CN109665516B - Method for simply preparing vertical graphene nanosheet array - Google Patents

Method for simply preparing vertical graphene nanosheet array Download PDF

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CN109665516B
CN109665516B CN201811589279.6A CN201811589279A CN109665516B CN 109665516 B CN109665516 B CN 109665516B CN 201811589279 A CN201811589279 A CN 201811589279A CN 109665516 B CN109665516 B CN 109665516B
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furnace
array
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CN109665516A (en
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栗军帅
郭鑫
李亚丽
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Lanzhou University
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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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01B2204/04—Specific amount of layers or specific thickness
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data

Abstract

A method for simply preparing a vertical graphene nanosheet array comprises the following steps: coating solution, powder, jelly and the like of a proper carbon-containing solid phase precursor on a substrate with a catalytic action and drying; step two: and (3) placing the carbon-containing precursor into a tube furnace, and raising the temperature in the furnace under the protection of inert gas to realize the preparation of the vertical graphene nanosheet array. The invention has the following advantages: firstly, the equipment is simple and easy to operate and maintain, and can be produced in a large scale; secondly, the preparation process is simple, the labor intensity is low, the energy consumption is low, the high temperature and the high pressure are not involved, and the safe and green production concept is met; thirdly, the grown vertical graphene nano-sheets can be single-layer or few layers (less than or equal to 10 layers).

