CN113716608A - Molybdenum dioxide-molybdenum carbide composite material and preparation method and application thereof - Google Patents

Molybdenum dioxide-molybdenum carbide composite material and preparation method and application thereof Download PDF

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CN113716608A
CN113716608A CN202110924329.7A CN202110924329A CN113716608A CN 113716608 A CN113716608 A CN 113716608A CN 202110924329 A CN202110924329 A CN 202110924329A CN 113716608 A CN113716608 A CN 113716608A
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molybdenum
composite material
carbide composite
molybdenum dioxide
dioxide
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CN113716608B (en
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欧阳柳章
陈沛荣
王辉
朱敏
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a molybdenum dioxide-molybdenum carbide composite material and a preparation method and application thereof. The composition of the molybdenum dioxide-molybdenum carbide composite material comprises MoO2And MoC, may further include Mo2C. The preparation method of the molybdenum dioxide-molybdenum carbide composite material comprises the following steps: mixing molybdenum dioxide, magnesium powder and carbonitride, carrying out solid-phase ball milling, acid washing and drying to obtain the molybdenum dioxide-molybdenum carbide composite material. The molybdenum dioxide-molybdenum carbide composite material has good catalytic activity when used as a catalyst for electrocatalytic hydrogen evolution reaction, and the preparation method is simple, low in energy consumption and low in cost, and is suitable for large-scale production and application.

Description

Molybdenum dioxide-molybdenum carbide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of heterostructure materials, in particular to a molybdenum dioxide-molybdenum carbide composite material and a preparation method and application thereof.
Background
The electrocatalytic hydrogen evolution is a method for preparing hydrogen by electrolyzing water, has the advantages of cleanness and no pollution, but has higher cost due to higher reaction energy barrier of the water electrolysis reaction. Therefore, the development of a water electrolysis catalyst with high efficiency and low cost has great significance for the hydrogen production industry.
Molybdenum-based materials (e.g., molybdenum carbide, molybdenum dioxide, molybdenum disulfide, etc.) have good catalytic effects when used as electrolytic water catalysts, and have received extensive attention from researchers in recent years. However, the existing molybdenum-based materials generally have the problems of complex preparation process, low yield, high energy consumption, environmental pollution in the preparation process and the like, and are difficult to truly realize large-scale industrial application, such as: CN 109499592A discloses a nanorod molybdenum carbide/molybdenum dioxide composite material, which is obtained by mixing an ammonium molybdate solution with a tannic acid solution and then carrying out high-temperature heat treatment at 800-900 ℃, wherein the nanorod molybdenum carbide/molybdenum dioxide composite material can be used in the field of catalysis, but the nanorod molybdenum carbide/molybdenum dioxide composite material needs to be subjected to high-temperature heat treatment in the preparation process, has high energy consumption, can also generate waste liquid, and needs to be subjected to harmless treatment subsequently; gao et al by treating Mo with oxygen plasma2C, in-situ generation of MoO on the surfacexTo obtain Mo2C/MoOxHeterostructure composite material shows excellent catalytic performance in electrocatalytic hydrolysis test, but is difficult to realize industrial application due to complex preparation process and low yield (Angew. chem. int. Ed.2020,59, 3544-.
Therefore, the development of an electrolytic water catalyst with good catalytic activity, simple preparation, low energy consumption and low cost is urgently needed.
Disclosure of Invention
The invention aims to provide a molybdenum dioxide-molybdenum carbide composite material, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the molybdenum dioxide-molybdenum carbide composite material comprises MoO2And MoC, may further include Mo2C。
The preparation method of the molybdenum dioxide-molybdenum carbide composite material comprises the following steps: mixing molybdenum dioxide, magnesium powder and carbonitride, carrying out solid-phase ball milling, acid washing and drying to obtain the molybdenum dioxide-molybdenum carbide composite material.
Preferably, the molar ratio of the molybdenum dioxide to the magnesium powder to the carbon nitride is 1: 6-9: 0.3-2.
