CN107913721A - A kind of method and catalysis material that rich defect catalysis material is prepared using magnesium reduction process - Google Patents
A kind of method and catalysis material that rich defect catalysis material is prepared using magnesium reduction process Download PDFInfo
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- CN107913721A CN107913721A CN201711225700.0A CN201711225700A CN107913721A CN 107913721 A CN107913721 A CN 107913721A CN 201711225700 A CN201711225700 A CN 201711225700A CN 107913721 A CN107913721 A CN 107913721A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 present invention provides a kind of method that rich defect catalysis material is prepared using magnesium reduction process, and this method comprises the following steps：By double base transition metal oxide material and NaHCO3Sealed after uniformly being mixed with magnesium powder in a kettle, the double base transition metal M and N in double base transition metal oxide material are any two kinds of combinations in Mo, V, Mn, W or Nb；Under inert protective atmosphere, when insulation 15 is small at 600 900 DEG C of temperature, obtained product pickling can be obtained to the double base richness defect carbides catalytic material of carbon parcel.The defects of material is rich in can provide substantial amounts of avtive spot during electrochemistry evolving hydrogen reaction, can effectively improve catalyst activity.Particle exterior surface wraps up a floor height crystallinity carbon at the same time, had not only improved material conductivity but also had improved the cyclical stability of material, it is suppressed that dissolving of the material in catalytic process.The method is simple, and it is clear and definite to obtain product, and has anticorrosive effect, and improving catalyst activity for electro-catalysis field provides a brand-new path.
Description
Technical field
The present invention relates to technical field of material chemistry, prepares rich defect using magnesium reduction process more specifically to one kind and urges
Change the method and catalysis material of material.
Background technology
Hydrogen (H2) it is considered as a kind of clean energy resource that can be used for substituting traditional fossil energy, while there is high heat
Value.Hydrogen energy source effective exploitation is realized, so that two emphasis links for successfully substituting fossil energy are producing and storing for hydrogen.Mesh
Before, industrial hydrogen manufacturing mode is very much, mainly using water electrolysis hydrogen production, catalyzed aqueous vapour reformation, Coal Gasification hydrogen manufacturing, petroleum cracking
And Catalytic Conversion of Natural Gas hydrogen manufacturing etc., but the shortcomings that these methods all urgently overcome there is some, as energy consumption is very high.Electricity
Xie Shui is most one of simple, most efficient method, its advantage is hydrogen purity height, but electrolysis evolving hydrogen reaction speed is slow, is needed
To accelerate dynamic process using catalyst, catalyst such as noble metal platinum (Pt) now, due to platinum it is expensive with
And reserves are limited, its large-scale use ultimately limit.So catalysis of the development non-noble metallic materials as electrochemistry liberation of hydrogen
Agent becomes the problem highly paid close attention to now.Transition metal carbide due to its abundant reserves, cheap price and
Outstanding catalytic performance has obtained extensive research.Most of catalyst on the market is block materials, and block pattern is due to lacking
Weary effective avtive spot, catalytic efficiency are relatively low.How improving the catalytic performance of material can start with from following several respects：1. increase
Add the specific surface area of material；2. by catalyst material by exfoliated, there is provided quick ion channel；3. improve the conduction of material
Property.4. the border of the excessive catalyst of manufacture, causes Cloud Distribution uneven, therefore obtains the activity of higher；Wherein first three
Method is provided to the avtive spot of increase unit area, and the 4th kind of method can fundamentally change catalytic effect.Therefore, such as
What selects suitable method to improve the difficult point that the catalytic performance of material is always those skilled in the art.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of richness for preparing superelevation catalytic performance using magnesium reduction process
The method of defect catalysis material and preparation-obtained catalysis material.
The technical solution adopted by the present invention to solve the technical problems is：
A kind of method that rich defect catalysis material is prepared using magnesium reduction process, is comprised the following steps：
By double base transition metal oxide material and NaHCO3Sealed after uniformly being mixed with magnesium powder in a kettle, it is described double
Double base transition metal M and N in element/transition metal oxide material are any two kinds of combination in Mo, V, Mn, W or Nb；
Under inert protective atmosphere, kept the temperature at 600-900 DEG C of temperature 1-5 it is small when, obtained product pickling can be obtained
To the double base richness defect carbides catalytic material of carbon parcel.
