CN113912051B - Preparation method of doped graphene - Google Patents
Preparation method of doped graphene Download PDFInfo
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- CN113912051B CN113912051B CN202111385313.XA CN202111385313A CN113912051B CN 113912051 B CN113912051 B CN 113912051B CN 202111385313 A CN202111385313 A CN 202111385313A CN 113912051 B CN113912051 B CN 113912051B
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Abstract
The invention relates to the technical field of graphene preparation, and particularly relates to a preparation method of doped graphene. The preparation method of the doped graphene comprises the following steps: dispersing graphene, metal salt and/or a non-metal compound in a solvent, and drying to prepare composite powder; and heating the reaction cavity to a preset temperature in a protective atmosphere or a vacuum atmosphere, performing microwave irradiation on the reaction cavity, and adding the composite powder to prepare the doped graphene. Wherein the preset temperature is 500-900 ℃. The preparation method is simple, the atom doping amount is high, and the metal atom-nonmetal atom co-doping can be realized.
Description
Technical Field
The invention relates to the technical field of graphene preparation, and particularly relates to a preparation method of doped graphene.
Background
Graphene is a two-dimensional thin film formed by periodically arranging carbon atoms in a benzene ring structure, the thickness of the graphene is only one atomic diameter (0.335 nm), the graphene is a novel two-dimensional crystal material, and the graphene has excellent physical and chemical properties such as electrical conductivity, thermal conductivity, structural strength and optical performance, and becomes a research hotspot in various fields. With the gradual progress of research, compounding or modifying graphene to endow the graphene with specific properties becomes the focus of the current research, and functionalized graphene materials are widely applied in various fields. The doped graphene can effectively regulate and control the physical and chemical properties of the graphene, and is an important graphene functional modification method. Doping of heteroatoms (such as nitrogen, boron, phosphorus, sulfur, halogen and the like) can open a zero band gap of graphene, change the electronic structure of the surface of the graphene and expose reactive active sites on the surface of the graphene. And the Fermi level of the graphene can be changed by doping metal atoms (such as transition metals of iron, copper, cobalt, nickel, zinc and the like), and the p-n doping is formed by coordination of the metal atoms and carbon atoms or hetero atoms in the graphene, so that the activities of electrocatalysis, organic catalysis, photocatalysis and enzyme catalysis can be further improved.
In order to ensure the successful application of the doped graphene, a stable and reliable preparation method is very important. In recent years, various methods of doping graphene have been developed, and CVD, heat treatment, plasma, etc. are most widely used for non-metal atoms. The doping preparation conditions of metal atoms have higher requirements, and the methods such as a high-energy electron beam irradiation method, atomic layer deposition, microwave irradiation and the like are commonly used at present. However, these methods have the problems of high equipment requirements, harsh preparation conditions, low doping amount and efficiency, high cost, poor continuity, etc.
Disclosure of Invention
Based on the method, the preparation method of the doped graphene can improve the atom doping amount and can realize continuous production.
The invention provides a preparation method of doped graphene, which comprises the following steps:
dispersing graphene, metal salt and/or non-metal compound in a solvent, and drying to prepare composite powder; and
heating a reaction cavity to a preset temperature in a protective atmosphere or a vacuum atmosphere, performing microwave irradiation on the reaction cavity, and adding the composite powder to prepare doped graphene;
the preset temperature is 500-900 ℃.
Optionally, in the preparation method of doped graphene, the preset temperature is 700 ℃ to 800 ℃.
Optionally, in the preparation method of doped graphene, the doping atoms in the doped graphene are one or more of Fe atoms, cu atoms, co atoms, ni atoms, zn atoms, N atoms, P atoms, S atoms, B atoms, and F atoms.
Optionally, in the preparation method of doped graphene, the mass ratio of the doping atoms to the carbon atoms in the graphene is 1 (1-100).
Optionally, in the preparation method of doped graphene, the graphene is graphene oxide, and the oxygen atom content of the graphene oxide is 0 to 50at%.
Optionally, in the preparation method of doped graphene, the oxygen atom content of the graphene oxide is 30at% to 40at%.
