method, in step S2, the obtained mixture is moved into a corundum boat with an arc bottom, and is placed in a horizontal high-temperature tube furnace, and the ultra-thin graphene is generated through thermal polymerization in an inert gas environment. The corundum boat with the arc bottom is as follows: the bottom is a container made of arc corundum. A vessel, similar to a crucible, is often used in high temperature solid phase processes.
In a preferred embodiment of the preparation method of the present invention, the thermal polymerization comprises the following steps: and raising the temperature of the mixture to 1000-1400 ℃ at a heating rate of 1-10 ℃/min, and preserving the heat for 3-10 h.
The invention provides an application of the ultrathin graphene in any scheme as an adsorbing material for adsorbing a hydrophobic organic matter, but not limited to the adsorption of the hydrophobic organic matter.
The technical principle of the invention is as follows: the method adopts a 'bottom-up' strategy, solid organic matters such as glucose, citric acid or fructose and the like are mixed with common metal chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride and the like as molten salts, and the mixture is subjected to thermal polymerization reaction under the conditions of inert atmosphere and high temperature. During the temperature rise, the molten salt gradually melts into liquid. In this case, the graphene oxide can be used as a good solvent for carbon polymerization reaction, enhances mass transfer effect of raw materials, reduces polymerization energy and reaction time, can be used as a polar medium, can inhibit stacking of carbon sheet layers at high temperature, and is beneficial to generation of ultrathin graphene. And gradually evaporating the molten salt along with the temperature rise to the highest point, and removing the molten salt from the product along with the inert atmosphere, so that the ultrathin and ultralight graphene material is obtained in one step.
(III) advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
1. the method does not need expensive instruments and raw materials, is simple, and can synthesize the graphene material in batches in a short time. The obtained graphene sheet layer is thin and uniform in size. The prepared graphene is an ultra-light hydrophobic material, has extremely high adsorption capacity on substances such as dyes, organic pollutants and the like, and is an adsorbent material with extremely high potential. The invention can better overcome the defects of the prior art displayed in the background technology and has wide application prospect.
2. The graphene synthesis method has the advantages of simple process flow, short time consumption, cheap and easily-obtained raw materials, uniform size of the obtained product, thinner lamella and the like.
Drawings
Fig. 1 is a structural diagram of an ultra-thin graphene SEM in accordance with the present invention;
FIG. 2 is a diagram showing the effects of ultra-thin graphene according to the present invention before and after adsorption of organic dyes;
fig. 3 is a diagram illustrating the effect of the ultra-thin graphene on the adsorption of pump oil to saturation.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention by way of specific embodiments thereof.
A preparation method of ultrathin graphene is characterized by comprising the following steps:
s1 mixing raw materials: mixing a solid organic matter formed by combining one or more than two of glucose, citric acid and fructose in any proportion and a molten salt formed by combining one or more than two of sodium chloride, potassium chloride and calcium chloride in any proportion uniformly according to a weight part ratio of 1: 5-100 to obtain a mixture;
s2 thermal polymerization: and moving the obtained mixture into a corundum boat at the bottom of the arc, placing the corundum boat in a horizontal high-temperature tube furnace, heating to 1000-1400 ℃ at a heating rate of 1-10 ℃/min in an inert gas environment formed by combining one or more than two of nitrogen, argon and helium with flow rate of 100-800 mL/min according to any proportion, and preserving heat for 3-10 hours to perform high-temperature thermal polymerization reaction to generate graphene.
The thickness of the graphene prepared by the invention is less than 3 nm.
Example 1
A method for preparing graphene, comprising the steps of:
s1 mixing raw materials: uniformly mixing the solid organic matter and the molten salt according to the weight part ratio of 1: 50 to obtain a mixture; wherein the solid organic matter is formed by mixing glucose, citric acid and fructose according to the weight part of 1: 1; wherein the fused salt is formed by mixing sodium chloride, potassium chloride and calcium chloride according to the weight part of 1: 1;
s2 thermal polymerization: moving the obtained mixture into a corundum boat at the bottom of an arc, placing the corundum boat in a horizontal high-temperature tube furnace, heating to 1200 ℃ at a heating rate of 6 ℃/min under an inert gas environment with a flow of 400mL/min, and preserving heat for 7 hours to perform high-temperature thermal polymerization reaction to generate ultrathin graphene; wherein, the inert gas is formed by mixing nitrogen, argon and helium according to the weight ratio of 1: 1.
The layer thickness of the graphene prepared in this example was 1 nm.