In such scheme, the double base transition metal oxide material, NaHCO3Mass ratio with magnesium powder is 1-10:1-
10:1-10。
In such scheme, the inert protective atmosphere is argon gas.
In such scheme, the particle size range of the double base transition metal oxide material powder is 5 μm -20 μm.
The catalysis material that the method is prepared, the catalysis material include carbon net and are wrapped in some in carbon net
Nano particle, some nano particles are the metal M carbide particles that rich defect phase nanoscale is cross-linked with each other and metal N carbonizations
Composition granule.
In such scheme, the size of the metal M carbide particles being cross-linked with each other and metal N carbide particles is 20-
100nm。
The present invention reaction principle be：Mg+MNO+NaHCO3=MgO+MC+NC+CO2(wherein M, N Mo, V, Mn, W or
Nb；MC is the metal carbides of M element, and NC is the metal carbides of N element, and molar ratio is not limited to 1：1).In protection gas
Under atmosphere, kept the temperature at 600-900 DEG C of temperature 1-5 it is small when, pickling is removed to prepare after magnesia and mutually received with rich defect
The particle that meter level is cross-linked with each other.Since this product is due to that predecessor is obtained by phase separation, two obtained kind carbide
It can at the same time separate out, but can not be kept completely separate out, therefore crystal lattice interface can be formed among two kinds of obtained products, this boundary
Face can provide huge catalytic activity；Sodium acid carbonate decomposes the carbon dioxide produced and is turned by magnesiothermic reduction reaction in this method
It is changed into the carbon network structure of high crystalline with high conductivity, it is online that nano particle can be wrapped in carbon.What the material was rich in lacks
Substantial amounts of avtive spot can be provided during electrochemistry evolving hydrogen reaction by falling into, and can effectively improve catalyst activity, and have
Excellent performance.Particle exterior surface wraps up the crystalline carbon of a floor height, had not only improved the electric conductivity of material but also had improved material
Cyclical stability, it is suppressed that dissolving of the material in catalytic process.
Beneficial effects of the present invention are：
1. by the raw material of micro-meter scale by magnesium thermit, there are CO2In the case of, can effectively it be crushed, and
It is translated into the material of nanoscale.
2. raw material used in simultaneously can be obtained widely for double base component in nature, utilize double base oxo transition metal
Compound and sodium acid carbonate and magnesium powder mix according to a certain percentage, handle at a certain temperature, can obtain rich in defect
The double base transition metal carbide being reduced, since this product is due to that predecessor is obtained by phase separation, two obtained
Kind carbide can separate out at the same time, but can not be kept completely separate out, therefore can form lattice among two kinds of obtained products
Interface, this interface can provide huge catalytic activity, and the method operation is easy, prepares and carries for high performance electrochemical catalyst
New method is supplied, this method is never reported in other documents or patent.
3. sodium acid carbonate decomposes the carbon dioxide produced and is changed into by magnesiothermic reduction reaction with highly conductive in this method
Property high crystalline carbon network structure, while the corresponding carbonized product of metallic element can be formed, the catalysis which is formed
On the one hand agent has outstanding electric conductivity, on the other hand also have good corrosion resistance and cyclical stability.
4. double base material can be carried out phase separation in situ by this method, obtained product can not be completely separated into isolated deposit
Individual, therefore the defects of a large amount of can be obtained in its coherence intersection, be very beneficial for the lifting of catalytic performance, urged in electricity
Change field application prospect is extensive.
Brief description of the drawings
Below in conjunction with accompanying drawings and embodiments, the invention will be further described：
Fig. 1 is the XRD spectrum that product is prepared in the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph that product is prepared in the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope picture that product is prepared in the embodiment of the present invention 1.
Fig. 4 is the electrochemical tests figure that final product is prepared in the embodiment of the present invention 1.
Fig. 5 is the Tafel slope comparison diagrams that the embodiment of the present invention 1 is prepared.
Fig. 6 is stable in catalytic performance contrast after the product circulation that the embodiment of the present invention 1 is prepared.
Fig. 7 is the Tafel figures that final product is prepared in the present embodiment 2.
Fig. 8 is the electrochemical tests figure that final product is prepared in the present embodiment 2.
Fig. 9 is the Tafel figures that final product is prepared in the present embodiment 3.