Optionally, in the preparation method of doped graphene, the number of layers of graphene is 1 to 10.
Optionally, in the preparation method of doped graphene, the power of microwave irradiation is 1kW to 15kW.
Optionally, in the preparation method of doped graphene, the microwave irradiation time is 5s to 300s.
Optionally, in the preparation method of doped graphene, the solvent is ethylene glycol, ethanol and/or water.
The research of the invention finds that the traditional heat treatment doping method has lower atom doping amount. And the conventional microwave method for preparing doped graphene is mostly normal-temperature single microwave, the next reaction can be carried out after the single reaction is finished and the material is taken, the microwave needs to be started repeatedly, and the production process is difficult to continue. And because the initial temperature in the reaction cavity is lower and the microwave temperature rise is unstable, the temperature conditions in the reaction cavity are different in each reaction, and the uniformity of the obtained product is poor. In addition, the traditional doping method of microwave irradiation also needs to add an initiator as a wave-absorbing site.
Compared with the traditional method for doping graphene, the method provided by the invention has the advantages that a thermal field environment is provided in advance, so that on one hand, the temperature in the reaction cavity in the microwave irradiation process is relatively stable, the consistency of the reaction environments of each batch of products entering the reaction cavity at different times is ensured, the uniformity of the products is relatively good, the temperature in the cavity does not need to be readjusted after each reaction, and the continuous production can be realized; on the other hand, the raw materials are pre-reduced to a certain degree after entering the high-temperature thermal field in the thermal field environment, so that wave-absorbing sites can be provided by the raw materials, other initiators do not need to be added, the operation is further simplified, and the production efficiency is improved. And the thermal field can assist the microwave to provide higher excitation energy, which is beneficial to improving the substitution efficiency of the doping atoms on the carbon atoms and improving the doping amount. The preparation method provided by the invention has universality and can be suitable for doping of various atoms such as metal atoms, non-metal atoms and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an X-ray photoelectron spectrum of doped graphene prepared in example 1 of the present invention;
fig. 2 is an X-ray photoelectron spectrum of the doped graphene prepared in example 2 of the present invention;
FIG. 3 is an X-ray photoelectron spectrum of doped graphene prepared in example 3 of the present invention;
FIG. 4 is an X-ray photoelectron spectrum of doped graphene prepared in example 4 of the present invention;
FIG. 5 is an X-ray photoelectron spectrum of doped graphene prepared in example 5 of the present invention;
FIG. 6 is an X-ray photoelectron spectrum of doped graphene prepared in example 6 of the present invention;
FIG. 7 is an X-ray photoelectron spectrum of doped graphene obtained in example 7 of the present invention;
FIG. 8 is an X-ray photoelectron spectrum of doped graphene prepared in example 8 of the present invention;
fig. 9 is an X-ray photoelectron spectrum of the doped graphene prepared in comparative example 1 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element. "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The invention provides a preparation method of doped graphene, which comprises the following steps:
dispersing graphene, metal salt and/or non-metal compound in a solvent, and drying to prepare composite powder; and
heating the reaction cavity to a preset temperature in a protective atmosphere or a vacuum atmosphere, performing microwave irradiation on the reaction cavity, and adding the composite powder to prepare doped graphene;
the preset temperature is 500-900 ℃.
Compared with the traditional method for doping graphene, the method provided by the invention has the advantages that a thermal field environment is provided in advance, so that on one hand, the temperature in the reaction cavity in the microwave irradiation process can be ensured to be relatively stable, the consistency of reaction environments of each batch of products entering the reaction cavity at different times is ensured, the uniformity of the products is better, the temperature in the cavity does not need to be readjusted after each reaction, and the continuous production can be realized; on the other hand, the raw materials are pre-reduced to a certain degree after entering the high-temperature thermal field in the thermal field environment, so that wave-absorbing sites can be provided by the raw materials, other initiators do not need to be added, the operation is further simplified, and the production efficiency is improved. And the thermal field can assist microwaves to provide higher excitation energy, so that the substitution efficiency of doping atoms on carbon atoms is improved, and the doping amount is increased. The preparation method provided by the invention has universality and can be suitable for doping of various atoms such as metal atoms, non-metal atoms and the like.
