CN107758668B - Method for rapidly preparing carbon-loaded molybdenum carbide through microwave heating - Google Patents
Method for rapidly preparing carbon-loaded molybdenum carbide through microwave heating Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of carbon-based catalytic materials, in particular to a method for quickly preparing carbon-supported molybdenum carbide by microwave heating, which comprises the following steps: (1) preparation of precursor, (2) microwave radiation treatment. The carbon-loaded molybdenum carbide prepared by the method has the advantages of uniform particle size distribution, easy size control, high crystallinity, difficult oxidation and good stability. The method has the advantages of wide applicability, environmental protection, simple and safe process, short time consumption, low energy consumption, easy large-scale production and the like.
Description
Technical Field
The invention relates to a method for rapidly preparing carbon-loaded molybdenum carbide by microwave heating, belonging to the technical field of preparation of carbon-based catalytic materials.
Background
The transition metal carbide is a kind of interstitial compound with metal property generated by carbon atoms entering crystal lattices of transition metals, has special chemical and physical properties such as high melting point, high hardness and the like, and is widely applied to the fields of energy, catalysis, environment and the like. Because of its low cost, electronic structure and catalytic activity similar to noble metals, molybdenum carbide is often used as a substitute for noble metal catalysts (Pt, Pd, etc.) in a variety of catalytic reactions, such as alkane isomerization, water gas shift, unsaturated hydrocarbon hydrogenation, carbon dioxide reforming, oil hydrodesulfurization and denitrification, fischer-tropsch synthesis, electrocatalytic water decomposition, and other catalytic reactions.
The current preparation methods of molybdenum carbide mainly comprise a temperature programming reaction method, a carbothermic reduction method, a metal precursor cracking method and the like. However, the existing synthesis methods have some disadvantages: such as the use of hazardous combustible gases (CH) at high temperatures4/H2Or C2H4/H2) The operation danger is high, the preparation process is complex and time-consuming, and the furnace body needs to maintain the high temperature required by the reaction for a long time, so that the energy consumption is high. Therefore, the method has important significance and wide application prospect in developing a strategy for synthesizing the molybdenum carbide catalytic material, which is green, safe, simple in process, short in time consumption and low in energy consumption.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for quickly preparing carbon-supported molybdenum carbide by microwave heating, wherein carrier carbon comprises: the method has the characteristics of wide applicability, environmental friendliness, simple and safe process, short time consumption, low energy consumption, easiness in large-scale production and the like. The carbon-loaded molybdenum carbide prepared by the method has uniform and controllable particle size, high crystallinity and good stability.
In order to achieve the purpose of the invention and solve the problems in the prior art, the invention adopts the technical scheme that: a method for rapidly preparing carbon-loaded molybdenum carbide by microwave heating comprises the following steps:
step 1, preparation of precursor
(a) Taking 10-50 mL of deionized water, adding 0.2-10 g of molybdenum salt, stirring for 2-30 min, then adding 0.2-5 g of powdered carbon material into the solution, continuing stirring for 2-30 min, performing ultrasonic treatment for 2-30 min, and drying the obtained dispersion at 40-150 ℃ to obtain a carbon-supported molybdenum carbide precursor;
(b) taking 10-50 mL of deionized water, adding 0.2-10 g of molybdenum salt, stirring for 2-30 min, then dipping the integral carbon carrier into a molybdenum salt solution, stirring for 2-20 min, carrying out ultrasonic treatment for 2-20 min, then taking out the integral carbon carrier, and drying at 40-150 ℃ to obtain an integral carbon-supported molybdenum carbide precursor;
the molybdenum salt in the step 1 is selected from one of ammonium heptamolybdate or sodium molybdate, the powdered carbon material is selected from one of carbon black, carbon nano tubes or graphene, and the monolithic carbon support is selected from carbon fiber paper;
step 2, microwave radiation treatment
(a) Transferring the carbon-loaded molybdenum carbide precursor obtained in the step (1) into a microwave reactor, and under the protection of inert gas, controlling the microwave radiation power at 500-2000W and the microwave radiation time at 5-1500 s to obtain a carbon-loaded molybdenum carbide material;
(b) mixing the integral carbon-loaded molybdenum carbide precursor obtained in the step (1) with a powdered carbon material, transferring the mixture into a microwave reactor, controlling the microwave radiation power to be 500-2000W and the microwave radiation time to be 5-1500 s under the protection of inert gas, and separating the powdered carbon material in the mixture to obtain an integral carbon-loaded molybdenum carbide material;
the inert gas in the step 2 is selected from one of nitrogen or argon, and the powdered carbon material is selected from one of graphene or graphite.
