CN107777681B - Method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis - Google Patents

Method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis Download PDF

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CN107777681B
CN107777681B CN201610729587.9A CN201610729587A CN107777681B CN 107777681 B CN107777681 B CN 107777681B CN 201610729587 A CN201610729587 A CN 201610729587A CN 107777681 B CN107777681 B CN 107777681B
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graphene
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transition metal
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CN107777681A (en
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陈珊珊
王伟伟
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Renmin University of China
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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
    • C01B2204/04—Specific amount of layers or specific thickness
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis. The method comprises the following steps: and growing graphene on the transition metal substrate under the catalytic action of the nano powder by adopting a chemical vapor deposition method, so as to obtain the double-layer and/or multi-layer graphene. According to the invention, the nano powder is used as a catalyst, and after the copper substrate is overgrown with the single-layer graphene, the nano powder can continuously provide a catalytic action to crack the hydrocarbon, so that a carbon source is further provided for preparing the double-layer and/or multi-layer graphene, the graphene cannot be deposited on the nano powder, and the nano powder can be recycled again, so that the preparation cost is saved.

Description

Method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis
Technical Field
The invention relates to a preparation method of double-layer and/or multi-layer graphene, in particular to a method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis.
Background
Graphene is a semi-metallic material with a zero band gap that is conductive like a metal, but has no free electrons. The application of the graphene in the field of semiconductor devices is limited by special band gap structures and physical properties, but as the number of layers is increased, the band gap of graphene is opened under certain conditions. For example, the band gap of the double-layer graphene can reach 250meV under the action of an external electric field. Due to the mechanical stripping method, the large-area double-layer graphene with accurate layer number is difficult to obtain. Therefore, the preparation of double-layer graphene by chemical vapor deposition has been one direction of research, but the coverage of double-layer and multi-layer graphene is not high and has poor uniformity. The double-layer graphene on the insulating substrate is also limited to a transfer method, and the transfer has a great influence on the quality of the graphene. The dissolution amount of different metals to carbon is different, when metals (iron and nickel) with high dissolution amount are taken as substrates, the growth mechanism of graphene is a precipitation-precipitation mechanism, and the number and uniformity of graphene layers are difficult to control; when metal (copper) with low dissolving capacity is used as a substrate, the growth mechanism of graphene is self-limited growth, and after the substrate is covered by the graphene, the growth is stopped without subsequent catalytic cracking of copper. At present, the growth technology of single-layer graphene is mature, but the double layers are obtained only through transfer, the stacking mode of the graphene cannot be guaranteed, and the quality cannot be high.
Today, a carbon-based device attracts people's extensive attention with its unique advantages, and graphene is the most explosive and hot two-dimensional nanomaterial, so that the demand for large-area high-quality double-layer graphene is more urgent, how to better control the number of layers and the stacking mode of graphene, and obtaining large-area graphene with controllable number of layers has great significance for the future research of people.
Disclosure of Invention
The invention aims to provide a method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis.
The invention provides a method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis, which comprises the following steps: and growing graphene on the transition metal substrate under the catalytic action of the nano powder by adopting a chemical vapor deposition method, so as to obtain the double-layer and/or multi-layer graphene.
In the above method, the nano powder may be a transition metal nano powder or a transition metal oxide nano powder. The transition metal nano powder may be any one of copper nano powder, iron nano powder, cobalt nano powder and nickel nano powder. The transition metal oxide nano powder may be any one of copper oxide nano powder, iron oxide nano powder, cobalt oxide nano powder and nickel oxide nano powder.
In the above method, the particle size of the nano-powder may be 0 to 100nm, but is not 0, preferably 10 to 50nm, and specifically 10 to 30nm, 50 nm.
In the method, the usage amount of the nano powder has no obvious influence on the growth effect of the multilayer graphene, and the addition amount of the nano powder can be 3-10 mg, such as 5 mg.
