CN112295581B - Electrocatalyst material and application thereof - Google Patents
Electrocatalyst material and application thereof Download PDFInfo
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- CN112295581B CN112295581B CN201910669273.8A CN201910669273A CN112295581B CN 112295581 B CN112295581 B CN 112295581B CN 201910669273 A CN201910669273 A CN 201910669273A CN 112295581 B CN112295581 B CN 112295581B
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- 239000000463 material Substances 0.000 title claims abstract description 17
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000012698 colloidal precursor Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 22
- 239000002105 nanoparticle Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 238000005121 nitriding Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal nitride Chemical class 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/50—
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- 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 invention provides an electrocatalyst material whose catalytically active component is Ni 2 Mo 3 N、Ni 2 Mo 3 One or more of N composite material, the Ni 2 Mo 3 N is cubic phase Ni 2 Mo 3 N; ni of the invention 2 Mo 3 The N nano-particle catalyst reaches a higher level in both catalytic activity and stability; the nitrogen source for preparing the nitride is derived from urea, and ammonia gas with strong corrosivity is not used as a nitriding atmosphere, so that the method is green and environment-friendly; the sol precursor is directly put at high temperature for nitridation reaction, so that the crystallization and solidification process is avoided, and the method is favorable for large-scale industrial production.
Description
Technical Field
The invention relates to an electrocatalyst material and applications thereof.
Background
Energy is an important material basis for economic growth and social development. Every epoch-like transition of energy technology is accompanied with the leap of productivity, and the great development and progress of the whole human society are promoted. With the increase of population and the rapid development of economy, the global demand for energy is increasing. Energy crisis and environmental issues have become the focus of important and scientific research in politics, economy, military, diplomatic and other areas of today's international society. The green renewable energy technology is explored and developed, and the dependence on fossil fuel can be fundamentally removed. Therefore, more and more scientific researchers are beginning to search for and develop sustainable energy devices, such as fuel cells, solar cells, metal-air batteries, lithium ion batteries, super capacitors, and the like, without losing their power. The hydrogen energy is used as green energy, has the advantages of wide sources, high specific energy, recycling and the like, is a creditable clean energy star, and the hydrogen production by electrolyzing water becomes a main hydrogen energy mode in the future. When the water is electrolyzed to produce hydrogen, the anode can generate oxygen evolution reaction along with hydrogen evolution of the cathode, and the over-high anode overpotential is the primary factor and the core problem of the energy consumption of the water electrolysis for producing the hydrogen. However, ir, ru and their oxide anode catalysts with high catalytic activity are expensive, scarce in resources and poor in stability. This has led to the active search for the development of a noble metal-substituted catalyst which is excellent in performance and low in cost. The non-noble transition metal nitride often has unsaturated d electron orbitals, excellent corrosion resistance and high electrical conductivity, and is expected to replace noble metals in the application and development of electrochemical catalysis through reasonable design regulation and control of the structure/composition and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: an electrocatalyst material and its applications are provided. The applicant of the present invention has found that cubic phase Ni is a problem in the prior art 2 Mo 3 The N material has excellent oxygen evolution electrocatalytic performance and can replace a noble metal catalyst (IrO) in electrolytic water 2 /CB) is used as an anode catalyst and has the characteristics of low cost, high activity and high stability.
The technical solution of the invention is as follows: an electrocatalyst material with Ni as its catalytically active component 2 Mo 3 N、Ni 2 Mo 3 One or more of N composite materials.
Preferably, the Ni is 2 Mo 3 N is cubic phase Ni 2 Mo 3 N。
The cubic phase Ni 2 Mo 3 The preparation method of N comprises the following steps:
1) Dissolving nickel chloride and molybdenum chloride in an ethanol solution to obtain a clear solution;
2) Adding a nitrogen source into the clear solution obtained in the step 1), and standing to obtain a colloidal precursor;
3) The precursor obtained in the step 2) isCalcining the body in inert gas at the temperature of more than 500 ℃ to obtain cubic phase Ni 2 Mo 3 And N nano-particles.
Preferably, the ethanol solution is absolute ethanol, and the nitrogen source is a nitrogen-containing organic substance.
The nitrogen-containing organic matter is urea, and the inert gas is nitrogen or argon.
The application of the electrocatalyst material comprises all electrocatalytic applications including water electrolysis and metal-air batteries containing oxygen evolution.
