CN113072070A - Preparation method of high-specific-surface-area carbon-coated transition metal carbide material - Google Patents

Preparation method of high-specific-surface-area carbon-coated transition metal carbide material Download PDF

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CN113072070A
CN113072070A CN202110326256.1A CN202110326256A CN113072070A CN 113072070 A CN113072070 A CN 113072070A CN 202110326256 A CN202110326256 A CN 202110326256A CN 113072070 A CN113072070 A CN 113072070A
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刘晓晖
王佳熠
王艳芹
郭勇
卫钶予
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East China University of Science and Technology
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Abstract

The invention provides a preparation method of carbon-coated transition metal carbide, which comprises the following steps: sugar or aldehyde and phenol are used as carbon sources, water-soluble metal salt is used as a metal precursor, and carbothermic reduction is carried out in an inert atmosphere after hydrothermal crystallization. The transition metal carbide prepared by the method has high specific surface area, low energy consumption in the preparation process and environmental friendliness, and is suitable for industrial production.

Description

Preparation method of high-specific-surface-area carbon-coated transition metal carbide material
Technical Field
The invention relates to a preparation method of high specific surface carbon-coated transition metal carbide M (Nb, Mo, W) @ C, and relates to synthesis of a novel material.
Background
Transition Metal Carbides (TMC) are a series of gap compounds with metal-like properties formed by metal elements and carbon elements, and because a covalent bond network is usually present in the structure of the gap compounds, the covalent bond function of the material is strong, so the TMC has high hardness, mechanical strength and good catalytic activity (hydrogenolysis reaction, reverse water gas reaction, electrocatalytic reaction, and the like).
Generally, the metal carbide is prepared by mixing metal oxide and carbon at 1800-20%00 oCIs carburized at high temperature in inert gas to obtain the product. However, the preparation process has high energy consumption, and the high synthesis temperature easily causes the agglomeration of the obtained metal carbide particles and has low specific surface area. The CN111203249A patent discloses a method for preparing graphene-coated transition metal carbide nanocapsules and application thereof in the field of microwave catalysis, wherein a transition metal block is placed on a direct current arc hydrogen plasma device, and hydrogen, inert gas and carbon-containing element gas are introduced to ensure that the total pressure of a cavity reaches 0.005-9.5 x 104 Pa, switching on a power supply to form a stable electric arc, evaporating the transition metal block to obtain the graphene-coated transition metal carbide nanocapsule. The CN101371988A patent discloses a method for preparing a transition metal carbide catalytic material and application thereof, the method takes a carbon material, an oxide or a molecular sieve and the like as a carrier, takes a transition metal compound as a precursor, and prepares a supported transition metal carbide catalyst by dipping or mechanically mixing the carrier and the transition metal precursor and adopting a microwave-assisted chemical deposition method, the specific surface area of the material is 69 m2(ii) in terms of/g. The CN 109201002A patent discloses a carbon-coated transition metal carbide composite material, a preparation method and an adsorption application thereof, wherein the composite material is TiAl C2Glucose, cellulose or wood dust as raw materials, alkaline solution as solvent, at 120- oCAnd the compound is prepared by a hydrothermal/solvothermal method in one step under the condition of 24-96 hours. In the system, alkaline solution NaOH is used as an etchant to etch TiAlC2Al in the carbon fiber is dissolved to finally form a rod-shaped and fibrous carbon-coated composite material (marked as C @ NaOTiC)x）。
Therefore, the problems of high energy consumption, complex process (needing alkali liquor for etching), small specific surface area and the like exist in the synthesis of the current transition metal carbide material. Aiming at the defects of the prior art, a proper organic matter is used as a carbon source, a water-soluble metal salt is used as a precursor, the two are mixed for hydrothermal treatment, and a hydrothermal product is subjected to a carbothermic reduction reaction to obtain a carbon-coated transition metal carbide. Compared with the reported metal carbide synthesis method, the method has the advantages of simple operation and low energy consumption, and can prepare the transition metal carbide material with high specific surface area.
Disclosure of Invention
Based on the purpose, the invention provides a preparation method of a high specific surface carbon-coated transition metal carbide M (Nb, Mo, W) @ C material with low energy consumption. The material is prepared by adopting water-soluble metal salt as a precursor, sugar or aldehyde and phenol as a carbon source, performing hydrothermal crystallization, and performing carbothermic reduction reaction in an inert atmosphere. The synthesis process of the transition metal carbide material has the advantages of simple operation, low energy consumption and high specific surface area of the metal carbide material.
The invention comprises a method for synthesizing a transition metal carbide catalyst, which is characterized in that under a relatively mild condition, sugar or aldehyde and a phenol organic polymer are used as a carbon source, the carbon source interacts with a metal precursor, and in a carbothermic process, a metal oxide formed by the metal precursor is reduced and reacts with carbon in the carbon source to finally synthesize a carbon-coated transition metal carbide M (Nb, Mo, W) @ C material with high specific surface area, wherein a method for synthesizing the metal carbide material is not reported.
The invention has the advantages that:
(1) the raw materials are easy to obtain. Organic matters such as saccharides and phenols prepared from renewable woody biomass are used as carbon sources, so that the carbon sources are green, cheap and renewable;
(2) a hydrothermal method is adopted, the preparation process is simple, strong acid and strong base reagents are not used in the process, and the environment is protected;