Preferably, the carbonitride is at least one of melamine and carbon nitride.
Preferably, the solid phase ball milling is performed in a protective atmosphere.
Preferably, the protective atmosphere is an argon atmosphere.
Preferably, the solid phase ball milling is performed at room temperature (15 ℃ C. to 35 ℃ C.).
Preferably, the ball mill used for the solid-phase ball milling is a high-speed pendulum vibration type ball mill, the ball-material ratio is 10: 1-100: 1, the rotating speed of the ball mill is 1000-1230 rpm, and the ball milling time is 2-6 h.
Preferably, the ball mill used for the solid-phase ball milling is a planetary ball mill, the ball-material ratio is 20: 1-100: 1, the rotating speed of the ball mill is 400-500 rpm, and the ball milling time is 8-20 h.
Preferably, the solid phase ball milling is carried out intermittently, and the ball milling is suspended for 30min every 30 min.
Preferably, the acid used for acid washing is one of hydrochloric acid, sulfuric acid and phosphoric acid.
Preferably, the concentration of the hydrochloric acid is 1mol/L to 6 mol/L.
Preferably, the concentration of the sulfuric acid is 1mol/L to 6 mol/L.
Preferably, the mass fraction of the phosphoric acid is 15% to 25%.
The invention has the beneficial effects that: the composition of the molybdenum dioxide-molybdenum carbide composite material comprises MoO2And MoC, may further include Mo2And C, the catalyst used for the electrocatalytic hydrogen evolution reaction has good catalytic activity, and the preparation method is simple, low in energy consumption and cost and suitable for large-scale production and application.
Specifically, the method comprises the following steps:
1) the invention carries out in-situ reduction and carburization on the surface of molybdenum dioxide by a solid-phase ball milling modeObtaining the molybdenum dioxide-molybdenum carbide heterostructure material which grows in situ, and regulating and controlling the MoC phase and the Mo through the magnesium powder2The proportion of the C phase;
2) the molybdenum dioxide-molybdenum carbide composite material shows excellent catalytic activity under both acidic and alkaline conditions, and has good application prospect;
3) the molybdenum dioxide-molybdenum carbide composite material has the advantages of simple preparation process, short production period, strong controllability, no need of high-temperature heat treatment, no need of introducing an additional heat source in the whole process, low energy consumption, low cost and little pollution.
Drawings
Figure 1 is an XRD pattern of the molybdenum dioxide-molybdenum carbide composite of examples 1, 4 and 7.
Fig. 2 is an LSV plot of electrochemical hydrogen evolution for the molybdenum dioxide-molybdenum carbide composites of examples 1, 4, 7, 10 and 13 under alkaline conditions.
Fig. 3 is an LSV plot of electrochemical hydrogen evolution for the molybdenum dioxide-molybdenum carbide composites of examples 1, 4, 7, 10 and 13 under acidic conditions.
Fig. 4 is an SEM image of the molybdenum dioxide-molybdenum carbide composite material of example 4.
Figure 5 is an XRD pattern of the molybdenum dioxide-molybdenum carbide composite of examples 10 and 13.
Figure 6 is an XRD pattern of the molybdenum dioxide-molybdenum carbide composite of examples 16 and 17.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to a molar ratio of 1:6:0.3, filling the mixture into a ball milling tank, adding a ball milling medium according to a ball material ratio of 50:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1230 revolutions per minute, carrying out ball milling in an argon atmosphere for 2 hours, adding a ball milling product into a hydrochloric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box for the night to obtain the molybdenum dioxide-molybdenum carbide composite material.
And (3) performance testing:
1) the X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 1.
As can be seen from fig. 1: MoC and Mo can be observed2C and MoO2The characteristic peak of (1), that is, the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2And (4) forming.
2) The molybdenum dioxide-molybdenum carbide composite material of the present example was subjected to an alkaline condition (1mol/L KOH solution) and an acidic condition (0.5mol/L H)2SO4Solution) in the same manner as shown in fig. 2 and 3, the electrochemical hydrogen evolution LSV curve (the test was completed in a three-electrode system, the counter electrode was a graphite electrode, the reference electrode was a silver/silver chloride electrode, and the scanning speed was 5 mV/s).