The invention has the beneficial effects that: a method for rapidly preparing carbon-loaded molybdenum carbide by microwave heating comprises the following steps: (1) preparation of precursor, (2) microwave radiation treatment. Compared with the prior art, the carbon-loaded molybdenum carbide prepared by the method has uniform and controllable particle size, high crystallinity and good stability. The method has the advantages of wide applicability, environmental protection, simple and safe process, short time consumption, low energy consumption, easy large-scale production and the like.
Drawings
FIG. 1 is a transmission electron micrograph of the carbon black-supported molybdenum carbide prepared in example 1.
Fig. 2 is an X-ray diffraction analysis chart of the carbon nanotube-supported molybdenum carbide prepared in example 2.
Fig. 3 is a scanning electron micrograph of the carbon fiber-supported molybdenum carbide prepared in example 3.
FIG. 4 is a transmission electron micrograph of carbon black-supported molybdenum carbide prepared in example 5.
Fig. 5 is an X-ray diffraction analysis chart of the carbon fiber-supported molybdenum carbide prepared in example 6.
FIG. 6 is an X-ray diffraction analysis chart of the carbon black-supported molybdenum carbide prepared in example 8.
Fig. 7 is a scanning electron micrograph of the carbon fiber-supported molybdenum carbide prepared in example 9.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
And (3) adding 0.22g of ammonium heptamolybdate into 20mL of deionized water, stirring for 10min, then adding 0.50g of carbon black into the solution, stirring for 5min, carrying out ultrasonic treatment for 10min, and drying the obtained dispersion at 80 ℃ to obtain the conductive carbon black loaded molybdenum salt compound. And transferring the carbon black loaded molybdenum carbide material into a microwave reactor, introducing nitrogen as protective gas, and performing microwave radiation for 360 seconds under the power of 1000W to obtain the carbon black loaded molybdenum carbide material. As can be seen from the transmission electron microscope picture (figure 1), molybdenum carbide (black particles) is uniformly distributed on the conductive carbon black, and the particle size distribution statistical result shows that the particle size of the molybdenum carbide is about 12 nm.
Example 2
And adding 1.46g of ammonium heptamolybdate into 50mL of deionized water, stirring for 20min, then adding 5.00g of carbon nano tube into the solution, stirring for 10min, performing ultrasonic treatment for 20min, and drying the obtained dispersion liquid at 100 ℃ to obtain the molybdenum salt loaded carbon nano tube compound. And transferring the carbon nano tube loaded molybdenum carbide material into a microwave reactor, introducing argon as a protective gas, and performing microwave radiation for 540s under 1300W power to obtain the carbon nano tube loaded molybdenum carbide material. From an XRD spectrogram (figure 2), the molybdenum carbide loaded on the carbon nano tube has no impurity peak, which shows that the molybdenum carbide has high purity and good crystallinity, and the average grain size of the molybdenum carbide in the material calculated according to the Sherre formula is 15 nm.
Example 3
And (3) adding 5.00g of ammonium heptamolybdate into 25mL of deionized water, stirring for 20min, then soaking the carbon fiber paper into a molybdenum salt solution, stirring for 5min, performing ultrasonic treatment for 20min, then taking out the carbon fiber paper, and drying at 90 ℃ to obtain the molybdenum salt-loaded carbon fiber paper compound. And mixing the carbon fiber paper and graphene, transferring the mixture into a microwave reactor, introducing argon as a protective gas, performing microwave radiation for 600s at the power of 800W, and separating the graphene to obtain the carbon fiber paper-loaded molybdenum carbide material. From the scanning electron microscope picture (fig. 3), it can be seen that molybdenum carbide particles are uniformly loaded on the carbon fibers, and the size distribution of the molybdenum carbide is mainly concentrated at about 1000nm according to the statistical result of the particle size distribution of the molybdenum carbide in the picture.
Example 4
And (3) adding 0.38g of sodium molybdate into 25mL of deionized water, stirring for 10min, then adding 0.60g of graphene into the solution, stirring for 5min, carrying out ultrasonic treatment for 15min, and drying the obtained dispersion liquid at 60 ℃ to obtain the graphene-supported molybdenum salt compound. And transferring the graphene loaded molybdenum carbide material to a microwave reactor, introducing argon as a protective gas, and performing microwave radiation for 300s under 1300W power to obtain the graphene loaded molybdenum carbide material.
Example 5
Taking 50mL of deionized water, adding 0.65g of ammonium heptamolybdate, stirring for 20min, then adding 1.50g of carbon black into the solution, stirring for 5min, carrying out ultrasonic treatment for 30min, and drying the obtained dispersion liquid at 120 ℃ to obtain the carbon black-loaded molybdenum salt compound. And transferring the carbon black loaded molybdenum carbide material into a microwave reactor, introducing argon as a protective gas, and performing microwave radiation for 500s under the power of 1000W to obtain the carbon black loaded molybdenum carbide material. From a transmission electron microscope picture (figure 4), the size of the molybdenum carbide particles is 5-10 nm, the molybdenum carbide particles have obvious lattice stripes, and the molybdenum carbide particles show higher crystallinity.