Example 2
The preparation method of the ultrathin graphene comprises the following steps:
s1 mixing raw materials: uniformly mixing glucose and sodium chloride molten salt according to the weight part ratio of 1: 5 to obtain a mixture;
s2 thermal polymerization: and moving the obtained mixture to a corundum boat at the bottom of the arc, placing the corundum boat in a horizontal high-temperature tube furnace, heating to 1000 ℃ at a heating rate of 1 ℃/min for 3 hours under a nitrogen environment with the flow of 100mL/min, and carrying out high-temperature thermal polymerization to generate graphene.
The layer thickness of the graphene prepared in this example was 2 nm.
Example 3
The preparation method of the ultrathin graphene comprises the following steps:
s1 mixing raw materials: uniformly mixing fructose and potassium chloride molten salt according to the weight part ratio of 1: 100 to obtain a mixture;
s2 thermal polymerization: and moving the obtained mixture to a corundum boat at the bottom of the arc, placing the corundum boat in a horizontal high-temperature tube furnace, heating to 1400 ℃ at a heating rate of 10 ℃/min for 10 hours under an argon environment with a flow of 800mL/min, and carrying out high-temperature thermal polymerization to generate graphene.
The layer thickness of the graphene prepared in this example was 1 nm.
Example 4
The preparation method of the ultrathin graphene comprises the following steps:
s1 mixing raw materials: uniformly mixing fructose and calcium chloride molten salt according to the weight part ratio of 1: 100 to obtain a mixture;
s2 thermal polymerization: and moving the obtained mixture to a corundum boat at the bottom of the arc, placing the corundum boat in a horizontal high-temperature tube furnace, heating to 1000 ℃ at a heating speed of 5 ℃/min for 10 hours under helium with a flow of 400mL/min, and carrying out high-temperature thermal polymerization to generate the ultrathin graphene.
The layer thickness of the graphene prepared in this example was 3 nm.
Example 5
The preparation method of the ultrathin graphene comprises the following steps:
s1 mixing raw materials: uniformly mixing the solid organic matter and the molten salt according to the weight part ratio of 1: 60 to obtain a mixture; wherein the solid organic matter is formed by mixing glucose and fructose according to the weight ratio of 1: 3; wherein the fused salt is formed by mixing sodium chloride and potassium chloride according to the weight ratio of 1: 2;
s2 thermal polymerization: moving the obtained mixture into a corundum boat at the bottom of an arc, placing the corundum boat in a horizontal high-temperature tube furnace, heating the corundum boat to 1000 ℃ at a heating rate of 7 ℃/min for 3 hours under inert gas with the flow rate of 700mL/min, and carrying out high-temperature thermal polymerization to generate ultrathin graphene; wherein, the inert gas is formed by mixing nitrogen and helium according to the weight portion of 1: 3.
The layer thickness of the graphene prepared in this example was 1 nm.
Example 6
The preparation method of the ultrathin graphene comprises the following steps:
s1 mixing raw materials: uniformly mixing the solid organic matter and the molten salt according to the weight part ratio of 1: 20 to obtain a mixture; wherein the solid organic matter is formed by mixing citric acid and fructose according to the weight ratio of 2: 7; wherein the fused salt is formed by mixing sodium chloride and calcium chloride according to the weight ratio of 3: 5;
s2 thermal polymerization: moving the obtained mixture into a corundum boat at the bottom of an arc, placing the corundum boat in a horizontal high-temperature tube furnace, heating to 1400 ℃ at a heating rate of 6 ℃/min for heat preservation for 9 hours under the inert gas with the flow rate of 600mL/min, and carrying out high-temperature thermal polymerization to generate ultrathin graphene; wherein, the inert gas is formed by mixing argon and helium according to the weight ratio of 3: 1.
The layer thickness of the graphene prepared in this example was 2 nm.
Example 7
The preparation method of the ultrathin graphene comprises the following steps:
s1 mixing raw materials: uniformly mixing the solid organic matter and the molten salt according to the weight part ratio of 1: 100 to obtain a mixture; wherein the solid organic matter is glucose; wherein the fused salt is formed by mixing sodium chloride and potassium chloride according to the weight ratio of 45: 55;
s2 thermal polymerization: moving the obtained mixture into a corundum boat at the bottom of an arc, placing the corundum boat in a horizontal high-temperature tube furnace, increasing the temperature rise rate to 1250 ℃ at the rate of 5 ℃/min under the inert gas with the flow rate of 300mL/min, and preserving the temperature for 5 hours to perform high-temperature thermal polymerization reaction to generate ultrathin graphene; wherein the inert gas is nitrogen.
The layer thickness of the graphene prepared in this example was 1 nm.
