CN110775959A - Preparation method for preparing nitrogen-sulfur co-doped porous graphene by supramolecular template method - Google Patents
Preparation method for preparing nitrogen-sulfur co-doped porous graphene by supramolecular template method Download PDFInfo
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- CN110775959A CN110775959A CN201911052563.4A CN201911052563A CN110775959A CN 110775959 A CN110775959 A CN 110775959A CN 201911052563 A CN201911052563 A CN 201911052563A CN 110775959 A CN110775959 A CN 110775959A
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Abstract
The invention relates to a preparation method of nitrogen and sulfur co-doped porous graphene by a supramolecular template method. Compared with the prior art, the preparation method disclosed by the invention has the advantages that no pore-forming agent or template agent is additionally introduced, the related heteroatom precursors are all cheap industrial raw materials, the operation is simple, the production cost is low, and the like, the nitrogen and sulfur co-doping is realized while the porous graphene is obtained, and the obtained nitrogen and sulfur co-doped porous graphene has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the field of energy storage material preparation, and relates to a preparation method for preparing nitrogen-sulfur co-doped porous graphene by a supramolecular template method.
Background
Graphene as a two-dimensional carbon material has excellent physical properties such as electric conductivity and heat conductivity, and has a series of deep researches in the energy storage fields such as super capacitors and lithium ion batteries. Due to the fact that the graphene sheet layer has large acting force, the sheet layer is prone to aggregation, permeation of electrolyte is not facilitated, and active sites are lost. In order to fully exert the advantages of the graphene in the field of energy storage, the electrochemical performance of the graphene can be improved by optimizing the pore structure of the graphene, introducing heteroatom doping and the like. At present, the doped porous graphene is mainly prepared by introducing a nitrogen/phosphorus/sulfur source and a pore-forming agent.
Document 1, "Du Zhu, Liu Bo Qing et al from Engineering the Li Storage Properties of graphene antibodies: Defect Evolution and Pore Structure Regulation [ J]，ACS AppliedMaterials&Interfaces, 2016,8,33712-33722 "report a preparation method of nitrogen-doped porous graphene, in which a surfactant sodium dodecyl sulfate and a metal salt FeCl are sequentially added into a dispersion liquid of graphene oxide
3Urea, obtaining Fe under hydrothermal condition
2O
3The composite of the particles and the nitrogen-doped graphene is washed for multiple times by deionized water, then is frozen and dried, and then is calcined under the high-temperature inert atmosphere, and Fe is utilized
2O
3And etching graphene for pore forming, finally removing an etching reagent by acid washing, washing with deionized water, and freeze-drying to obtain the nitrogen-doped porous graphene.
Patent 1, which is a kind of preparation method of nitrogen-doped porous graphene [ P ], application No. 201711333966.7, of Ningbo, Wumingchang, etc., discloses a preparation method of nitrogen-doped porous graphene, which comprises the steps of adding a surfactant, an aniline monomer and an acidic solution for initiating polymerization into a graphene oxide solution in sequence, and obtaining a mixture of polyaniline and graphene oxide after full reaction. Adding a mixture of polyaniline and graphene oxide into metal salt for hydrothermal treatment, drying the product, calcining, and forming holes by using polyaniline to provide a nitrogen source and the metal salt to obtain the porous nitrogen-doped graphene material.
The nitrogen-doped porous graphene obtained by the two methods needs to be added with various reagents such as a surfactant, a doped nitrogen source, a pore-forming metal salt and the like, and relates to multi-step operation and complex post-treatment, and the obtained nitrogen-doped porous graphene is easy to be attached with impurities such as metal oxides and the like, and needs to be further subjected to acid treatment to remove the pore-forming agent.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a preparation method of nitrogen and sulfur co-doped porous graphene by a supramolecular template method, which avoids the problems of additional addition of a doping source and a pore-forming agent, reduction of post-treatment and the like.
Technical scheme
A preparation method for preparing nitrogen and sulfur co-doped porous graphene by a supramolecular template method is characterized by comprising the following steps:
step 1: preparing a graphene oxide aqueous solution with the mass concentration of 1-5 mg/mL, performing ultrasonic dispersion, and adding nitrogen-nitrogen dimethylformamide to obtain a dispersion liquid; the volume ratio of the water to the nitrogen-nitrogen dimethyl formamide is 1: 0.5-1: 2;
step 2: sequentially adding melamine and trithiocyanuric acid into the dispersion liquid under the stirring condition of 50-80 ℃, and reacting for 1-10 h; the molar weight ratio of the melamine to the trithiocyanuric acid is 1: 1;
and step 3: washing with deionized water for multiple times, and drying in a drying oven to obtain a compound of graphene oxide and melamine cyanurate;
and 4, step 4: carrying out heat treatment on the compound in a tubular furnace under the inert atmosphere condition to obtain nitrogen and sulfur co-doped porous graphene; the heat treatment parameters in the tube furnace are as follows: the temperature rise speed of the tubular furnace is 2-5 ℃/min, the heat treatment temperature is 450-900 ℃, and the heat treatment time is 1-2 h.
