CN110642245B - Preparation method of metal monoatomic doped graphene - Google Patents
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Abstract
The invention relates to a preparation method of metal monoatomic doped graphene, which comprises the following steps: dispersing graphene and KOH in a solvent, and stirring, drying and grinding to obtain graphene/KOH powder; placing graphene/KOH powder and metal salt in protective gas for heat treatment to obtain a metal monoatomic doped graphene precursor, placing the metal salt in a first temperature zone for first heat treatment, placing the graphene/KOH powder in a second temperature zone for second heat treatment, wherein the first temperature zone is communicated with the second temperature zone, and the first temperature zone is positioned at the upstream of the second temperature zone; and treating the metal monoatomic doped graphene precursor by using an acid solution to obtain the metal monoatomic doped graphene.
Description
Technical Field
The invention relates to the technical field of doped carbon materials, in particular to a preparation method of metal monatomic doped graphene.
Background
Graphene, a composition consisting of sp2Two-dimensional carbon nanomaterials composed of hybrid carbon have attracted considerable attention since their discovery. Chemical functionalization through covalent or non-covalent interactions is an effective way to confer specific properties to graphene and can promote its functional properties in various application fields. Among the numerous functionalization methods, heteroatom (e.g., nitrogen, boron, phosphorus, sulfur, halogen, etc.) doping has been widely used to tune the physicochemical properties of graphene, making doped graphene attractive for catalytic, energy storage, electronic, sensor, and gas storage properties. In recent years, the graphene doping with metal atoms attracts a great deal of attention, and the graphene functionalization method is greatly expanded. Both theoretical and experimental studies indicate that metal monatomic doped graphene has surprising catalytic, electronic, and magnetic properties. In addition, in graphene, metal monoatomic atoms coordinated with carbon or hetero atoms (nitrogen, oxygen, sulfur, etc.) have high activities on electrocatalysis, organic catalysis, photocatalysis, and enzyme catalysis.
In order to explore the properties and applications of the metal atom doped graphene, it is important to develop an effective synthesis method. In recent years, many techniques for synthesizing metal atom doped graphene, such as electron/ion irradiation atomic layer deposition, high-energy ball milling, and the like, have appeared. However, these methods either have problems of difficult scale-up or require special instrumentation. As an alternative, the metal-organic framework pyrolysis method has been proven to be a simple and scalable method for synthesizing metal monoatomic doped graphene, however, this method usually causes aggregation of metal atoms, and the content of metal monoatomic atoms in the graphene material is low with the formation of metal nanoparticles, which limits the performance of metal monoatomic atoms. Therefore, there is a need for a simple method for synthesizing high-content metal monatomic doped graphene.
Disclosure of Invention
In view of the above, it is necessary to provide a method for preparing metal monatomic-doped graphene, aiming at the problem of low doping amount of metal monatomic in graphene.
The invention provides a preparation method of metal monoatomic-doped graphene, which comprises the following steps:
dispersing graphene and KOH in a solvent, and stirring, drying and grinding to obtain graphene/KOH powder;
placing graphene/KOH powder and metal salt in protective gas for heat treatment to obtain a metal monoatomic doped graphene precursor, placing the metal salt in a first temperature zone for first heat treatment, placing the graphene/KOH powder in a second temperature zone for second heat treatment, wherein the first temperature zone is communicated with the second temperature zone;
and treating the metal monoatomic doped graphene precursor by using an acid solution to obtain the metal monoatomic doped graphene.
In one embodiment, the target temperature of the first temperature zone is 300 ℃ to 1500 ℃.
In one embodiment, the target temperature of the second temperature zone is 500 ℃ to 800 ℃.
In one embodiment, the target temperature of the second temperature zone is 600 ℃ to 700 ℃.
In one embodiment, the mass ratio of the graphene to the KOH is 1: (2-12).
In one embodiment, the protective gas contains ammonia gas and/or inert gas.
In one embodiment, the heating rate of the heat treatment is 1 ℃/min to 20 ℃/min.
In one embodiment, the first temperature zone and the second temperature zone reach the target temperature simultaneously.
In one embodiment, the atomic mass percent of oxygen in the graphene is 0 to 40 wt%.
In one embodiment, the graphene is few-layer graphene with 1-10 layers.