Figure 10 is the electrochemical tests figure that final product is prepared in the present embodiment 3.
Figure 11 is the Tafel figures that final product is prepared in the present embodiment 4.
Figure 12 is the electrochemical tests figure that final product is prepared in the present embodiment 4.
Figure 13 is the Tafel figures that final product is prepared in the present embodiment 5.
Figure 14 is the electrochemical tests figure that final product is prepared in the present embodiment 5.
Figure 15 is the Tafel figures that final product is prepared in the present embodiment 6.
Figure 16 is the electrochemical tests figure that final product is prepared in the present embodiment 6.
Figure 17 is the schematic diagram that the product that the present invention obtains participates in evolving hydrogen reaction.
Embodiment
In order to which the technical features, objects and effects of the present invention are more clearly understood, now compare attached drawing and describe in detail
The embodiment of the present invention.
Embodiment 1
(1) by micron order V2MoO8Powder and magnesium powder and NaHCO3In mass ratio 1:1.5:Sealing is put into 1.5 being uniformly mixed instead
Answer in kettle；
(2) 800 DEG C are heated under Ar protective atmospheres, soaking time obtains Mo for 1-2h2C/V8C7Mixture；
(3) nano-scale particle of carbon parcel can be obtained by products therefrom in (2) being carried out pickling.
The reactional equation of the principle of this reaction be for：2NaHCO3=Na2CO3+CO2+H2O, decomposites CO at low temperature2, so
After pass through 2Mg+CO2=2MgO+C, finally by C+V2MoO8---Mo2C+V8C7+CO2Deng product.
In the present embodiment, V2MoO8The particle diameter of powder is 5 μm -20 μm.
Catalysis material includes carbon net and some nano particles being wrapped in carbon net, and nano particle is rich defect phase nanoscale
The Mo being cross-linked with each other2C particles and V8C7Particle.The Mo being cross-linked with each other2C particles and V8C7The size of particle is 20-100nm.
Obtained product is subjected to XRD diffracting spectrum characterizations, in Fig. 1, it is Mo to obtain product2C/V8C7, except oxidation
Magnesium has no other dephasigns with sodium carbonate；From the scanning electron microscope (SEM) photograph of Fig. 2, the product that the present embodiment is prepared is nano level
Loose structure；From the transmission electron microscope picture of Fig. 3, product is prepared as not exclusively phase separation in situ in the present embodiment, has rich
The defects of rich, and all wrapped by the carbon network of high conductivity.Fig. 4 be reaction product electrocatalysis characteristic, with raw material with
And comparative run Mo2C and V8C7Have greatly improved compared to catalytic performance.Fig. 5 is Tafel slope figures, and Tafel slope numerical value is smaller
The required overpotential of proved response is smaller, i.e., performance is better, understands product of the present invention numerically by being contrasted in figure
Close to Pt, there is good electrocatalysis characteristic.Fig. 6 is the Mo that the embodiment of the present invention 1 is prepared2C/V8C7Followed as catalyst
The comparison diagram of catalytic performance after ring 10000 times, it can be seen that it is little to circulate front and rear performance change, therefore shows that reaction product has
There are good stability and durability.
Embodiment 2
(1) by micron order V2MoO8Powder and magnesium powder and NaHCO3In mass ratio 1:3:10 uniformly mixed are put into seal reaction
In kettle；
(2) 600 DEG C are heated under Ar protective atmospheres, soaking time obtains Mo for 1-2h2C/V8C7Mixture；
(3) nano-scale particle of carbon parcel can be obtained by products therefrom in (2) being carried out pickling.
In the present embodiment, V2MoO8The particle diameter of powder is 5 μm -20 μm.The Mo being cross-linked with each other2C particles and V8C7The ruler of particle
Very little is 30-100nm.
Embodiment 3
(1) by micron order V2MoO8Powder and magnesium powder and NaHCO3In mass ratio 1:4:2 be uniformly mixed be put into sealing reaction kettle
In；
(2) 700 DEG C are heated under Ar protective atmospheres, soaking time obtains Mo for 1-2h2C/V8C7Mixture；
(3) nano-scale particle of carbon parcel can be obtained by products therefrom in (2) being carried out pickling.
In the present embodiment, V2MoO8The particle diameter of powder is 5 μm -20 μm.The Mo being cross-linked with each other2C particles and V8C7The ruler of particle
Very little is 40-60nm.
