CN108889326B - Preparation method of three-dimensional network frame of molybdenum disulfide and graphite phase carbon nitride - Google Patents

Preparation method of three-dimensional network frame of molybdenum disulfide and graphite phase carbon nitride Download PDF

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CN108889326B
CN108889326B CN201810738052.7A CN201810738052A CN108889326B CN 108889326 B CN108889326 B CN 108889326B CN 201810738052 A CN201810738052 A CN 201810738052A CN 108889326 B CN108889326 B CN 108889326B
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molybdenum disulfide
steps
carbon nitride
phase carbon
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CN108889326A (en
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仪德启
秦培凡
郝建薇
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Beijing Institute of Technology BIT
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
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Abstract

The invention discloses a preparation method of a three-dimensional network frame of molybdenum disulfide and graphite-phase carbon nitride, belonging to the field of preparation of porous materials. Molybdenum disulfide, cyanuric acid and melamine are added into a reaction kettle which takes water as solvent, stirred and dried at a fixed temperature to obtain a precursor. And placing the precursor in a furnace body with the function of introducing gas, controlling the gas flow rate and the heating rate, and calcining to obtain the molybdenum disulfide and graphite phase carbon nitride layer-by-layer composite three-dimensional network frame material. The invention has the advantages that: the method is characterized in that melamine and cyanuric acid are self-assembled in a solution to form melamine cyanurate, the melamine cyanurate is intercalated between layers of molybdenum disulfide and then used as a carbon source and a nitrogen source of graphite-phase carbon nitride, the carbon source and the nitrogen source are calcined in inert gas to generate a thermal polycondensation reaction, the molybdenum disulfide-graphite-phase carbon nitride layer-by-layer composite material is prepared, the aperture of a three-dimensional network frame is controlled by a method capable of changing the mass ratio of raw materials, and the process is simple.