In one embodiment, the metal salt is one or more of chlorides of Fe, Co, Ni, Zn, Cu, Mg.
In one embodiment, the acid solution is one or more of sulfuric acid, hydrochloric acid and nitric acid, and the acid solution contains H+The concentration is 0.01mol/L to 5 mol/L.
According to the preparation method of the metal monatomic doped graphene, KOH is used as an activating agent, graphene and metal salt are used as raw materials, a two-temperature-zone heat treatment method is adopted, so that the graphene loses carbon atoms and functional groups under the action of KOH and heat treatment to form defect sites, and further, the metal atoms in the metal salt are independently and dispersedly doped in the defect sites of the graphene in a metal monatomic mode, and the metal monatomic doped graphene material is constructed. According to the preparation method of the metal monatomic doped graphene, metal atoms cannot be agglomerated, the doping amount of the metal monatomic is controllable, the doped graphene material with high metal monatomic doping amount can be realized, and the preparation method is simple and easy to operate.
Drawings
Fig. 1 is a high-angle annular dark-field scanning transmission electron microscope photograph of the iron metal monoatomic doped graphene obtained in examples 1 to 4.
Fig. 2 to 10 are raman spectrum representations of the metal monoatomic-doped graphene obtained in examples 1 to 9.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of metal monoatomic-doped graphene, which comprises the following steps:
s100, dispersing graphene and KOH in a solvent, and stirring, drying and grinding to obtain graphene/KOH powder;
s200, placing graphene/KOH powder and metal salt in protective gas for heat treatment to obtain a metal monoatomic doped graphene precursor, placing the metal salt in a first temperature zone for heat treatment, placing the graphene/KOH powder in a second temperature zone for heat treatment, wherein the first temperature zone and the second temperature zone are communicated with each other, and the first temperature zone is positioned at the upstream of the second temperature zone;
s300, treating the metal monoatomic doped graphene precursor by an acid solution to obtain the metal monoatomic doped graphene.
According to the preparation method of the metal monatomic doped graphene, KOH is used as an activating agent, the graphene and the metal salt are subjected to heat treatment in the same temperature zone, the metal salt is subjected to heat treatment in the other temperature zone independently, the addition of the KOH enables the graphene to lose carbon atoms and functional groups to form defect positions, the two-temperature-zone heat treatment method enables the defect positions formed by the graphene and the metal monatomic doping to be carried out synchronously, and further the metal atoms in the metal salt are independently and dispersedly doped in the defect positions of the graphene in a metal monatomic mode, so that the metal monatomic doped graphene material is constructed.
The graphene can be graphene oxide, redox graphene, nitrogen-doped graphene, single-layer graphene, 2-10 layers of few-layer graphene, 10-100 layers of multi-layer graphene sheets or functionalized graphene. The organic matter used for the functionalized graphene can be polyvinyl alcohol, polyvinylpyrrolidone, polyaniline, polyaziridine or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer. The mass ratio of the graphene to the functionalized organic matter in the functionalized graphene is any proportion within the range of 0-100%. Preferably, the number of layers is 1 to 10. The mass percentage of oxygen atoms in the graphene of the present invention is preferably 0 to 40 wt%.
In step S100, the mass ratio of graphene to KOH is 1: (2-12) may be any ratio within the range. In this step, the solvent is not limited as long as it can effectively disperse the graphene and KOH, for example, water or ethanol or a mixed solution of water and ethanol. The amount of the solvent is not limited, so that the drying is preferable. Graphene and KOH can be dispersed in a solvent together, or a graphene dispersion solution can be prepared first and then KOH is added, or graphene and KOH can be dispersed in a solvent respectively and then the two dispersion solutions are mixed together. Preferably, the step of dispersing graphene and KOH in a solvent comprises:
s110, dispersing graphene in a first solvent to prepare a graphene dispersion liquid;
s120, dispersing KOH in a second solvent to prepare KOH dispersion;
and S130, dropwise adding the KOH dispersion liquid into the graphene dispersion liquid prepared in the step S110.
The purpose of stirring in step S100 is to better disperse the graphene and KOH, and any other operation that can achieve the purpose of dispersion, such as ultrasonic oscillation, is also within the scope of the present invention. The temperature for drying in this step is preferably 60 to 90 ℃. The particle size of the graphene/KOH powder obtained by grinding is preferably 500nm to 5 μm.