The invention discloses a ternary transition metal nitride Ni 2 Mo 3 A preparation method of N nano-particles and application of electrocatalytic oxygen evolution. The method uses two metal chlorides as metal sources and urea as a nitrogen source, and the pure-phase Ni can be obtained by heating in an inert atmosphere 2 Mo 3 An N-nitride catalyst. The precursor used for high-temperature nitridation is sol-like and can be obtained by dissolving metal chloride and urea in absolute ethyl alcohol and standing for a certain time. Ni obtained after nitriding 2 Mo 3 The N particles have uniform nano-morphology, can be used as an electrocatalyst for catalyzing an oxygen evolution reaction, and have higher catalytic activity and stability. The synthesis method provides great possibility for the electric oxygen evolution catalytic material with controllable synthesis components, controllable nano structure, high specific surface area and good durability. The method is simple and easy to implement, low in cost, green and environment-friendly, is suitable for large-scale production, and shows superior commercial IrO in electrochemical oxygen evolution reaction 2 The excellent activity and stability of the/CB catalyst have good industrial application prospect.
The invention has the beneficial effects that: compared with the prior art, the method of the invention has obvious differences:
1) Ni obtained by the method of the invention 2 Mo 3 The N nano-particle catalyst reaches a higher level in both catalytic activity and stability;
2) The nitrogen source for preparing the nitride is derived from urea, and ammonia gas with strong corrosivity is not used as a nitriding atmosphere, so that the method is green and environment-friendly;
3) The invention directly puts the sol precursor at high temperature for nitridation reaction, thereby avoiding the crystallization and solidification process and being beneficial to large-scale industrial production;
4) Nitridation of oxide precursor NiMoO by traditional method 4 The preparation process can directly adjust the initial charge ratio of the nickel element and the molybdenum element, so that the charge ratio is equal to the crystal structure element ratio, and the additional purification process is avoided;
5) Preparation of Ni 2 Mo 3 When N nano-particle catalyst is used, a small amount of other metal salts, such as other metal chlorides, are directly mixed into the precursor to obtain doped Ni 2 Mo 3 An N nanoparticle catalyst;
6) The raw materials used in the method are all common industrial products which are easy to obtain.
Drawings
FIG. 1 shows Ni prepared in examples of the present invention 2 Mo 3 X-ray diffraction pattern of N nanoparticle catalyst.
FIG. 2 shows Ni prepared in an example of the present invention 2 Mo 3 An X-ray photoelectron spectrum of the N nanoparticle catalyst Ni2 p.
FIG. 3 shows Ni prepared in an example of the present invention 2 Mo 3 An X-ray photoelectron spectrum of the N nanoparticle catalyst Mo3 d.
FIG. 4 shows Ni prepared in an example of the present invention 2 Mo 3 Scanning electron microscopy of N nanoparticle catalyst.
FIG. 5 shows Ni prepared in an example of the present invention 2 Mo 3 N nanoparticle catalyst and commercial IrO 2 Rotating disk electrode polarization plot (disk rotation speed 1600 rpm) versus Tafel plot for the/CB catalyst. In the figure, a and Ni 2 Mo 3 N；b、IrO 2 /CB。
FIG. 6 shows Ni prepared in examples of the present invention 2 Mo 3 Stability test results of N nanoparticle catalysts. In the figure, a and Ni 2 Mo 3 N；b、IrO 2 /CB。
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Examples
Preparing an electrocatalyst:
a. dissolving 3 mmol of anhydrous molybdenum chloride and 2 mmol of nickel chloride hexahydrate in 2 mL of ethanol solution to obtain clear and transparent solution;
b. adding 1 g of urea into the solution obtained in the step a, and standing for more than 12 hours at room temperature to obtain a sol precursor;
c. and c, placing the precursor obtained in the step b in a sealed tube furnace, calcining for 3 hours at the temperature of more than 800 ℃ in the argon atmosphere, and raising the temperature at the speed of 2 ℃/min. Naturally cooling to room temperature to obtain Ni 2 Mo 3 N nanoparticle catalysts. The X-ray diffraction result of the obtained product is shown in figure 1, the X-ray photoelectron spectroscopy is shown in figures 2 and 3, and the scanning electron microscope is shown in figure 4;
electrochemical Performance test
Weighing 5 mg of catalyst powder obtained by the method of the invention, dispersing the catalyst powder in 1 mL of isopropanol aqueous solution containing 0.05% of naphthol solution (the volume ratio of water to isopropanol is 1. Specifically, the polarization curve graph of the rotating disk electrode and the Tafel plot are shown in FIG. 5, and the stability test is shown in FIG. 6.