(3) the energy consumption is low. Most of the transition metal carbide is synthesized by high-temperature roasting at 1500-2000 ℃, the roasting temperature range of the invention is 800-1200 ℃, and the energy consumption is reduced.
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, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of carbon-coated niobium carbide nanoparticles NbC @ C-1 of example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of NbC @ C-11 prepared by carbonization at 800 ℃ in example 11 of the present invention.
FIG. 3 shows carbon-coated molybdenum carbide nanoparticles Mo of example 12 of the present invention2X-ray diffraction pattern of C @ C-1.
FIG. 4 is an X-ray diffraction pattern of carbon-coated tungsten carbide nanoparticles WC @ C-1 of example 15 of the present invention.
FIG. 5 is a scanning electron micrograph of NbC @ C-1 material in example 1 of the present invention.
FIG. 6 is a transmission electron micrograph of NbC @ C-1 material in example 1 of the present invention.
FIG. 7 is a transmission electron micrograph of the MoC @ C-1 material of example 12 of the present invention.
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 with reference to specific embodiments and the accompanying drawings.
A typical preparation method for the above material is as follows:
(1) the metal salt precursor was weighed and mixed with aldehyde/saccharide and phenolic organic, 100 mL of deionized water was added. The mass ratio of the metal precursor to the organic matter is 0.05-0.5;
(2) stirring the mixture solution in a water bath at 50 ℃ for 0.5 hour;
(3) transferring the suspension obtained by the treatment in the step (2) into a polytetrafluoroethylene hydrothermal kettle, and reacting for 12 to 72 hours at the temperature of 140-;
(4) recovering solid precipitate by suction filtration, and drying at 60 deg.C for 24 hr;
(5) grinding the solid product obtained in the step (4), and performing carbothermal reduction reaction at 800-1200 ℃ for 0.5-12 hours in an inert atmosphere.
Example 1
0.4 g of niobium (V) oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-1. Characterization measurements are made on the material to determine its characteristics. The obtained X-ray powder diffraction pattern is shown in figure 1, and the niobium carbide is identified by X-ray powder diffraction. FIG. 5 shows a scanning electron micrograph. FIG. 6 shows a transmission electron micrograph.
Example 2
0.4 g of niobium pentachloride powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-2. The product is identified as niobium carbide by X-ray powder diffraction.
Example 3
0.4 g of ammonium niobium oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 12 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-3. The product is identified as niobium carbide by X-ray powder diffraction.
Example 4
0.4 g of niobium (V) oxalate powder, 2 g of formaldehyde and 2 g of phenol were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-4. The product is identified as niobium carbide by X-ray powder diffraction.
Example 5
0.4 g of niobium (V) oxalate powder, 2 g of xylose and 2 g of hydroquinone were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 78 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-5. The product is identified as niobium carbide by X-ray powder diffraction.
Example 6
0.2 g of niobium (V) oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-6. The product is identified as niobium carbide by X-ray powder diffraction.
Example 7
2 g of niobium (V) oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-7. The product is identified as niobium carbide by X-ray powder diffraction.
Example 8
0.4 g of niobium (V) oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 140 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-8. The product is identified as niobium carbide by X-ray powder diffraction.
Example 9
0.4 g of niobium (V) oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 200 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. The sample was labeled NbC @ C-9. The product is identified as niobium carbide by X-ray powder diffraction.
Example 10
0.4 g of niobium (V) oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1200 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 4 hours. The sample was labeled NbC @ C-10. The product is identified as niobium carbide by X-ray powder diffraction.
Example 11
0.4 g of niobium (V) oxalate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. And recovering the solid precipitate in a centrifugal suction filtration mode, and continuously washing with deionized water. Finally, the product was dried in a forced air drying oven at 60 ℃ for 24 hours to obtain a niobium-organic polymer precursor. The niobium-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 800 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 12 hours. The sample was labeled NbC @ C-11. The niobium pentoxide is identified by X-ray powder diffraction.
Example 12
0.6 g of ammonium molybdate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. 4 g of glucose and 4 g of resorcinol powder were mixed with the above solution and hydrothermal stirring was continued for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and crystallizing in stainless steelIn the kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. The solid precipitate is recovered by means of centrifugal filtration and the like, and is continuously washed with deionized water. And finally, drying the product in a 60 ℃ forced air drying oven for 24 hours to obtain the molybdenum-organic polymer precursor. The molybdenum-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 12 hours. Sample designation Mo2C @ C-1. Characterization measurements are made on the material to determine its characteristics. The obtained X-ray powder diffraction pattern is shown in FIG. 3, and Mo is identified by X-ray powder diffraction2C. FIG. 7 shows a transmission electron micrograph.
Example 13
0.6 g of molybdenum hexacarbonyl (Mo (CO))6) Powder, 2 g glucose and 2 g resorcinol powder were mixed with 100 mL deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. 4 g of glucose and 4 g of resorcinol powder were mixed with the above solution and hydrothermal stirring was continued for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. The solid precipitate is recovered by means of centrifugal filtration and the like, and is continuously washed with deionized water. And finally, drying the product in a 60 ℃ forced air drying oven for 24 hours to obtain the molybdenum-organic polymer precursor. The molybdenum-polymer precursor is crushed into powder, placed in a corundum porcelain boat, and roasted to 1000 ℃ in a tube furnace under the inert gas atmosphere. The calcination time was 6 hours. Sample designation Mo2C @ C-2. Identified as Mo by X-ray powder diffraction2C。