In the present invention, the metal salt is preferably one or more of chlorides of Fe, Co, Ni, Zn, Cu and Mg, and more preferably FeCl3、CuCl2、MgCl2One or more of (a).
In step S200, the mass ratio of the graphene/KOH powder and the metal salt is 0.5 to 3, and may be any ratio within the range. The protective gas in the step contains ammonia gas and/or inert gas, and the inert gas comprises one or more of nitrogen, argon and helium. The protective gas preferably contains ammonia gas, so that the doping amount of metal single atoms can be further improved. The gas flow rate of the shielding gas is 50sccm to 200 sccm.
The heat treatment in the step comprises a first heat treatment and a second heat treatment, wherein the first heat treatment is a heat treatment process for metal salt, and the second heat treatment is a heat treatment process for graphene/KOH powder. The first heat treatment and the second heat treatment may be performed simultaneously at different temperatures, and the first heat treatment and the second heat treatment are in the same protective gas. The first heat treatment and the second heat treatment are both heated to the target temperature under the protective gas, the heat preservation treatment is carried out for 5 minutes to 1 hour, and the heating rate is preferably 1 ℃/min to 20 ℃/min. The temperature rising rate is too fast or too slow, and has certain influence on the doping amount of metal single atoms. The heating rates of the first temperature zone and the second temperature zone can be the same or different, and preferably, the first temperature zone and the second temperature zone reach the target temperature simultaneously.
According to the invention, the metal salt and the graphene/KOH powder are placed in a device with two different temperature areas for heat treatment, the metal salt is placed in an upstream first temperature area, and the graphene/KOH powder is placed in a downstream second temperature area. In one embodiment, the temperature of the first temperature zone is 300 ℃ to 1500 ℃. The temperature of the first temperature zone can be adjusted according to different types of metal salts. In one embodiment, the temperature of the second temperature zone is 500 ℃ to 800 ℃, and may be 500 ℃, 600 ℃, 700 ℃, 800 ℃, and any value within the range is within the protection scope of the present invention. More preferably 600 to 700 c, and any value within the same interval is within the scope of the present invention.
In step S300, the acid solution may be one or more of sulfuric acid, hydrochloric acid, and nitric acid. And H in the acid solution+The concentration is 0.01mol/L to 5 mol/L.
The types of the metal monoatomic atoms can be one or more than two, and the proportion of the more than two metal monoatomic atoms can be randomly regulated and controlled within the range of 0-1 according to the content of the added metal salt. The mass content of the doped metal single atom is adjustable within the range of 0.1 wt% to 8 wt%.
The following are specific examples
Example 1
1. Weighing 200mg of graphene (few-layer graphene with 1-10 layers and 30 wt% of oxygen atom mass%) and dispersing in 200mL of deionized water to obtain a graphene dispersion solution. 1.2g of KOH was weighed out and dissolved in 200mL of deionized water to obtain a KOH solution. And dropwise adding the KOH solution into the graphene dispersion liquid, and stirring and drying at 80 ℃ to obtain the graphene/KOH dry powder.
2. 1g of FeCl was weighed3Placing 1.4g of graphene/KOH dry powder in a crucible; will be loaded with FeCl3The crucible and the crucible of the graphene/KOH dry powder are respectively placed in the upstream area and the downstream area of the tubular furnace, and the tubular furnace is sealed. And introducing Ar gas into the tubular furnace, heating the upstream temperature zone of the tubular furnace from room temperature to 500 ℃ at the heating rate of 10 ℃/min under the Ar atmosphere, preserving heat for 1h at 500 ℃, simultaneously heating the downstream temperature zone of the tubular furnace from room temperature to 700 ℃ at the heating rate of 14 ℃/min, and preserving heat for 1h at 700 ℃ to obtain the metal monatomic doped graphene precursor.
3. And (3) adding the metal monatomic doped graphene precursor obtained in the step (2) into 100ml of dilute hydrochloric acid with the concentration of 1mol/L, stirring, carrying out vacuum filtration, washing and drying to obtain the metal monatomic doped graphene.
The obtained metal monatomic doped graphene sample is subjected to structural characterization, and the result is shown in fig. 1, wherein fig. 1(a) shows that iron atoms exist on the surface of graphene in a monatomic form. Inductively coupled plasma emission spectroscopy showed that the iron monatomic doping was about 7 wt%.