Fig. 8 is V2MoO8700 DEG C of obtained polarization curves and Tafel slope figures are heated in Ar, can be seen by curve
Go out, then the catalyst material excellent performance arrived under the conditions of this, can be with practical application.
Embodiment 4
(1) by micron order V2MoO8Powder and magnesium powder and NaHCO3In mass ratio 1:1.5:1.5 uniformly mixed are put into seal instead
Answer in kettle；
(2) 900 DEG C are heated under Ar protective atmospheres, soaking time obtains Mo for 1-2h2C/V8C7Mixture；
(3) nano-scale particle of carbon parcel can be obtained by products therefrom in (2) being carried out pickling.
In the present embodiment, V2MoO8The particle diameter of powder is 5 μm -20 μm.The Mo being cross-linked with each other2C particles and V8C7The ruler of particle
Very little is 20-100nm.
Fig. 9 is V2MoO8900 DEG C of obtained polarization curves and Tafel slope figures are heated in Ar, can be seen by curve
Go out, then the catalyst material excellent performance arrived under the conditions of this, can be with practical application.
Embodiment 5
(1) by micron order MnMoO4Powder and magnesium powder and NaHCO3In mass ratio 1:1.5:1.5 uniformly mixed are put into seal instead
Answer in kettle；
(2) 800 DEG C are heated under Ar protective atmospheres, soaking time obtains product for 1-5h；
(3) nano-scale particle of carbon parcel can be obtained by products therefrom in (2) being carried out pickling.
In the present embodiment, V2MoO8The particle diameter of powder is 5 μm -20 μm.The Mo being cross-linked with each other2C particles and V8C7The ruler of particle
Very little is 20-100nm.
Figure 10 is MnMoO4800 DEG C of obtained polarization curves and Tafel slope figures are heated in Ar, can be with by curve
Find out, then the catalyst material excellent performance arrived under the conditions of this, can be with practical application, therefore dual element MnMoO4Powder also may be used
To obtain two kinds of unseparated carbonized products, applied in practice.
Embodiment 6
(1) by micron order WMoO4Powder and magnesium powder and NaHCO3In mass ratio 1:1:1.5 uniformly mixed are put into seal reaction
In kettle；
(2) 800 DEG C are heated under Ar protective atmospheres, soaking time obtains product for 1-2h；
(3) nano-scale particle of carbon parcel can be obtained by products therefrom in (2) being carried out pickling.
In the present embodiment, V2MoO8The particle diameter of powder is 5 μm -20 μm.The Mo being cross-linked with each other2C particles and V8C7The ruler of particle
Very little is 20-100nm.
Figure 10 is WMoO4800 DEG C of obtained polarization curves and Tafel slope figures are heated in Ar, can be with by curve
Find out, then the catalyst material excellent performance arrived under the conditions of this, can be with practical application, therefore dual element WMoO4Powder also may be used
To obtain two kinds of unseparated carbonized products, applied in practice.
It is understood that the atmosphere of the present invention is not limited to Ar one kind, other can do protection gas and be not involved in the equal of reaction
Can, such as helium, nitrogen.
The present invention utilizes the CO decomposited by simple magnesium reduction process2To cause micro materials to be broken to nano-catalytic
Material.Wherein involved magnesium reduction process has been reported that in related patents technology, such as " one kind utilizes magnesiothermic reduction legal system
Silica-carbon presoma is mixed with magnesium powder in the method for standby Si-C composite material " (CN106374088A) and carries out magnesium heat also
Original finally obtains Si-C composite material.And for example in patent " a kind of method of preparing porous silicon by magnesiothermic reduction " (CN102259858A)
Using the oxide of silicon as raw material, the porous silicon of self-supporting is obtained after generating the mixture processing of silicon and magnesia by magnesium thermit
Material.2 patents of the above reduce reaction temperature merely by Mg thermal reduction reactions, are not related to broken process, and we carry
A kind of new mode is gone out, using solid phase reaction, and has been related to itself decomposing generation CO2, so as to produce broken effect, realize
The process of part phase separation.