In some embodiments, any value within the predetermined temperature range is within the protection scope of the present invention, and may be, for example, 550 ℃, 600 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, and the like, and preferably 700 ℃ to 800 ℃.
In some embodiments, the doping atoms in the doped graphene may be doping atoms commonly used in the art, and may be metal atoms or non-metal atoms, for example. Specifically, but not limited to, one or more of Fe atom, cu atom, co atom, ni atom, zn atom, N atom, P atom, S atom, B atom, and F atom.
In some embodiments, when the dopant atom is a metal atom, a metal salt is generally selected as a dopant atom donor, and the metal ion in the metal salt may be Fe 3+ 、Cu 2+ 、Co 2+ 、Ni 2+ And Zn 2+ And the acid radical ion can be Cl - 、NO 3 - 、SO 3 2- 、S 2 O 8 2- 、PO 4 3- 、BO 3 3- And CH 3 COO - One or more of (a). Preferably, when the doping atom in the doped graphene is a metal atom, the acid radical ion in the metal salt is preferably Cl - 、NO 3 - And CH 3 COO - One or more of (a); when the doping atom is a non-metal atom, the doping atom donor can be selected from metal salt and/or non-metal compound, and when the metal salt is selected, the acid radical ion in the metal salt is preferably SO 3 2- 、S 2 O 8 2- 、PO 4 3- And BO 3 3- When selected from non-metalsWhen the compound is used, the compound can be ammonium salt, ammonia water, urea and inorganic acid, and the inorganic acid can be phosphoric acid, boric acid and the like. More preferably, the atoms doped in the invention can be one or more than two metal atoms, also can be one or more than two nonmetal atoms, also can be metal atoms and nonmetal atoms, and the proportion of the two or more metal atoms can be arbitrarily regulated and controlled within the range of 0-1 according to the content of the metal salt. Similarly, the ratio of two or more non-metal atoms and the ratio of metal atoms to non-metal atoms can be arbitrarily controlled within a range of 0 to 1 depending on the content of the metal salt and/or the non-metal compound.
In some embodiments, the mass ratio of doping atoms in the doped graphene to carbon atoms in the graphene is 1 (1 to 100), and any value in this range is within the scope of the present invention, and may be, for example, 1.
In some embodiments, the graphene may be graphene oxide, doped graphene oxide, activated graphene, including but not limited to nitrogen-doped graphene oxide, sulfur-doped graphene oxide, fluorine-doped graphene oxide. In addition, the graphene can also be single-layer graphene, few-layer graphene or multi-layer graphene, wherein the number of the few-layer graphene layers is 2-10, and the number of the multi-layer graphene layers is 10-100. Preferably, the content of oxygen atoms in the graphene is 0 to 50at%. More preferably, the graphene contains 30at% to 40at% of oxygen atoms and has 1 to 10 layers.
In some embodiments, the power of the microwave irradiation may be 1kW to 15kW, and may also be 3kW, 5kW, 8kW, 10kW, 12kW, or the like.
In some embodiments, the microwave irradiation time may be 5s to 300s, and may also be 10s, 30s, 40s, 60s, 70s, 90s, 120s, 180s, 200s, 230s, and the like.
In some embodiments, the solvent is selected to effectively disperse the graphene, the metal salt and the nonmetal compound, and may be, for example, ethylene glycol, ethanol, water or a mixed solution thereof. The amount of the solvent is also not limited, and is preferably such that the dispersing effect is ensured and drying is facilitated.
In some embodiments, the graphene, the metal salt, and the nonmetal compound may be dispersed together in the solvent, or the respective dispersions may be prepared and then mixed, or the graphene may be dispersed in the solvent to obtain a graphene dispersion, and then the metal salt and/or the nonmetal compound may be added to the graphene dispersion.
In some embodiments, any operation process such as stirring, ultrasonic vibration, cell pulverization, etc. can be used during the dispersion process to promote the dispersion effect.