In order to verify the structure and function of the ultrathin graphene prepared by the specific embodiment of the invention, the following experiment is carried out:
example 8
The structure diagram of SEM obtained by scanning the ultrathin graphene obtained in example 7 of the present invention with an electron microscope is shown in fig. 1. 1 μm plus the horizontal line in fig. 1, as a relative scale in fig. 1, the horizontal line in fig. 1 represents such a length of 1 μm in the figure.
Example 9
Carrying out an adsorption experiment on organic dye by using the ultrathin graphene obtained in the embodiment 7 of the invention, adding 1mg of graphene obtained in the embodiment 2 into 10mL of Congo red aqueous solution (10mg/L) while stirring, and quickly filtering to obtain a clear solution after adsorption; the experimental result is shown in fig. 2, the tube a on the left is the organic dye solution before adsorption, and the tube b on the right is the clear liquid obtained after the ultrathin graphene is adsorbed for 5 minutes; it can be seen that the ultrathin graphene obtained in embodiment 7 of the present invention has a good organic dye adsorption function.
Example 10
The ultra-thin graphene obtained in example 4 of the present invention adsorbs the pump oil until saturation, and as shown in fig. 3, it is determined that 1mg of the ultra-thin graphene obtained in example 4 can adsorb 6.5g of the pump oil. The prepared ultrathin graphene has strong adsorption capacity on pump oil.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A preparation method of ultrathin graphene is characterized by comprising the following steps:
s1 mixing raw materials: uniformly mixing the solid organic matter and the molten salt to obtain a mixture;
s2 thermal polymerization: and carrying out thermal polymerization reaction on the obtained mixture in an inert gas environment to generate the ultrathin graphene.
2. The method of preparing the ultra-thin graphene of claim 1, wherein: in step S1, the solid organic matter and the molten salt are mixed according to the weight ratio of 1: 5-100.
3. The method of preparing the ultra-thin graphene of claim 1, wherein: the solid organic matter is one or a mixture of more than two of glucose, citric acid or fructose.
4. The method of preparing the ultra-thin graphene of claim 1, wherein: the molten salt is a mixed metal chloride formed by combining one or more than two of sodium chloride, potassium chloride and calcium chloride.
5. The method of preparing the ultra-thin graphene of claim 1, wherein: the inert gas is one or the combination of more than two of nitrogen, argon and helium.
6. The method of preparing the ultra-thin graphene of claim 5, wherein: the flow rate of the inert gas is 100-800 mL/min.
7. The method of preparing the ultra-thin graphene of claim 1, wherein: in step S2, the obtained mixture is moved to a corundum boat with an arc bottom, and placed in a horizontal high-temperature tube furnace, and subjected to thermal polymerization in an inert gas environment to generate ultrathin graphene.
8. The method of preparing the ultra-thin graphene of claim 2 or 7, wherein: the thermal polymerization reaction comprises the following steps: and raising the temperature of the mixture to 1000-1400 ℃ at a heating rate of 1-10 ℃/min, and preserving the heat for 3-10 h.
9. Use of the ultra-thin graphene as claimed in any one of claims 1 to 7 as an adsorbing material for adsorbing hydrophobic organic substances.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111547709A (en) * | 2020-05-09 | 2020-08-18 | 九江学院 | Biomass three-dimensional porous graphene and preparation method thereof |
| CN114180560A (en) * | 2021-12-21 | 2022-03-15 | 山西大学 | Preparation method of coal-based graphene in molten salt system |
| CN115321525A (en) * | 2022-08-19 | 2022-11-11 | 河南师范大学 | Preparation method of graphene nano-net with macroporous structure |
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| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
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| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111547709A (en) * | 2020-05-09 | 2020-08-18 | 九江学院 | Biomass three-dimensional porous graphene and preparation method thereof |
| CN114180560A (en) * | 2021-12-21 | 2022-03-15 | 山西大学 | Preparation method of coal-based graphene in molten salt system |
| CN115321525A (en) * | 2022-08-19 | 2022-11-11 | 河南师范大学 | Preparation method of graphene nano-net with macroporous structure |
| CN115321525B (en) * | 2022-08-19 | 2024-02-27 | 河南师范大学 | Preparation method of graphene nano-network with macroporous structure |
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Inventor after: Zhang Mingwen Inventor after: Liu Xin Inventor after: Wang Gunyuan Inventor after: Chen Yibin Inventor after: Lu Xiuqiang Inventor after: Yang Jinbei Inventor before: Liu Xin Inventor before: Wang Gunyuan Inventor before: Chen Yibin Inventor before: Lu Xiuqiang Inventor before: Yang Jinbei |
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Application publication date: 20200110 |