Example 14
0.6 g of ammonium paramolybdate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. 4 g of glucose and 4 g of resorcinol powder were mixed with the above solution and hydrothermal stirring was continued for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. The solid precipitate is recovered by means of centrifugal filtration and the like, and is continuously washed with deionized water. And finally, drying the product in a 60 ℃ forced air drying oven for 24 hours to obtain the molybdenum-organic polymer precursor. Pulverizing the molybdenum-polymer precursor into powder, and placing the powder in a corundum porcelain boatAnd roasting the mixture to 1000 ℃ in a tube furnace under an inert gas atmosphere. The calcination time was 6 hours. Sample designation Mo2C @ C-3. Identified as Mo by X-ray powder diffraction2C。
Example 15
0.6 g of ammonium metatungstate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. The solid precipitate is recovered by means of centrifugal filtration and the like, and is continuously washed with deionized water. And finally, drying the product in a 60 ℃ forced air drying oven for 24 hours to obtain the tungsten-organic polymer precursor. The precursor of tungsten-polymer is crushed into powder, put into a corundum porcelain boat and roasted to 1000 ℃ in a tube furnace under the atmosphere of inert gas. The calcination time was 12 hours. The sample was labeled WC @ C-1. Characterization measurements are made on the material to determine its characteristics. The obtained X-ray powder diffraction pattern is shown in FIG. 4, and is identified as WC/W by X-ray powder diffraction2C, mixing the phases.
Example 16
0.6 g of ammonium tungstate powder, 2 g of glucose and 2 g of resorcinol powder were mixed with 100 mL of deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.c for 24 hr. The solid precipitate is recovered by means of centrifugal filtration and the like, and is continuously washed with deionized water. And finally, drying the product in a 60 ℃ forced air drying oven for 24 hours to obtain the tungsten-organic polymer precursor. The precursor of tungsten-polymer is crushed into powder, put into a corundum porcelain boat and roasted to 1000 ℃ in a tube furnace under the atmosphere of inert gas. The calcination time was 12 hours. The sample was labeled WC @ C-2. Is identified as WC/W by X-ray powder diffraction2C, mixing the phases.
Example 17
0.6 g of tungsten hexacarbonyl (W (CO))6) Powder, 2 g glucose and 2 g resorcinol powder were mixed with 100 mL deionized water, and the mixture solution was stirred in a water bath at 50 ℃ for 1 hour. Transferring the mixed solution into a polytetrafluoroethylene lining, and placing the polytetrafluoroethylene lining into a stainless steel crystallization kettle. Hydrothermal crystallization at 160 deg.CTake 24 hours. The solid precipitate is recovered by means of centrifugal filtration and the like, and is continuously washed with deionized water. And finally, drying the product in a 60 ℃ forced air drying oven for 24 hours to obtain the tungsten-organic polymer precursor. The precursor of tungsten-polymer is crushed into powder, put into a corundum porcelain boat and roasted to 1000 ℃ in a tube furnace under the atmosphere of inert gas. The calcination time was 12 hours. The sample was labeled WC @ C-3. Is identified as WC/W by X-ray powder diffraction2C, mixing the phases.
Table 1 shows the BET results for NbC @ C-1, MoC @ C-1 and WC @ C-1 for examples 1, 12 and 15 of the present invention.
Table 1 specific surface area of NbC @ C material.
Figure 26913DEST_PATH_IMAGE001
It can be seen from table 1 that the specific surface area of the material NbC @ C-1 of embodiment 1 is about 513 m/g, the specific surface area of the material MoC @ C-1 of embodiment 12 is about 463 m/g, and the specific surface area of the material WC @ C-1 of embodiment 15 is about 525 m/g.
FIG. 1 is an X-ray diffraction pattern of the carbon-coated niobium carbide nanoparticles NbC @ C-1 of example 1, from which five sets of diffraction peaks ((111), (200), (220), (311), (222)) were observed, which confirmed that the main phase in the structure of the carbon-coated niobium carbide material was NbC.
FIG. 2 is an X-ray diffraction pattern of the material NbC @ C-11 obtained by carbothermic reduction at 800 ℃ in example 11, in which it was observed that the main crystal phase of the material was niobium pentoxide and no NbC phase was formed.
FIG. 3 is the carbon-coated molybdenum carbide nanoparticle Mo of example 122The X-ray diffraction pattern of C @ C-1 shows eight diffraction peaks ((100), (002), (101), (102), (110), (103), (112), (201)) and confirms that the main phase in the structure of the carbon-coated molybdenum carbide material is Mo2C。
FIG. 4 is an X-ray diffraction pattern of carbon-coated tungsten carbide nanoparticles WC @ C-1 of example 15, from which diffraction peaks ((001), (100), (101), (110), (002), (111), (200), (102)) observed therein were determined for carbon-coated tungsten carbideThe tungsten material structure contains a WC phase; the diffraction peaks ((100), (002), (101), (102), (110), (103), (200), (112), (201)) observed in the figure confirm that the carbon-coated tungsten carbide material contains W in the structure2And C phase.
FIG. 5 is a scanning electron micrograph of the NbC @ C-1 material of example 1, in which it can be seen that the surface of the material is relatively uniform and has a spherical structure.
FIG. 6 is a transmission electron microscope image of the NbC @ C-1 material of example 1, which shows that the niobium carbide nanoparticles are spherical and uniformly distributed on the surface of the material, the particle size is about 10-20 nm, and the outer surface of the material is coated with a carbon film.
FIG. 7 is a transmission electron micrograph of the MoC @ C-1 material of example 12, which shows that the molybdenum carbide nanoparticles are spherical and uniformly distributed on the surface of the material, the particle size is about 10-15 nm, and the surface of the material is coated with a carbon film.