In some embodiments, the skilled person will be able to select the method for drying according to the actual needs, including but not limited to freeze drying, spray drying, forced air drying, etc.
In some embodiments, the protective atmosphere may be provided by nitrogen and/or an inert gas, which may be helium and/or argon.
In some embodiments, the reaction chamber can reach the preset temperature by one or more of microwave heating, infrared heating and resistance wire heating.
In some embodiments, the preparation method further comprises a step of blowing the prepared doped graphene out by air blowing. The doped graphene in the reaction cavity is blown out by blowing air, so that the temperature and microwave irradiation of the reaction cavity can be kept, namely, the temperature environment and the microwave environment for next charging are ensured, and the doped graphene among batches has uniform performance. But also can ensure continuous feeding and discharging under the action of microwaves, has continuous and quick reaction process, convenient operation and extremely short reaction time, can be prepared continuously, and is easy to realize batch industrial production.
The preparation method of doped graphene according to the present invention is further described in detail with reference to specific examples and comparative examples.
Example 1
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 40at% and the number of layers of 2) and dispersing in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 40.55mg of FeCl were weighed out 3 Dissolving the mixture in graphene oxide dispersion liquid, and uniformly stirring and mixing to obtain graphene oxide/FeCl 3 The dispersion liquid is frozen and dried to prepare the graphene oxide/FeCl 3 Compounding the powder;
3) In Ar protective atmosphere, preheating the reaction cavity to 700 ℃ by utilizing infrared heating, performing 10kW microwave irradiation on the reaction cavity after the reaction cavity reaches a set temperature, and obtaining graphene oxide/FeCl 3 And adding the composite powder into the reaction cavity, reacting for 90s, blowing the product into a collector by air blowing, and obtaining the Fe monoatomic doped graphene powder.
As shown in FIG. 1, the X-ray photoelectron spectroscopy analysis revealed that the Fe single atom doping amount was 5.36wt%.
Example 2
This example is prepared substantially identically to example 1, except that: graphene oxide powder and FeCl 3 Are different. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 40at% and the number of layers of 2) and dispersing in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 121.65mg of FeCl was weighed 3 Dissolving the mixture in graphene oxide dispersion liquid, and uniformly stirring and mixing to obtain graphene oxide/FeCl 3 The dispersion liquid is frozen and dried to prepare the graphene oxide/FeCl 3 Compounding powder;
3) Preheating the reaction cavity to 700 ℃ by utilizing infrared heating in Ar protective atmosphere, performing 10kW microwave irradiation on the reaction cavity after the reaction cavity reaches a set temperature, and obtaining graphene oxide/FeCl 3 And adding the composite powder into the reaction cavity, reacting for 90s, blowing the product into a collector by air blowing, and obtaining the Fe monoatomic doped graphene powder.
As shown in FIG. 2, the X-ray photoelectron spectroscopy analysis revealed that the amount of Fe single atom doped was 15.71wt%.
Example 3
This example is prepared substantially identically to example 2, except that: the doping atoms are Cu, and the preset temperature of the reaction cavity is 800 ℃. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 40at% and the number of layers of 2) and dispersing the graphene oxide powder in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 136.24mg of Cu (CH) was weighed 3 COO) 2 Dissolving the mixture in graphene oxide dispersion liquid, and stirring and mixing the mixture uniformly to obtain graphene oxide/Cu (CH) 3 COO) 2 The dispersion is frozen and dried to prepare the graphene oxide/Cu (CH) 3 COO) 2 Compounding powder;
3) Preheating the reaction cavity to 800 ℃ by utilizing infrared heating in Ar protective atmosphere, carrying out 10kW microwave irradiation on the reaction cavity after the temperature reaches a set temperature, and obtaining graphene oxide/Cu (CH) 3 COO) 2 And adding the composite powder into the reaction cavity, reacting for 90s, and blowing the product into a collector by air blowing to obtain the Cu monatomic doped graphene powder.