In the above method, the transition metal substrate refers to a transition metal or its alloy with catalytic properties, including but not limited to: a copper substrate, a platinum substrate, a nickel substrate, a ruthenium substrate, a rhodium substrate, an iridium substrate, a rhenium substrate, an iron substrate, a cobalt substrate, a silver substrate, a molybdenum substrate, a palladium substrate, a copper-nickel alloy substrate, a platinum-rhodium alloy substrate, a nickel-molybdenum alloy substrate, or a nickel-titanium alloy substrate. The transition metal substrate can be horizontally arranged in a reaction furnace; and the nano powder is arranged at the front end of the transition metal substrate along the flowing direction of the carbon source and the carrier gas.
In the above method, the method further includes a step of recovering the nano-powder after obtaining the multilayer graphene. Because the nano powder is granular, the cracked carbon is not easy to gather on the nano powder to form a film, and the nano powder can be repeatedly used, so that the preparation cost is saved.
In the above method, before the growing of the graphene, a step of annealing the copper substrate in a vacuum or hydrogen atmosphere is further included. The annealing temperature can be 800-1040 ℃, specifically 1030 ℃, and the time can be 10-120 minutes, specifically 30 minutes. The gas pressure in the vacuum environment may be 2 × 10-1～5×10-1Pa, e.g. 3X 10-1Pa。
In the above method, the carbon source used in the chemical vapor deposition method can be methane, and the flow rate can be 1 to 100sccm, specifically 2 to 10sccm, 2sccm or 10 sccm; the carrier gas used can be hydrogen gas, and the flow rate can be 1-500 sccm, specifically 10-20 sccm, 10sccm or 20 sccm; the system pressure intensity can be 3-1000 Pa, and specifically can be 23 Pa; the deposition temperature can be 800-1040 ℃, specifically 1030 ℃, and the deposition time can be 30-180 minutes, specifically 30-40 minutes, 30 minutes or 40 minutes. The nucleation density and size of the double layer and the multiple layers can be controlled by controlling the temperature, time and gas ratio.
In the above method, after the graphene grows, the method further includes a step of cooling to room temperature within 6 to 30 minutes (e.g., 10 minutes); and in the temperature reduction process, the flow rates of the carrier gas and the carbon source are kept unchanged.
The invention has the following beneficial effects:
according to the invention, a chemical vapor deposition method is adopted, the nano powder is used as a catalyst, and after the copper substrate is overgrown with the single-layer graphene, the nano powder can continuously provide a catalytic action to crack the hydrocarbon, so that a carbon source is further provided for preparing the double-layer and/or multi-layer graphene, the graphene cannot be deposited on the nano powder, and the nano powder can be recycled again, so that the preparation cost is saved.
Drawings
FIG. 1 is a schematic diagram of the CVD growth of the present invention.
Fig. 2 is an SEM image of single-layer graphene grown under the same conditions without nano-powder release in example 1.
Fig. 3 is an SEM image of nano iron powder catalyzed growth of bi-layer and multi-layer graphene in example 1.
Fig. 4 is a raman spectrum of the nano iron powder catalyzed double-layer graphene in example 1.
Fig. 5 is an SEM image of the nano iron powder before the first catalytic growth in example 1.
Fig. 6 is an SEM image of the nano iron powder after the first catalytic growth in example 1.
Fig. 7 is a raman spectrum of the nano iron powder after the first catalytic growth in example 1.
FIG. 8 is an SEM image of the two-layer graphene and the multi-layer graphene catalytically grown by the nano-copper powder in example 2.
FIG. 9 is a Raman spectrum of multilayer graphene grown under catalysis of the copper nanopowder in example 2.
Fig. 10 is an SEM image of the first catalytic growth of bi-layer and multi-layer graphene from the nano nickel powder in example 3.
Fig. 11 is a raman spectrum of the first catalytic growth of double-layer graphene from the nano nickel powder in example 3.
FIG. 12 is an SEM photograph of the nano nickel powder before the first catalytic growth in example 3.
FIG. 13 is an SEM photograph of the nano nickel powder after the first catalytic growth in example 3.