Example 2
1. Weighing 200mg of graphene (few-layer graphene with 1-10 layers and 30 wt% of oxygen atom mass%) and dispersing in 200mL of deionized water to obtain a graphene dispersion solution. 1.2g of KOH was weighed out and dissolved in 200mL of deionized water to obtain a KOH solution. And dropwise adding the KOH solution into the graphene dispersion liquid, and stirring and drying at 80 ℃ to obtain the graphene/KOH dry powder.
2. 1g of FeCl was weighed3Placing 1.4g of graphene/KOH dry powder in a crucible; will be loaded with FeCl3The crucible and the crucible of the graphene/KOH dry powder are respectively placed in the upstream area and the downstream area of the tubular furnace, and the tubular furnace is sealed. Introducing Ar gas into the tube furnace, and heating the upstream temperature zone of the tube furnace from room temperature to 500 ℃ at a heating rate of 10 ℃/min under the Ar atmosphereAnd keeping the temperature at 500 ℃ for 1h, simultaneously heating a downstream temperature zone of the tube furnace from room temperature to 600 ℃ at the heating rate of 12 ℃/min, and keeping the temperature at 600 ℃ for 1h to obtain the metal monatomic doped graphene precursor.
3. And (3) adding the metal monatomic doped graphene precursor obtained in the step (2) into 100ml of dilute hydrochloric acid with the concentration of 1mol/L, stirring, carrying out vacuum filtration, washing and drying to obtain the metal monatomic doped graphene.
The obtained metal monatomic doped graphene sample is subjected to structural characterization, and the result is shown in fig. 1, and fig. 1(b) shows that iron atoms exist on the surface of graphene in a monatomic form. Inductively coupled plasma emission spectroscopy showed that the iron monatomic doping was about 5.5 wt%.
Example 3
1. Weighing 200mg of graphene (few-layer graphene with 1-10 layers and 30 wt% of oxygen atom mass%) and dispersing in 200mL of deionized water to obtain a graphene dispersion solution. 1.2g of KOH was weighed out and dissolved in 200mL of deionized water to obtain a KOH solution. And dropwise adding the KOH solution into the graphene dispersion liquid, and stirring and drying at 80 ℃ to obtain the graphene/KOH dry powder.
2. 1g of FeCl was weighed3Placing 1.4g of graphene/KOH dry powder in a crucible; will be loaded with FeCl3The crucible and the crucible of the graphene/KOH dry powder are respectively placed in the upstream area and the downstream area of the tubular furnace, and the tubular furnace is sealed. And introducing Ar gas into the tubular furnace, heating the upstream temperature zone of the tubular furnace from room temperature to 500 ℃ at the heating rate of 10 ℃/min under the Ar atmosphere, preserving heat for 1h at 500 ℃, simultaneously heating the downstream temperature zone of the tubular furnace from room temperature to 800 ℃ at the heating rate of 16 ℃/min, and preserving heat for 1h at 800 ℃ to obtain the metal monatomic doped graphene precursor.
3. And (3) adding the metal monatomic doped graphene precursor obtained in the step (2) into 100ml of dilute hydrochloric acid with the concentration of 1mol/L, stirring, carrying out vacuum filtration, washing and drying to obtain the metal monatomic doped graphene.
The obtained metal monatomic doped graphene sample is subjected to structural characterization, and the result is shown in fig. 1, and fig. 1(c) shows that iron atoms exist on the surface of graphene in a monatomic form. Inductively coupled plasma emission spectroscopy showed that the iron monatomic doping was about 3 wt%.
Example 4
1. Weighing 200mg of graphene (few-layer graphene with 1-10 layers and 30 wt% of oxygen atom mass%) and dispersing in 200mL of deionized water to obtain a graphene dispersion solution. 1.2g of KOH was weighed out and dissolved in 200mL of deionized water to obtain a KOH solution. And dropwise adding the KOH solution into the graphene dispersion liquid, and stirring and drying at 80 ℃ to obtain the graphene/KOH dry powder.