As can be seen from fig. 2 and 3: the molybdenum dioxide-molybdenum carbide composite material of the present example exhibited excellent catalytic performance under both alkaline and acidic conditions.
Example 2:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:0.3, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 50:1, adding the ball milling tank into a high-energy pendulum vibration type ball mill, adjusting the rotating speed of the ball mill to 1100 r/min, carrying out ball milling in an argon atmosphere for 2h, adding a ball milling product into a sulfuric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and placing the solid in a drying box for drying overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition and the catalytic performance of the composite material are very close to those of the molybdenum dioxide-molybdenum carbide composite material in example 1.
Example 3:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:0.3, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 10:1, adding the ball milling tank into a high-energy pendulum vibration type ball mill, adjusting the rotating speed of the ball mill to 1000 r/min, carrying out ball milling in an argon atmosphere for 2h, adding a ball milling product into a phosphoric acid solution with the mass fraction of 25%, stirring, centrifuging, washing the centrifuged solid to be neutral, and placing the solid in a drying box for drying overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition and the catalytic performance of the composite material are very close to those of the molybdenum dioxide-molybdenum carbide composite material in example 1.
Example 4:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:1, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 50:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1230 revolutions per minute, carrying out ball milling for 6 hours in an argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
And (3) performance testing:
1) the X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 1.
As can be seen from fig. 1: MoC and Mo can be observed2C and MoO2Wherein MoC is the main phase, i.e. the molybdenum dioxide-molybdenum carbide composite material of the embodiment is composed of MoC and Mo2C and MoO2And (4) forming.
2) A Scanning Electron Microscope (SEM) image of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 4.
As can be seen from fig. 4: the final product after acid washing has no special appearance, the large-particle material is formed by agglomeration of the surfaces of nano particles, and a pore channel structure exists in the bulk phase.
3) The molybdenum dioxide-molybdenum carbide composite material of the present example was subjected to an alkaline condition (1mol/L KOH solution) and an acidic condition (0.5mol/L H)2SO4Solution) is shown in fig. 2 and 3 in sequence as shown in fig. 1.
As can be seen from fig. 2 and 3: the molybdenum dioxide-molybdenum carbide composite material of the present example exhibited excellent catalytic performance under both alkaline and acidic conditions.
Example 5:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:1, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 50:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1100 r/min, carrying out ball milling in an argon atmosphere for 2h, adding a ball milling product into a sulfuric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition and the catalytic performance of the composite material are very close to those of the molybdenum dioxide-molybdenum carbide composite material in example 4.
Example 6:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:1, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 10:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1000 r/min, carrying out ball milling in an argon atmosphere for 2h, adding a ball milling product into a phosphoric acid solution with the mass fraction of 20%, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition and the catalytic performance of the composite material are very close to those of the molybdenum dioxide-molybdenum carbide composite material in example 4.
Example 7:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to a molar ratio of 1:6:2, filling the mixture into a ball milling tank, adding a ball milling medium according to a ball material ratio of 50:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1230 r/min, carrying out ball milling in an argon atmosphere for 6h, adding a ball milling product into a hydrochloric acid solution with the concentration of 6mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
And (3) performance testing:
1) the X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 1.
As can be seen from fig. 1: MoC and MoO can be observed2The characteristic peak of (1), that is, the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and MoO2And (4) forming.
2) The molybdenum dioxide-molybdenum carbide composite material of the present example was subjected to an alkaline condition (1mol/L KOH solution) and an acidic condition (0.5mol/L H)2SO4Solution) is shown in fig. 2 and 3 in sequence as shown in fig. 1.
As can be seen from fig. 2 and 3: the molybdenum dioxide-molybdenum carbide composite material of the present example exhibited excellent catalytic performance under both alkaline and acidic conditions.