Example 6
And (3) adding 1.25g of ammonium heptamolybdate into 20mL of deionized water, stirring for 20min, then soaking the carbon fiber paper into a molybdenum salt solution, stirring for 15min, performing ultrasonic treatment for 20min, taking out the carbon fiber paper, and drying at 80 ℃ to obtain the molybdenum salt-loaded carbon fiber paper compound. And then mixing the carbon fiber paper with graphite powder, transferring the mixture into a microwave reactor, introducing argon gas as a protective gas, performing microwave radiation for 600s under the power of 1000W, and separating the graphite powder to obtain the carbon fiber paper-loaded molybdenum carbide material. From the XRD spectrogram (figure 5), the carbon fiber loaded molybdenum carbide has high crystallinity and does not have impurity peaks such as molybdenum oxide and the like, which indicates that the prepared molybdenum carbide is purer.
Example 7
And (3) adding 0.25g of sodium molybdate into 30mL of deionized water, stirring for 20min, then adding 0.68g of carbon nano tube into the solution, stirring for 15min, carrying out ultrasonic treatment for 30min, and drying the obtained dispersion liquid at 130 ℃ to obtain the molybdenum salt loaded carbon nano tube compound. And transferring the carbon nano tube loaded molybdenum carbide material into a microwave reactor, introducing argon as a protective gas, and performing microwave radiation for 1200s under the power of 800W to obtain the carbon nano tube loaded molybdenum carbide material.
Example 8
Taking 50mL of deionized water, adding 0.75g of ammonium heptamolybdate, stirring for 30min, then adding 1.25g of carbon black into the solution, stirring for 15min, carrying out ultrasonic treatment for 20min, and drying the obtained dispersion liquid at 80 ℃ to obtain the carbon black-loaded molybdenum salt compound. And then transferring the carbon black loaded molybdenum carbide material into a microwave reactor, introducing argon as a protective gas, and performing microwave radiation for 480s under the power of 1000W to obtain the carbon black loaded molybdenum carbide material. From the XRD spectrum (figure 6), the conductive carbon black loaded molybdenum carbide has higher crystallinity and purity, and the average grain size of the molybdenum carbide in the material calculated according to the Sherrer formula is 17 nm.
Example 9
And (3) adding 0.50g of ammonium heptamolybdate into 40mL of deionized water, stirring for 20min, then soaking the carbon fiber paper into a molybdenum salt solution, stirring for 15min, performing ultrasonic treatment for 20min, taking out the carbon fiber paper, and drying at 100 ℃ to obtain the molybdenum salt-loaded carbon fiber paper compound. And then mixing the carbon fiber paper and graphene, transferring the mixture into a microwave reactor, introducing argon as a protective gas, performing microwave radiation for 10s under 850W power, and separating the graphene to obtain the carbon fiber paper-loaded molybdenum carbide material. From the scanning electron microscope picture (fig. 7), it can be seen that the molybdenum carbide particles are small and uniformly loaded on the carbon fibers, and the size distribution of the molybdenum carbide is mainly concentrated around 80nm according to the statistical result of the particle size distribution of the molybdenum carbide in the picture.
Claims (1)
1. A method for rapidly preparing carbon-loaded molybdenum carbide by microwave heating is characterized by comprising the following steps:
step 1, preparation of precursor
Adding 0.2-10 g of molybdenum salt into 10-50 mL of deionized water, stirring for 2-30 min, then dipping the integral carbon carrier into the molybdenum salt solution, stirring for 2-20 min, performing ultrasonic treatment for 2-20 min, and then mixingTaking out the integral carbon carrier at 40-150 deg.coDrying under the condition of C to obtain an integral carbon-loaded molybdenum carbide precursor, wherein the molybdenum salt is selected from one of ammonium heptamolybdate or sodium molybdate, and the integral carbon carrier is selected from carbon fiber paper;
step 2, microwave radiation treatment
Mixing the integral carbon-loaded molybdenum carbide precursor obtained in the step (1) with a powdered carbon material, transferring the mixture into a microwave reactor, controlling the microwave radiation power to be 500-2000W and the microwave radiation time to be 5-1500 s under the protection of protective gas, and separating the powdered carbon material in the mixture to obtain an integral carbon-loaded molybdenum carbide material; the protective gas is selected from one of nitrogen or argon, and the powdered carbon material is selected from one of graphene or graphite.
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