Fig. 14 is a raman spectrum of the nano nickel powder after the first catalytic growth in example 3.
FIG. 15 is an SEM photograph of the nano nickel powder after the sixth catalytic growth in example 3.
Fig. 16 is a raman spectrum of the nano nickel powder after the sixth catalytic growth in example 3.
Fig. 17 is an SEM image of sixth catalytic growth of bi-and multi-layer graphene in example 3.
Fig. 18 is a raman spectrum of sixth catalytic growth of bi-and multi-layer graphene in example 3.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of double-layer and multilayer graphene by catalysis of nano iron powder
Preparing double-layer and multi-layer graphene by using nano iron powder catalysis according to the following steps:
(1) copper foil treatment: the copper foil is firstly cut into a proper size, such as a rectangle (3 x 4cm), and an oxide layer on the surface of the copper is removed by an electrochemical polishing method, so that the surface of the copper foil is smooth and flat. The copper foil was wrapped in a box and 5mg of nano iron powder (from aladdin, particle size 50nm, purity 99.9%) was added to one end of the copper box.
(2) Preparing by using a CVD system: as shown in FIG. 1, the copper box was placed in the heating zone of the CVD system, the end containing the nanopowder was placed on the top of the gas flow, and the chamber was evacuated (gas pressure about 3X 10)-1Pa), when the air pressure of the cavity is stable, starting to heat the reaction cavity, when the temperature reaches a preset value of 1030 ℃, keeping the temperature for 30 minutes, annealing and recrystallizing the copper foil, then introducing methane and hydrogen with the amount of 10sccm, the system pressure being 23Pa, after growing for 30 minutes, quickly reducing the temperature to room temperature within 10 minutes, keeping the amounts of the methane and the hydrogen unchanged in the quick reduction process, after reducing the temperature to the room temperature, finishing the growth, taking out the copper box and cutting the copper box, and obtaining double-layer and/or multi-layer graphene on the inner surface. And recovering the nano iron powder.
(3) Transfer technique: and (3) utilizing wet transfer, firstly spin-coating PMMA glue on the graphene copper sheet with double layers and multiple layers, baking the glue for 30min, removing the copper sheet by utilizing persulfuric acid, fishing up the film by using a target substrate, naturally air-drying for one night, and removing the PMMA glue on the surface of the sample by utilizing acetone to obtain the graphene film transferred on the target substrate.
The SEM photograph of the double-layer and multi-layer graphene catalytically grown by using nano iron powder through the above steps is shown in fig. 3. For comparison, the SEM photograph of the prepared graphene is shown in fig. 2 without placing the nano powder to catalyze the growth of graphene under the same conditions as the above steps. As can be seen from comparing fig. 2 and fig. 3, the double-layer and/or multi-layer graphene can be catalytically grown under the catalysis of the nano iron powder. The raman spectrum of the bilayer graphene is shown in fig. 4. SEM photographs of the nano iron powder before and after the first catalytic growth of graphene are shown in fig. 5 and 6. The Raman spectrum of the nanometer iron powder after the first catalytic growth is shown in figure 7.
Example 2 preparation of double-layer and multilayer graphene under catalysis of nano copper powder
Preparing double-layer and multi-layer graphene by utilizing nano-copper catalysis according to the following steps:
(1) the oxide layer on the surface of the copper foil was removed by electrochemical polishing as in example 1, 5mg of copper nanopowder (available from aladdin, particle size 10-30 nm, purity 99.9%) was weighed, the copper nanopowder was placed on a quartz plate (1 x 1cm), and the quartz plate was sealed on one end of the copper foil.
(2) The CVD system of example 1 was used for the preparation of the same procedure except that the amounts of methane and hydrogen were 2 and 20sccm, respectively, and the growth time was 40min (the optimum ratio for multilayer growth was achieved by controlling the time due to the decrease in the carbon to hydrogen ratio), and after the growth was completed, the copper nanoparticles were recovered.
(3) The transfer technique was the same as in example 1.