Example 8:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:2, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 50:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1100 r/min, carrying out ball milling in an argon atmosphere for 6h, adding a ball milling product into a sulfuric acid solution with the concentration of 6mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The molybdenum dioxide-molybdenum carbide composite material of the embodiment is tested to be composed of MoC and MoO2The composition of the composite material is very close to the catalytic performance of the molybdenum dioxide-molybdenum carbide composite material in example 7.
Example 9:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:2, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 10:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1000 r/min, carrying out ball milling in an argon atmosphere for 2h, adding a ball milling product into a phosphoric acid solution with the mass fraction of 25%, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The molybdenum dioxide-molybdenum carbide composite material of the embodiment is tested to be composed of MoC and MoO2The composition of the composite material is very close to the catalytic performance of the molybdenum dioxide-molybdenum carbide composite material in example 7.
Example 10:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:0.3, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
And (3) performance testing:
1) the X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 5.
As can be seen from fig. 5: MoC and Mo can be observed2C and MoO2Wherein MoC is the main phase, i.e. the molybdenum dioxide-molybdenum carbide composite material of the embodiment is composed of MoC and Mo2C and MoO2And (4) forming.
2) The molybdenum dioxide-molybdenum carbide composite material of the present example was subjected to an alkaline condition (1mol/L KOH solution) and an acidic condition (0.5mol/L H)2SO4Solution) is shown in fig. 2 and 3 in sequence as shown in fig. 1.
As can be seen from fig. 2 and 3: the molybdenum dioxide-molybdenum carbide composite material of the present example exhibited excellent catalytic performance under both alkaline and acidic conditions.
Example 11:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:0.3, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 50:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a sulfuric acid solution with the concentration of 1mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition has catalytic performance which is very close to that of the molybdenum dioxide-molybdenum carbide composite material in the example 10.
Example 12:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:0.3, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 20:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 8h in argon atmosphere, adding a ball milling product into a phosphoric acid solution with the mass fraction of 15%, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition has catalytic performance which is very close to that of the molybdenum dioxide-molybdenum carbide composite material in the example 10.
Example 13:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:1, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 500 r/min, carrying out ball milling for 15h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
And (3) performance testing:
1) the X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 5.
As can be seen from fig. 5: MoC and Mo can be observed2C and MoO2Wherein MoC is the main phase, i.e. the molybdenum dioxide-molybdenum carbide composite material of the embodiment is composed of MoC and Mo2C and MoO2And (4) forming.
2) The molybdenum dioxide-molybdenum carbide composite material of the present example was subjected to an alkaline condition (1mol/L KOH solution) and an acidic condition (0.5mol/L H)2SO4Solution) is shown in fig. 2 and 3 in sequence as shown in fig. 1.
As can be seen from fig. 2 and 3: the molybdenum dioxide-molybdenum carbide composite material of the present example exhibited excellent catalytic performance under both alkaline and acidic conditions.
Example 14:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:8:1, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 50:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 450 revolutions per minute, carrying out ball milling for 15 hours in argon atmosphere, adding a ball milling product into a sulfuric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition of the composite material is very close to the catalytic performance of the molybdenum dioxide-molybdenum carbide composite material in example 13.
Example 15:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:9:1, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 20:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 400 r/min, carrying out ball milling for 15h in argon atmosphere, adding a ball milling product into a phosphoric acid solution with the mass fraction of 20%, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition of the composite material is very close to the catalytic performance of the molybdenum dioxide-molybdenum carbide composite material in example 13.
Example 16:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and carbon nitride in the glove box according to a molar ratio of 1:6:1, filling the mixture into a ball milling tank, adding a ball milling medium according to a ball material ratio of 50:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1230 revolutions per minute, carrying out ball milling for 6 hours in an argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
Characterization and performance testing:
the X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 6.
As can be seen from fig. 6: MoC and Mo can be observed2C and MoO2The characteristic peak of (1), that is, the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2And (4) forming.