Description

Preparation method of three-dimensional network frame of molybdenum disulfide and graphite phase carbon nitride
Technical Field
The invention relates to a preparation method of a three-dimensional network frame of molybdenum disulfide and graphite-phase carbon nitride, belongs to the field of preparation of porous materials, and can be used in the field of photocatalysis and the field of lithium ion battery cathode materials.
Background
Molybdenum disulfide (molybdenum disulfide), abbreviated MoS2Transition metal disulfides are typical two-dimensional sheet materials. Single-layer MoS2Is a sandwich structure of two layers of sulfur atoms and one layer of molybdenum atoms, the layers are combined together by Van der Waals force, and the distance between each layer is about 0.65 nm. Molybdenum disulfide possesses an energy band gap of 1.8eV, has great development potential in a nano transistor, and can be used as a linear photoconductor and a semiconductor for displaying P-type or N-type conductivity. Graphite-phase carbon nitride (graphic carbon nitride), abbreviated as g-C3N4It is the most stable carbon nitride allotrope and a very promising non-metal catalyst. Has been widely applied to the fields of hydrogen production by photolysis, photocatalysis, and the like. Has received much attention because of its excellent properties.
At present, graphite-phase carbon nitride (adv.Funct.Mater.2013,23(29): 3661-3667.) can be effectively prepared by adopting the thermal polycondensation reaction of the melamine cyanurate supramolecular assembly under the high-temperature condition, and the lamellar structure of the graphite-phase carbon nitride can induce stronger light absorption, and the energy band gap can be effectively increased by 0.16 eV. The three-dimensional reticular framework structure has high specific surface area and rich pore channels, can expose more active point sites, and further improves the performance of application in catalytic reaction and the like and the mass transfer diffusion of reactants and products in multiphase reaction. Molybdenum disulfide is sufficiently contacted with graphite phase carbon nitride to form heterojunction, and because of the difference between conduction band and valence band, electrons or holes generated by graphite phase carbon nitride due to photoexcitation can be transferred into conduction band or valence band of the compound, so that electron-hole separation and recombination rate are reduced, and thus active particles generated by photoexcitation can be more effectively utilized, and the catalytic efficiency is improved (Chemical Reviews,2016,116(12): 7159-7329.). In the application aspect of the lithium ion battery cathode material, the graphite-phase carbon nitride can block the movement of the molybdenum disulfide sheet layer to prevent the molybdenum disulfide sheet layer from agglomerating, and relieve the mechanical stress caused by the volume change of the molybdenum disulfide sheet layer. The three-dimensional network frame can accelerate the diffusion of lithium ions, so that the lithium ions can be fully contacted with molybdenum disulfide, and the rapid charge and discharge of the material are facilitated (adv. Mater.2014,26, 964-969).
At present, the patents for preparing a network structure by molybdenum disulfide modification include: a three-dimensional porous network composite material of molybdenum disulfide and carbon and a preparation method (publication number: CN 104966817A, 2015, 10 months and 7 days, Tianjin university) are adopted, sodium chloride is used as a dispersing agent and a template, ammonium molybdate and sodium molybdate are adopted, thiourea is dissolved in ionized water and freeze-dried, and a mixture is calcined in a tubular furnace and washed with water to remove the sodium chloride, so that a product is obtained. The three-dimensional porous graphene-loaded molybdenum disulfide composite material and the preparation method (publication number: CN104966812A, 10 months and 7 days in 2015, Tianjin university) adopt sodium chloride as a dispersing agent and a template, fully dissolve and mix the sodium chloride with a molybdenum source, a sulfur source and an organic carbon source, freeze-dry and grind to obtain a mixture; and putting the mixture into a tubular furnace, and calcining under the protection of argon to obtain a calcined product, thereby obtaining the three-dimensional porous graphene-like molybdenum disulfide-loaded composite material.
Patents for the preparation of graphite phase carbon nitride include: a method for preparing graphite phase carbon nitride material (publication number: CN106540733A, 3 and 29 days in 2017, and university of Tai Yuan chemical) uses dicyandiamide and nano-silica as precursors, and prepares graphite-like carbon nitride with high specific surface area by microwave roasting and muffle furnace roasting. A process for synthesizing porous graphite-phase carbon nitride includes such steps as preparing the microemulsion of polystyrene or polymethyl methacrylate as hard template, preparing cyanamide, dicyandiamide or guanidine hydrochloride as precursor, direct mixing, drying and calcining in inert gas atmosphere.
Disclosure of Invention
The invention aims to provide a preparation method of a three-dimensional network frame of molybdenum disulfide and graphite phase carbon nitride. The composite material can be used as a porous material in the fields of photocatalysis and lithium ion battery cathode materials. Has wide application prospect, simple preparation method process and large-scale production.
The three-dimensional network frame is a three-dimensional network frame structure which is built by compounding flaky molybdenum disulfide nanosheets and graphite phase carbon nitride layers, the network aperture is 10-200nm, the total mass of the compound is 100%, the mass percentage of molybdenum disulfide is 50-95%, and the mass percentage of graphite phase carbon nitride is 5-50%.
The preparation method of the three-dimensional network frame of the molybdenum disulfide and graphite phase carbon nitride layer-by-layer composite material with the structure is characterized by comprising the following steps:
(1) adding molybdenum disulfide, melamine and cyanuric acid into a reaction kettle using water as a solvent, stirring for 4 hours at a fixed temperature, removing the solvent and drying to obtain a precursor. The molybdenum disulfide comprises n-butyllithium modified molybdenum disulfide, the precursor only comprises molybdenum disulfide and melamine cyanurate, and the mass ratio of the melamine cyanurate is 0.05-20 calculated by taking the mass of the molybdenum disulfide as 1. The melamine cyanurate is obtained by hydrogen bond self-assembly of equal mass of melamine and cyanuric acid in aqueous solution. The fixed temperature range of the reaction is between room temperature and 100 ℃, and the optimal temperature is 80 ℃.
(2) Will be described in detail(1) The prepared precursor is placed in a tubular furnace, a muffle furnace or other heatable furnace bodies with the function of gas introduction, protective gas is introduced into the furnace bodies at a certain gas flow rate, and the temperature is raised. And keeping the fixed gas flow and the heating rate, heating to a fixed temperature, keeping the temperature, and calcining for 30-200 minutes to obtain the three-dimensional network frame of the molybdenum disulfide and graphite phase carbon nitride layer-by-layer composite material. The protective gas is nitrogen (N)2) Argon (Ar) or helium (He). The gas flow is 100-400 ml/min, wherein the optimal gas flow is 200 ml/min. The heating rate is 1-50 ℃/min, and the optimal heating rate value is 10-30 ℃/min. The fixed temperature is 300-700 ℃.
The invention has the advantages and positive effects that: by adopting the technical scheme, the melamine and the cyanuric acid are self-assembled in hydrogen bonds between the molybdenum disulfide layers to form the melamine cyanurate, so that the effect of intercalation between the molybdenum disulfide layers is achieved. And then the melamine cyanurate is thermally condensed into graphite-phase carbon nitride under the protection of inert gas and heating at controlled temperature. The aperture size of the three-dimensional network frame is controlled by controlling the mass ratio of the molybdenum disulfide to the melamine cyanurate. The method has the advantages of low cost, simple reaction process and strong controllability.
Drawings
FIG. 1 is a scanning electron micrograph of a three-dimensional network framework of a layer-by-layer composite of molybdenum disulfide and graphite-phase carbon nitride obtained in example 3 of the present invention. The three-dimensional network framework structure of the material is evident from the figure.
Detailed Description
The invention is further illustrated by the following examples, which do not limit the scope of the invention. (all the raw materials are commercially available analytical pure)
Example 1
Weighing 0.517 g of molybdenum disulfide, 0.602 g of melamine and 0.602 g of cyanuric acid, adding the materials into a reaction kettle containing 1000ml of deionized water, heating to 95 ℃, stirring for 3h, filtering to obtain a precursor product, and drying in vacuum for 4h at 80 ℃. And (3) placing the precursor in a tube furnace, introducing argon gas with the gas flow rate of 500ml/min, heating to 550 ℃ at the heating rate of 2.3 ℃/min, and preserving heat for 1 h. And after the reaction is finished, cooling to room temperature under the protection of argon atmosphere to obtain a three-dimensional network frame of the molybdenum disulfide and graphite phase carbon nitride layer-by-layer composite material, and measuring the aperture of a product prepared by the formula to be 98 nm.
Example 2
Weighing 0.511 g of n-butyllithium modified molybdenum disulfide, 1.011 g of melamine and 1.089 g of cyanuric acid, adding the materials into a reaction kettle containing 1000ml of deionized water, heating to 80 ℃, stirring for 4 hours, and filtering to obtain a precursor product. And (3) placing the precursor in a tube furnace, introducing nitrogen gas with the gas flow rate of 300ml/min, heating to 650 ℃ at the heating rate of 10 ℃/min, and preserving heat for 1 h. And after the reaction is finished, cooling to room temperature under the protection of nitrogen atmosphere to obtain a three-dimensional network frame of the molybdenum disulfide and graphite phase carbon nitride layer-by-layer composite material, and measuring the aperture of a product prepared by the formula to be 10 nm.
Example 3
Weighing 0.501 g of n-butyllithium modified molybdenum disulfide, 0.595 g of melamine and 0.612 g of cyanuric acid, adding the weighed materials into a reaction kettle containing 1000ml of deionized water, heating to 70 ℃, stirring for 4 hours, and filtering to obtain a precursor product. Placing the precursor in a tube furnace, introducing helium gas with the gas flow rate of 100ml/min, heating to 650 ℃ at the heating rate of 50 ℃/min, and preserving heat for 1 h. And after the reaction is finished, cooling to room temperature under the protection of helium atmosphere to obtain a three-dimensional network frame of the molybdenum disulfide and graphite phase carbon nitride layer-by-layer composite material, and measuring the aperture of a product prepared by the formula to be 27 nm.