As shown in FIG. 3, the X-ray photoelectron spectroscopy analysis revealed that the Cu single atom doping amount was 12.71wt%.
Example 4
This example is prepared substantially identically to example 1, except that: the doping atoms are S, the preset temperature of the reaction cavity, the protective atmosphere, the microwave irradiation power and the time are different. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 35at% and the number of layers of 3) and dispersing in 60mL of ethanol to obtain a graphene oxide dispersion liquid;
2) Weighing 54.06mg of ethylene sulfite, dissolving the ethylene sulfite into the graphene oxide dispersion liquid, stirring and mixing uniformly to obtain graphene oxide/ethylene sulfite dispersion liquid, and drying by air blowing to obtain graphene oxide/ethylene sulfite composite powder;
3) At N 2 In a protective atmosphere, preheating a reaction cavity to 800 ℃ by utilizing infrared heating, carrying out 6kW microwave irradiation on the reaction cavity after the temperature reaches a set temperature, adding the obtained graphene oxide/vinyl sulfite composite powder into the reaction cavity, reacting for 3min, and blowing the product into a collector by blowing to obtain S-monatomic doped graphene powder.
As shown in FIG. 4, X-ray photoelectron spectroscopy showed that the S monoatomic doping amount was 4.51wt%.
Example 5
This example is prepared substantially identically to example 1, except that: the doping atoms are N and the protective atmosphere is different. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 30at% and the number of layers of 3) and dispersing in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 2.5mL of NH with a concentration of 1mol/L was measured 3 ·H 2 Dissolving O in the graphene oxide dispersion liquid, and uniformly stirring and mixing to obtain graphene oxide/NH 3 ·H 2 O dispersion liquid, and freeze drying to obtain graphene oxide/NH 3 ·H 2 O composite powder;
3) At N 2 In a protective atmosphere, preheating the reaction cavity to 700 ℃ by utilizing infrared heating, performing 10kW microwave irradiation on the reaction cavity after the temperature reaches a set temperature, and obtaining graphene oxide/NH 3 ·H 2 And adding the O composite powder into the reaction cavity, reacting for 90s, and blowing the product into a collector by air blowing to obtain the N monoatomic-doped graphene powder.
As shown in FIG. 5, the X-ray photoelectron spectroscopy showed that the N monoatomic doping amount was 9.07wt%.
Example 6
This example is prepared substantially identically to example 1, except that: the preset temperature is 500 ℃. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 40at% and the number of layers of 2) and dispersing in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 40.55mg of FeCl was weighed 3 Dissolving the mixture in graphene oxide dispersion liquid, and uniformly stirring and mixing to obtain graphene oxide/FeCl 3 The dispersion liquid is frozen and dried to prepare the graphene oxide/FeCl 3 Compounding the powder;
3) In Ar protective atmosphere, preheating the reaction cavity to 500 ℃ by utilizing infrared heating, carrying out 10kW microwave irradiation on the reaction cavity after the reaction cavity reaches a set temperature, and obtaining graphene oxide/FeCl 3 And adding the composite powder into the reaction cavity, reacting for 90s, and blowing the product into a collector by air blowing to obtain the Fe monoatomic-doped graphene powder.
As shown in FIG. 6, the X-ray photoelectron spectroscopy analysis revealed that the amount of Fe single atom doped was 3.04wt%.
Example 7
This example is substantially the same as example 1 except that: the preset temperature is 800 ℃. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 40at% and the number of layers of 2) and dispersing in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 40.55mg of FeCl was weighed 3 Dissolving the mixture in graphene oxide dispersion liquid, and uniformly stirring and mixing to obtain graphene oxide/FeCl 3 The dispersion liquid is frozen and dried to prepare the graphene oxide/FeCl 3 Compounding powder;
3) Preheating the reaction cavity to 800 ℃ by utilizing infrared heating in Ar protective atmosphere, performing 10kW microwave irradiation on the reaction cavity after the reaction cavity reaches a set temperature, and obtaining graphene oxide/FeCl 3 And adding the composite powder into the reaction cavity, reacting for 90s, and blowing the product into a collector by air blowing to obtain the Fe monoatomic-doped graphene powder.