2. 1g of FeCl was weighed3Placing 1.4g of graphene/KOH dry powder in a crucible; will be loaded with FeCl3The crucible and the crucible of the graphene/KOH dry powder are respectively placed in the upstream area and the downstream area of the tubular furnace, and the tubular furnace is sealed. And introducing Ar gas into the tubular furnace, heating the upstream temperature zone of the tubular furnace from room temperature to 500 ℃ at the heating rate of 10 ℃/min under the Ar atmosphere, preserving heat for 1h at 500 ℃, simultaneously heating the downstream temperature zone of the tubular furnace from room temperature to 500 ℃ at the heating rate of 10 ℃/min, and preserving heat for 1h at 500 ℃ to obtain the metal monatomic doped graphene precursor.
3. And (3) adding the metal monatomic doped graphene precursor obtained in the step (2) into 100ml of dilute hydrochloric acid with the concentration of 1ml/L, stirring, carrying out vacuum filtration, washing and drying to obtain the metal monatomic doped graphene.
The obtained metal monatomic doped graphene sample is subjected to structural characterization, and the result is shown in fig. 1, and fig. 1(d) shows that iron atoms exist on the surface of graphene in a monatomic form. Inductively coupled plasma emission spectroscopy analysis showed that the iron monatomic doping was about 2 wt%.
As can be seen from examples 1 to 4, the temperatures of the graphene/KOH heat treatment are different, and the finally formed metal monatomic doped graphene has different iron monatomic doping amounts, the highest iron monatomic doping amount at 700 ℃, the second highest iron monatomic doping amount at 600 ℃, and relatively low iron monatomic doping amounts at 500 ℃ and 800 ℃.
Example 5
1. Weighing 200mg of graphene (few-layer graphene with 1-10 layers and 30 wt% of oxygen atom mass%) and dispersing in 200mL of deionized water to obtain a graphene dispersion solution. 400mg of KOH was weighed and dissolved in 200mL of deionized water to obtain a KOH solution. And dropwise adding the KOH solution into the graphene dispersion liquid, and stirring and drying at 80 ℃ to obtain the graphene/KOH dry powder.
2. 1g of FeCl was weighed3Placing 600mg of graphene/KOH dry powder in a crucible; will be loaded with FeCl3The crucible and the crucible of the graphene/KOH dry powder are respectively placed in the upstream area and the downstream area of the tubular furnace, and the tubular furnace is sealed. And introducing Ar gas into the tubular furnace, heating the upstream temperature zone of the tubular furnace from room temperature to 500 ℃ at the heating rate of 10 ℃/min under the Ar atmosphere, preserving heat for 1h at 500 ℃, simultaneously heating the downstream temperature zone of the tubular furnace from room temperature to 700 ℃ at the heating rate of 14 ℃/min, and preserving heat for 1h at 700 ℃ to obtain the metal monatomic doped graphene precursor.
3. And (3) adding the metal monatomic doped graphene precursor obtained in the step (2) into 100ml of dilute hydrochloric acid with the concentration of 1mol/L, stirring, carrying out vacuum filtration, washing and drying to obtain the metal monatomic doped graphene.
Inductively coupled plasma emission spectroscopy showed that the iron monatomic doping was about 3 wt%.
Example 6
1. Weighing 200mg of graphene (few-layer graphene with 1-10 layers and 30 wt% of oxygen atom mass%) and dispersing in 200mL of deionized water to obtain a graphene dispersion solution. 2.4g of KOH was weighed out and dissolved in 200mL of deionized water to obtain a KOH solution. And dropwise adding the KOH solution into the graphene dispersion liquid, and stirring and drying at 80 ℃ to obtain the graphene/KOH dry powder.
2. 1g of FeCl was weighed3Placing 2.6g of graphene/KOH dry powder in a crucible; will be loaded with FeCl3The crucible and the crucible of the graphene/KOH dry powder are respectively placed in the upstream area and the downstream area of the tubular furnace, and the tubular furnace is sealed. Introducing Ar gas into the tube furnace, heating the upstream temperature zone of the tube furnace from room temperature to 500 ℃ at the heating rate of 10 ℃/min under the Ar atmosphere, preserving heat at 500 ℃ for 1h, and simultaneously heating the downstream temperature zone of the tube furnace from room temperature to 70 ℃ at the heating rate of 14 ℃/minAnd keeping the temperature at 0 ℃ for 1h at 700 ℃ to obtain the metal monoatomic doped graphene precursor.