Claims (11)

1. A preparation method of a three-dimensional network frame of molybdenum disulfide and graphite phase carbon nitride comprises the following steps: (1) adding molybdenum disulfide, melamine and cyanuric acid into a reaction kettle using water as a solvent, stirring for 4 hours at a fixed temperature, removing the solvent and drying to obtain a precursor; (2) placing the precursor prepared in the step (1) in a tubular furnace, a muffle furnace or other heatable furnace bodies with the function of introducing gas, introducing protective gas into the furnace bodies at a certain gas flow rate, and starting to heat; keeping the fixed gas flow and the heating rate, heating to a fixed temperature, keeping the temperature and calcining for a period of time to obtain the three-dimensional network frame of the molybdenum disulfide and graphite phase carbon nitride layer-by-layer composite material.
2. The method of claim 1, wherein the method comprises the steps of: the molybdenum disulfide used as the raw material is unmodified molybdenum disulfide or n-butyl lithium modified molybdenum disulfide.
3. The method of claim 1, wherein the method comprises the steps of: the precursor comprises molybdenum disulfide and melamine cyanurate, the mass ratio of the melamine cyanurate is 0.05-20 calculated by taking the mass of the molybdenum disulfide as 1, wherein the melamine cyanurate is obtained by self-assembling equal mass of melamine and cyanuric acid in hydrogen bonds in an aqueous solution.
4. The method of claim 1, wherein the method comprises the steps of: the fixed temperature range in the reaction process is room temperature-100 ℃.
5. The method of claim 1, wherein the method comprises the steps of: the solvent removing process comprises natural drying, suction filtration or vacuum rotary evaporation.
6. The method of claim 1, wherein the method comprises the steps of: and (3) placing the precursor in the step (1) in a furnace body of a tubular furnace, a muffle furnace or other furnace bodies with controllable heating rate and gas introduction functions.
7. The method of claim 1, wherein the method comprises the steps of: the protective gas introduced into the furnace body is nitrogen (N)2) Argon (Ar) orHelium (He).
8. The method of claim 1, wherein the method comprises the steps of: the gas flow rate of introducing the protective gas into the furnace body is 100-400 ml/min.
9. The method of claim 1, wherein the method comprises the steps of: the heating rate is 1-50 ℃/min in the heating process.
10. The method of claim 1, wherein the method comprises the steps of: the furnace body is heated to a fixed temperature, and the fixed temperature range is 300-700 ℃.
11. The method of claim 1, wherein the method comprises the steps of: the calcination time at a fixed temperature is 30-200 min.
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CN110075901B (en) * 2019-05-14 2021-10-19 东南大学 Preparation of porous sulfur-doped graphite phase carbon nitride-reduced graphene oxide nanosheet
CN111111700B (en) * 2020-01-22 2022-01-14 复旦大学 Few-layer molybdenum disulfide/nitrogen-doped porous carbon composite catalyst and preparation method thereof
CN114156093B (en) * 2021-12-09 2023-06-20 桂林理工大学 N/O co-doped molybdenum sulfide@porous carbon composite electrode material and preparation method and application thereof

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