Prepared Ni 2 Mo 3 The N nano-particle catalyst has higher catalytic activity, and the catalyst is 10 mA cm -2 The overpotential under the current density is 290 mV, and the Tafel slope is 68 mV dec -1 And has excellent stability.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (5)
1. Use of an electrocatalyst material, wherein: the catalytic active component of the electrocatalyst material is one or more of Ni2Mo3N and Ni2Mo3N composite materials, and the electrocatalyst material is applied to all electrocatalysis containing oxygen evolution, including water electrolysis and metal-air batteries.
2. Use of an electrocatalyst material according to claim 1, wherein: the Ni2Mo3N is cubic phase Ni2Mo3N.
3. Use of an electrocatalyst material according to claim 2, wherein: the preparation method of the cubic phase Ni2Mo3N comprises the following steps:
1) Dissolving nickel chloride and molybdenum chloride in an ethanol solution to obtain a clear solution;
2) Adding a nitrogen source into the clear solution obtained in the step 1), and standing to obtain a colloidal precursor;
3) Calcining the precursor obtained in the step 2) in inert gas at the temperature of more than 500 ℃ to obtain cubic phase Ni2Mo3N nano
And (3) granules.
4. Use of an electrocatalyst material according to claim 3, characterised in that: the ethanol solution is absolute ethanol, and the nitrogen source is a nitrogen-containing organic matter.
5. Use of an electrocatalyst material according to claim 4, wherein: the nitrogen-containing organic matter is urea, and the inert gas is nitrogen or argon.
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| CN201910669273.8A CN112295581B (en) | 2019-07-24 | 2019-07-24 | Electrocatalyst material and application thereof |
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| CN201910669273.8A CN112295581B (en) | 2019-07-24 | 2019-07-24 | Electrocatalyst material and application thereof |
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| CN112295581B true CN112295581B (en) | 2022-10-14 |
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|---|---|---|---|---|
| CN101091917A (en) * | 2006-06-23 | 2007-12-26 | 中国石油天然气股份有限公司 | Catalyst of deep additional treatment of hydrogenising base oil for lubricant, preparation method and application |
| CN101099934A (en) * | 2006-07-04 | 2008-01-09 | 中国石油天然气股份有限公司 | Aromatic saturated hydrogenation catalyst and its preparing process |
| CN101099933A (en) * | 2006-07-04 | 2008-01-09 | 中国石油天然气股份有限公司 | Diesel oil aromatic saturated hydrogenation catalyst and its application |
| CN101837294A (en) * | 2010-03-03 | 2010-09-22 | 巴州东辰工贸有限公司 | Preparation method for solid acid catalyst r-AI203 |
| RU2535990C1 (en) * | 2013-07-05 | 2014-12-20 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | METHOD OF OBTAINING CATALYST OF CARBONIC ACID METHANATION BASED ON BI-METAL NITRIDE Ni2Mo3N |
| CN107522174A (en) * | 2017-08-09 | 2017-12-29 | 江苏理工学院 | A kind of new method for preparing ternary molybdenum system nitride nano-material |
-
2019
- 2019-07-24 CN CN201910669273.8A patent/CN112295581B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101091917A (en) * | 2006-06-23 | 2007-12-26 | 中国石油天然气股份有限公司 | Catalyst of deep additional treatment of hydrogenising base oil for lubricant, preparation method and application |
| CN101099934A (en) * | 2006-07-04 | 2008-01-09 | 中国石油天然气股份有限公司 | Aromatic saturated hydrogenation catalyst and its preparing process |
| CN101099933A (en) * | 2006-07-04 | 2008-01-09 | 中国石油天然气股份有限公司 | Diesel oil aromatic saturated hydrogenation catalyst and its application |
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| RU2535990C1 (en) * | 2013-07-05 | 2014-12-20 | Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" | METHOD OF OBTAINING CATALYST OF CARBONIC ACID METHANATION BASED ON BI-METAL NITRIDE Ni2Mo3N |
| CN107522174A (en) * | 2017-08-09 | 2017-12-29 | 江苏理工学院 | A kind of new method for preparing ternary molybdenum system nitride nano-material |
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