Description

Method for simply preparing vertical graphene nanosheet array
Technical Field
The invention relates to a method for manufacturing Vertical Graphene Nanosheets, in particular to a large-scale preparation method of an array of Vertical Graphene Nanosheets (Vertical Graphene Nanosheets).
Background
Vertical Graphene nanoplatelets (also known as carbon nanowalls) are two-dimensional nanostructures with open edges. The unique carbon nano structure enables the carbon nano structure to be widely applied to the aspects of chemistry, biosensing, energy storage and the like.
Currently, the manufacturing methods of the vertical graphene nanosheets mainly include Plasma Enhanced Chemical Vapor Deposition (PECVD), Hot Filament Chemical Vapor Deposition (HFCVD), and the latest Thermal Chemical Vapor Deposition (TCVD). However, these methods are complicated to operate, expensive in equipment, and difficult to realize industrial production of the graphene.
Therefore, the problems of the prior art are to be further improved and developed.
Disclosure of Invention
The object of the invention is: in order to solve the problems in the prior art, the invention aims to provide a method for growing upright graphene nanosheets based on a thermochemical process of a solid-phase precursor in a tube furnace.
The technical scheme is as follows: in order to solve the above technical problems, the present technical solution provides a method for simply preparing an array of upright graphene nanoplatelets, comprising the following steps,
the method comprises the following steps: coating solution, powder, jelly and the like of a proper carbon-containing solid phase precursor on a substrate with a catalytic action and drying;
step two: and (3) placing the carbon-containing precursor into a tube furnace, and raising the temperature in the furnace under the protection of inert gas to realize the preparation of the vertical graphene nanosheet array.
Preferably, the first step comprises the following steps:
carrying out ultrasonic cleaning on the substrate with the catalytic action to remove organic and inorganic impurities on the surface of the stainless steel substrate;
and coating the carbon-containing solid-phase precursor on the surface of the substrate with a catalytic function, drying the carbon-containing solid-phase precursor at 60 ℃, and then putting the carbon-containing solid-phase precursor into a tubular furnace.
Preferably, the substrate is subjected to ultrasonic cleaning for 1-30min in acetone, ethanol and deionized water cleaning solutions in sequence;
firstly, ultrasonically cleaning in an acetone solution for 30min, then cleaning in an ethanol solution for 30min, and finally ultrasonically cleaning in a deionized water solution for 15 min.
Preferably, the second step comprises the following steps:
placing the carbon-containing solid-phase precursor coated on the surface of the substrate with the catalytic function in a tubular furnace, evacuating air in the tubular furnace, and introducing protective gas;
and raising the temperature in the furnace to enable the temperature in the furnace to reach the growth temperature of 700 + 900 ℃, and controlling the growth temperature to be 0-60min to realize the controllable preparation of the vertical graphene nanosheet array.
Preferably, the pressure of the inert gas is 1KPa-1atm, and the inert gas can be argon or nitrogen.
Preferably, when the temperature in the furnace is increased, the temperature increase rate is 5-10 ℃ per min.
Preferably, the carbon-containing solid-phase precursor is CxHyOz，CxHyOzCan be completely decomposed into C and H at high temperature2O, the reaction is as follows:
CxHyOz → xC +
Figure 358395DEST_PATH_IMAGE001
H2O。
preferably, the substrate is a 304 stainless steel sheet containing multiple catalysts such as Fe, Ni, Co, and the like.
(III) the beneficial effects are as follows:
compared with the prior art, the invention has the following advantages:
firstly, the equipment is simple and easy to operate and maintain, and can be produced in a large scale;
secondly, the preparation process is simple, the labor intensity is low, the energy consumption is low, the high temperature and the high pressure are not involved, and the safe and green production concept is met;
thirdly, the grown vertical graphene nano-sheets can be single-layer or few layers (less than or equal to 10 layers).
Drawings
Fig. 1 is a raman diagram of an upright graphene nanoplate prepared using the technique of the present invention;
FIG. 2 is a topographical view of an array of upstanding graphene nanoplatelets prepared using the technique of the present invention.
Detailed Description
The present invention will be described in further detail with reference to preferred embodiments, and more details are set forth in the following description in order to provide a thorough understanding of the present invention, but it is apparent that the present invention can be embodied in many other forms different from the description herein and can be similarly generalized and deduced by those skilled in the art based on the practical application without departing from the spirit of the present invention, and therefore, the scope of the present invention should not be limited by the contents of this detailed embodiment.
The drawings are schematic representations of embodiments of the invention, and it is noted that the drawings are exemplary only and are not drawn to scale and should not be considered as limiting the true scope of the invention.
A simple method for preparing an upright graphene nano-sheet array comprises the following steps,
the method comprises the following steps: coating solution, powder, jelly and the like of a proper carbon-containing solid phase precursor on a substrate with a catalytic action and drying;
step two: and (3) placing the carbon-containing precursor into a tubular furnace, and raising the temperature in the furnace under the protection of protective gas to realize the preparation of the vertical graphene nanosheet array.
Wherein, the first step comprises the following steps:
sequentially carrying out ultrasonic cleaning on the substrate with the catalytic action in cleaning solutions of acetone, ethanol and deionized water for 1-30min to remove organic and inorganic impurities on the surface of the stainless steel substrate, and providing a good growth base for the growth of the next vertical graphene nanosheet array;
wherein, ultrasonic cleaning includes: firstly, ultrasonically cleaning in an acetone solution for 30min, then cleaning in an ethanol solution for 30min, and finally ultrasonically cleaning in a deionized water solution for 15 min.
And coating the carbon-containing solid-phase precursor on the surface of the substrate with a catalytic function, drying the carbon-containing solid-phase precursor at 60 ℃, and then putting the carbon-containing solid-phase precursor into a tubular furnace.
Wherein the second step comprises the following steps:
placing a carbon-containing solid phase precursor coated on the surface of a substrate with a catalytic function in a tubular furnace, then evacuating air in the tubular furnace, introducing protective gas, wherein the protective gas is inert gas, such as argon, nitrogen or other inert gases, the pressure of the protective gas is 1KPa-1atm, and the protective gas is used for preventing the oxidation of the material caused by the permeation of external air in the processes of temperature rise and growth;
the temperature in the furnace can be raised by resistance heating or other heating methods. When the temperature in the furnace rises, the temperature rise rate is 5-10 ℃ per min, the temperature in the furnace reaches the growth temperature of 700 + 900 ℃, and the growth temperature is controlled to be 0-60min, so that the controllable preparation of the vertical graphene nanosheet array is realized.
Wherein the carbon-containing solid phase precursor is CxHyOz，CxHyOzCan be completely decomposed into C and H at high temperature2O, the reaction is as follows:
CxHyOz → xC +
Figure 844871DEST_PATH_IMAGE001
H2O
the carbon-containing solid phase precursor can be organic matters such as ethanol and glucose, and can also be carbon-containing substances containing doping elements such as polyaniline and urea.
Wherein the substrate is a 304 stainless steel sheet containing multiple catalysts such as Fe, Ni, Co and the like.
The tube furnace is the most common tube furnace, and compared with the common plasma and radio frequency chemical vapor deposition method, the tube furnace has the advantages of simple structure, low price and easy operation.
Wherein, the attached figure 1 is a Raman diagram of the vertical graphene nano-sheet prepared by the technology of the invention, and the Raman diagram shows that the wave number is 1360 cm-1Near and wavenumber 1590 cm-1Two characteristic peaks of graphene with wave number of 1360 cm are respectively arranged-1The peak is the D peak of the graphene, represents the internal defect of the graphene and the substrate defect of the vertical graphene film, and has stronger D peak strength compared with the vertical graphene nanosheet array film prepared by the traditional PECVD method, because the film obtained by the method is caused by the amorphous carbon film formed in the initial growth stage.
Wherein, fig. 2 is a topography of the vertical graphene nano-sheet array prepared by the technology of the invention, in fig. 2, (a), (b), (c) and (d) are respectively scanning images obtained by testing under different resolutions, and as can be seen from the scanning images with low resolution, the grown vertical graphene nano-sheet array is uniformly distributed, and the nano-sheets are relatively uniform in size; the graphene nanosheets vertically and uniformly grow on the substrate in a flower shape according to a high-resolution scanning image, and in the graph (d) in fig. 2, the graphene nanosheets are in a semitransparent state, which shows that the prepared upright graphene nanosheets are thin in thickness and have good conductivity.
A method for simply preparing an upright graphene nanosheet array is simple in equipment, low in price, easy to operate and maintain and capable of realizing large-scale production; the preparation process is simple, the labor intensity is low, the energy consumption is low, the high temperature and high pressure are not involved, and the safe and green production concept is met; the grown vertical graphene nano sheet can be a single layer or a few layers (less than or equal to 10 layers).
The above description is provided for the purpose of illustrating the preferred embodiments of the present invention and will assist those skilled in the art in more fully understanding the technical solutions of the present invention. However, these examples are merely illustrative, and the embodiments of the present invention are not to be considered as being limited to the description of these examples. For those skilled in the art to which the invention pertains, several simple deductions and changes can be made without departing from the inventive concept, and all should be considered as falling within the protection scope of the invention.