The present invention innovative point be react primary raw material be to use double base transition metal oxide, with sodium acid carbonate,
Saleratus, calcium carbonate etc., which can decompose, produces CO2Raw material and magnesium mixing after, it is endless that two-phase can be obtained by magnesium thermit
Fully separating material, resulting boundary effect produce high activity.Another of the present invention has the prominent advantages that carbonic acid
The CO that hydrogen sodium decomposes2Material granule can be wrapped after participating in reaction as the carbon of carbon source reduction generation high crystalline, there is provided
Excellent electric conductivity.The invention raw material is cheap, is raw material using double base transition metal oxide and sodium acid carbonate and magnesium powder,
By simple magnesium thermit, the reduzate rich in defect is obtained, is readily produced and for the electrochemical catalyst of high quality
Preparation provides new method, can be widely applied to electro-catalysis field.
The embodiment of the present invention is described above in conjunction with attached drawing, but the invention is not limited in above-mentioned specific
Embodiment, above-mentioned embodiment is only schematical, rather than restricted, those of ordinary skill in the art
Under the enlightenment of the present invention, in the case of present inventive concept and scope of the claimed protection is not departed from, it can also make very much
Form, these are belonged within the protection of the present invention.
Claims (6)
- A kind of 1. method that rich defect catalysis material is prepared using magnesium reduction process, it is characterised in that comprise the following steps：By double base transition metal oxide material and NaHCO3Sealed after uniformly being mixed with magnesium powder in a kettle, the double base mistake The double base transition metal M in metal oxide materials and N are crossed as any two kinds of combination in Mo, V, Mn, W or Nb；In inertia Under protective atmosphere, kept the temperature at 600-900 DEG C of temperature 1-5 it is small when, obtained product pickling can be obtained to the double base of carbon parcel Rich defect carbides catalytic material.
- 2. a kind of method that rich defect catalysis material is prepared using magnesium reduction process according to claim 1, its feature are existed In the double base transition metal oxide material, NaHCO3Mass ratio with magnesium powder is 1-10:1-10:1-10.
- 3. a kind of method that rich defect catalysis material is prepared using magnesium reduction process according to claim 1, its feature are existed In the inert protective atmosphere is argon gas.
- 4. a kind of method that rich defect catalysis material is prepared using magnesium reduction process according to claim 1, its feature are existed In the particle size range of the double base transition metal oxide material powder is 5 μm -20 μm.
- 5. the catalysis material that method according to any one of claims 1 to 4 is prepared, it is characterised in that described rich scarce Falling into catalysis material includes carbon net and some nano particles being wrapped in carbon net, and the nano particle is rich defect phase nanoscale phase Mutual crosslinked metal M carbide particles and metal N carbide particles.
- 6. catalysis material according to claim 5, it is characterised in that the metal M carbide particles being cross-linked with each other and The size of metal N carbide particles is 20-100nm.
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| CN201711225700.0A CN107913721B (en) | 2017-11-29 | 2017-11-29 | Method for preparing defect-rich catalytic material by using magnesiothermic reduction method and catalytic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110721714A (en) * | 2019-10-29 | 2020-01-24 | 广东工业大学 | Mo2C catalyst and preparation method and application thereof |
| CN110721713A (en) * | 2019-10-29 | 2020-01-24 | 广东工业大学 | Mo2C catalytic material and preparation method and application thereof |
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| CN104120457A (en) * | 2014-07-10 | 2014-10-29 | 上海大学 | Preparing method of metal-carbide-containing multi-layer multi-component composite material |
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| CN104120457A (en) * | 2014-07-10 | 2014-10-29 | 上海大学 | Preparing method of metal-carbide-containing multi-layer multi-component composite material |
| CN106374088A (en) * | 2016-10-14 | 2017-02-01 | 浙江天能能源科技股份有限公司 | Method for preparing silicon/carbon composite material with magnesiothermic reduction process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721714A (en) * | 2019-10-29 | 2020-01-24 | 广东工业大学 | Mo2C catalyst and preparation method and application thereof |
| CN110721713A (en) * | 2019-10-29 | 2020-01-24 | 广东工业大学 | Mo2C catalytic material and preparation method and application thereof |
| CN110721714B (en) * | 2019-10-29 | 2022-07-29 | 广东工业大学 | Mo 2 C catalyst and preparation method and application thereof |
| CN110721713B (en) * | 2019-10-29 | 2022-07-29 | 广东工业大学 | Mo 2 C catalytic material and preparation method and application thereof |
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