3. And (3) adding the metal monatomic doped graphene precursor obtained in the step (2) into 100ml of dilute hydrochloric acid with the concentration of 1mol, stirring, carrying out vacuum filtration, washing and drying to obtain the metal monatomic doped graphene.
Inductively coupled plasma emission spectroscopy showed that the iron monatomic doping was about 6 wt%.
As can be seen from example 1, example 5, and example 6, since the mass ratios of graphene and KOH are different, the doping amount of the metal monoatomic atom in the finally formed metal monoatomic-doped graphene is different, and the mass ratio of graphene to KOH is reduced, which can increase the doping amount of the metal monoatomic atom, but when the mass ratio of graphene to KOH reaches 1:6, the mass ratio of graphene to KOH is continuously reduced, and the doping amount of the metal monoatomic atom is slightly reduced instead.
Example 7
The procedure was substantially the same as in example 1, except that NH was introduced into the tube furnace3Gas in NH3Heat treatment is performed in an atmosphere.
Inductively coupled plasma emission spectroscopy showed that the iron monatomic doping was about 8 wt%.
Example 8
Substantially the same as the preparation method of example 1 except that FeCl was added3Substitution to MgCl2。
Inductively coupled plasma emission spectroscopy showed that the doping level of magnesium single atoms was about 7.5 wt%.
Example 9
Substantially the same as the preparation method of example 1 except that FeCl was added3Replacement with CuCl2。
Inductively coupled plasma emission spectroscopy showed that the doping of copper single atoms was about 6 wt%.
Performing Raman spectrum characterization on the metal monatomic doped graphene samples obtained in the embodiments 1 to 9, wherein the metal monatomic doped graphene samples obtained in the embodiments 1 to 9 all maintain the graphene structure. FIGS. 2 to 10 show the Raman spectra of examples 1 to 9, which can be seen from FIGS. 2 to 10 at 1350cm-1、1582cm-1And 2705cm-1The positions are respectively a D peak, a G peak and a 2D peak of the graphene, and the higher intensity ratio of the D/G peak indicates that a large number of defects are formed in the graphene, and more metal single atoms are doped at the defects of the graphene.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of metal monatomic doped graphene is characterized by comprising the following steps:
dispersing graphene and KOH in a solvent, and stirring, drying and grinding to obtain graphene/KOH powder;
placing graphene/KOH powder and metal salt in protective gas for heat treatment to obtain a metal monoatomic doped graphene precursor, placing the metal salt in a first temperature zone for first heat treatment, placing the graphene/KOH powder in a second temperature zone for second heat treatment, wherein the first temperature zone is communicated with the second temperature zone, and the metal salt is FeCl3The target temperature of the first temperature zone is 300-1500 ℃, and the target temperature of the second temperature zone is 500-800 ℃;
and treating the metal monoatomic doped graphene precursor by using an acid solution to obtain the metal monoatomic doped graphene.
2. The method for preparing metal monatomic-doped graphene according to claim 1, wherein the target temperature of the second temperature zone is 600 ℃ to 700 ℃.
3. The method for preparing metal monatomic doped graphene according to claim 1, wherein the mass ratio of the graphene to the KOH is 1: (2-12).
4. The method according to claim 1, wherein the protective gas contains ammonia gas and/or an inert gas.
5. The method according to claim 1, wherein the temperature increase rate of the heat treatment is 1 ℃/min to 20 ℃/min.
6. The method according to claim 1, wherein the first temperature zone and the second temperature zone reach a target temperature simultaneously.
7. The method for preparing the metal monatomic doped graphene according to any one of claims 1 to 6, wherein the mass percentage of oxygen atoms in the graphene is 0 to 40 wt%, and the graphene is a few-layer graphene having 1 to 10 layers.
8. The method for preparing metal monatomic-doped graphene according to any one of claims 1 to 6, wherein the acid solution is one or more of sulfuric acid, hydrochloric acid, and nitric acid, and H is contained in the acid solution+The concentration is 0.01mol/L to 5 mol/L.
9. The method for preparing metal monatomic doped graphene according to any one of claims 1 to 6, wherein the particle size of the graphene/KOH powder obtained by grinding is 500nm to 5 μm.
10. The method for preparing metal monatomic doped graphene according to any one of claims 1 to 6, wherein the graphene/KOH powder and the metal salt FeCl are3Is 0.5 to 3.
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