As shown in FIG. 7, the X-ray photoelectron spectroscopy analysis revealed that the amount of Fe single atom doped was 6.45wt%.
Example 8
This example is substantially the same as example 1 except that: the doping atoms are Fe and N. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 35at% and the number of layers of 3) and dispersing the graphene oxide powder in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 40.55mg of FeCl were weighed out 3 And 80.24mg of NH 4 Dissolving Cl in the graphene oxide dispersion liquid, and uniformly stirring and mixing to obtain graphene oxide/FeCl 3 /NH 4 The Cl dispersion liquid is frozen and dried to prepare the graphene oxide/FeCl 3 /NH 4 Cl composite powder;
3) Preheating the reaction cavity to 850 ℃ by utilizing infrared heating in Ar protective atmosphere, performing 10kW microwave irradiation on the reaction cavity after the reaction cavity reaches a set temperature, and obtaining graphene oxide/FeCl 3 /NH 4 And adding Cl composite powder into the reaction cavity, reacting for 90s, blowing the product into a collector by air blowing, and obtaining Fe-N co-doped graphene powder.
As shown in FIG. 8, the X-ray photoelectron spectroscopy showed that the doping amounts of Fe atom and N atom were 3.93wt% and 5.87wt%, respectively.
Comparative example 1
This comparative example is the same as example 1 in terms of starting materials and proportions, except that: the preparation method is a traditional normal-temperature microwave method. The method comprises the following specific steps:
1) Weighing 500mg of graphene oxide powder (with the oxygen atom content of 40at% and the number of layers of 2) and dispersing the graphene oxide powder in 60mL of deionized water to obtain a graphene oxide dispersion liquid;
2) 40.55mg of FeCl was weighed 3 Dissolving the mixture in graphene oxide dispersion liquid, and uniformly stirring and mixing to obtain graphene oxide/FeCl 3 The dispersion liquid is frozen and dried to prepare the graphene oxide/FeCl 3 Compounding powder;
3) The obtained graphene oxide/FeCl 3 And adding the composite powder into the reaction cavity, performing 10kW microwave irradiation on the reaction cavity, reacting for 90s, and taking out a product to obtain the Fe monatomic doped graphene powder.
As shown in FIG. 9, the X-ray photoelectron spectroscopy analysis revealed that the amount of Fe monoatomic doping was 1.15wt%.
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 should be subject to the appended claims.
Claims (10)
1. A preparation method of doped graphene is characterized by comprising the following steps:
dispersing graphene, metal salt and/or non-metal compound in a solvent, and drying to prepare composite powder; and
heating a reaction cavity to a preset temperature in a protective atmosphere or a vacuum atmosphere, performing microwave irradiation on the reaction cavity, and adding the composite powder to prepare doped graphene;
the preset temperature is 500-900 ℃.
2. The method for preparing doped graphene according to claim 1, wherein the preset temperature is 700 ℃ to 800 ℃.
3. The method according to claim 1, wherein the doping atoms in the doped graphene are one or more of Fe atoms, cu atoms, co atoms, ni atoms, zn atoms, N atoms, P atoms, S atoms, B atoms, and F atoms.
4. The preparation method of doped graphene according to claim 3, wherein the mass ratio of the doping atoms to the carbon atoms in the graphene is 1 (1-100).
5. The method according to claim 1, wherein the graphene is graphene oxide, and the graphene oxide has an oxygen atom content of 0 to 50at%.
6. The method according to claim 5, wherein the graphene oxide has an oxygen atom content of 30at% to 40at%.
7. The method according to any one of claims 1 to 6, wherein the number of graphene layers is 1 to 10.
8. The method for preparing doped graphene according to any one of claims 1 to 6, wherein the power of the microwave irradiation is 1kW to 15kW.
9. The method for preparing doped graphene according to any one of claims 1 to 6, wherein the microwave irradiation time is 5s to 300s.
10. The method of any one of claims 1 to 6, wherein the solvent is ethylene glycol, ethanol and/or water.
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