And 3, drying the oven at 50-100 ℃.
And the drying time in the step 3 is 2-6 h.
Advantageous effects
The invention provides a preparation method of nitrogen and sulfur co-doped porous graphene by a supramolecular template method, which is used for co-doping nitrogen and sulfur atoms of graphene and introducing a porous structure at the same time. Firstly, adding melamine and trithiocyanuric acid into a dispersion liquid of graphene oxide under low-temperature stirring, generating melamine trithiocyanate by utilizing a supermolecule hydrogen bond effect between the melamine and the trithiocyanuric acid, and adsorbing the melamine trithiocyanuric acid on a graphene oxide lamellar layer. The composite material is calcined in an inert atmosphere, and a large amount of gas containing nitrogen and sulfur is generated when the supramolecular compound is cracked, so that the supramolecular compound can be used as a nitrogen and sulfur source to realize doping of graphene; on the other hand, the graphene sheet layer can be expanded by the internal stress generated by gas release, so that the porous graphene is obtained. In addition, due to the cracking of the supermolecular template, the calcined product is the nitrogen-sulfur doped porous graphene, and no post-treatment is needed.
The invention has the beneficial effects that: because a large amount of gas containing nitrogen and sulfur sources can be released instantly when the supramolecular compound melamine tristhiocyanate is decomposed, larger internal stress is generated, and graphene sheet layers expand to form a porous structure; meanwhile, the nitrogen and sulfur source gas can form in-situ doping at the active site of the deoxidized graphene oxide to obtain the nitrogen and sulfur co-doped porous graphene. The preparation method has the characteristics of low cost, easy large-scale synthesis, simple and convenient operation process and the like.
Drawings
FIG. 1 is an SEM image of nitrogen and sulfur co-doped porous graphene prepared in example 1 of the invention
FIG. 2 is a partial enlarged view of FIG. 1
FIG. 3 is a pore size distribution diagram of nitrogen and sulfur co-doped porous graphene prepared in example 1 of the present invention
FIG. 4 is an X-ray photoelectron spectrum of nitrogen and sulfur co-doped porous graphene prepared in example 1 of the present invention
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
Step one, preparing 150mL of graphene oxide aqueous solution with the concentration of 2mg/mL, performing ultrasonic dispersion for 30min, and adding 100mL of nitrogen-nitrogen dimethylformamide.
And step two, adding 420mg of melamine and 570mg of trithiocyanuric acid into the graphene oxide dispersion liquid under the condition of stirring at 80 ℃, and reacting for 5 hours.
And step three, carrying out hot filtration on the reaction product, washing for many times, and drying in a constant-temperature oven at 90 ℃ for 12 hours to obtain the graphene oxide and melamine cyanurate compound.
And step four, placing the compound in a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and continuously heating for 2 hours to prepare the nitrogen-sulfur co-doped porous graphene.
Fig. 1 is an SEM image of the nitrogen and sulfur co-doped porous graphene prepared in this example, and fig. 2 is an enlarged view of fig. 1, from which it can be seen that the material contains a porous structure.
Fig. 3 is a pore size distribution diagram of the nitrogen and sulfur co-doped porous graphene prepared in this embodiment, and it can be seen that the graphene contains a macroporous, mesoporous, and microporous structure.
Fig. 4 is an X-ray photoelectron spectrum of the nitrogen-sulfur co-doped porous graphene prepared in this embodiment, and it can be seen from the graph that carbon, nitrogen and sulfur elements exist in the material, which indicates that nitrogen-sulfur atom co-doping is successfully introduced in the present invention.
Example 2
Step one, preparing 150mL of graphene oxide aqueous solution with the concentration of 2mg/mL, performing ultrasonic dispersion for 30min, and adding 100mL of nitrogen-nitrogen dimethylformamide.
And step two, adding 420mg of melamine and 570mg of trithiocyanuric acid into the graphene oxide dispersion liquid under the condition of stirring at 60 ℃, and reacting for 10 hours.