The SEM photograph of the double-layer graphene and the multi-layer graphene which are grown by the catalysis of the nano copper powder through the steps is shown in figure 8, and the Raman spectrum of the multi-layer graphene is shown in figure 9.
Example 3 preparation of double-layer and multilayer graphene by catalysis of nano nickel powder
A. First-time catalytic preparation of double-layer and multi-layer graphene by using nano nickel powder
Preparing double-layer and multi-layer graphene by using nano nickel powder as catalyst according to the following steps
Bi-and multi-layer graphene was first catalytically grown according to the procedure of example 1 using nano nickel powder (available from aladdin, particle size 50nm, purity 99.996%).
SEM photographs of the bi-and multi-layer graphene prepared through the above steps are shown in fig. 10, and raman spectrograms are shown in fig. 11. The SEM photos before and after the nano nickel powder catalyzes and grows the graphene are shown in the figure 12 and the figure 13. The raman spectrum of the nano nickel powder after the first catalytic growth is shown in fig. 14.
B. Sixth catalytic preparation of double-layer and multi-layer graphene by reusing nano nickel powder
Preparing double-layer and multi-layer graphene by using the nanometer nickel powder which is repeatedly used for five times as a catalyst according to the following steps:
(1) the oxide layer on the surface of the copper foil was removed by the electrochemical polishing method of example 1, and the reused nano nickel powder (in order to reduce the loss of nickel powder during the recovery of the nickel powder, the copper foil carrying the nickel powder can be cut off together to facilitate the reuse later) was wrapped on one end of the copper foil and sealed.
(2) The CVD system of example 1 was used to prepare the final product in the same manner except that the amount of methane and hydrogen gas was 2sccm and 20sccm, respectively, the growth time was 40min, and the nano nickel powder was recovered after the growth was completed.
(3) The transfer technique was the same as in example 1.
In this example, the SEM photograph of the nano nickel powder after the sixth catalytic growth is shown in fig. 15, and the raman spectrum is shown in fig. 16. SEM photographs of the prepared bi-and multi-layer graphene are shown in fig. 17, and a raman spectrum is shown in fig. 18.

Claims (6)

1. A method for preparing double-layer and/or multi-layer graphene by utilizing nano powder catalysis comprises the following steps: growing graphene on a transition metal substrate under the catalytic action of nano powder by adopting a chemical vapor deposition method to obtain the double-layer and/or multi-layer graphene;
the nano powder is transition metal nano powder or transition metal oxide nano powder;
along the direction of introducing a carbon source and a carrier gas, the nano powder is arranged at the front end of the transition metal substrate;
the transition metal substrate refers to transition metal or alloy thereof with catalytic performance;
the transition metal nano powder is any one of copper nano powder, iron nano powder, cobalt nano powder and nickel nano powder; the transition metal oxide nano powder is any one of copper oxide nano powder, iron oxide nano powder, cobalt oxide nano powder and nickel oxide nano powder;
the particle size of the nano powder is 10-50 nm.
2. The method of claim 1, wherein: the method further comprises a step of recovering the nano-powder after obtaining the multilayer graphene.
3. The method according to claim 1 or 2, characterized in that: the method also comprises the step of annealing the transition metal substrate in a vacuum or hydrogen environment before the graphene is grown.
4. The method of claim 3, wherein: the annealing temperature is 800-1040 ℃, and the annealing time is 30-120 minutes.
5. The method according to claim 1 or 2, characterized in that: in the chemical vapor deposition method, the adopted carbon source is methane, and the flow rate is 1-100 sccm; the adopted carrier gas is hydrogen, and the flow rate is 1-500 sccm; the system pressure is 3-1000 Pa; the deposition temperature is 800-1040 ℃, and the deposition time is 30-180 minutes.
6. The method according to claim 1 or 2, characterized in that: the method also comprises the step of cooling to room temperature within 6-30 minutes after the graphene grows; and in the temperature reduction process, the flow rates of the carrier gas and the carbon source are kept unchanged.
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