Claims (9)

1. A method of making a carbon-coated transition metal carbide material, the method comprising: uniformly stirring the aqueous solution of the metal precursor and the organic matter to obtain a mixture solution, carrying out hydrothermal crystallization on the mixture solution to obtain a solid product, filtering, washing and drying the obtained solid product, and carrying out carbothermic reduction reaction on the solid product in an inert atmosphere to obtain the carbon-coated transition metal carbide material.
2. The method of claim 1, wherein the metal precursor is selected from the group consisting of: at least one of water-soluble niobate, molybdate and tungstate, preferably one of niobium oxalate or ammonium molybdate or ammonium metatungstate.
3. The method of claim 1, wherein the organic substance is a mixture of a sugar or an aldehyde and a phenol, wherein the sugar is one of glucose, xylose, maltose and sucrose, preferably glucose; the aldehyde can be one of formaldehyde, acetaldehyde and furfural, and is preferably formaldehyde; the phenol can be at least one of phenol, hydroquinone, resorcinol and catechol, and is preferably resorcinol.
4. The method according to claim 1, wherein the mass ratio of the metal salt precursor to the total weight of the organic material is between 0.05 and 0.5, preferably 0.1.
5. The method as claimed in claim 1, wherein the hydrothermal crystallization temperature is 140-oC, preferably 160, in a reactor oC。
6. The method according to claim 1, characterized in that the hydrothermal crystallization time is between 12 and 72 hours, preferably 24 hours.
7. The method of claim 1, wherein the inert gas is one or a mixture of two or more of nitrogen, helium, neon, or argon.
8. The method as claimed in claim 1, wherein the carbothermic reduction reaction is at 800- oCIs preferably carried out at 1000 deg.C oC。
9. The method according to claim 1, characterized in that the carbothermic reduction reaction time is between 1 and 12 hours, preferably 6 hours.
CN202110326256.1A 2021-03-26 2021-03-26 Preparation method of high-specific-surface-area carbon-coated transition metal carbide material Pending CN113072070A (en)

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