And step three, carrying out hot filtration on the reaction product, washing for many times, and drying in a constant-temperature oven at 90 ℃ for 12 hours to obtain the graphene oxide and melamine cyanurate compound.
And step four, placing the compound in a tubular furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and continuously heating for 2 hours to prepare the nitrogen-sulfur co-doped porous graphene.
Example 3
Step one, preparing 100mL of graphene oxide aqueous solution with the concentration of 2mg/mL, performing ultrasonic dispersion for 30min, and adding 100mL of nitrogen-nitrogen dimethylformamide.
And step two, adding 250mg of melamine and 350mg of trithiocyanuric acid into the graphene oxide dispersion liquid under the condition of stirring at 80 ℃ in sequence, and reacting for 2 hours.
And step three, carrying out hot filtration on the reaction product, washing for many times, and drying in a constant-temperature oven at 90 ℃ for 12 hours to obtain the graphene oxide and melamine cyanurate compound.
And step four, placing the compound in a tubular furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and continuously heating for 1 hour to prepare the nitrogen-sulfur co-doped porous graphene.
Claims (3)
1. A preparation method for preparing nitrogen and sulfur co-doped porous graphene by a supramolecular template method is characterized by comprising the following steps:
step 1: preparing a graphene oxide aqueous solution with the mass concentration of 1-5 mg/mL, performing ultrasonic dispersion, and adding nitrogen-nitrogen dimethylformamide to obtain a dispersion liquid; the volume ratio of the water to the nitrogen-nitrogen dimethyl formamide is 1: 0.5-1: 2;
step 2: sequentially adding melamine and trithiocyanuric acid into the dispersion liquid under the stirring condition of 50-80 ℃, and reacting for 1-10 h; the molar weight ratio of the melamine to the trithiocyanuric acid is 1: 1;
and step 3: washing with deionized water for multiple times, and drying in a drying oven to obtain a compound of graphene oxide and melamine cyanurate;
and 4, step 4: carrying out heat treatment on the compound in a tubular furnace under the inert atmosphere condition to obtain nitrogen and sulfur co-doped porous graphene; the heat treatment parameters in the tube furnace are as follows: the temperature rise speed of the tubular furnace is 2-5 ℃/min, the heat treatment temperature is 450-900 ℃, and the heat treatment time is 1-2 h.
2. The preparation method of nitrogen and sulfur co-doped porous graphene by the supramolecular template method according to claim 1, which is characterized in that: and 3, drying the oven at 50-100 ℃.
3. The preparation method of nitrogen and sulfur co-doped porous graphene by the supramolecular template method according to claim 1, which is characterized in that: and the drying time in the step 3 is 2-6 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938969A (en) * | 2021-03-23 | 2021-06-11 | 复旦大学 | Method for preparing nitrogen-sulfur co-doped activated carbon by pore-forming/doping integrated activating agent and application of method |
| CN114783783A (en) * | 2022-05-17 | 2022-07-22 | 晋江瑞碧科技有限公司 | Preparation method of nitrogen and sulfur co-doped graphene-based composite porous aerogel |
| CN115520856A (en) * | 2022-08-19 | 2022-12-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material with elemental iodine and sulfur particles anchored in nitrogen-doped graphene axial plane |
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| CN109019565A (en) * | 2018-06-15 | 2018-12-18 | 陕西科技大学 | A kind of preparation method of three-dimensional porous nitrogen sulfur doping carbon nanosheet |
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| US20180212248A1 (en) * | 2016-06-08 | 2018-07-26 | Lg Chem, Ltd. | Self-assembled composite of carbon nitride and graphene oxide, manufacturing method for same, positive electrode having same applied thereto, and lithium-sulfur battery comprising same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938969A (en) * | 2021-03-23 | 2021-06-11 | 复旦大学 | Method for preparing nitrogen-sulfur co-doped activated carbon by pore-forming/doping integrated activating agent and application of method |
| CN114783783A (en) * | 2022-05-17 | 2022-07-22 | 晋江瑞碧科技有限公司 | Preparation method of nitrogen and sulfur co-doped graphene-based composite porous aerogel |
| CN114783783B (en) * | 2022-05-17 | 2023-08-18 | 武夷学院 | Preparation method of nitrogen-sulfur co-doped graphene-based composite porous aerogel |
| CN115520856A (en) * | 2022-08-19 | 2022-12-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material with elemental iodine and sulfur particles anchored in nitrogen-doped graphene axial plane |
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Application publication date: 20200211 |