Example 17:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and carbon nitride in the glove box according to a molar ratio of 1:9:2, filling the mixture into a ball milling tank, adding a ball milling medium according to a ball material ratio of 50:1, adding the ball milling tank into a high-energy vibration type ball mill, adjusting the rotating speed of the ball mill to 1230 revolutions per minute, carrying out ball milling for 6 hours in an argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material.
The X-ray diffraction (XRD) pattern of the molybdenum dioxide-molybdenum carbide composite material of the present example is shown in fig. 6.
As can be seen from fig. 6: MoC and MoO can be observed2The characteristic peak of (1), that is, the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and MoO2The composition, the morphology structure and the catalytic performance of the composite material are very close to those of the molybdenum dioxide-molybdenum carbide composite material in the example 16.
Example 18:
a preparation method of a molybdenum dioxide-molybdenum carbide composite material comprises the following steps:
filling argon into a glove box until the pressure in the glove box is 0.1MPa, mixing molybdenum dioxide, magnesium powder and melamine in the glove box according to the molar ratio of 1:6:1, filling the mixture into a ball milling tank, adding a ball milling medium according to the ball material ratio of 100:1, adding the ball milling tank into a planetary ball mill, adjusting the rotating speed of the ball mill to 500 r/min, carrying out ball milling for 15h in argon atmosphere, adding a ball milling product into a hydrochloric acid solution with the concentration of 3mol/L, stirring, centrifuging, washing the centrifuged solid to be neutral, and drying in a drying box overnight to obtain the molybdenum dioxide-molybdenum carbide composite material
The test proves that the molybdenum dioxide-molybdenum carbide composite material of the embodiment consists of MoC and Mo2C and MoO2The composition, the morphology structure and the catalytic performance of the composite material are very close to those of the molybdenum dioxide-molybdenum carbide composite material in the example 16.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The molybdenum dioxide-molybdenum carbide composite material is characterized by comprising MoO2And MoC.
2. The molybdenum dioxide-molybdenum carbide composite material according to claim 1, wherein: the composition of the molybdenum dioxide-molybdenum carbide composite material also comprises Mo2C。
3. The method for preparing a molybdenum dioxide-molybdenum carbide composite material according to claim 1 or 2, comprising the steps of: mixing molybdenum dioxide, magnesium powder and carbonitride, carrying out solid-phase ball milling, acid washing and drying to obtain the molybdenum dioxide-molybdenum carbide composite material.
4. The method for preparing a molybdenum dioxide-molybdenum carbide composite material according to claim 3, wherein: the molar ratio of the molybdenum dioxide to the magnesium powder to the carbon nitride is 1: 6-9: 0.3-2.
5. The method for producing a molybdenum dioxide-molybdenum carbide composite material according to claim 3 or 4, wherein: the carbonitride is at least one of melamine and carbon nitride.
6. The method for producing a molybdenum dioxide-molybdenum carbide composite material according to claim 3 or 4, wherein: the solid phase ball milling is carried out in a protective atmosphere.
7. The method for producing a molybdenum dioxide-molybdenum carbide composite material according to claim 3 or 4, wherein: the ball mill adopted by the solid-phase ball milling is a high-speed shimmy ball mill, the ball-material ratio is 10: 1-100: 1, the rotating speed of the ball mill is 1000-1230 rpm, and the ball milling time is 2-6 h.
8. The method for producing a molybdenum dioxide-molybdenum carbide composite material according to claim 3 or 4, wherein: the ball mill adopted by the solid-phase ball milling is a planetary ball mill, the ball-material ratio is 20: 1-100: 1, the rotating speed of the ball mill is 400-500 rpm, and the ball milling time is 8-20 h.
9. The method for producing a molybdenum dioxide-molybdenum carbide composite material according to claim 3 or 4, wherein: the acid adopted by the acid cleaning is one of hydrochloric acid, sulfuric acid and phosphoric acid.
10. Use of the molybdenum dioxide-molybdenum carbide composite material according to claim 1 or 2 for the preparation of a catalyst for the electrocatalytic hydrogen evolution reaction.
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