Claims (7)

1. A simple method for preparing an upright graphene nanosheet array is characterized by comprising the following steps of,
the method comprises the following steps: coating the solution, powder and jelly of the carbon-containing solid phase precursor on a substrate with a catalytic effect and drying;
step two: placing the carbon-containing precursor in a tube furnace, and raising the temperature in the furnace under the protection of inert gas to realize the preparation of the vertical graphene nanosheet array;
the carbon-containing solid phase precursor is CxHyOzCan be completely decomposed into C and H at high temperature2O; the substrate is a 304 stainless steel sheet containing Fe, Ni and Co catalysts; the growth temperature in the furnace is 700 + 900 ℃, and the growth time is 0-60 min.
2. The method for simply preparing an array of upright graphene nanoplatelets according to claim 1, wherein the first step comprises the following steps:
carrying out ultrasonic cleaning on the substrate with the catalytic action to remove organic and inorganic impurities on the surface of the stainless steel substrate;
and coating the carbon-containing solid-phase precursor on the surface of the substrate with a catalytic function, drying the carbon-containing solid-phase precursor at 60 ℃, and then putting the carbon-containing solid-phase precursor into a tubular furnace.
3. The method for simply preparing an array of upstanding graphene nanoplatelets according to claim 2, wherein the substrate is sequentially subjected to ultrasonic cleaning in a cleaning solution of acetone, ethanol, deionized water for 1-30 min;
firstly, ultrasonically cleaning in an acetone solution for 30min, then cleaning in an ethanol solution for 30min, and finally ultrasonically cleaning in a deionized water solution for 15 min.
4. The method for simply preparing an array of upright graphene nanoplatelets according to claim 1, wherein the second step comprises the following steps:
placing the carbon-containing solid-phase precursor coated on the surface of the substrate with the catalytic function in a tubular furnace, evacuating air in the tubular furnace, and introducing protective gas;
and raising the temperature in the furnace to enable the temperature in the furnace to reach the growth temperature of 700 + 900 ℃, and controlling the growth time to be 0-60min to realize the controllable preparation of the vertical graphene nanosheet array.
5. The method for simply preparing an array of upright graphene nanoplatelets according to claim 4, wherein the pressure of the inert gas is 1KPa-1atm, and the inert gas is argon or nitrogen.
6. The method for simply preparing an array of upstanding graphene nanoplatelets according to claim 4, wherein the temperature rise rate is 5-10 ℃ per min when the temperature in the furnace is raised.
7. The method for simply preparing an array of upright graphene nanoplatelets according to claim 1,the carbon-containing solid phase precursor CxHyOzComplete decomposition into C and H at high temperature2O, the reaction is as follows:
CxHyOz→ xC+
Figure DEST_PATH_IMAGE001
H2O。
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CN110395720A (en) * 2019-09-03 2019-11-01 王志朋 The method for preparing vertical graphene film as raw material using biomass
CN115894061B (en) * 2022-10-24 2023-08-11 中国科学院兰州化学物理研究所 Vertical graphene nano-sheet composite heat dissipation film and preparation method and application thereof

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